Polypropylene Uses and Benefits

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POLYMER SCIENCE AND TECHNOLOGY
POLYPROPYLENE
PROPERTIES, USES AND BENEFITS
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POLYPROPYLENE
PROPERTIES, USES AND BENEFITS
PAULA GARCIA
EDITOR
New York

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Names: Garcia, Paula (Chemistry writer)
Title: Polypropylene : properties, uses, and benefits / Paula Garcia, editor.
Description: Hauppauge, New York : Nova Science Publishers, Inc., [2016] |
Series: Polymer science and technology | Includes bibliographical
references and index.
Identifiers: LCCN 2016036234 (print) | LCCN 2016040503 (ebook) | ISBN
9781536100082 (hardcover) | ISBN 9781536100297
Subjects: LCSH: Polypropylene.
Classification: LCC TP1180.P68 P655 2016 (print) | LCC TP1180.P68 (ebook) |
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Published by Nova Science Publishers, Inc. † New York

CONTENTS
Preface vii
Chapter 1 Self-Assembly β-Nucleating Agents and
Their Effects on Structure and
Performance of Polypropylene 1
Yijun Li, Min Nie and Qi Wang
Chapter 2 Molecular Structure of Stereoregular
Polypropylene Gel 21
Takahiko Nakaoki
Chapter 3 Polypropylene: A Thermal Insulation Material for
Solar Collectors 69
Wei Chuen Khaw and Chien Hwa Chong
Chapter 4 Mechanical Properties, Crystallization and
Degradation of Polypropylene due to Nucleating
Agents, Fillers and Additives 83
Javier Vallejo-Montesinos, Ulises Morales Muñoz
and J. A. Gonzalez-Calderon
Chapter 5 Polypropylene Biodegradation 141
Celso Luis de Carvalho and Derval dos Santos Rosa
Chapter 6 Lignocellulosic Biomasses, Sustainable Platform for
Bio-Based Materials with Polypropylene 175
Tri-Dung Ngo and Thoi Ho
Index 211

PREFACE
Polypropylene (PP) is a typical polymorphic polymer with α-form, β-

form, γ-form, and mesomorphic smectic form modifications, and crystallizes
into diverse morphologies. In this book, Chapter One comprehensively
reviews the kinds of self-assembly β-nucleating agents and the manipulation
strategies in the practical processing to control the crystal structure and
prepare high-performance PP products. Chapter Two discusses the molecular
structure at the cross-linking point of stereoregular isotactic polypropylene
(iPP) and syndiotactic polypropylene (sPP) gels in comparison with the crystal
formed in the solid state such as film. Chapter Three investigates the thermal
insulation performance of polypropylene as thermal insulator for a solar air
collector in comparison with coconut fibre. Chapter Four reviews the
mechanical properties, crystallization and degradation of polypropylene due to
nucleating agents, fillers and additives. Chapter Five examines polypropylene
biodegradation. Chapter Six addresses the potential utilization of different
lignocellulosic biomasses for the development of green materials based on
polypropylene, with the objective to elucidate the possibility of using the bio
based materials for various industrial applications.
Chapter 1 - The performances of polymers not only are relative to the
chemical structure, but also depend on the final crystalline structure.
Polypropylene (PP) is a typical polymorphic polymer with α-form, β-form, γ-
form, and mesomorphic smectic form modifications, and crystallizes into
diverse morphologies, such as spherulite and shish-kebab. Generally, β-form
crystal displays superior impact resistance and ductility to α-form while shish-
kebab with preferred orientation can bring out remarkable reinforcement along
the orientation direction compared to isotropic spherulite. Therefore, much
attention has been directed toward microstructure optimization and property

viii Paula Garcia
enhancement via controlled crystallization. Polymer crystallization is

nucleation-dominated and can be regulated by adding certain nucleating agent.
Recently, some β- nucleating agents are reported to dissolve in the polymer
melt and self-assemble into different topological structures upon cooling,
which provide a facile and versatile way to precisely design and control the
crystal modification and morphology of PP. This chapter will comprehensively
review the kinds of self-assembly β-nucleating agents and the manipulation
strategies in the practical processing to control the crystal structure and
prepare high-performance PP products.
Chapter 2 - The crystalline structure at the cross-linking point and
coagulation of solvent in isotactic and syndiotactic polypropylene (abbreviated
as iPP and sPP, respectively) gels were investigated by high-resolution solid-
state 13C nuclear magnetic resonance (NMR), thermal analysis, infrared
spectroscopy, etc. [1-6]. In general, gelation is accompanied with the
formation of a 3D network structure with a cross-linking point. The cross-
linking point for crystalline polymers such as iPP and sPP comprised crystal.
Polarized optical microscopic measurements revealed that spherulite formed
for both iPP and sPP/o-dichlorobenzene gels during gelation. The
conformation in the crystal constructed at the cross-linking point in the iPP
and sPP gels exhibited trans-gauche (tg) and ttgg sequences, respectively,
which are the most stable conformations for the solid state such as film.
However, the packing structures in the unit cell were different from the stable
crystal form for both gels. For the solvent in the gel, three states of free,
freezable bound, and nonfreezable solvents were noted. When differential
scanning calorimetric measurements were performed after freezing o-
dichlorobenzene in the iPP and sPP gels, two endothermic peaks were
observed for the frozen o-dichlorobenzene; one is concerning the free solvent
with the same melting temperature as pure o-dichlorobenzene and the other
was freezable bound solvent observed below the normal melting temperature
and strongly dependent on the gel concentration and gelation temperature.
This temperature depression was due to the coagulation size of o-
dichlorobenzene in the gel; that is, the smaller the coagulation, the lower the
melting temperature. The coagulation radii of o-dichlorobenzene in 30 wt%
iPP and sPP gels were 5.4 and 6.7 nm, respectively. The solvent molecule
could not enter the crystal unit, but the noncrystalline region provided space
for the solvent molecule. Therefore, the solvent with high melting temperature
was located in the noncrystalline region between spherulites, whereas that with
low melting temperature was located in the noncrystalline region between
lamellae in spherulite.

Preface ix
Chapter 3 - As polypropylene undergoing phenomenal growth in

production and end-used application in the 21st century, researchers continues
to identify new application and expands its share of the market.
Conventionally, coconut fibre is used as a thermal insulation material due to
low cost and environmental friendly. However, coconut fibre will degrade and
requires replacement on yearly basis. Therefore, the objective of this
experiment is to investigate the thermal insulation performance of
polypropylene as a thermal insulator for a solar air collector in comparison
with coconut fibre. The absorber of the solar collector is made of a rectangular
aluminium plate with area of 20.0 x 47.0 cm2 and thickness of 3.0 mm. The
experiment was carried out in Malaysia and setup of the solar collector
followed the ISO/WD 9806-1 standard. The experimental results showed that
the thermal efficiency of the coconut coir insulated collector is 13.7% higher
than the polypropylene insulated collector and the average outlet-air
temperature of the polypropylene insulated collector was 1.46% lower than the
coconut coir insulated collector. However, the independent samples t-test
found no significant difference between the coconut fibre and the
polypropylene-insulated solar collector based on the outlet-air temperature and
thermal efficiency (p ≥ 0.05). The result showed that polypropylene has
similar thermal insulation performance in comparison with coconut fibre.
Moreover, polypropylene is more versatile subject to different processing
techniques to enhance its properties such as higher modulus or higher heat
distortion temperature (HDT) compared to others.
Chapter 4 - Nowadays polypropylene is one of the three most important
synthetic polymers worldwide due to its multiple applications due to its
mechanical properties, chemical resistance, low cost and processing ease
among others. But even with this properties that result very useful, the
polypropylene continues being improved via the use of nucleating agents that
modify their crystallization, therefore their mechanical properties. The variety
of nucleating agents goes from the common and well known dicarboxilic salts
which could be used alone or functionalized to various metal oxides improving
highly the amount of certain kind of crystal above the others. The main
crystalline phases are known as α-, β-, γ-, and mesomorphic or smectic form.
The α form is the primary form of polypropylene obtained under normal
processing conditions; however, the β-crystal is perhaps the most interesting
crystalline phase for certain applications because of its hardness and impact
resistance. Therefore, different nucleating agents have been used to promote
this type of crystal in iPP composites. In terms of nucleating agents, there are
substances that contain aromatic rings, rare earth metals (referred to as WBG),

x Paula Garcia
and salts from dicarboxylic acids, such as calcium salts from pimelic and
suberic acids. Particularly, calcium salts from pimelic and suberic acids have
demonstrated an extremely high efficiency to promote β-crystals without
secondary effects. It was reported that the salts from PA were able to induce
approximately 90% of the β growth and it also was demonstrated that the raw
PA is considered an ineffective β-agent. Different substrates have been
explored as supports for depositing calcium pimelate, e.g., carbonates,
silicates, zeolites, oxides, metallic salts, clays, and carbon nanotubes, which
are responsible for more than 90% of the β-crystals. β nucleating agents
continue as the main route to obtain β-phase in isotactic polypropylene.
Different kinds of nucleating agents, such as multiwalled carbon nanotubes
modified with calcium pimelate supported on nano CaCO3, monoglycerolates,
and potassium salts have been studied. In these works all of them exhibit
interesting properties related to the β-phase present in the composites studied.
These results increase their applications that range from medical to
engineering whit very interesting features in their respective fields. However
the polypropylene faces that it’s very chemical resistance has made a very
important pollutant along with most of the organic synthetic polymers. An
important effort in order to address this problem has been increasing the
degradation (either thermodegradation or photodegradation) capacity of the
polypropylene via chemical modification of the chain or by the use of fillers
and additives that promotes the degradation of the material. Photodegradation
involves the natural tendency of most polymers to undergo gradual reaction
with atmospheric oxygen in the presence of light. Typically, a photosensitizing
agent is employed to accelerate this natural tendency. The mechanism of
photodegradation involves the absorption of UV light, which then leads to the
generation of free radicals. An auto-oxidation process then occurs which leads
to the eventual disintegration of the plastic. It is believed that the instability of
polyolefins is brought about by the presence of impurities (such as carbonyl
and hydroperoxide groups) that form during the fabrication or processing of
the polyolefin products. Degradable polyolefins are designed to oxo-degrade,
undergoing changes in chemical structure as a result of oxidation in air,
causing the breakdown of the molecules into small fragments that are then
bioassimilated. For the reasons cited above the authors consider important to
give a review on the major advances that this polymer has faced over the years
in the areas considered before.
Chapter 5 - The difficulty of metabolism by living organisms does not
give to polypropylene the biodegradable characteristic as a function of the
high molar mass, which does not permeate through the cell membrane of

Preface xi
microorganisms. The biodegradation depends on to biotic phase, which start

the breaking reaction and remains on biotic reaction. To understanding and
research of different aspects of the abiotic degradation of the polypropylene,
this chapter proposes to show the degradation caused by polyacetal (POM) and
pro-oxidant additives. Some analysis of the polypropylene in the natural life
cycle - "cradle to cradle" was realized. The concentration of 3% by weight of
the POM can enhance the thermal stability of the PP in the conditions
investigated, however, above 3% wt. of the POM caused oxidation of the
polyolefin and the synergistic effect of degradation maximized the miscibility
of POM with PP (in the interface region). The oxidative degradation of the
polypropylene with d2w® agent evolves the formation of new areas arranged in
the structure of the PP. The oxidation caused with the incorporation of POM
leads to increased structural disorder thus allowing diffusion of new agents
decomposition during the life cycle of the PP.
Chapter 6 - Lignocellulosic biomasses are becoming very interesting for
bio-based materials development when they possess the advantages of their
reasonable mechanical properties, low density, economic feasibility,
environmental benefits, and renewability. Wood fibers have been used as
reinforcement for polymers for many years, the annual plant fibers obtained
from different sources, such as wheat, triticale, rice husk, sisal, jute, coconut,
hemp and flax, have good potential as a source of low-cost reinforcements for
polymers. Lignin is considered a natural polyol and polyphenol in plant stem
and the second most abundant natural polymers coming only next to cellulose.
Lignin is also an attractive biomass since it is readily available and relatively
inexpensive. Recently, nanotechnology is helping improve products that we
use every day and creating new, exciting products for the future. To
completely change the forest product industry through nanotechnology, top-
down approaches from bulk cellulose have been used to generate cellulose at
nanoscale (nanocellulose) such as cellulose nanocrystals and cellulose
nanofibrils. As the demand for “green” materials and products is growing, the
use of renewable resources and recycled materials prove to be great
attractions. Thermoplastic biocomposites have appeared as low cost, light
materials for different applications, and have attracted much interest. Among
the thermoplastic, Polypropylene (PP) is used in various applications including
packaging, laboratory equipment, automotive component, etc. This chapter
addresses the potential utilization of different lignocellulosic biomasses for the
development of green materials based on PP, with the objective to elucidate
the possibility of using the bio based materials for various industrial
applications.

In: Polypropylene: Properties, Uses and Benefits ISBN: 978-1-53610-008-2
Editor: Paula Garcia © 2016 Nova Science Publishers, Inc.
Chapter 1
SELF-ASSEMBLY β-NUCLEATING AGENTS

AND THEIR EFFECTS ON STRUCTURE
AND PERFORMANCE OF POLYPROPYLENE
Yijun Li, Min Nie and Qi Wang

State Key Laboratory of Polymer Materials Engineering,
Polymer Research Institute of Sichuan University, Chengdu, China
ABSTRACT
The performances of polymers not only are relative to the chemical
structure, but also depend on the final crystalline structure. Polypropylene
(PP) is a typical polymorphic polymer with α-form, β-form, γ-form, and
mesomorphic smectic form modifications, and crystallizes into diverse
morphologies, such as spherulite and shish-kebab. Generally, β-form
crystal displays superior impact resistance and ductility to α-form while
shish-kebab with preferred orientation can bring out remarkable
reinforcement along the orientation direction compared to isotropic
spherulite. Therefore, much attention has been directed toward
microstructure optimization and property enhancement via controlled
crystallization. Polymer crystallization is nucleation-dominated and can
be regulated by adding certain nucleating agent. Recently, some β-
nucleating agents are reported to dissolve in the polymer melt and self-
assemble into different topological structures upon cooling, which
provide a facile and versatile way to precisely design and control the

Corresponding Author Email: poly.nie@gmail.com.

2 Yijun Li, Min Nie and Qi Wang
crystal modification and morphology of PP. This chapter will

comprehensively review the kinds of self-assembly β-nucleating agents
and the manipulation strategies in the practical processing to control the
crystal structure and prepare high-performance PP products.
Keywords: controlled crystallization, polypropylene, β-nucleating agent, self-

assembly, crystal structure
INTRODUCTION
Polypropylene (PP) is a typical polymorphic polymer with α-form, β-
form, γ-form, and mesomorphic smectic forms modifications, all sharing a
conformation of a 3/1 helix of (TG)3 or (TG*)3 but different lamellar packing
models [1-4]. The different modifications are significantly related to the final
properties of PP materials [5, 6]. For example, α-form crystal consists of
unique parent-daughter lamellae structure where the daughter lamellae grow
perpendicular to the parent one to form cross-hatched architecture, and thus
displays outstanding resistance to deformation but deterioration to impact. The
specific banded structure of β-form crystal leads to loose stack of lamellae.
When subjected to impact, the β-form lamellae are keen to slip with huge
energy absorbed. Compared to α-form crystal, β-form crystal can offer
superior toughness and ductility. Now, the preparation and optimization of β-
crystal has gained much attention from scientific areas and industrial
applications [7]. However, β-form crystal is metastable and generated only at
some special conditions, such as crystallization under temperature gradient and
with the presence of β-nucleating agent. Incorporation of β-nucleating agent is
the simplest and most effective way to increase the content of β-form crystals
and enhance the toughness of PP [8, 9].
The performance of semi-crystalline polymer does not only depend on the
crystalline modification, but also on the supermolecular structure formed
during processing [10-12]. For example, spherulites and shish-kebabs present
different structure and properties. Spherulites are composed of radial lamellae
with molecular coil connecting with each other, while shish-kebabs consist of
highly stretched molecular chains and the lamellae growing laterally on the
surface of the shish [13, 14]. Compared with isotropic spherulites, shish-
kebabs exhibit high strength in the orientated direction. With the help of the
reinforcing effect of shish-kebabs, the tensile strength of the PP can reach as
high as 450MPa, higher than ~30MPa of the spherulites-dominated matrix [15,

Self-Assembly β-Nucleating Agents and Their Effects … 3
16]. In addition, Luo [17] reported that the toughness of PP not only depended
on the content of the β-crystal, but was also governed by the morphology.
Specially, the dendric-like β-crystals with more connection between
crystallites exhibit the superior impact strength than spherulite one.
For pure PP, nuclei are generated through transient molecular clusters
resulting from density fluctuations [18, 19]. At static conditions, spherulites
prevail as a result of dot-like nuclei. Under flow field, constrained by the side-
methyl groups in PP backbone, the spiral configuration augments the difficulty
of the molecular extension, which is the premise to the formation of shish [20-
22]. Moreover, even if the stretched shish forms under the flow, it will quickly
relax back to the random coil due to the molecular thermal movement [23].
Only spherulites are available in the conventional processing of PP without
any benefits from morphological control. Therefore, in order to achieve the
controlled crystallization and tailor the resultant morphology, initiative
introduction of nuclei with preferred structure is necessary. Nucleating agents
(NAs) are a kind of small molecular compounds which display excellent
capability in acceleration of crystallization, promotion of crystallinity and
selective induction of specific crystalline modification in semi-crystalline
polymers and thus have never fail to attract researchers’ interests in both
academic and industry due to their impressive efficiency and convenience in
broadening the application spectrum of the polymeric materials [24-26]. On
contrast to precursors made from molecular chains, the nuclei of NA can retain
in the processing owing to long relaxation time and via the epitaxial
crystallization mechanism, the initial topological structure of the NA nuclei
can be transformed into the crystalline morphology of polymer [9, 27, 28].
Typical spot-like nuclei induce the radical growth of the lamellae giving rise to
spherulites, while trans-crystal emerges if the growing direction is restricted in
a 2D plane [29]. Recently, the self-assembly behaviors of the β-NAs have been
revealed and given to distinct solubility of β-NA in the PP melt, NAs will
ether partially or completely dissolve in the binary system and
correspondingly, self-assemble into needle-like, dendritic aggregates and
networks, so as to promote the formation of some special supramolecular
structures of PP composted of β-crystals, such as shish-kebab, lamellae
interlock and microcrystallinity agglomerates [30-34]. This offers us a new
route to expected design and control of the initial topological structure of the
PP nuclei and the resultant performance of PP products via tunning the
dissolution and self-assembly of β-NAs. Lots of research works have been
concentrated in this quick developing field [35-38].

The high efficiency of selective induction of β-crystal and the designed

morphology induced by self-assembling β-NAs undoubtedly push the
boundaries of ingenuity and engineering, and overcome the fundamental
limitation of the current β-PP based PP materials. In this chapter, we will
systematically review the available β-form NAs and the self-assembling
mechanism. Moreover, some methodologies for morphological manipulation
are introduced. Finally, the effects of the specific crystalline morphology
induced by NA on the performance of PP are comprehensively reviewed.
β-NUCLEATING AGENT AND ITS SELF-ASSEMBLING
β-Form Nucleating Agent
Addition of nucleating agent not only can accelerate the crystallization

rate but also can subtly regulate expected crystalline modification. To the best
of our knowledge, it is probably the most convenient and effective way to
tailor high amount of β-crystals by adding β-form NAs. Nowadays, many
novel β-form NAs have been synthesized and the most applicable ones are
listed in Table 1.
Despite heated debates on the inducing mechanism remains, the lattice
matching is the most-accepted one [67, 68]. The NA molecules prefer to align
into the lattice of the PP crystal and thus affect the crystallization procedure by
breaking down the nucleation barrier for PP.
It is noticeable that some β-form NAs such as TMB-5 and NU-100, also
show the dual selective effect, which not only promote the formation of the β-
crystal but also induce the α-one. Based on the pioneering work of Varga [9]
on NU-100, it is demonstrated that the α-nuclei are in abundant large density
on the lateral surface of the needles of the β-form NA, while triangular
spherulites slices grow randomly (Figure 1). The crystallization is divided into
two stages. At the initial stage, both the α- and β-crystalline fronts grow
unrestrictedly. When the temperature is in the range of 100oC~140oC [2, 7], β-
spherulites slices grow faster and thus hinder the expansion of the α-
transcrystalline front in the later stages of the crystallization.

Table 1. β-form nucleating agent used in polypropylene
Name Chemical structure Activity

Kβ (%)
TMB-5 (aromatic amide 80 [31,
derivative) 36-51]
N, N’-dicyclohexyl-2,6- 96 [9,
naphthalenedicarboxamide 52, 53]
(NJSTAR NU100)
Linear trans γ- 72~84

quinacridone [54-57]
WBG-II (heteronuclear A general formula of CaxLa1−x(LIG1)m(LIG2)n, 75 [17,
dimetal complex of where x and 1 – x is the proportion of Ca2+ and La3+ 30, 32,
lanthanum and calcium ion in the complex, while LIG1 and LIG2 are 35, 58]
with some specific respectively a dicarboxylic acid and amide-type
ligands: CaxLa1- ligand with coordination numbers of m and n.
x(LIG1)m(LIG2)n)
NAB83 84 [59,
60]
The substituent groups of R1-8 are independently

selected from: hydrogen, C1-C9 alkyl group,
hydroxyl, phenyl group and halogen, while M is
metal cation selected from barium, calcium,
magnesium, strontium and zinc.
Calcium pimelate 84~99.9
[61-66]
Figure 1. Model for the mechanism of crystal growth on the surface of iPP on the
surface of NJS leading to the formation of a mixed polymorphic composition: (a) free
growth of the α- and β-crystalline front; (b) free growth of the β-phase after the
inclusion of the α-phase [9]. Reproduced by permission of American chemical society.

Impacts on the Nucleating Efficiency of the β-Form

Nucleating Agents
The stereo defects distribution. Chen and his coworkers [47] studied the
combination effect of concentration of β-form NAs and stereo-defect
distribution on the crystallization behavior of β-nucleated isotactic
polypropylene (β-iPP). It is found that the more uniform stereo defect
distribution, the more effective β-form NA is for PP; moreover, the amounts of
NAs are needed to reach the threshold above which the β-phase can be
generated. The dependency of this phenomenon relates significantly to the
capability of the molecular chain to participate into the crystallization
procedure, since the stereo-defects restrain the regular insertion of molecular
chains.
The molecular weight. Higher molecular weight of PP is more favorable
for the formation of β-phase. The lower the molecular weight, the less the
proportion of β-phase will be [69]. A rational interpretation is ascribed to the
distinct mobility of the molecular chain by Men [70], that is, sluggish
movement of long molecular chain hinders the growth of α-crystal while the
short one quickly solidifies from the melt leading to typical self-seeded
crystallization rather than taking NA as template for epitaxial growth. A
completely contrast results are also reported in extremely low concentration of
NU-100 blends [71]. In this case, NA partial dissolves in PP melt and a
competition between heterogeneous β-nucleation and self α-nucleation takes
place.
Pressure. It is generally demonstrated that high pressure is the main way
to achieve high amount of γ-phase and the competition between the nucleating
effect of β-NA (TMB-5) and the high pressure was observed by Yang [72]. At
the initial stage of crystallization, β-crystals on the tip and lateral surface of the
needle-like NAs as well as α-crystals on the lateral side grew under the dual
selective effect of TMB-5. Then γ-crystals take the α-form lamellae as seeds to
grow. With the association of high pressure, the formation of β-lamellae is
restrained and eventually γ-phase is regularly organized in the local area of the
NA needles.
Temperature. The temperature plays a predominating role in determining
the efficiency and effect of the β-NA. Li [31] and Mu [44, 45] systematically
analyzed the effect of final melting temperature on the efficiency of TMB-5.
The results indicated that with increasing temperature, more TMB-5 dissolved
into PP melt and the homogenous dispersion was achieved via recrystallization
upon cooling so that the relative fraction of β-phase increase drastically.

Another study on the isothermal crystallization of PP/TMB-5 blend

demonstrated only β-crystals or α-crystals formed at crystallization
temperatures of 135 or 145oC, respectively while both β and α crystals could
be found at 140°C [73].
The Self-Assembly of β-Nucleating Agent
Many researchers have observed an interesting phenomenon by polarized

optical microscope (POM) during the heating procedure of certain polymer/β-
NA blends where the NAs can self-assemble to various structures [40, 43, 74-
77]. If the NA retains its physical state during the melting of PP, typical
spherulites will occupy the final matrix [75, 77]. However, when the NA
completely or partially dissolves in the PP melt, diverse morphologies of NA
appear in the PP melt during cooling. A brief mechanism is ascribed to the
solubility of NA [9, 17, 37]. In dissolution state, NA molecules spread
uniformly in the matrix, and upon recrystallization, the dissolved NAs
preferentially aggregate near the existed or preformed NA particles and then
settle down on the tip of their stem. By repeating this procedure, distinct
morphology such as network and slider needles can be generated.
But here is the question, what is the mechanism of the self-assembly in
molecular level? The answer is supposed to relate significantly to the chemical
structure of NA. For organic NA such as TMB-5 and NU-100, the species
generally comprise two functional moieties: (i) hydrophobic center with apolar
substituents to ensure the dissolution in the polymeric melt, and meanwhile to
enable the subtle manipulation of the formation of certain crystal modification.
(ii) the other moiety permits the formation of hydrogen bonds which exhibit
the most suspicious role in triggering the self-assembly. Recently, this
hypothesis is demonstrated by the temperature-dependent Fourier transform
infrared spectroscopy of the PP/β-NA(DCTH) blends [43]. In the heating
procedure, “free” DCTH molecules are generated during the dissociation of
the hydrogen-bond, which provides opportunity for the conformational
rotation of cyclohexyl groups toward co-plane direction with the aromatic core
plane. Upon cooling, the hydrogen bond association triggers the self-
assembly/recrystallization of “free” DCTH molecules into supramolecular
aggregations via conformational rotation.
Compared to the organic NAs, inorganic NAs are usually constructed in a
simpler way. The essence of such NAs is heteronuclear metal complex with
some specific ligands that are also capable to form intermolecular interactions.

For instance, the WBG-II molecules are constructed by the dicarboxylic acid
and amide-type ligands [78]. As a result, complex-based inorganic NAs
exhibit a similar morphological evolution and self-assembly behavior to the
organic ones [79].
The Morphological Manipulation of the Self-Assembling

Nucleating Agent
Many efforts have been dedicated to achieve the subtle manipulation of

the specific morphology, and the fundamental principles are to control the
solubility of β-NA. The two mostly utilized factors are processing temperature
and the concentration of the NA.
Kristiansen and his coworkers [33, 34, 80] studied three different α-NAs
and successfully drew the binary phase diagram of the PP/NA system as a
function of concentration of the NA. These intelligent works reveal the nature
of phase separation of NAs follows the simple monotectic behavior, which
commonly is found for mixtures of two species of limited liquid miscibility
and a high immiscibility in the solid state. Elaborate work on the phase
diagram of the β-form NA (TMB-5) by Han [37] proposed the results gathered
from α-form NAs can also be applied to the β-form ones (Figure 2). The
dissolution temperature of β-NAs (TMB-5) varies from 210°C to 290°C in the
concentrations ranges from 0.05 wt% to 2 wt%. Positive correlation between
dissolution temperature of TMB-5 and the concentration is apparent when the
concentration is lower than 0.2 wt%. Nevertheless, once the threshold is
exceeded, a plateau appears where the dissolution temperature elevates
sluggishly from 270oC to 290oC. It can be concluded that with increasing
concentration, higher temperature is necessary for the dissolution of the β-
form NAs, and simultaneously is limited in the higher concentration regime. A
possible interpretation is based on the partial polar chemical structure of TMB-
5 as we reviewed above.
In order to verify the impact of solubility, the temperature gradient is
conducted by Wu [30]. In the temperature gradient, β-NAs with different
solubility can be captured simultaneously in an identical observing window
and the morphological evolution is easily divided into 3 regimes. In the high
temperature regime i.e., the highest solubility, the dendritic morphology
dominates the matrix while needle-like framework emerges in the low
temperatures due to the decreasing solubility. An interesting morphology
which consists of long needle-like stem and snow-flake like aggregates is

detected in the intermedium range of the temperature gradient. This unique

morphology best describes the possible procedure of dendrite formation: under
the condition of completely dissolved β-NA, microfibrillar entities with very
short lengths appear at first, and then the furcate on the two tips of a
microfibril. Accordingly, a 2D growth mode replaces the 1D growth along the
length direction, resulting in a furcated branch-like morphology.
It is notable that apart from the thermal conditions, kinetic factors also
display their significance on determining the self-assembling morphology of
β-NAs. Morphological diversities are detected when shearing is exerted at
different stages of the self-assembly [38]. Shearing has nothing to do with the
final morphology if shearing ends when the temperature is still above the onset
of the self-assembling. Under this condition, the structure of precursor stays as
perfect as that in quiescent condition, and hence the dendritic morphology is
formed regardless of the shear rate. However, when shearing is applied at the
temperature when self-assembly for β-NA is happening or has completed, the
dendritic morphology turns into long needle-like fibers. In this case, the
furcation is restrained because the branches in the dendritic structure will be
substantially scraped from the aggregates once the shear is applied.
Figure 2. Temperature/composition diagram of the PP/TMB-5 blends. In the diagrams,

the symbols refer to the melting temperature of PP ( ) and the dissolution temperature
of TMB-5 ( ). The letter T refers to TMB-5, P to PP, S to solid, L to liquid [37].
Reproduced by permission of the royal society of chemistry.

Figure 3. SEM photographs for the supermolecular structures of β-nucleated iPP bars
compression-molded under various Tf values: (A)Tf = 180oC, (B) Tf = 200oC, (C) Tf =
220oC, and (D) Tf = 240oC. [17] Reproduced by permission of American chemical
society.
The self-assembled morphology of β-NA also influences the crystalline

morphology of the PP following the epitaxial crystallization mechanism.
Herrin, we would like address two issues. Firstly, the template effect of the
NA is the most visible and apparent phenomenon. As shown in Figure 3, the
crystalline morphology of the PP alters according to the topological structure
of the NA, namely spherulites, need-like and dendritic aggregates, which is
attributed to numerous nucleating sites existing in the surface of the NAs.
Consequently, by taking the NA as template, PP inherits the morphology to
crystalize into various supermolecular structures. Secondly, the nucleating
efficiency also links with the topological structure of NA. The relative content
of the β-crystal increases once the morphology of the β-form NA changes from

dot-like particles to slender fiber [31, 36]. The increasing specific surface area
and the promoting dispersion may be responsible for the enhancement.
Figure 4. High-magnification SEM micrograph of PTC and the schematic diagram of

the lamella orientation in β-modification hybrid shish-kebab [37]. Reproduced by
permission of the royal society of chemistry.
THE STRUCTURE-PROPERTIES RELATIONSHIP
The Reinforcing Effect of the Hybrid Shish-Kebabs
Since the performance of the semicrystalline polymer intensively relies on

the morphology of the crystal, it is rational and expected to utilize the
templating effect of the NAs in designing unique supermolecular structure to
reinforce the PP materials. It is demonstrated by Zhang [81] that the loss of
tensile strength after the individual addition of β-NA can be compensated by
tailoring oriented bundle-like β spherulite. However, is it possible to further
reinforce the β-form PP by much higher orientated hierarchical structure?
A fascinating β-form hybrid shish-kebabs consisting of anisotropic shish
of needle-like NA and β-form lamellae growing perpendicularly on the lateral
surface is firstly introduced and characterized by Nie [31, 36, 37, 82-84].

This cylindrical symmetrical architecture is constructed by two kinds of β-

form lamellas arranging along the fibrous NA needles. Namely, the edge-on
lamellae are parallel while the flat-on lamellae are perpendicular to the
nucleating agent, indicating a double-orientation of the molecular chains
(Figure 4). Moreover, a two order formation mechanism are also demonstrated
that flat-on lamellae forming first at high temperature, followed by the
formation of edge-on lamellae during the cooling process.
Figure 5. POM photos of pure PP samples prepared at (a) 190°C and (b) 270°C and
TMB-5-modified PP samples prepared at (c) 190°C, (d) 210°C, (e) 230°C, and (f)
270°C [31]. Reproduced by permission of John Wiley and Sons.

Figure 6. Schematic illustration of the relation between the dissolution and self-
assembly of the nucleating agent and the subsequent morphology of PP [31].
Reproduced by permission of John Wiley and Sons.
The hybrid shish-kebabs do not only inherit the high resistance of β-phase
to impact, but also exhibit the reinforcing effect of orientated crystalline
morphology. The key to generate the special crystal is the formation of fibrous
β-NAs. Compared to the oriented molecules, the NAs have longer relaxation
time and the structure keeps constant once formed. As a result, hybrid shish-
kebabs composed of β-crystals can be achieved in mild processing while the
shish kebab morphology is available only under special processing conditions,
such as high-speed injection or dynamic packing molding. Now, it has been a
new strategy to produce PP product with the controllable reinforcement of
stiffness and toughness via thermally induced self-assembly of β-NAs. For
example, the tensile strength and impact strength of the injection-molded bars
of the TMB-5 modified PP can reach 40.5 MPa and 9.3 kJ/m2, respectively,
35% and 186% higher than that of pure PP sample. Especially with increasing
processing temperature, TMB-5 will experience more complete dissolution-
recrystallization, leading to more valid nucleating sites for epitaxial
crystallization. Moreover, during processing, continuous shear will force the
NA recrystallize into long fibers rather than dendritic which is always formed
in quiescent condition. Accordingly, the hybrid shish-kebabs with extremely
high aspect ratio is generated, which lead to superior reinforcement due to
more effective stress transfer from the matrix to the hybrid shish-kebabs
(Figure 5 and 6). It is notable that this reinforcing technology is verified to be
versatile in many other conventional processing methodologies, such as piping
[83, 84] and film extrusion [36] in which NA modified PP samples present
improved tensile strength and yield strength over the pure samples. More

improvement of mechanical properties can be achieved at higher concentration

of NA because the density of the hybrid shish-kebabs is increasing.
Enhanced Properties by Other Unique Morphologies
The role of dendritic aggregates on toughing PP. When the NAs are
heated to the temperature for complete dissolution, dendritic morphology will
dominate the matrix and simultaneously greatly enhance tensile elongation and
impact toughness of the PP. Luo [17] demonstrated the morphological
dependence on the toughness of β-nucleated PP bars. By observing the
additional reinforcement storage modulus within the range from 190 to 180oC,
formation of network structures before the crystallization of PP is verified. β-
nucleated PP lamellae grow basically on the network of NAs and thus possess
good integrity and synergic effect of numerous β-crystals to resist the
deformation and destruction. Similar results are also obtained in the PPR/iPP
blends in which the dendritic morphology enhances the toughness of PPR at
low temperature by forcing more segments of the PPR to participate into the
crystallization of β-crystal.
The morphological influence on the creep resistance. Well-developed β-
spherulites have integrated crystalline structure, exhibiting poor creep
resistance. For the needle-like morphological β-PP prepared by adjusting the
self-assembly of β-NAs, the crystalline phase displays better creep resistance
[85].
The interfacial adhesive enhanced by heterogeneous self-assembling NA.
Liu [32] takes advantage of the self-assembling of the NA to enhance the
fiber-matrix adhesion and resist crack propagation. In this case, the NA
diffuses to the surface of the fibers and self-assembles into 3D network which
cause interlinks between the incompatible phases via trans-crystal in the
interphase. Recently, a new horizon in improving the interfacial adhesive of
the PP/fiber composites is introduced by He [86] by utilizing the
heterogeneous self-assembly of β-NAs. They prepared the novel root-like fiber
composed of glass fiber as stem and β-nucleating agents as branch via self-
assembly on the surface of GF. The root-like glass fiber have the strong
mechanical interlocking with polymer matrix to potentially facilitate load
transfer to reinforcing fiber, solving the interfacial problems of the composites.

CONCLUSION
This chapter elucidates in details the self-assembling β-form nucleating
agents and the manipulation strategies in the practical processing to control the
crystal structure and prepare high-performance PP products. The highlighting
conclusions are summarized below.
 The β-form NAs are capable to achieve high fraction of β-crystals in

the PP-based materials.
 With altered solubility of the β-NA in the matrix, NAs can self-
assemble to diverse morphologies, namely needle-like and dendritic
aggregates. Both thermodynamic factors like concentration of the NA
and the processing temperature and the kinetic ones like shearing
determine the final morphology of NA and the resultant superstructure
of the PP crystals. With increasing dissolution, the NA aggregates
gradually transform form 1D (needles) to 3D (dendritic) structure,
while only needles forms if shearing is exerted during self-assembly.
 By subtle manipulation of the morphology of β-NA, the β-form
hybrid shish-kebabs are accessible. Consisting of both edge-on and
flat-on lamellae growing on the stem of the shish, the β-form hybrid
shish-kebabs exhibit simultaneous enhancement in both strength and
toughness.
 The other morphologies also display unique properties. For example,
the dendritic morphology can endow best toughening effect for the PP
materials and the needle one has better creep resistance. Moreover,
the root-like fibers via the heterogeneous self-assembly of nucleating
agent have the mechanical interlocking with polymer matrix.
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Chapter 2
MOLECULAR STRUCTURE OF
STEREOREGULAR POLYPROPYLENE GEL
Takahiko Nakaoki *
Department of Materials Chemistry, Ryukoku University, Kyoto, Japan
ABSTRACT
The crystalline structure at the cross-linking point and coagulation of
solvent in isotactic and syndiotactic polypropylene (abbreviated as iPP
and sPP, respectively) gels were investigated by high-resolution solid-
state 13C nuclear magnetic resonance (NMR), thermal analysis, infrared
spectroscopy, etc. [1-6]. In general, gelation is accompanied with the
formation of a 3D network structure with a cross-linking point. The cross-
linking point for crystalline polymers such as iPP and sPP comprised
crystal. Polarized optical microscopic measurements revealed that
spherulite formed for both iPP and sPP/o-dichlorobenzene gels during
gelation. The conformation in the crystal constructed at the cross-linking
point in the iPP and sPP gels exhibited trans-gauche (tg) and ttgg
sequences, respectively, which are the most stable conformations for the
solid state such as film. However, the packing structures in the unit cell
were different from the stable crystal form for both gels. For the solvent
in the gel, three states of free, freezable bound, and nonfreezable solvents
were noted. When differential scanning calorimetric measurements were
performed after freezing o-dichlorobenzene in the iPP and sPP gels, two
endothermic peaks were observed for the frozen o-dichlorobenzene; one
* Corresponding Author address; Email: nakaoki@rins.ryukoku.ac.jp.

22 Takahiko Nakaoki
is concerning the free solvent with the same melting temperature as pure
o-dichlorobenzene and the other was freezable bound solvent observed
below the normal melting temperature and strongly dependent on the gel
concentration and gelation temperature. This temperature depression was
due to the coagulation size of o-dichlorobenzene in the gel; that is, the
smaller the coagulation, the lower the melting temperature. The
coagulation radii of o-dichlorobenzene in 30 wt% iPP and sPP gels were
5.4 and 6.7 nm, respectively. The solvent molecule could not enter the
crystal unit, but the noncrystalline region provided space for the solvent
molecule. Therefore, the solvent with high melting temperature was
located in the noncrystalline region between spherulites, whereas that
with low melting temperature was located in the noncrystalline region
between lamellae in spherulite.
Keywords: polypropylene, gel, stereoregularity, molecular structure, bound

solvent
INTRODUCTION
Stereoregularity is an important factor to determine physical properties. In
1955, the highly isotactic polymer of poly(propylene) (iPP) was successfully
synthesized by Ziegler–Natta catalyst [7]. The long stereoregular sequence
induces the regular arrangement of conformation and leads to crystallization.
Natta et al. revealed that iPP can crystallize with the regular trans-gauche (tg)
sequence (3/1 helix) in the monoclinic unit cell, which is known as α-form [8].
Subsequently, two other crystalline forms with trigonal (β-form) [9-15] and
orthorhombic (γ-form) [16-19] cells were reported. Conversely, highly
syndiotactic polypropylene (sPP) was synthesized by metallocene catalyst by
Kaminsky et al. in 1988 [20]. The molecular structure of sPP includes four
crystalline modifications: trans-trans-gauche-gauche (t2g2) (Forms I and II),
[21-31] planar zigzag (Form III), [32-40] and t2g2t6g2 (Form IV)
conformations [41, 42]. Form I is the most stable crystalline form. The planar
zigzag conformation is a metastable form that can be prepared by cold drawing
[32-35] or by holding in ice water after quenching from the melt [36-40].
Interest in the gel structure has grown from a scientific perspective in the
last decade. The network structure with a cross-linking point formed in the gel
is closely associated with macroscopic physical properties. Therefore,
elucidation of the molecular structure is fundamentally important to clarify the
whole scope of gel. The cross-linking point is constructed either by chemical

Molecular Structure of Stereoregular Polypropylene Gel 23
reaction or physical coagulation. The former makes an irreversible gel because

of the formation of covalent bonds. The latter is classified into the following
models: crystalline, hydrogen bond, ionic bond, coordinate bond, multi-helical
structure, and nodule structure. In general, the crystalline polymers form
microcrystallite as a cross-linking point during gelation.
Most investigations on gel have focused on the molecular structure at the
cross-linking point. However, studies on solvent bound in gel are few. In
general, the solvent in gel is classified into free, freezable bound, and
nonfreezable solvents. Thermal analysis is a powerful tool to study the
coagulation of solvent in gel. Nonfreezable solvent provides no melting
enthalpy, and the melting peak of free solvent in gel has the same temperature
as pure solvent. For the freezable bound solvent, thermal behavior depends on
the molecular morphology of the gel. Higuchi et al. investigated the melting
behavior of water in a polyvinyl alcohol (PVA) swollen hydrogel [43]. They
showed the existence of two endothermic peaks for ice frozen in the gel, and
these peaks corresponded to the free and freezable bound water. The melting
temperature of freezable bound water (ice) was observed at a temperature
lower than the normal melting temperature of ice. This temperature depression
can be explained by the small coagulation size of ice. The coagulation
dimension of water in the PVA hydrogel formed by freeze/thaw cycles was
estimated around the radius of 4–23 nm [44, 45]. This method will be applied
to estimate the coagulation size of solvent in iPP and sPP organogels.
In this chapter, the molecular structure at the cross-linking point of
stereoregular iPP and sPP gels will be discussed in comparison with the crystal
formed in the solid state such as film. In addition, the solvent bound in gel will
be investigated in terms of coagulation size.
EXPERIMENTAL
Samples
iPP was purchased from Showa Denko Co. Ltd. and purified by soxhlet
extraction with n-heptane. The weight average molecular weight (Mw) and
meso triad (mm) were estimated at 2.1×105 and 98.5%, respectively. Two sPP
samples with different stereoregularity were provided from Sumitomo
Chemical Co. Ltd. The racemic diads were estimated at 98.0% and 83.0%,
which were abbreviated as sPP98 and sPP83, respectively.

24 Takahiko Nakaoki
Gel Preparation
The gel was prepared as follows. Both polymer and o-dichlorobenzene

were placed in an ampoule, degassed in vacuum, and sealed. The solution was
homogeneously dissolved at 150°C and then quenched in ice water. Gels were
kept in ice water for 24 h to produce a stable gel.
Measurements
Thermal analysis was performed using Rigaku TAS200 and 8230D

differential scanning calorimetry (DSC). The samples were scanned at a
heating rate of 5°C/min under nitrogen flow. Calibration of the instrument for
temperature and enthalpy was accomplished with indium. High-resolution
13
solid-state C NMR spectra were obtained with Bruker MSL200 and Avance
300wb spectrometers at field strength of 4.7 and 7.05 T, respectively. Small-
angle neutron scattering (SANS) measurement was carried out at Japan
Atomic Energy Agency SANS-J. The SANS profile was measured by using a
low-temperature cryostat. The wavelength of 0.65 nm was used. The sample–
detector distances were 10.2 and 2.25 m. A quartz cell was used as a sample
holder, and the scattering intensity was normalized by aluminum. Deuterated
o-dichlorobenzene and normal iPP were used for measurement. Incoherent
scattering from hydrogenated iPP was eliminated by subtracting the scattering
of iPP from that of the gel.
RESULTS AND DISCUSSION
Isotactic Polypropylene Gel
Molecular Structure at the Cross-Linking Point in iPP Gel

In general, the crystal is constructed at the cross-linking point in gel for
the crystalline polymer such as iPP. Thus, the molecular structure at the cross-
linking point of the iPP chain in iPP/o-dichlorobenzene gel was investigated
by high-resolution solid-state 13C NMR. Figure 1 shows the cross polarization
(CP)/magic angle spinning (MAS) 13C NMR spectrum of the iPP/o-
dichlorobenzene gel (14 wt%). For comparison, the spectrum of the α-iPP

crystal is also shown in this figure. The spectra consisted of three regions
assigned to the methylene, methine, and methyl carbon groups from the
downfield. The spectral pattern of α-iPP was characterized by doublets for the
methylene and methyl resonance peaks around 44 and 21 ppm, respectively.
However the apparent peak shape of the gel was different from that of the α-
iPP crystal. The chemical shift in the methylene resonance peak provides
important information on the conformational structure, which is closely
associated with the γ-gauche effect. The γ-gauche effect occurs when the
methylene resonance peak shifts upfield by 5.1 ppm, and the conformational
structure becomes gauche [46]. The methylene resonance peak for α-iPP with
tg conformation receives one γ-gauche effect. The chemical shift of methylene
resonance in the gel was observed around 44 ppm, which was the same
chemical shift as that of α-iPP. This finding indicated the formation of regular
tg conformation in the gel. To clarify the molecular mobility of polymer
chains, the spin-lattice relaxation time (T1C) was observed by saturation
recovery pulse sequence. Figure 2 shows a series of spectra obtained in the
time progression depending on the delay time to recover magnetization. The
methylene and methine peaks at 45.1 and 27.4 ppm, respectively, appeared in
short delay time so these peaks were assigned to the amorphous component.
For the methyl group, the recovery of the peak was fast because of rotational
motion along the C-CH3 axis. The peak intensity (I) for saturation recovery
pulse sequence is shown by the delay time (τ) as follows.


I  I 0 (1  e T2 C
) (1)
where I0 denotes the equilibrium peak intensity. Figure 3 shows the plot of
ln(1-I/I0) against τ for methylene and methine resonance peaks, thereby
providing T1C from the slope. The estimated T1Cs are listed in Table 1. The T1C
for the amorphous component was 0.2 s, but that for the crystalline component
was in the order of some tens of seconds. The T1C’s for crystalline methylene
and methine carbons were 48 and 24 s, respectively. These values were
compatible with those of the α-iPP crystal. Thus, the rigid domain of the
crystal, which was comparable with the α-iPP, was constructed at the cross-
linking point in the gel. The peak profile of methylene and methyl carbons of
α-iPP was characterized by a well-resolved doublet, but that of the gel was
very broad and the resolution was not good enough to obtain detailed
information on the molecular structure. The peak shape in the NMR spectrum

26 Takahiko Nakaoki
is generally represented by the Lorentzian function. To obtain high resolution,

narrow signals can be obtained by converting from the Lorentzian to the
Gaussian function. Figure 4 shows the CP/MAS 13C NMR spectrum and the
result of conversion from the Lorentzian to Gaussian functions for methylene
carbon. The resonance line was decomposed to four components, although the
original peak was unclear because of broadness. Two peaks at 43.3 and 44.3
ppm showed the same chemical shift as those of the α-iPP crystal,
corresponding to the crystalline component. The most downfield peak at 45.1
ppm was assumed as the amorphous component. According to Kitamaru et al.,
the shoulder component at 44.0 ppm is attributed to the contribution from the
intermediate phase between crystalline and amorphous phases [47]. By using
these four resonance lines, we attempted curve fitting analysis for the original
to evaluate the phase fraction. However, the CP/MAS 13C NMR spectrum was
unsuitable for quantifying the phase fraction because of different CP
efficiencies between the crystalline and amorphous phases. Dipolar decoupling
(DD)/MAS 13C NMR spectrum with a waiting time over five times longer than
the longest T1C reflected all components irrespective to the molecular mobility,
although the CP/MAS 13C NMR spectrum enhanced the components with slow
molecular mobility, such as the crystalline phase. The longest T1C for iPP/o-
dichlorobenzene gel was 48 s for methylene carbon, so the waiting time after a
single pulse sequence was 300 s, which was sufficient time to recover all
components. Figure 5 shows the DD/MAS 13C NMR spectrum with a waiting
time of 300 s for the methylene resonance peak. The result of curve fitting
analysis is also shown in Figure 5, and the fraction evaluated by integral
intensity is listed in Table 2. The total fraction of two components at 44.3 and
43.3 ppm was 0.6, corresponding to crystallinity. This value was comparable
with the bulk crystallized α-iPP [47]. The intensity ratio of the peak at 43.3
and 44.3 ppm was 2:1. However, this ratio was opposite to the ratio of 1:2
reported for the α-iPP crystal [48]. The splitting for the α-iPP crystal was
attributed to the inequivalent environment of methylene carbon in the
monoclinic unit cell. Therefore, this result suggested that the chain
arrangement in the unit cell of the gel differed from the α-iPP crystal. The
crystal formed in the gel might be disordered α-form, which is called the α1-
form, but this subject needs further investigation.

Table 1. T1C values for methylene and methine carbons of iPP in the
iPP/o-dichlorobenzene gel (14 wt%) [1]
Chemical shift/ ppm T1C / s Assignment

CH2 45.1 0.2 Amorphous
43.3 48 Crystalline
CH 27.4 0.2 Amorphous
26.0 24 Crystalline
Table 2. Results of curve fitting analysis formethylene

carbon of iPP in the gel [1]
Chemical Shift / ppm Fraction Assignment

45.1 0.21 Amorphous
44.3 0.20 Crystalline
44.0 0.19 Interphase
43.3 0.40 Crystalline
Figure 1. CP/MAS 13C NMR spectra of iPP/o-dichlorobenzene gel (14 wt%) and α-iPP
crystal [1].

28 Takahiko Nakaoki
Figure 2. 13C NMR spectra in the time progression of the saturation recovery (T1C
relaxation) of iPP/o-dichlorobenzene gel (14 wt%). The recycle delays are drawn in the
spectra [1].
Figure 3. 13C spin-lattice relaxation process for methylene (■ : 43.3 ppm and □ : 45.1
ppm) and methine (● : 26.0 ppm and ○ : 27.4 ppm) carbons [1].

Figure 4. CP/MAS 13C NMR spectra of iPP/o-dichlorobenzene gel (14 wt%) (a) and
the result converted from Lorentzian to Gaussian functions (b). The peaks shown by
stars are assumed as the crystalline components [1].
Figure 5. Curve fitting analysis of methylene carbon in the fully relaxed 13C NMR
spectrum of iPP/o-dichlorobenzene gel (14 wt%) [1].
Phase Structure Depending on Concentration in iPP Gel

To investigate the molecular structure dependent on the gel concentration,
the DD/MAS 13C NMR spectra were observed for iPP/o-dichlorobenzene with
the concentrations of 14, 22, and 50 wt% (Figure 6). The spectral shape was
basically the same, indicating that the same molecular structure was

30 Takahiko Nakaoki
constructed at the cross-linking point. The crystallinity estimated from the

methine resonance peaks at 27.4 and 26.0 ppm attributed to the crystalline and
amorphous phases, respectively, was 60% irrespective of the concentration.
DSC measurements were carried out to obtain further information on the
crystallinity. Figure 7 shows the DSC chart of the iPP/o-dichlorobenzene gel
(14 wt%), which showed a broad endothermic peak at 117°C corresponding to
the gel-melting temperature. In Figure 8, the gel-melting enthalpy was plotted
against concentration. The estimated values increased linearly as the polymer
concentration increased. This linear relationship indicated that the crystallinity
of the gels was constant. In the case of isotactic polystyrene (iPS) gel, Guenet
et al. showed the maximum enthalpy when the concentration was around 50
wt% [49-51]. They concluded that the formation of a polymer-solvent
complex or a stoichiometric compound yields the maximum enthalpy. The iPP
gel showed different behavior from the iPS gel. The solvent molecule was
excluded from the crystalline domain during gelation to form the gel. The
difference in the gelation mechanism between iPP and iPS could be explained
by the bulkiness of the side group. The phenyl group had sufficient space for
the solvent molecule to enter the crystal cell. By contrast, the methyl group for
iPP was too small to form a complex structure between the iPP chain and the
solvent molecule.
Figure 6. Single pulse 13C NMR spectra of iPP/o-dichlorobenzene gel with polymer
concentrations of 50, 22, and 14 wt%. The waiting time of 300 s is sufficient to
provide the thermoequilibrium state [1].

Figure 7. DSC thermogram of iPP/o-dichlorobenzene gel (14 wt%). Heating and

cooling rate was 5°C/min [1].
Figure 8. Gel-melting enthalpy depending on polymer concentration [1].
Coagulation Size of o-Dichlorobenzene in iPP Gel

As reported for the PVA hydrogel, ice frozen in the gel provided the
melting temperature depression from the normal melting temperature of ice
[43-45]. Therefore, the iPP/o-dichlorobenzene gel was cooled below the
melting temperature of o-dichlorobenzene, and the melting process of o-

32 Takahiko Nakaoki
dichlorobenzene trapped in the gel was investigated by DSC. Figure 9 shows

the DSC chart of the 20 wt% gel in the temperature range from −100°C to
10°C. In addition to the main peak around −15°C, a small endothermic peak
was observed at −26.5°C. The main peak was observed near the melting
temperature of pure o-dichlorobenzene at −17°C, which corresponded to the
melting of free solvent in the gel. To obtain further information on these
melting peaks, the melting behavior depending on polymer concentration was
observed (Figure 10). Two endothermic peaks were observed for all gels; the
high melting temperature was almost constant, but the low melting peak
shifted toward lower temperatures with increasing concentration. These
melting temperatures are plotted in Figure 11. The low melting temperature of
the 5 wt% gel was −17.7°C, whereas that of the 30 wt% gel significantly
lowered to −34.1°C. To make clear this large temperature depression, cyclic
DSC measurement was carried out for the 20 wt% gel, as shown in Figure 12.
The first run was performed from −60°C to −17°C, which was lower than the
high melting temperature around −15°C. The broad endothermic peak was
observed around −26°C. After cooling to −60°C, the heating process was
repeated. Notably, the low melting peak was reproduced. This result indicated
that the low melting peak was thermally reversible. Given that the low melting
temperature significantly shifted depending on the polymer concentration, a
close relation was noted between the bound state of solvent and the molecular
morphology of the polymer chain.
Figure 9. DSC thermogram of 20 wt% iPP/o-dichlorobenzene gel. High and low

melting peaks caused by o-dichlorobenzene in the gel were observed at -17°C and
26.5°C, respectively [2].

Figure 10. Melting behavior of o-dichlorobenzene in the gel depending on gel

concentration [2].
Figure 11. Melting temperature of o-dichlorobenzene in the gel as a function of

polymer concentration. ●: high melting temperature, ■: low melting temperature [2].

34 Takahiko Nakaoki
Figure 12. DSC thermogram of 20 wt% iPP/o-dichlorobenzene gel. The first heating
process was stopped at −17°C. After cooling to −60°C, the second heating process
started [2].
Melting Behavior of the Solvent in iPP Gel after Partial Drying

The 10 wt% iPP/o-dichlorobenzene gel was allowed to stand for a few
weeks at room temperature, and the solvent was evaporated in the draft
chamber. The gel was concentrated until the polymer concentration became
30, 60, and 90 wt%. Subsequently, DSC measurements were carried out. The
heating processes between −100°C and 10°C are shown in Figure 13. For the
gel concentrated to 30 wt%, two endothermic peaks were observed. The high
melting peak was close to that of the 10 wt% gel, but it became small in
intensity. The low melting peak shifted toward low temperatures compared
with the 10 wt% gel. In the DSC chart of the gel concentrated to 60 wt%, no
trace of a high melting peak was found, but only the low melting peak was
observed at −39°C. Furthermore, the gel concentrated to 90 wt% provided no
peaks, which suggested that all solvent molecules were in a nonfreezable state.
These results indicated that the solvent with high melting temperature was
evaporated with ease during drying, whereas that with low melting
temperature took a longer time to evaporate. Thus, the solvents with high and

low melting temperatures were weakly and strongly bound in the gel,
respectively. Figure 14 plots the endothermic temperature as a function of
polymer concentration after evaporating the solvent. The low melting peak
shifted toward low temperature with polymer concentration. This thermal
behavior was associated with the molecular morphology of the iPP chain, so
polarized optical microscopy was conducted.
Figure 13. DSC thermogram of 30, 60, and 90 wt% gels concentrated from 10 wt% gel
during drying [2].
Figure 14. Melting temperature of high and low endothermic peaks depending on
concentration after evaporation of o-dichlorobenzene from 10 wt% gel [2].

36 Takahiko Nakaoki
Polarized Optical Microscopic Photograph of iPP Gel

To clarify the relationship between the molecular morphology and the
solvent bound in the gel, polarized optical microscope images were observed.
Figure 15 shows the microscopic photographs of the 2, 5, 10, and 20 wt% gels.
The maltese cross was clearly observed for all gels, indicating the formation of
spherulites. With increasing polymer concentration, the number and size of
spherulite increased. No solvent was located in the crystal unit, so the space
for the solvent was limited in the noncrystalline region between spherulites or
that between lamellae in spherulite. The spherulites in the 2 wt% gel were
isolated from others such that the space between spherulites was very large.
Given that the polymer chain between spherulites was regarded as a
noncrystalline phase, the solvent could coagulate under a large size. This
finding indicated that the solvent with high melting temperature was located in
this region.
Figure 15. Polarized optical microscopic photographs of the various concentrations of

the iPP/o-dichlorobenzene gel formed at 0°C[2].
The low melting peak was attributed to the melting of strongly bound
solvent because of slow evaporation during gel drying. Based on the formation

of spherulite, the solvent molecules were located in the noncrystalline phase

between lamellae in spherulite. In general, spherulite consists of a layer
structure of crystalline lamella and amorphous phase. Thus, the solvent with
low melting temperature was located in the noncrystalline phase in spherulite.
The layer size corresponding to the long period was generally a few tens of
nanometers. The coagulation of o-dichlorobenzene in this amorphous phase
was smaller than a few tens of nanometers. The schematic model of free and
freezable bound solvents is depicted in Figure 16. Figure 16(a) shows the free
solvent with high melting temperature located in the noncrystalline region
between spherulites. Meanwhile, Figure 16(b) shows the freezable bound
solvent with low melting temperature located in the noncrystalline region
between lamellae in the spherulites.
Figure 16. Schematic model of bound solvent in the gel. Free solvent in the gel, which
provides the same melting temperature as pure solvent, was located between
spherulites. (a) Freezable bound solvent with melting temperature lower than pure
solvent was located in the noncrystalline region between lamellae in spherulite (b).

38 Takahiko Nakaoki
Melting Behavior of o-Dichlorobenzene depending on Gelation

Temperature for iPP Gel
Gelation is a type of crystallization from a homogeneous solution, and the
annealing effect is an important factor to control molecular morphology.
Figure 17 shows the DSC thermogram for 10 wt% gel depending on the
gelation temperature. The high melting peak was almost constant irrespective
of the gelation temperature, whereas the low melting peak strongly depended
on the gelation temperature. These temperatures are plotted in Figure 18. As
described in the above section, this temperature shift was related to spherulite.
Thus, the polarized optical microscopic photographs were observed to clarify
the relationship between the melting behavior and molecular morphology.
Figure 19 shows the photographs of the 10 wt% gels incubated at various
temperatures. The spherulites were large for high gelation temperature. This
molecular morphology was associated with the melting behavior of the
solvent. For the low melting peak, a low melting temperature corresponded to
a large spherulite size. This trend was consistent with concentration
dependence; when spherulite was large, the temperature depression of the low
melting peak was high.
Figure 17. DSC heating curve for the 10 wt% gel depending on gelation temperature
[3].

Figure 18. Melting temperature of o-dichlorobenzene in 10 wt% gel as a function of

gelation temperature. ● : high melting peak; □: low melting peak [3].
Figure 19. Photograph of spherulites taken by a polarizing microscope with cross

nicols in the 10 wt% iPP gel depending on gelation temperature: (a) 0°C, (b) 30°C, (c)
50°C, and (d) 70°C [3].

40 Takahiko Nakaoki
Relationship between Temperature Depression and Coagulation Size of

o-Dichlorobenzene
Ishikiriyama et al. reported that the coagulation radius of ice filled in the
porous silica gel can be estimated by the melting temperature depression from
the normal melting temperature of ice at 0°C [52, 53]. Similarly, the
temperature depression of the low melting peak in the gel can be interpreted
by small coagulation of o-dichlorobenzene. The coagulation radius of o-
dichlorobenzene was estimated as a function of temperature depression from
the melting point of pure solvent (ΔT) by following their procedure. The
coagulation radius of freezable solvent r(T) is shown by the temperature
depression as follows:
 (T )
r (T )  (2)
T
where α(T) is a thermodynamical parameter. Four silica gels with different

pore radius were used to obtain the calibration curve between the pore radius
of silica gel and the melting temperature depression of o-dichlorobenzene.
Figure 20 shows the melting process of o-dichlorobenzene filled in silica gels.
Two melting peaks attributed to o-dichlorobenzene were separately observed
in the DSC chart; these peaks showed the same trend as thermal behavior of o-
dichlorobenzene in the iPP gel. One corresponded to the melting of normal o-
dichlorobenzene around −17°C, and the other was observed at a lower
temperature than the normal one. The latter corresponded to the melting of
solvent filled in the pore of silica gel. Following the analytical procedure of a
previous report, α(T) was plotted against the temperature depression of low
melting peak in Figure 21. The experimental result could be fitted by the
following equation.
α (T) = 0.356 ΔT + 82.9 (3)
This relationship was applied to estimate the coagulation radius of o-

dichlorobenzene in the gel.

Figure 20. Melting process of o-dichlorobenzene filled in the porous silica gel. The
pore radius is shown at the left [4].
Figure 21. Parameter α(T) in Eq. (1) as a function of temperature depression. The fitted
line estimated by average values was drawn by a solid line. The maximum and
minimum values were fitted by broken lines [4].

42 Takahiko Nakaoki
Coagulation Size of Freezable Bound Solvent in iPP Gel

Figure 22 shows the DSC chart of the melting process of o-
dichlorobenzene in iPP/o-dichlorobenzene gel depending on the concentration
from 20 wt% to 70 wt%. The low melting peak became smaller in intensity
with increasing concentration, and it was not observed above 70 wt%. This
finding indicated that all solvent molecules were in a nonfreezable state.
Equations (2) and (3) were applied to estimate the coagulation size of solvent
in the gel. Figure 23 illustrates the coagulation radius of o-dichlorobenzene as
a function of concentration of the iPP gel. The coagulation radius decreased
with increasing concentration. For example, the coagulation radius of 20 wt%
gel was 6.1 nm, whereas that of 50 wt% gel was 4.1 nm. As described in the
previous section, the freezable bound solvent with low melting temperature
was located in the noncrystalline region between crystalline lamellae in
spherulite. Therefore, the amorphous layer between lamellae in spherulite was
small for high concentration gel such that the solvent was coagulated in small
size.
Figure 22. DSC chart of the melting process of o-dichlorobenzene in the iPP/o-
dichlorobenzene gel depending on concentration [4].

Figure 23. Coagulation radius of o-dichlorobenzene in the iPP gel depending on

concentration [4].
SANS Measurement of iPP Gel

As described in the previous section, thermal analysis is one of the most
powerful tools to evaluate the coagulation size of solvent in the gel. However,
it cannot directly determine the coagulation size. SANS measurement was
carried out, and the coagulation size of o-dichlorobenzene in the iPP gel was
compared with thermal analysis. Figure 24 shows the SANS profile of 30 wt%
iPP/o-dichlorobenzene-d4 gel observed between −60°C and 0°C. The
scattering profile changed in intensity at q = 0.1 nm−1 between −40°C and
−30°C. This temperature was identical with the melting of freezable bound
solvent observed by thermal analysis (Figure 22). The scattering profile was
fitted by unified scattering function containing multiple levels of structural
units reported by Beaucage et al. [54].
 q 2R g2
R  G exp  B(q*)- 4 (4)
3

44 Takahiko Nakaoki
where Rg and q denote the average particle size and the scattering vector,
respectively, and G and B are Guinier and Porod constants, respectively.
q
q*  (5)
[erf (qR g / 61/ 2 )]3
where erf() is the error function. For example, curve fitting analysis of the 30
wt% gel at −60°C is shown in Figure 25. The experimental profile was in good
agreement with the theoretical one. Rg corresponding to the coagulation size of
o-dichlorobenzene was 4.6 nm at −60°C. Notably, this coagulation radius was
almost identical with that observed by DSC, which was 5.4 nm for the 30 wt%
gel. In Figure 26, the coagulation radius of solvent in the gel was plotted as a
function of temperature. The coagulation size changed from 4.6 nm to 4.1 nm
between −40°C and −30°C, which corresponded to the low melting
temperature of around −30°C for the 30 wt% gel. This change might be
explained by the transformation from freezable bound to nonfreezable
solvents. The coagulated domain of freezable solvent was surrounded by the
swollen iPP chains containing nonfreezable solvent. After the solvent was
melted, some solvent possibly penetrated in the region of swollen iPP chains
and decreased the coagulation size of freezable solvent.
a
Figure 24. (Continued)

Figure 24. Temperature dependence of SANS profile for the 30 wt% iPP/ o-
dichlorobenzene-d4 gel. (a). The expanded profile is shown in (b). The SANS profiles
observed at −60°C and −50°C were overlapped and shown by a solid line. The profile
changed above −40°C. The profiles at −10°C and 0°C were overlapped and shown by a
dotted line [4].
Figure 25. SANS profile of the 30 wt% iPP/o-dichlorobenzene-d4 gel at −60°C ( ) and
the theoretical curve ( ) [4].

46 Takahiko Nakaoki
Figure 26. Coagulation radius of freezable bound o-dichlorobenzene in the gel as a

function of temperature estimated by SANS measurement [4].
SANS Profile of iPP Gel Depending on Concentration

Figure 27 shows the SANS profile of iPP/o-dichlorobenzene-d4 gel
depending on the concentration. The scattering intensity at 0.01 nm−1 was
larger for the high concentration gel, whereas that at 0.1 nm−1 was smaller for
the high concentration gel. The coagulation radius of freezable bound solvent
was estimated by curve fitting analysis and plotted depending on the
concentration shown by an open triangle in Figure 28. The coagulation size
decreased from 4.8 nm for the 20 wt% gel to 4.0 nm for the 50 wt% gel. For
reference, the coagulation radius estimated by thermal analysis was also
plotted by closed circles. Both results were in the same order with a few
nanometers. Therefore, freezable bound solvent with the coagulation radius in
the order of a few nanometers was present in the iPP/o-dichlorobenzene gel.
In our report on PVA hydrogel, the coagulation size of water in the PVA
hydrogel was evaluated as a function of concentration [46, 47]. The
coagulation radius for the 10 wt% PVA gel was as large as 15.1 nm, but it
decreased to 1.5 nm for the 70 wt% gel. The range of coagulation size
depending on the concentration was very large compared with the iPP gel at
6.1 nm for the 20 wt% gel and 4.1 nm for the 50 wt% gel. This finding could
be explained by the molecular morphology formed throughout gelation. The
iPP gel formed the crystal consisting of spherulites, whereas the PVA gel

provided low crystallinity without spherulite [55-57]. In the PVA hydrogel,

phase separation throughout density fluctuations provides the coagulations of
water and swollen PVA chains containing water in low and high density
domains, respectively. Therefore, the biggest factor to define the coagulation
size of water is how large the density fluctuation is. Meanwhile, the iPP gel
consists of spherulite, which is constructed in the high density domain
throughout density fluctuation. Therefore, the molecular morphology
consisting of crystal is regulated by thermodynamical factors such as gelation
temperature and crystallization mechanism. The molecular morphology is the
most important factor for the coagulation of solvent in the iPP gel. In this
study, the quenching temperature at 0°C was adopted to form gel. Therefore,
the coagulation size of o-dichlorobenzene bound in the noncrystalline region
between crystalline lamellae varied in a small range against concentration.
Figure 27. SANS profile for iPP/o-dichlorobenzene-d4 gel depending on concentration

[4].
The long-range order consisting of repeating lamellar and noncrystalline

layers was reported for the α-iPP crystal by small-angle X-ray scattering [58].
The long period was estimated as 18.6 nm. When the crystallinity of this α-iPP
was 60%, the noncrystalline layer corresponded to 7.4 nm. Gelation was

48 Takahiko Nakaoki
regarded as a kind of crystallization from the solution, so the long-range order

demonstrated the same order with the bulk iPP crystal. Given that the
coagulation radius in the gel was 3–6 nm as shown in Figure 28, the layer size
of the noncrystalline phase between lamellae was a suitable size for the
coagulation of solvent.
Figure 28. Coagulation radius of freezable bound o-dichlorobenzene in the gel. Δ :

SANS and ● :DSC [4].
Syndiotactic Polypropylene Gel
Molecular Structure at the Cross-Linking Point in sPP Gel

The stereoregular counterpart of iPP is sPP. In this section, sPP gel is
discussed from the perspective of the molecular structure at the cross-linking
point, as well as the coagulation of solvent. A stable and homogeneous gel was
formed for sPP98/ o-dichlorobenzene at room temperature. A typical DSC
chart for the sPP98/o-dichlorobenzene gel (14 wt%) quenched at 0°C is shown
in Figure 29. An endothermic peak at 80°C on heating and an exothermic peak
at 44°C on cooling were observed, corresponding to the melting of the gel and
re-gelation, respectively. These temperatures were much lower than those for
the iPP/o-dichlorobenzene gel shown in Figure 1. Inherently, gelation is
regarded as crystallization from dilute solution accompanied with the

formation of a 3D network structure. Gelation strongly depends on

concentration and temperature, so the time for gel formation obtained by the
tilting method was plotted against temperature for the 5 and 10 wt% gels in
Figure 30. The gelation time increased monotonically with temperature. In the
vicinity of 80°C–90°C, no gel was formed even after a long time period. This
temperature was regarded as a critical temperature for gelation, and it was
almost the same temperature as the melting temperature observed by DSC.
Figure 29. DSC thermogram of sPP/o-dichlorobenzene gel (13.6 wt%) [5].
Figure 30. Gelation time at different temperatures measured by the tilting method for
sPP/o-dichlorobenzene system: ●, 5 wt% and ○, 10 wt% [5].

50 Takahiko Nakaoki
Molecular Structure at the Cross-linking Point in sPP Gel

Figure 31 shows the DD/MAS 13C NMR spectrum for the sPP98/o-
dichlorobenzene gel. To obtain all components of the crystal, amorphous, and
interphase, the waiting time was fixed at 300 s, which was five times longer
than the longest T1c. For comparison, the spectrum of Form I of sPP, which is
the most stable form, is also shown in this figure. Several additional resonance
peaks that were not observed in Form I of sPP were observed in the spectrum
of the sPP98 gel.
Table 3. Chemical shifts and T1C and T2C of sPP/o-dichlorobenzene gel

(14 wt%) and Form I crystal [5]
Form I Gel
ppm T1C (s) T2C (ms) ppm T1C (s) T2C (ms)
CH3 19.9 0.3 14
20.7 0.2 0.077 20.6 0.3 0.052
20.9 0.2 0.077 20.8 0.3 14
CH 26.2 30 0.022 26.2 23 0.010

26.4 0.2 11
27.4 0.2 11
CH2 39.1 63 0.014 39.0 58 0.012
46.4 0.2 13
47.7 63 0.014 47.7 53 0.015
49.0 53 0.016
The resonance peaks at ca. 20 ppm were assigned to methyl carbon, and
those in the ranges of 25–30 and 35–55 ppm were attributed to methine and
methylene carbons, respectively. To provide further information on the
molecular mobility, T1C and spin–spin relaxation time (T2C) were observed.
Figure 32 shows a series of spectra obtained in the time progression of the
saturation recovery pulse sequence. For this pulse sequence, the mobile
components were observed under a short delay time, whereas the rigid
component-like crystalline region had a long delay time. For T2C measurement,
the following pulse sequence was used. The magnetization recovered in the
direction of the static field by the saturation recovery pulse for 30 s was turned
to 90°. After allowing transverse relaxation for a certain time, the free
induction decay was observed. Figure 33 shows a series of spectra in the time
progression of T2C. In this pulse sequence, the short T2c component
disappeared quickly and a longer T2C component remained. The T1C and T2C
values are summarized in Table 3 together with those of Form I of sPP. The

sharp resonance peaks at 19.9, 27.4, and 46.4 ppm provided short T1C, whereas
these peaks remained for a relatively long waiting time because of long T2C.
These behaviors were typical of the amorphous state of polymer.
Figure 31. Equilibrium DD/MAS 13C NMR spectra of sPP/o-dichlorobenzene gel (13.6
wt%) and Form I crystal [5].
Figure 32. Time progression of 13C NMR spectra observed by saturation recovery
pulse sequence for sPP/o-dichlorobenzene gel [5].

52 Takahiko Nakaoki
Figure 33. Time progression of 13C NMR spectra for T2C relaxation for sPP/o-
dichlorobenzene gel [5].
The resonance peaks with long T1C and short T2C were assigned to the
crystalline component. The peaks at 26.2 ppm for methine carbon and at 39.0,
47.7, and 49.0 ppm for methylene carbon were due to the crystalline
component. The peaks at 19.9 and 20.6 ppm for methylene carbon
demonstrated the same T1C of 0.3 s, whereas the T2C values were 14 and 0.052
ms, respectively. Given that a long T2C corresponds to the mobile component
such as amorphous, the peak at 19.9 ppm was attributed to the amorphous
phase, and that at 20.6 ppm was assigned to the crystalline phase.
For Form I of sPP, the doublet was observed for methylene carbon at 39.0
and 47.7 ppm. This split was due to the γ-gauche effect. The peak at 47.7 ppm
was assigned to methylene carbon centered at the tg-gt sequence irrespective
of the γ-gauche effect. The peak at 39.0 ppm was assumed as methylene
carbon centered at the gt-tg sequence and associated with two γ-gauche
effects, providing about 10 ppm upfield shift from the peak at 47.7 ppm.
However, the spectral pattern for the gel was characterized by three peaks at
39.0, 47.7, and 49.0 ppm for methylene carbon, and its intensity ratio was
3:2:1 from the upfield. The chemical shifts at 39.0 and 47.7 ppm were the
same as those of Form I of sPP, and that at 49.0 ppm was identical to Form III

with all-trans conformation. If the crystalline structure took Form IV with

t2g2t6g2 conformation, the methylene carbons centered at the tt-tt, gt-tg, and gt-
tt sequences split into three components. However, in the spectrum of the gel,
no peak was present at 44 ppm because of the gt-tt sequence with one γ-
gauche effect. This finding indicated that Form IV was not formed in the gel.
Given the possibilities for the gel to adopt t2g2 and all-trans conformations, the
infrared (IR) spectrum was measured. The IR spectrum reflects the number of
normal vibrational modes depending on the molecular conformation based on
the selection rule of the symmetry species. Figure 34 shows the IR spectra of
Form I with t2g2 conformation and Form III with all-trans conformation and
the gel. In this study, the spectrum of the gel was obtained by subtracting the
contribution from o-dichlorobenzene via computational analysis. The
absorption bands characteristic of all-trans conformation at 1234, 1131, and
830 cm−1 were not observed in the spectrum of the gel, whereas those for the
t2g2 conformation were completely the same as those for the gel. This result
indicated that the two crystal forms with t2g2 and all-trans conformation did
not coexist in the gel, but the conformation formed in the gel showed a t2g2
conformation.
Figure 34. Infrared spectra of Form III (all trans), Form I (t2g2), and the gel (13.6
wt%). The spectrum of the gel shows the contribution from the polymer that was
obtained by subtracting the contribution from the solvent component [5].
A possible explanation for the results of 13C NMR and IR spectra will be
given by considering a molecular packing effect to yield a triplet resonance to

54 Takahiko Nakaoki
the methylene carbon in the DD/MAS l3C NMR spectrum. Therefore, the split
of 47.7 and 49.0 ppm was due to the molecular packing effect. The splitting
width of 1.3 ppm was comparable with that of 1.0 ppm in the case of doublet
for the α-iPP crystal.
Phase Structures of Crystalline, Amorphous, and Interphase in sPP Gel

As shown in the previous section, iPP chain in the gel consisted of three
phases; crystalline, amorphous, and interphase. The 13C NMR spectrum was
used to study the phase structure of sPP98 gel. Figure 35 shows the line shape
analysis of methine and methyl resonance peaks of the DD/MAS 13C NMR
spectrum, where a Lorentzian function was assumed for each component. The
sharp components were assigned to the crystalline and amorphous
components, but the third component was required to fit the peak shape at 26.4
and 20.8 ppm for methine and methyl carbons, respectively. These
components were attributed to the interphase between the crystalline and
amorphous phases. The fractions of these phases were estimated from the
integral intensities, and the results are listed in Table 4. The fraction of the
crystalline component was 0.48–0.49, which corresponded to crystallinity.
This range was much lower than the crystallinity of iPP gel at 0.60.
Figure 35. Component analysis of methane (upper) and methyl (lower) peaks [5].

Table 4. Phase fraction of sPP/o-dichlorobenzene gel (14 wt%) [5]
Crystalline Interphase Amorphous

CH 0.48 0.33 0.19
CH3 0.49 0.29 0.22
Coagulation Size of o-Dichlorobenzene Bound in Different

Stereoregular sPP Gels
In addition to sPP98 with highly syndiotactic sequence, less stereoregular
samples of sPP83 were also investigated for the coagulation of solvent in the
gel. Figure 36 shows the DSC profiles for the melting process of o-
dichlorobenzene in the sPP98 and sPP83 gels formed at 0°C for various
concentrations. One peak was observed for pure o-dichlorobenzene, whereas
two endothermic peaks were observed in the gel. This type of melting
behavior was similar to that of the iPP/o-dichlorobenzene gel. As concluded
in the previous section, the high and low melting temperature peaks
corresponded to the melting of free and freezable bound solvents located in
the noncrystalline regions of inter- and intra-spherulites, respectively. In
Figure 37, these melting temperatures are plotted as a function of the
concentration of sPP gel. The high melting temperature was almost constant
regardless of the concentration, whereas the low-temperature melting peak
shifted to a lower temperature with increasing concentration. For the sPP98
gel, the low melting temperature was lower than that of the sPP83 gel. The
temperature depression of the melting peak was dependent on the coagulation
size of the solvent in the polymer network. The coagulation radius of o-
dichlorobenzene was associated with the melting temperature depression, as
shown in Equations (2) and (3). Figure 38 shows the coagulation radii of o-
dichlorobenzene in the sPP98 and sPP83 gels as a function of concentration.
The coagulation radius of o-dichlorobenzene was of nanometer order and
decreased with increasing sPP concentration. The sPP98 gel exhibited a
smaller coagulation size than the sPP83 gel. For example, the coagulation
radii of the 30 wt% sPP98 and sPP83 gels were 6.7 and 8.2 nm, respectively,
corresponding to the large noncrystalline region in the sPP83 gel in which the
solvent molecules could be located. In the iPP/o-dichlorobenzene gel, the
coagulation radius of the solvent was reported as 5.6 nm for the 30 wt% gel,
and this value was smaller than those for the sPP gels. This difference could
also be explained by the molecular morphology. The crystallinity of the iPP
gel was higher than that of the sPP gels, leading to small noncrystalline
regions for the iPP gel.

56 Takahiko Nakaoki
Figure 36. DSC thermograms for the melting process of o-dichlorobenzene in the (a)
sPP98 and (b) sPP83 gels for various concentrations [6].
Figure 37. High and low melting temperatures of o-dichlorobenzene in the sPP98
(closed symbols) and sPP83 (open symbols) gels [6].

Figure 38. Coagulation radius R of freezable bound o-dichlorobenzene in the sPP98

(■) and sPP83 (Δ) gels as a function of concentration [6].
Polarized optical microscopic measurements were conducted to confirm

the molecular morphology. Figure 39 shows the polarized optical micrographs
of 10 wt% sPP98 and sPP83 gels. Maltese crosses were clearly observed for
the sPP98 gel, which corresponded to the formation of spherulites. The long
stereoregular sequence allowed the formation of spherulites. As shown in
Figure 38, the coagulation size of the solvent was small for high
concentrations. Therefore, the noncrystalline region between lamellae in
spherulite was small. By contrast, no spherulites were observed in the sPP83
gel because the low stereoregularity restricted the formation of long ordered
helices. However, a trace of crystalline regions was noted. Therefore, the large
noncrystalline region was present between the crystalline regions, which
resulted in the large coagulation size of the solvent.
Figure 39. Polarized optical micrographs of the (a) 10 wt% sPP98 and (b) 10 wt%
sPP83 gels formed at 0°C [6].

58 Takahiko Nakaoki
Figure 40. Weight contents of the free (●), freezable bound (□), and nonfreezable
solvents (▲) as a function of concentration for the (a) sPP98 and (b) sPP83 gels [6].
Fraction of Free, Freezable Bound, and Nonfreezable Solvents in

sPP Gel
Thermal analysis involves the melting temperature and enthalpy. The
melting temperature depression is closely associated with the coagulation size
of the solvent in the gel. Meanwhile, the melting enthalpies of the high- and
low-temperature melting peaks provided the fraction of free and freezable
bound solvents, respectively. The remaining solvent, which provided no
melting enthalpy, was assumed as the nonfreezable solvent. Figure 40 shows
the fractions of free, freezable bound, and nonfreezable solvents in the sPP98
and sPP83 gels. The fraction of free solvent was approximately 50 wt% for
the 20 wt% sPP98 gel, whereas that for the 20 wt% sPP83 gel was over 90
wt%. The low stereoregular sPP83 had large domains of noncrystalline phases
because of incomplete stereoregularity, so that more solvent molecules were
trapped in the noncrystalline region. The fraction of freezable bound solvent
peaked at around 30 and 45 wt% for the sPP98 and sPP83 gels, respectively.
For high concentration gels over 60 wt%, only nonfreezable solvent was
evident in both gels.
Phase Structure of sPP Gel

The DD/MAS 13C NMR spectra were observed to investigate the phase
structure. The cycle time of 300 s was adopted to obtain the contributions from
all structural components of the crystalline, amorphous, and intermediate
phases. Figure 41 shows the DD/MAS 13C NMR spectra of methylene carbon
for the 30 wt% sPP98 and sPP83 gels. As described in the previous section,

three peaks at 49.0, 47.7, and 39.0 ppm were assigned to the crystalline
component. The signal at 46.4 ppm, with a short T1C of 0.5 s, was attributed to
the amorphous phase. The peak intensity of the amorphous component in the
sPP98 gel was smaller than that in the sPP83 gel, which corresponded to the
low crystallinity of the sPP83 gel. In addition to the crystalline and amorphous
components, the interphase exhibited an intermediate mobility between the
crystalline and amorphous phases. Notably, the resonance peak of the
interphase was observed at different chemical shifts at 44.0 and 45.3 ppm for
sPP98 and sPP83, respectively. The chemical shift of the sPP83 gel was
observed downfield from that of the sPP98 gel. The chemical shift of the
methylene resonance for sPP corresponded to the molecular conformation;
therefore, the interphase of sPP83 showed the trans conformation. In addition,
the half width of the sPP83 gel was narrower than that of the sPP98 gel, which
suggested that the interphase in the sPP83 gel was more mobile than that in the
sPP98 gel. The low stereoregularity of sPP83 enhanced interphase molecular
mobility. The fraction of each component for the 30 wt% gel was estimated by
curve fitting analysis, and the results are listed in Table 5. The fraction of the
sPP98 gel crystalline component was 52 wt%, whereas that of the sPP83 gel
was as low as 23 wt%. In the case of the iPP gel, the crystallinity was reported
at 60 wt%, which was higher than that for the sPP gels. The fraction of the
interphase for the sPP98 and sPP83 gels was almost the same at around 17–18
wt%. The fraction of the amorphous component of the sPP83 gel was twice as
large as that of the sPP98 gel. Solvent molecules could not enter into the
crystalline region, so the solvent was bound in the noncrystalline phase.
Melting Behavior of o-Dichlorobenzene Depending on Gelation

Temperature for sPP Gel
The molecular morphology of the sPP gel is dependent on the gelation
temperature. To study the molecular morphology, several gelation
temperatures were examined. Figure 42 shows the DSC profiles for the 30
wt% sPP98 and sPP83 gels formed at 0°C, 30°C, and 60°C quenched from the
homogeneous solution at 150°C. Gelation was not observed for sPP83 at 60°C,
which corresponded to the temperature above the gel-forming temperature. For
the sPP98 gel, the peak intensity of the low temperature melting peak was
larger than that of the high melting peak, indicating that a large amount of
solvent was in the freezable bound state. In contrast to the sPP98 gel, the peak
intensity of the high melting peak for the sPP83 gel was larger than that of the
low melting peak, which suggested that a large amount of solvent was in the
free state.

60 Takahiko Nakaoki
Figure 41. DD/MAS 13C NMR spectra for the 30 wt% (a) sPP98 and (b) sPP83 gels. C:
crystalline, A: amorphous, and I: interphase [6].
Figure 42. DSC thermograms for the melting process of o-dichlorobenzene in the (a)
sPP98 and (b) sPP83 gels for various gelation temperatures [6].

Table 5. Weight fraction of 30 wt% sPP98 and sPP83

gels determined by curve fitting analysis of the
DD/MAS 13C NMR spectra [6]
sPP98 sPP83
Crystalline 0.52 0.23
Interphase 0.18 0.17
Amorphous 0.30 0.60
Polarized Optical Microscopic Photograph of sPP Gel

The molecular morphology was observed using a polarized optical
microscope, and the results are shown in Figure 43. Maltese crosses were
clearly observed for the sPP98 gel but not for the sPP83 gel at any gelation
temperature because of its low stereoregularity. The spherulites in the sPP98
gel became larger when annealed at higher temperatures. As the annealing
temperature increased, the low-temperature melting peak shifted toward that of
pure o-dichlorobenzene. The coagulation radius of the solvent was calculated
using Equations (2) and (3), and the findings are plotted in Figure 44. The
coagulation radius increased with the gelation temperature for both the sPP98
and sPP83 gels. For example, the coagulation radius of the solvent formed at
0°C for the 30 wt% sPP98 gel was 6.7 nm and then increased to 13.6 nm when
annealed at 60°C. The coagulation size of the solvent was closely associated
with the noncrystalline regions sandwiched between lamellae. The schematic
model for solvent in the spherulite of sPP is shown in Figure 45(a). After
nucleation of a small crystallite, the lamellae grew toward the outside from the
nucleation center. In the case of sPP, a large space between lamellae was
formed at the edge of spherulites to provide a large region for coagulation of
the solvent. In contrast to the results for the sPP gels, the coagulation size of
the solvent in iPP gel decreased with increasing gelation temperature. This
result might be explained by second-order crystallization, in which the growth
of lamellae was accompanied with branching as shown in Figure 45(b). This
phenomenon provided a small noncrystalline region for the coagulation of the
solvent.

62 Takahiko Nakaoki
Figure 43. Polarized optical micrographs of the (a) sPP98 and (b) sPP83 gels as a
function of gelation temperature: (a1) 0°C, (a2) 30°C, (a3) 60°C, (b1) 0°C, and (b2)
30°C [6].
Figure 44. Coagulation radius R of o-dichlorobenzene in the sPP98 (●) and sPP83 (○)
gels as a function of the gelation temperature [6].

Figure 45. Schematic models of solvent trapped in spherulites formed in (a) sPP and
(b) iPP gels. The lamellar and solvent were represented by a line and circle,
respectively [6].
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BIOGRAPHICAL SKETCH
Takahiko Nakaoki
Affiliation: Department of Materials Chemistry, Faculty of Science and

Technology, Ryukoku University (Japan)
Education:
1987 B.S, Faculty of Science, Osaka University, Osaka, Japan
1989 MSc, Graduate School of Science, Osaka University, Osaka, Japan
1992 Ph. D, Graduate School of Science, Osaka University, Osaka, Japan
Research and Professional Experience:

1999-2000 Visiting Scientist at Polytechnic University, New York, USA
2009: Visiting Scientist at Freiburg University, Freiburg, Germany
2010: Visiting Scientist at Salerno University, Salerno, Italy
Professional Appointments:
2005-present: Professor at Department of Materials Chemistry, Ryukoku
University, Shiga, Japan
1992-2005: Associate Professor at Department of Materials Chemistry,
Ryukoku University, Shiga, Japan
Publications Last 3 Years:

1. T. Nakaoki, R. Yamagishi, D. Ishii, Biosynthetic Process and
Characterization of Poly (3-hydroxybutyrate-co-3-hydroxyvalerate)-
block-poly(3-hydroxybutyrate) by R. eutropha, J. Polym. Environ.,
23, 487-492(2015).

2. T. Fukumori, T. Nakaoki, High Strength Poly(Vinyl Alcohol) Films

obtained by Drying and then Stretching Freeze/Thaw Cycled Gel,
Journal of Applied Polymer Science, 132, 41318 (2015).
3. M. Nakaoki, K. Yamashita, Bound Solvent in Different Stereoregular
Syndiotactic Polypropylene Gels, J. Mol. Struct., 1075, 413-418
(2014).
4. M. Sakamoto, Y. Kimura, D. Ishii, and T. Nakaoki, Biosynthesis of
Poly(3-hydroxyalkanoate) from Amino Acids in Medium with
Nitrogen, Phosphate, and Magnesium, or some Combination of these
Nutrientsels, J. Polym Environ, 22, 488-493(2014).
5. T. Fukumori, T. Nakaoki, High-Tensile-Strength Polyvinyl Alcohol
Films Prepared from Freeze/Thaw Cycled Gels, Journal of Applied
Polymer Science, 131, 40578 (2014).
6. T. Fukumori, T. Nakaoki, Significant Improvemnet of Mechanical
Properties for Polyvinyl Alcohol Film Prepared from Freeze/Thaw
Cycled Gel, Open Journal of Organic Polymer Materials, 3, 110-116
(2013).
7. T. Nakaoki and D. Fukui, Single-Helix Crystal in Atactic
Polypropylene, J. Mol. Struct., 1051, 271-275 (2013).
8. T. Miura, D. Ishii, and T. Nakaoki, Production of Poly(3-
hydroxyalkanoate)s by Pseudomonas putida Cultivated in a
Glycerol/Nonanoic Acid-Containing Medium, J. Polym. Environ., 21,
760-765 (2013).
9. K. Furukawa, and T. Nakaoki, Absorption Kinetics of Phenol into
Different Size Nanopores Present in Syndiotactic Polystyrene and
Poly(p-methylstyrene) Polymer Science, Chapter 5, 133-150 (2013).
10. N. Fujiwara,H. Tanimura, T. Nakasugi, T. Nakaoki, K. Inoue, J. Miki,
M. Ohyanagi, D. Yamaguchi, S. Koizumi, Coagulation Dimension of
freezable bound Solvent in Isotactic Polypropylene / o-
Dichlorobenzene Gel, Polymer Journal,45, 173-178 (2013).
11. K. Tanigami, D. Ishii, T. Nakaoki, and P. Stroeve, Characterization of
Toluene and 2-Methylnaphthalene Transport separated by
Syndiotactic Polystyrene having Various Crystalline Forms, Polymer
Journal, 45, 173-178 (2013).

Chapter 3
POLYPROPYLENE: A THERMAL INSULATION

MATERIAL FOR SOLAR COLLECTORS
Wei Chuen Khaw and Chien Hwa Chong, PhD

School of Engineering, Taylor’s University,
Taylor’s University Lakeside Campus, Selangor, Malaysia
ABSTRACT
As polypropylene undergoing phenomenal growth in production and
end-used application in the 21st century, researchers continues to identify
new application and expands its share of the market. Conventionally,
coconut fibre is used as a thermal insulation material due to low cost and
environmental friendly. However, coconut fibre will degrade and requires
replacement on yearly basis. Therefore, the objective of this experiment is
to investigate the thermal insulation performance of polypropylene as a
thermal insulator for a solar air collector in comparison with coconut
fibre. The absorber of the solar collector is made of a rectangular
aluminium plate with area of 20.0 x 47.0 cm2 and thickness of 3.0 mm.
The experiment was carried out in Malaysia and setup of the solar
collector followed the ISO/WD 9806-1 standard. The experimental
results showed that the thermal efficiency of the coconut coir insulated
collector is 13.7% higher than the polypropylene insulated collector and
the average outlet-air temperature of the polypropylene insulated
collector was 1.46% lower than the coconut coir insulated collector.

Corresponding author: Chienhwa.Chong@taylors.edu.my.

70 Wei Chuen Khaw and Chien Hwa Chong
However, the independent samples t-test found no significant difference

between the coconut fibre and the polypropylene-insulated solar collector
based on the outlet-air temperature and thermal efficiency (p ≥ 0.05). The
result showed that polypropylene has similar thermal insulation
performance in comparison with coconut fibre. Moreover, polypropylene
is more versatile subject to different processing techniques to enhance its
properties such as higher modulus or higher heat distortion temperature
(HDT) compared to others.
Keywords: solar collector, coconut fibre, polypropylene, thermal insulation,

heat transfer
INTRODUCTION
Solar energy becomes a major renewable energy sources to solve energy
crisis nowadays. The energy is absorbed through solar radiation and
converting into thermal energy, and thus exchanges the energy with fluid
passing through the collector from inlet to outlet [1]. This energy can be used
for various processes such as drying, water heating, electricity supply and etc.
It is an environmentally friendly kind of energy, unlike nuclear or fossil fuel.
Solar energy can be harvested either using a solar collector or a solar
panel. The solar collector absorbs sunlight and converts it into thermal energy.
Fluid used in the collectors can be categorised into two models: air or liquid
collectors. Thermal efficiency of a solar air collector is lower than a liquid
collector due to the low thermal capacity of air and low convective coefficient
between absorber plates and flowing air in the collector. However, the solar air
collector can be enhanced through modification of an absorber, an installation
of a reflector, optimization of air flow for a better heat exchange rate,
integration of a thermal storage system, and so on. For instance, it was found
that different type of roughness geometries with different shapes, sizes and
orientation of absorbers can enhance the heat transfer rate with little penalty of
friction [2]. Chauhan and Chaudhary (2012) reported that an M-shape
roughness geometry on an absorber plate increase thermal efficiency of solar
collectors from 60% to 85% due to enhancement in Nusselt number over a
smooth duct [3]. Apart from that, several findings showed that an air flow
pattern also has a dominant role on thermal efficiency of solar collectors. For
example, it was discovered that by changing the air flow inside a solar
collector from a natural convection to a forced convection, it decreased the air
temperature difference between inlet and outlet, which caused lower heat loss

Polypropylene: A Thermal Insulation Material For Solar Collectors 71
[4]. In case of mass production, an application of a thermal storage system is

used to keep large amount of thermal energy for a long period of time.
Moreover, it also ensure the thermal energy supply is stable and constant to
increase the overall efficiency. A recent studies used a cylinder container made
of a copper that composed of a 90%-porous open-cell aluminium foam filled
with a paraffin-based PCM to store thermal energy in a solar collector, it was
found that the heat transfer rate increased with increasing of airflow rates [5].
Modification of a solar collector structure also show a promising result on the
overall efficiency. For instance, an investigation on the thermal efficiency of a
double-pass solar air heater showed a temperature rise of 35°C with respect to
the inlet air temperature in a solar irradiance around 900 W/m2 [6].
Type of thermal insulation used in a collector influence the thermal
efficiency of solar collectors. Previous study reported that thermal
performance of two collectors with the coconut coir and the glass-wool as
thermal insulators showed that coconut coir insulation can save 25% of
manufacturing cost and gave 7°C outlet temperature differences [7].
Moreover, it was found that thermal insulation performance of coconut coir
with polypropylene has better economical values [8]. Thus, an optimal thermal
insulation design influence the solar collector performance as well as the
operating cost. It is required to select the best thermal insulation material for
optimal operating condition for a solar collector.
PRINCIPLE OF THERMAL PROPERTIES FOR THERMAL

INSULATION MATERIAL
Thermal insulation material can be shaped in the form of a film, a block,
an open/closed cell, mechanically or chemically bound, or combination of
fibrous materials [9]. Thermal insulation materials, natural or artificial
synthetic materials, exhibit temperature dependence properties. The properties
of materials are governed by several factors including thermal conductivity,
thermal transmittance, thermal diffusivity, and specific heat. The governing
factors characterise the interaction of heat with atom particles from the
material in order to describe its thermos-physical properties [10]. At steady
state, the thermal insulation performance can be defined by thermal
conductivity and transmittance. Thermal conductivity is defines as a heat flow
passing through a unit area of a material (1m thick) with 1 Kelvin temperature
difference on the surface of the material. Conventional insulation material

usually has a thermal conductivity lower than 0.07 W/mK [11]. On the other
hand, thermal transmittance has similar principle as thermal conductivity
except it involves convective and radiative heat transfer. However, material at
un-steady state (such as liquid or gas) are mostly defined by thermal
diffusivity to determine its performance on storing and transferring thermal
energy.
THERMAL PROPERTIES OF INSULATION MATERIAL
Thermal Properties of Natural Insulation Material
The thermal properties of selected natural insulation materials are

summarized in Table 1. Referring to Table 1, the lowest thermal conductivity
was found in a cellulose fibre (0.040 W/mK) with a density of 30 kg/m3.
Thermal insulation made of a Sansevieria fibre showed the highest thermal
conductivity (0.132 W/mK) with the highest density as well (1410 kg/m3).
This is because a low density insulation material tend to have lower thermal
conductivity than an insulation material with a higher density value [12].
However, thermal insulation material made of rice showed a similar thermal
conductivity with coconut husk (0.046 W/mK) with densities of 154 and 350
kg3, respectively. Thus, it also showed that density may not be the only
dominant criteria on evaluation of thermal insulation performance of
insulation material. Further investigation should be carried out on thermal
insulation made of rices and coconut husks to understand their thermophysical
properties details. The second highest thermal conductivity was a corn cob
(0.101 W/mK) followed by a cotton stalk (0.058 W/mk). Although there are
large availability and low cost corn cob, but its thermal insulation performance
is not as good as coconut husks or rices.
Table 1. Summary of thermal properties of natural insulation material
Material Density (kg/m3) Thermal conductivity (W/mK) References

Coconut husk 250-450 0.046-0.068 [12]
Cotton (stalk) 150-200 0.058-0.081 [12]
Cellulose fibre 30-80 0.040-0.045 [12]
Rice 154-168 0.046-0.57 [11]
Corn cob 171-334 0.101 [11]
Sansevieria fibre 1410 0.132 [11]

Thermal Properties of Artificial Synthetic Insulation Material
The thermal properties of selected artificial synthetic insulation material

are summarised in Table 3. From Table 3, it showed that a super-high density
polystyrene (SHD) has the lowest thermal conductivity (0.030 W/mK).
However, the lack of information on density is unable to define its thermal
properties and compare with other insulation materials. The second lowest
thermal conductivity was obtained from an Expanded Polystyrene (EPS)
(0.031 W/mK) followed by a Rock wool (0.033 W/mK) with densities of 15
and 40 kg/m3, respectively. The EPS and rock wool are commercialised
products that constantly used in the industry as thermal insulation materials.
The highest thermal conductivity was found to be polypropylene (PP) (0.24
W/mK) with a density of 910 kg/m3. Although the results showed that the PP
is less promising to use as a thermal insulation material, but the good
mechanical properties (Table 2) and lifespan make it suitable for devices that
require the least maintenance.
Table 2. Summary of properties for polypropylene [10]
Properties
Denier 900
Elongation 26%
Tenacity 3.53 gpd
Weight average molecular mass 6.3 x 105
Table 3. Summary of thermal properties of artificial synthetic

insulation materials
Material Density Thermal conductivity References

(kg/m3) (W/mK)
Rock wool 40-200 0.033-0.040 [11]
Expanded Polystyrene (EPS) 15-35 0.031-0.038 [11]
Sheep wool 10-25 0.038-0.054 [11]
Recycled polyethylene 30 0.036 [11]
Polypropylene laminated paper (PPLP) N/A 0.23-0.26 [13]
High density polystyrene (HD) N/A 0.035 [9]
Ultra-high density polystyrene (UHD) N/A 0.032 [9]
Super-high density polystyrene (SHD) N/A 0.030 [9]
Polypropylene (PP) 910 0.24 [10]

Table 4. Thermal efficiencies of different type of insulation
Type of insulation Io (W/m2) Tdifference (°C) η (average) (%) References

(thickness)
Glass-wool (50 mm) 979.1 38.9 45.2 [4]
Glass-wool (50 mm) 925.0 35.0 40.0 [6]
Coconut fibre (50 mm) 1000 43.0 64.0 [7]
Glass-wool (50 mm) 1000 50.0 64.0 [7]
Glass-wool (76 mm) 1000 - 60.0 [3]
THERMAL EFFICIENCY OF INSULATION MATERIAL

ON SOLAR COLLECTOR
Different types of materials used for insulation have been conducted by

several researchers. Table 4 showed that the solar radiation on every square
meter of the collector, temperature differences and thermal efficiency of
insulation using a glass-wool from range of 50 to 76 mm and a coconut coir of
50 mm in thickness. From Table 4, it showed that a coconut fibre (50 mm)
insulated solar collector gave the highest thermal efficiency (64%) along with
a glass-wool (50 mm) under same solar radiation (1000 W/m2). However, the
results also showed that the temperature difference between an inlet and outlet
of solar collector was lower in a coconut fibre insulated solar collector
compared to a glass-wool. This indicated that the coconut fibre insulated
collector had better thermal performance by reducing heat loss.
EXPERIMENTAL METHOD
Preparation for Thermal Insulated Solar Air Collector
Coconut fibre was purchased from a local plantation in Malaysia.

Polypropylene drinking straw was used as the second thermal insulation
materials with 4.0 cm average length to compare with coconut coir. A solar air
collector with dimension of 50.0 x 30.0 x 8.2 cm3 was fabricated using a
plywood. It has an absorber plate that made of aluminium with a thickness of
0.3 cm. The absorber plate surface was coated with black paint which has an
absorptivity of 0.96 and emissivity of 0.88. The inner walls of the solar

collector were covered using aluminium foil, which is able to reflect some
radiant heat back to the absorber plate [14]. Tempered glass is used as the top
cover for the collector. Bottom and side walls of the two solar collectors were
insulated with coconut coir and polypropylene drinking straw in a thickness of
10.0 mm. The schematic cross-sectional diagram and actual diagram of the
solar air collector are shown in Figure 1.
Figure 1. A schematic cross section view and an actual diagram of a solar air collector.

Preparation for Experimental Procedure
A solar collector was installed at Subang Jaya, Malaysia, which located at

3 ° 1’26.5”N, 101 ° 25’54.2”E magnitude. Referring to the ISO/WD 9806-1
(5.3), the tilt angle is set at 30 ° and directed to 160 ° south. The air
temperatures and wall temperatures were measured using an Infrared
thermometer (uncertainty is ±2°C) and a digital meter with a thermocouple
(uncertainty is ±2%). Solar heat flux values were collected using an IPhone 5
(Apple, USA) front sensor with a Hukseflux pyrometer (USA) application
installed in it (deviation is 30% compared to local meteorological station). All
ambient, air and wall temperatures data were recorded at an hour interval. The
data were collected for six consecutive days started from 12:00 pm. to 5:00
pm. A statistical analysis was conducted using the SPSS Statistic version 21.0
(IBM, US). Significance differences (p ≤ 0.05) between means were evaluated
using independent samples t test of six measurements.
THERMAL EFFICIENCY OF SOLAR COLLECTORS

Thermal efficiency of solar collector systems is defined as the ratio of
useful energy gain by the air to solar radiation incident on the absorber of solar
collector, the formula is shown as:
𝑚̇𝐶𝑝(𝑇𝑜 −𝑇𝑖 )
η= 𝐴𝑐 𝐼0
(1)
By considering the materials used, the design of an absorber plate,

properties of glass and weather conditions, the formula above could express in
the form of this following equation [15]:
𝑇𝑎𝑏𝑠− 𝑇𝑎
Thermal efficiency, η = F’(𝜏𝛼) – F’UG ( ) (2)
𝐼𝑜
where F’(𝜏𝛼) is a parameter that indicates how energy is absorbed by the

absorber and F’UG (W/m2°C) is the parameter of how energy lost. F’ is the
collector efficiency factor.

Table 5. Summary of measuring data in a coconut fibre

insulated solar air collector
Local 𝑚̇ (kg/s) Inlet air Outlet air Temperature

time Temperature Ti Temperature To difference
(pm) (°C) (°C) Tdifference (°C)
12:00 0.0033 ± 0.0048 31.83 ± 2.23 36.50 ± 2.81 4.67 ± 3.50
1:00 0.0040 ± 0.0060 32.00 ± 3.52 41.83 ± 7.36 9.83 ± 5.95
2:00 0.0057 ± 0.0026 32.67 ± 2.25 41.83 ± 7.81 9.17 ± 6.71
3:00 0.0056 ± 0.0025 34.00 ± 1.79 43.17 ± 6.49 9.17 ± 5.31
4:00 0.0036 ± 0.0049 32.83 ± 2.86 39.33 ± 3.98 6.50 ± 1.97
5:00 0.0044 ± 0.0056 31.00 ± 2.76 35.67 ± 4.41 4.67 ± 2.25
Table 6. Summary of measuring data in a polypropylene insulated

solar air collector
Local 𝑚̇ (kg/s) Inlet air Outlet air Temperature

time Temperature Ti Temperature To difference
(pm) (°C) (°C) Tdifference (°C)
12:00 0.0033 ± 0.0048 31.33 ± 2.66 36.83 ± 2.64 5.50 ± 4.04
1:00 0.0040 ± 0.0060 32.50 ± 3.88 44.00 ± 7.16 11.50 ± 5.65
2:00 0.0057 ± 0.0026 32.83 ± 2.23 43.17 ± 10.25 10.33 ± 9.11
3:00 0.0056 ± 0.0025 32.83 ± 1.17 43.83 ± 7.08 11.00 ± 6.63
4:00 0.0036 ± 0.0049 32.17 ± 2.40 38.83 ± 4.07 6.67 ± 2.88
5:00 0.0044 ± 0.0056 30.50 ± 3.15 35.17 ± 5.42 4.67 ± 2.34
INFLUENCE OF HOT AIR CONDITIONS

The experimental data was recorded and summarized in Table 5 and Table
6. From Table 5, it showed that outlet temperature for a coconut fibre insulated
collector was in the range of 35.1-44.0°C The coconut fibre insulated collector
reached maximum outlet temperature at 3:00 pm (43.17°C) with mass flow
rate of 0.0056 kg/s. The lowest outlet temperature was observed at 5pm as
35.67°C with mass flow rate of 0.0044 kg/s in the coconut fibre insulated solar
collector. The average outlet temperature difference between the two
collectors was 0.59°C. From Table 6, the highest outlet temperature occur at 1
pm (44°C) with mass flow rate of 0.004 kg/s. The lowest outlet temperature
from the polypropylene insulated solar collector occur at 5 pm (35.17°C) with

a mass flow rate of 0.0044 kg/s. The average outlet air temperature of the
polypropylene insulated collector was 1.46% lower than the coconut fibre
insulated collector. The highest temperature difference in both coconut fibre
and polypropylene insulated collectors were 9.17°C (2-3 pm) and 11.50 (1
pm), respectively. The average temperature difference of air from
polypropylene insulated collector was 14.5% higher than coconut fibre
insulated solar collector. An independent samples t test was used to compare
the average outlet (n = 6) of a coconut fibre insulated solar collector to the
polypropylene insulated collector. Levene’s test was non-significant, thus
equal variances can be assumed. The t test showed no significant difference
between the coconut fibre and polypropylene in terms of outlet temperatures
(p ≥ 0.05). From the statistical analysis, it showed that no significant
difference on outlet temperature between coconut fibre and polypropylene
insulated solar collectors. Therefore, it showed that the polypropylene was
able to use as a thermal insulation material for a solar air collector, which is
not easily degrade and able to last longer than a coconut fibre.
INFLUENCE OF THERMAL EFFICIENCY

Referring to Table 5 and 6, the average mass flow rate of the air were in
the range between 0.0033-0.0060 kg/s. Moreover, the average heat flux of
incident on the solar collector was recorded and measured in the range of
589.5-1050.8 W/m2. From Figure 2, it showed that the maximum thermal
efficiency for coconut fibre insulated collector was 44.59% at 3:00 pm and
minimum efficiency was 14.26% at 12:00 pm. The maximum thermal
efficiency for polypropylene insulated collector has maximum thermal
efficiency of 36.0% at 3:00 pm and minimum 10.95% at 12:00 m. Average
thermal efficiency for both collectors were 25.18% and 21.74% respectively.
Coconut fibre insulated solar collector average thermal efficiency was 13.7%
higher than polypropylene insulated solar collector. According to Duffie and
Beckman [17], F’(𝜏𝛼) factor and F’UG factors can determined the quality of
the solar collector by comparing which collector absorber the most energy and
release the least. The optimal design collector is expect to have factor value of
0.8 and 4.5 Wm-2°C [16]. Figure 3 showed that the coconut fibre insulated
collector had a pair of values 0.0636 and 39.92 Wm-2°C and the polypropylene
had a pair of values 0.0573 and 35.12 Wm-2°C. The results showed that
coconut fibre insulated collector absorbed more energy than the polypropylene
insulated collector by 0.1%. Independent samples t test was carried out to

compare the average thermal efficiency (n = 6) of a coconut fibre insulated

solar collector to the polypropylene insulated collector. Levene’s test result
was non-significant, therefore equal variances can be assumed. The t test
showed no significant difference between coconut fibre and polypropylene in
terms of thermal efficiency (p ≥ 0.05). In conclusion, it showed that
polypropylene is as suitable as coconut fibre to use as a thermal insulation
material in the solar air collector.
Figure 2. Thermal efficiency of a solar air collector versus time.
Figure 3. Thermal efficiency of a solar air collector versus time.

OUTLOOK
The thermal performances of using the coconut fibre and polypropylene as
thermal insulation have been investigated. The comparative performance of
using coconut coir and polypropylene as thermal insulation for the solar air
collector showed that thermal efficiency of the coconut coir insulated collector
is only 13.7% better than the polypropylene insulated collector. However,
referring to the statistical analysis, it was found that there is no significant
difference between coconut coir and polypropylene (p ≥ 0.05). It shows that a
recycling synthetic material or an industrial by-product such as polypropylene
can be used as a sustainable material to resolve disposal of non-degradable
polymer. As a consequence, it reduce the amount of landfill and mitigate water
pollution issue from landfill. Moreover, using synthetic material can avoid
unnecessary deforestation due to the expansion of huge plantation. Further
study on different polymer and chemically or mechanically enhanced polymer
can be used to improve the thermal efficiency of solar air collector.
REFERENCES
[1] N. Madhukeshwara, E. S. Prakash, An investigation on the performance
characteristics of solar flat plate collector with different selective surface
coatings, International Journal of Energy and Environment 3 (2012) 99-
108.
[2] S. Saurav, M. M. Sahu, Heat transfer and thermal efficiency of solar air
heater having artificial roughness: a review, International Journal of
Renewable Energy Research 3 (2013) 498-508.
[3] M. K. Chauhan, Varun, S. Chaudhary, Performance evaluation of
roughened solar air heater having M-shaped as roughness geometry on
the absorber plate, International Journal of Energy and Environment 3
(2012) 881-894.
[4] A. Hematian, Y. Ajabshirchi, A. A. Bakhtiari, Experimental analysis of
flat plate solar collector efficiency, Indian Journal of Science and
Technology 5 (2012) 3183-3187.
[5] N. Dukhan, C. Chen, Metal-foam enhanced PCM storage system: the
cylinder-in-cylinder geometry, ASHRAE Transactions 118 (2012) 293-300.

[6] S. Gonzalez, S. F. Larsen, A. Hernandez, Thermal evaluation and

modeling of a double-pass solar collector for air heating, in: Proceeding,
28th PLEA Conference, Peru, 2012, pp. 1-5.
[7] H. Y. Andoh, P. Gbaha, P. M. E. Koffi, S. Touré, G. Ado, Experimental
study on the comparative thermal performance of a solar collector using
coconut coir over the glass-wool thermal insulation for water heating
system. Journal of Applied Sciences 7 (2002) 3187-3197.
[8] U. Thomas, Jr. Ganiron, Investigation on the use of coconut coir
polypropylene as thermal Insulator, International Journal of Advanced
Science and Technology 59 (2013) 13-26.
[9] M. Khoukhi, N. Fezzioui, B. Draoui, L. Salah, The impact of changes in
thermal conductivity of polystyrene insulation material under different
operating temperatures on the heat transfer through the building
envelope, Applied Thermal Engineering (2016) 3-15.
[10] S. A. Paul, A. Boudenne, L. Ibos, Y. Candau, K. Joseph, and S. Thomas,
Effect of fiber loading and chemical treatments on thermophysical
properties of banana fiber/polypropylene commingled composite
materials, Composites: Part A 39 (2008) 1582-1588.
[11] F. Asdrubali, F. D’Alessandro, and S. Schiavoni, A review of
unconventional sustainable building insulation materials, Sustainable
Materials and Technologies 4 (2015) 1-17.
[12] S. Panyakaew and S. Fotios, New thermal insulation boards made from
coconut husk and bagasse, Energy and Buildings 43 (2011) 1732-1739.
[13] M. Furuse and S. Fuchino, Analysis and measurement of thermal
conductivity of polypropylene laminated paper impregnated with
subcooled liquid nitrogen, Cryogenics 63 (2014) 125-128.
[14] N. Bonifacius, N. E. Sri Nastiti, I. G. N. Antaryama, Effect of aluminum
foil as roof insulation on thermal and energy performance of RIPV
building under warm-humid conditions of Indonesia, International
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[15] A. Karaghouli, W. Alnaser, Experimental study on thermosiphon solar
water heater in Bahrain, Renewable Energy 24 (2001) 389-396.
[16] J. A. Duffie, W. A. Beckman, Solar engineering of thermal processes,
first ed., Wiley, New York, 1980.

Chapter 4
MECHANICAL PROPERTIES,
CRYSTALLIZATION AND DEGRADATION OF
POLYPROPYLENE DUE TO NUCLEATING
AGENTS, FILLERS AND ADDITIVES
Javier Vallejo-Montesinos1, Ulises Morales Muñoz1

and J. A. Gonzalez-Calderon1,2
1
Universidad de Guanajuato, División de Ciencias Naturales y Exactas,
Departamento de Química
2
Posgrado en Ciencias en Ingeniería Bioquímica,
Instituto Tecnológico de Celaya
ABSTRACT
Nowadays polypropylene is one of the three most important synthetic
polymers worldwide due to its multiple applications due to its mechanical
properties, chemical resistance, low cost and processing ease among
others. But even with this properties that result very useful, the
polypropylene continues being improved via the use of nucleating agents
that modify their crystallization, therefore their mechanical properties.
The variety of nucleating agents goes from the common and well known
dicarboxilic salts which could be used alone or functionalized to various
metal oxides improving highly the amount of certain kind of crystal
above the others. The main crystalline phases are known as α-, β-, γ-, and
mesomorphic or smectic form. The α form is the primary form of

84 Javier Vallejo-Montesinos, Ulises Morales Muñoz et al.
polypropylene obtained under normal processing conditions; however,

the β-crystal is perhaps the most interesting crystalline phase for certain
applications because of its hardness and impact resistance. Therefore,
different nucleating agents have been used to promote this type of crystal
in iPP composites. In terms of nucleating agents, there are substances that
contain aromatic rings, rare earth metals (referred to as WBG), and salts
from dicarboxylic acids, such as calcium salts from pimelic and suberic
acids. Particularly, calcium salts from pimelic and suberic acids have
demonstrated an extremely high efficiency to promote β-crystals without
secondary effects. It was reported that the salts from PA were able to
induce approximately 90% of the β growth and it also was demonstrated
that the raw PA is considered an ineffective β-agent. Different substrates
have been explored as supports for depositing calcium pimelate, e.g.,
carbonates, silicates, zeolites, oxides, metallic salts, clays, and carbon
nanotubes, which are responsible for more than 90% of the β-crystals. β
nucleating agents continue as the main route to obtain β-phase in isotactic
polypropylene. Different kinds of nucleating agents, such as multiwalled
carbon nanotubes modified with calcium pimelate supported on nano
CaCO3, monoglycerolates, and potassium salts have been studied. In
these works all of them exhibit interesting properties related to the β-
phase present in the composites studied. These results increase their
applications that range from medical to engineering whit very interesting
features in their respective fields. However the polypropylene faces that
it’s very chemical resistance has made a very important pollutant along
with most of the organic synthetic polymers. An important effort in order
to address this problem has been increasing the degradation (either
thermodegradation or photodegradation) capacity of the polypropylene
via chemical modification of the chain or by the use of fillers and
additives that promotes the degradation of the material. Photodegradation
involves the natural tendency of most polymers to undergo gradual
reaction with atmospheric oxygen in the presence of light. Typically, a
photosensitizing agent is employed to accelerate this natural tendency.
The mechanism of photodegradation involves the absorption of UV light,
which then leads to the generation of free radicals. An auto-oxidation
process then occurs which leads to the eventual disintegration of the
plastic. It is believed that the instability of polyolefins is brought about by
the presence of impurities (such as carbonyl and hydroperoxide groups)
that form during the fabrication or processing of the polyolefin products.
Degradable polyolefins are designed to oxo-degrade, undergoing changes
in chemical structure as a result of oxidation in air, causing the
breakdown of the molecules into small fragments that are then
bioassimilated. For the reasons cited above we consider important to give
a review on the major advances that this polymer has faced over the years
in the areas considered before.

Mechanical Properties, Crystallization and Degradation … 85
1. INTRODUCTION
Recently, nanomaterials have drawn widespread attention due to their
applications in many emerging areas because of their tailorable morphology.
During the last decades, remarkable efforts have been made on the
investigations for novel processing methodologies to prepare materials,
combining the excellent properties of the plastics and the novelty of
nanomaterials, resulting in better technical control and significant
improvements in the physio-chemical properties [1-30]. The nanotechnology
experienced in the last decades opened a wide range of opportunities in
various science fields, with new applications and materials being developed,
nanomodifications may result in completely different materials at a
macroscopic scale, with high consequences in their properties and
performance [20-50]. The plastics industry is one of the fields where
nanotechnology offers more interesting perspectives of development, with the
emergence of new structural materials and the improvement of the properties
of existing materials, such as polypropylene and polyethylene. Also in this
field, the scope of application of nanotechnology is very large, ranging from
nanoadditions in plastics to the application of nanoparticles in membranes and
polymer matrix. This is mainly due to the high potential of these materials.
While mechanical properties improved by the addition of nanocomposites are
the primary area of interest, several other properties and potential applications
are relevant such as barrier properties, flammability resistance or improved
electrical/electronic properties [51]. The structure of a nanocomposite material
may be summarized as follows: multiphasic and heterogeneous solid material
with a matrix reinforced by nanoparticles. Moreover, polymer materials are
already being used in various industries due to their ease of production, light
weight and often ductile nature. Thus, this theme is focused on these types of
nanocomposites. Besides the type of matrix, the type of additions used plays a
crucial role on the properties of the nanocomposites. Polypropylene (PP) has
good mechanical properties and chemical resistance and can be processed
well; this thermoplastic can be used in various products for functional and
structural applications by chemical and/or physical modifications, designing
different synthesis routes, and controlling the processing procedures.

2. CRYSTALLIZATION PROCESS OF POLYPROPYLENE
2.1. Polypropylene Properties
Polypropylene (PP) is a semi-crystalline thermoplastic, belonging to the

group of polyolefins, which is used in a wide variety of applications including
food packaging, clothes, laboratory equipment, automotive components and
films, for this reason the PP is considered as one of the thermoplastic products
that have an important development in the future. In addition, the PP is an
inert, fully recyclable product, its incineration has no polluting effect, and its
production process has lower environmental impact [1-30]. This is an
attractive feature against alternative materials such as polyethylene,
polystyrene and polyvinyl that not have the aforementioned properties.
Additionally, the PP has a high resistance to chemicals attack because it is
composed mainly of carbon atoms and hydrogen, although in some cases a
small presence of oxygen and nitrogen atoms are incorporated into their
structure during polymerization. Hydrophobicity of PP allows it to resist
chemical attack of polar solvents, such as those found in: cleaners, wetting
agents and alcohols. However, the PP is easily affected by the presence of
liquid hydrocarbons or chlorinated solvents which can cause cracking, or
swelling, as happens with hot nitric acid or sulfuric which produce chemical
degradation [3].
Commercially, polymerization of PP occurs in the presence of a specific
stereo- catalyst. During the polymerization reaction, the propylene molecules
join to form a long polypropylene molecule. This is accomplished by reacting
propylene with an organometallic compound to provide a reaction site, and
thus, the propylene molecules adhere sequentially by reaction of the functional
group bonded to the metal where grow the molecule by breaking the double
bond of the molecule of propylene as can be seen in Figure 1.
The polypropylene can be divided into three types depending on the
orientation of the methyl groups hanging over the main chain resulting in
polypropylenes with different properties and are known as isotactic and,
syndiotactic and atactic.
Isotactic polypropylene (iPP) is the most widely used commercially. In
this polymer, the methyl groups are arranged in the same configuration and the
same side relative to the polymer backbone; due to this regular and repeating
array has a high degree of crystallinity [1-20].

Figure 1. Polymerization reaction mechanism of propylene by metallic catalyst.
In the case of syndiotactic PP, methyl hanging chain of opposite sides are
alternated periodically. Currently this type of polypropylene is obtained using
metallocene catalysts [30]. Due to the configuration of its methyl this polymer
exhibits greater elasticity and less resistance with respect isotactic material.
Finally, in the atactic polypropylene methyl groups are randomly in the
polymer backbone and reaches commonly found in a lower percentage than
2% in the synthesis of iPP [30].
2.2. Morphology and Crystal Structure of

Isotactic Polypropylene
When iPP molecules are cooled below its melting temperature, these
chains associate to form supramolecular structures. In this arrangement called
crystallization, they vary the kind of crystals that may be formed as well as the
degree of crystallinity reached. The formation of crystal kinds depend on the
stereochemical structure of the PP, processing conditions and the presence of
additives [24, 31-36].
IPP crystallization occurs when the molten material solidifies or when the
solvent is evaporated (in solution). Because the energy heat of the fluid is
removed during processing, the molecules begin to lose the ability to move
freely, and the fluid tends to increase its viscosity. Upon reaching the

crystallization temperature, the molecules begin to manage themselves in

crystals, showing well-defined crystalline regions around disordered
amorphous regions [22-23, 26, 30]. The crystal growth can be spontaneously
(when the molecular structure seeks self-arranged in a more orderly manner)
or induced by the presence of external particles to the polymer matrix (such as
nucleating agents). For nucleating agents, these also cause the decrease in the
size of the spherulites as can be observed in Figure 2.
The optimum crystallization occurs under slow cooling rates and
subsequent orientation of the material; however high cooling rates tend to limit
the crystallization process favoring the amorphous phase within the structure
of iPP. Within the phenomenon of crystallization, kind of crystal obtained it is
identified by the unit cell that compose it [22-23].
A unit cell is the smallest unit composing a crystal and its dimensions are
in the order of angstroms (Å) 10-10 meters equivalent. The unit cells show
geometric shapes with parallel sides (tetragonal, cubic and hexagonal
commonly) representing the arrangement of atoms. The atomic arrangement in
the unit cell of a polymer is repeated in three dimensional space million
sometimes it is resulting in the final crystal structure.
During the crystallization process (at a larger magnitude level), the
polymer chains of iPP are grouped to form helical arrangements, which are
grouped round to form thin and ordered structures called lamellae. Typically,
the lamellae have a thickness of 50-200 Å; thickness depends directly on the
crystallization temperature and the processing method. Lamellae growing
radially form structures called spherulites, which are spherical structures that
radiate outwardly from a central core as a pompom [30].
Figure 2. Polarized light microscopy image of iPP (Left) and iPP with nucleating
agents (Right).

The lamellae are interconnected by amorphous regions called tie points,

resulting from the irregularities in the polymer chain. The tie points provide
flexibility and impact resistance to the crystalline regions. A polymer with a
larger amount of tie points is generally stronger, but in turn an excess of the
same results in brittleness, low toughness and low impact resistance.
When the lamellae of two spherulites reach each other, spherulite lamellae
extend across adjacent boundaries of the amorphous region of the material and
tends to maintain its structure. When crystallization occurs rapidly as in the
case of injection process, the lamellae can crystallize connecting with more
than one lamella, resulting in different structural conformations [24].
2.2.1. Polymorphism in Isotactic Polypropylene

The polypropylene can exist in various crystalline forms depending on the
tacticity of the material and the conditions to which crystallization takes place.
The main iPP crystalline forms are α, β and γ, these crystalline forms can
coexist where a polymorphic form can change to another as the conditions of
material changes [31-37].
The polymer chains in the α crystal of iPP form a helical structure with a
monoclinic unit cell with dimensions of 20.8 * 6.6 * 6.5 Å. The radial lamella
growth is predominant, however the lamellae can be arranged tangentially,
leaving the plane almost orthogonal to form spherulites. The α form of iPP is
the primary form of iPP obtained under normal processing conditions [38-39].
The β crystal of iPP presents its hexagonal unit cell with more clutter than
the α form. Its lamellae are mostly parallel, and these do not show obvious
crosslinking [1-10, 30]. It has been observed that their lamellae are arranged to
form spherulites interconnected randomly limits, unlike the well-defined
spherulites of the α phase boundaries. In experiments iPP with high purity of β
phase, this structure has resulted in lower elastic modulus and reduced
resistance to flow, while exhibiting higher impact resistance and breakdown
resistance than the α form of iPP. The iPP may crystallize in the β phase at
relatively low crystallization temperatures and under mechanical stress
(orientation of the material during cooling), induced vibration (ultrasound) or
in the presence of heterogeneous nucleating agents, so it is important to
identify the processing conditions that favor this stage and be able to control
[30-31, 38].
The γ crystal iPP has a orthorhombic unit cell so intertwined with non-
parallel lamellae. This are not processing under normal conditions, but
presents certain characteristics such as low molecular weight, high pressure or
chains with regular defects produced by metallocene catalysts. Under

atmospheric pressure the α phase is favored but as the pressure is increased

coexist α and γ forms up to a limit of 200 MP in which the γ form becomes
predominant.
Of all the crystalline phases of iPP, the β phase provides an advantage in
the performance of parts made with this material because its properties are
improved as high impact strength and elongation at break. Since these
properties do not occur naturally in the iPP, a high interest has been acquired
in recent years by several scientific research groups and industrials to induce
this crystalline phase. By this reason, multiple methods have been developed,
which include the use of nucleating agents with high selectivity to promote
this type of crystal. However, to improve the performance of those nucleating
agents, they must be supported on particles to confer improved properties to
iPP in addition to those providded by the β phase. Within the nucleating
particles are preferred those that have been shown to improve, by themselves,
the performance of iPP to confer unique properties as the nano-particles [1-
20].
2.3. Reinforcing of Polymeric Materials
The ability to manipulate matter at the nanoscale promises a huge

potential for various applications and innovations, involving new materials to
such diverse areas as food, textile, chemical, medicine, information
technologies and energy to mention just a few.
Because of the importance of nanotechnology in the field of chemistry has
been worked extensively in generating new applications for nano-materials
such as insertion into polymer matrices that currently have a large industrial
application [40]. Currently alumina, glass, boron and carbon fibers are used for
the reinforcement of nanocomposites in the form of conventional fibers with
diameters of tens of microns and lengths of the order of millimeters [23, 30,
33].
The term includes natural or synthetic nanomaterial particles with at least
one dimension less than 100 nanometers (nm); while nanoparticles include at
least two of its dimensions between 1 and 100 nm. Nanoparticles are
synthesized and modified to improve its performance in technological
processes and industrialized countries. They are manufactured from different
sources depending on their applications, and their surface composition differs
according to their potential use. Within nanomaterials are two main types, that
are organic and inorganic, it is in the first group where multiwalled carbon

nanotubes (MWCNT) is located and in the second group the titanium dioxide
particles (TiO2), which both have been found to have very interesting features
and a high potential for application [26, 32-36].
2.3.1. Variables that Affect Reinforcing Process

For proper reinforcement of polymeric matrixes, some of the main
requirements are a good dispersion, orientation and transfer of interfacial
stress. With a good dispersion is intended that each of the added particles and
is isolated completely surrounded by polymer. Adequate dispersion of the
material within the matrix allows uniform stress distribution as in systems
where it exceeds the saturation limit, poor dispersion is observed and this is
accompanied by a decrease in the strength of the material and its Young
modulus [20, 26, 32-33].
The hydrophobicity of the nanostructured polymeric materials surfaces
(affected by the number and type of functional groups) plays a key role in
optical, electrochemical and adsorption properties [35, 41]. An alternative to
overcome this problem is the functionalization of the particles used with
similar groups to the polymer matrix intended use.
The incorporation of functional groups covalently bonded to the surface of
nucleating agents has increased the affinity of such nanostructures with other
materials such as plastics [1-11]. Once this functional group incorporated is
capable of reacting to form or be replaced by another through subsequent
chemical reactions. It should be noted that at present has been difficult to
adequately control the amount and position of these functional groups on the
surfaces of the particles; i.e., so far been able to functionalize the surface but
without full control over the process. By derivatization reactions a carboxylic
acid functional group may be converted to amide, ester or thiol, among others
[36, 41 to 42].
Although the problem of hydrophobicity can be attenuated when
performing nano-structuration at low percentages, thus reinforcing the matrix-
interaction increases to be completely surrounded by the polymer and avoid
the attractions between nucleating particles (clusters formation).
2.3.2. Obtaining Reinforced Composites by Extrusion

Extrusion is the process most used in the world for polypropylene.
Approximately 45% of iPP processing is performed by this method. Of this
amount, the fibers and filaments comprise about two thirds of iPP extrusion
processing [20, 30].

The extrusion process consists of feeding material pellets to be processed

into a hopper that serves as a guide for insertion into the barrel. The canyon is
one of the key parts consisting of a cylinder within which is one or two augers
that allow the dual task of mixing and transporting the material in a fluid state
by applying a shear stress. This is achieved by adding resistors energy systems
with which energy is injected to the polymer molecules and its viscosity is
achieved decays and therefore the iPP tend to flow. This is done to bring the
molten state as it will give the final shape after crystallization material. It can
be said that the purpose of the extruder is to heat the plastic material and
creating a fluid homogeneous mixture through a die at a constant flow.
The single screw extruder consists essentially of a screw rotating in a
fixed axial position with a barrel covering it to contain material. The motor
which rotates the screw is constituted by a speed reducer that allows speeds
between 0 and 200 revolutions per minute (rpm) normally and transfers the
force directly to shear generated by the screw for flowing the molten mixture.
The helical shape of the spindle causes the movement is transferred in
strength, coupled with the warming that is given by controlled by
thermocouples which causes a mixture of extruded materials and a good flow
when working at temperatures below the decomposition devices material.
2.4. Induced β-Crystals into Polypropylene by Using

Nucleating Agents
Multiple molecules have been studied for use as promoters agents of β

phase into iPP, such as dye molecules, derivatives with aromatic rings,
phthalic acids and crystalline substances [1-11, 16-17]. In general, the best
results have been thrown with molecules that have a quasi-planar structure, in
this line, derivatives of dicarboxylic acids are the handiest for its high
selectivity.
J.X. Li et al. in 1997 [8] used pimelic acid, sodium pimelate and calcium
pimelate to stimulate the β phase in iPP. The doped resin was analyzed by two
handiest techniques to quantify the crystals in polymers, which are differential
scanning calorimetry (DSC) and wide angle X ray diffraction (WAXD). Their
results showed that the use of pimelic acid was ineffective for use as a
nucleating agent β, while pimelates were able to induce percentages above
64%, in particular using calcium pimelate under controlled conditions reached
above 90% of β phase, with a higher and more consistent behavior compared

to its counterpart with sodium. This performance was attributed to the smaller
particle size thereof and the improvement in the dispersion of nucleating agent.
On this same line, Xiaojun Li et al. in 2002 [7] tested 7 different calcium
salts with different core chains (Succinate, adinato, pimelate, suberate,
sebacate, phthalate and calcium terephthalate). Of the studied species, they
found that those with a space d between 10 to 13 Å show higher selectivity as
β nucleating agent. Among the studied salts, suberate and calcium pimelate are
those with better yields, being explained this phenomenon by a cooperative
effect of the polar parts (carboxyl groups) and nonpolar (methyl) chain into the
nucleating agent. These researchers concluded that iPP chains are forced to
settle on the non-polar part of the nucleating agent, aligned perpendicularly;
which at the same time the translation and rotation of preventing polymer
containing β → α transition and stabilizing the core.
Due to the high selectivity, efficiency and simplicity of pimelic acid
molecule, this has been widely used as a nucleating agent. Combination with
calcium surface provided with the surface of calcium carbonate improves the
thermal stability of this molecule, allowing its scope and extends the concept
arises β supported nucleating agent [31]. That is why in 2011, Zishou Zhang et
al. used this molecule to be supported on a wide range of metal oxides
commonly used at industrial level (CaO, BaO, MgO, ZnO and TiO2) and
tested their efficiency. The addition of these metal oxides, which act as
reinforcing agents are able to provide into iPP some properties of interest as
antioxidants, antibacterial properties, color, sunscreen, among others [3].
Unfortunately, these reinforcing particles cause a decrease in impact
resistance in iPP, which is attributed to the formation of α-iPP as these
particles are α nucleating agents. The advantage of using this kind of material
present good dispersion in polymer matrices, and the idea of supporting the
pimelic acid as a β nucleating (not easily dispersed in iPP) allows you to create
iPP materials to retain the properties conferred by support, coupled with high
performance to the impact that provides β nucleation.
In the previously discussed work, it was not possible to achieve chemical
bonding of the pimelate on the surface of TiO2 instead of 5 other metal salts
pimelate the presence of the respective evidenced. Pimelic acid deposition by
chemical bonds with metal ions causes the surface were α nucleating surfaces
are now β. However, as mentioned above, the best results are obtained when
this combination occurs with calcium ions, which reached to obtain the
supported species containing β crystals similar to those obtained with the
calcium pimelate.

The calcium pimelate is expensive to obtain and difficult to disperse in the

iPP matrix therefore is a good alternative the synthesize in situ on the particle
surface which function as support to minimize costs, improve the dispersion
and thereby the β nucleating capacity of particles.
Using this principle, the research that contemplates the use of pimelic acid
supported on different substrates has received great interest and has had a great
development in the present era. Multiple recent studies have focused on
modification of particles (which are commonly used as reinforcement of
polymers) by depositing calcium pimelate on its surface. Such is the case of
carbonates, silicates, zeolites, metal oxides, metal salts, clay and even carbon
nanotubes.
Carbon nanotubes have shown to be good nucleating agents for most
semi-crystalline polymers, even when added at low percentages, changing the
peak temperature during the crystallization process; however, it is well known
that this kind of reinforcing lacks the nucleating ability to obtain β crystals in
iPP matrix. For these reasons Wang et al. in 2010 [6], joined pimelic acid in
the form of calcium pimelate to the surface of carbon nanotubes, showing that
its functionalized carbon nanotubes have the ability to nucelate β-iPP. The
chemical reaction between the calcium pimelate and the surface of the
nanotubes was verified by infrared spectroscopy and photoelectron
spectroscopy x rays. In the infrared spectrum, researchers attribute the
appearance of the band at 1541 cm-1 to calcium pimelate (chelating species),
and the amount promoted were above 50% of β phase with 1% w/w of
functionalized nanotubes.
In all the works mentioned above, researchers have not demonstrated the
importance of how the molecule is attached to the support surface, and how
this affects the ability of selective nucleation of particles. This information can
directly influence the amount of nucleating agent used in reinforcement and
processes for preparing nanostructurated composites. Recalling that without
proper nucleating agent, the reinforcing particles have an alpha nucleating
effect [44-50].
Using a lower amount of nucleating agent affects the process performance
by using a small quantity to promote a particular crystalline phase of high
interest as is the β-phase reducing material use. With the information discussed
above, it is clear that a reaction route that minimizes nucleating material
needed. A cost decrease is associated with the amount of particles required to
induce beta phase of iPP promoting its use and scaling; and this will impact
especially in the environmental area if the amount of solvents used in the
processes of chemical reaction with the support decreases.

3. POLYPROPYLENE AND NANOMATERIALS
3.1. Improving Properties
The Thermal Properties of PP, thereby restricting its applicability in other

fields, thus the thermal conductivity of PP needs improvement. Usually
modified with the introduction of inorganic fillers, such as talcum powder
[52], calcium carbonate [53, 54], mica [55], wood powder [56], metallic
powder [57, 58], glass fiber [59], carbon fiber [60], graphite-like carbon
nitride and functionalized layered double hydroxide [61], etc. Incorporating
thermally conductive fillers into a matrix is the most common and convenient
method used to improve the thermal conductivity (TC).
Mechanical Properties of PP however, the applications of PP are certainly
limited due to some disadvantages, including high molding shrinkage, low
stiffness, and poor impact toughness. Mechanical properties including tensile,
impact and flexural properties are important service performances. There have
been a number of studies on the mechanical properties of PP composites [62],
for PP the typical behavior of a ductile material is observed with a very high
elongation at break (620%). The strain hardening region appears at about
400% of elongation and after which tensile strength increases almost linearly
with strain until fracture eventually occurs. Also, in case of nano composites
with lower loading a ductile behavior is observed with necking, but with lower
strain at fracture and without strain hardening. In general, Nanocomposites
bearing showed a brittle behavior with breaking after the yield point.
The two main challenges in developing nanocomposite materials are

the following:
The use of nanoparticles requires an interfacial interaction and/or
compatibility with the polymer matrix.
Processing technique should offer uniform dispersion and distribution of
nanoparticles.
3.2. Fillers
3.2.1. Carbon Nanofillers

Great attention has been paid to the preparation of polypropylene (PP)
nanocomposites using carbon nanomaterials due to the tremendous

enhancement of the mechanical, thermal, electrical, optical and structural

properties. This is due to the unique combination of structural, mechanical,
electrical, and thermal transport properties of PP-nanocarbon composites.
However, it is well-known that the properties of polymer-based
nanocomposites strongly depend on the dispersion of nanofillers, into
nanocomposites are strongly related to their microstructure. PP
nanocomposites were, mainly, prepared by melt mixing and in situ
polymerization. Good control over various mixing parameters during melt
mixing is essential to obtain homogeneous composite materials. The
improvement in thermal stability can be attributed to good matrix–nanofiller
interaction and also due to the thermal conductivity of the nanocarbon
materials.
CNTs have been considered as unique reinforcements for different
polymers due to their exceptional electrical, thermal, chemical and mechanical
properties. CNTs have high aspect ratio and surface reactive groups, which
prompt the interactions between nanotubes, and thus very difficult can be
separated and intercalated into polymer matrix. Good control over various
mixing parameters during melt mixing is essential to obtain homogeneous
composite materials. The microstructure and CNTs dispersion into PP matrix
is very crucial in order a high performance material to be achieved.
As the CNTs are good thermal conductors the tubes easily take up the heat
that is applied to the nanocomposite fibers. The good dispersion of the
nanotubes in the polymer matrix allows the spreading of heat uniformly along
the fiber. Another factor that can potentially contribute to the thermal stability
is the formation of a relatively uniform network-structured layer which covers
the entire sample surface without any cracks or gaps forming during heating.
This layer re-emits much of the incident radiation back from its hot surface,
thereby reducing the heat transmitted to the PP layers below. The
microstructure and CNTs dispersion into PP matrix is very crucial in order a
high performance material to be achieved. CNTs/PP nanocomposites exhibit
superior thermal stability compared to polyolefin materials. Electrical and
thermal conductivity are also enhanced by the addition of CNTs creating a
conductive network in the polymer matrix [62].
Roumeli et al. [63] synthetize small amounts of multiwall CNTs,
nanodiamonds(NDs), graphite nanoplatelets (GNPs), and combinations
between them affect the properties and performance of polypropylene (PP).
An improvement on the mechanical properties of the nanocomposites as a
consequence of the incorporation of CNTs and NDs is detected which is also
related to their crystalline characteristics as well as melting and crystallization

kinetics. In specific ratios, property enhancements caused by the combined

incorporation of the nanofillers exceed the corresponding reinforcements
induced by each type of filler separately and are probably linked with their
dispersion state. The incorporation of CNTs, NDs, GNPs does also increase
effectively the TC of PP, while the tree fillers affect this property distinctly.
The detected cumulative trends of the separate effects of the fillers confirm
their distinct contributions on heat capacity and thermal diffusivity, marking a
notable difference in the reinforcement mechanism of the mechanical versus
thermal properties. Prepared polypropylene random copolymer mixtures with
small amount of multi-walled carbon nanotubes and nanodiamonds in order to
examine the effects and mechanism that govern the incorporation of different
forms of carbon nanofillers in the mechanical and thermal properties of PP.
The nanocomposites containing 1 and 3 wt.-% of CNTs, 1 and 3 wt.-% NDs,
and combinations thereof, were prepared by melt mixing. When both types of
filler were incorporated in the matrix, large arrays consisting of CNTs/NDs
bundles were formed having the seemingly better dispersion.
The incorporation of CNTs increased the thermal diffusivity of PP by 50
and 65% for filler concentrations 1 and3 wt.-%, respectively. Therefore, the
presence of CNTs yields an important enhancement in the TC of PP which is
associated to a notable increase in the thermal diffusivity of the materials and a
less pronounced enhancement of specific heat capacity. NDs were found to
notably enhance both of these properties. Specifically, increasing amount of
NDs leads to a 43–46% higher thermal diffusivity and 30 and 35%,
respectively higher specific heat capacity. The combination of notable
enhancements in both these properties resulted in a significant reinforcement
of the TC of PP/NDs composites, which reached 80 and 90% higher values
compared to neat PP. The fact that CNTs enhance more significantly the
thermal diffusivity of PP compared to NDs, can be attributed to their different
geometrical characteristics. In particular, the elongated nanotubes offer larger
phonon paths thus allowing a more efficient thermal transport than the
spherically bound nanodiamond particles. On the contrary, the clearly superior
specific heat capacity of samples containing NDs compared to those
containing CNTs, can be associated to the highest heat capacity of diamond
particles.
Graphite Nanoplatelets (GNPs) are composed of a few of layers of
graphene, which endows its excellent thermal property. Li [64] study mainly
aimed to prepare GNPs that are thinner than the existing ones via oxide-
intercalated method: mold pressing method and the effects of GNPs and Ag-
plated GNPs on the thermal properties of PP nanocomposites prepared

GNPs/PP nanocomposites. The significant enhancement of the thermal

stability of the PP nanocomposites was caused by several positive factors of
the fillers. The strong interaction between the filler and PP matrix increases
the thermal decomposition of nanocomposite activity energy, and restricts the
thermal motion of the PP molecular chains [65]. In addition, the fillers
dispersed in the matrix act as a physical barrier [66-67], which greatly delayed
the transmission of degradation products. Termomechanical analysis (TMA)
follows the changes in the physical state of the polymer during temperature
change. The softening temperature increased by 5–8°C compared with that of
PP, whereas the increscent temperatures were between 1–5°C for Ag-GNP/PP.
This enhancement can be attributed to the large heat capacity of the fillers. The
materials with large heat capacity could absorb large amounts of heat before
any physical changes occur. Thus, when temperatures increased, the fillers
inserted into the matrix did not significantly change the nanocomposites. The
thermal conductivity of the nanocomposites filled with GNPs increased from
0.18 W/(m K) to1.05 W/(m K). This result was attributed to embedding of
highly conductive materials and the interconnectivity between the conducting
particles. Graphite offer an alternative source for producing nano-scale
materials for producing polymer nanocomposites.
3.2.2. Inorganic Nanofillers

Generally inorganic fillers have much larger TC than polymers [68] so
incorporation of rigid inorganic particle is a promising approach to improve
TC. The effect of metal and oxide particles on the thermal transport properties,
heat capacity, and density of polymers was investigated by Weidenfeller et al.
[69] They prepared composite samples of PP with various fillers such as
magnetite, barite, talc, copper, and glass fiber in different fractions (up to 50
vol%), with an injection molding process. TC of the polypropylene (PP) was
increased with addition of the fillers. The large specific surface area of
nanoparticles which leads to strong interfacial interactions with the
surrounding polymer matrix, nanoscaled particles are believed to be more
effective for the improvement of the mechanical properties of polymers.
Calcium carbonate, which is abundantly found in nature, is low cost filler,
which has large size distribution, higher stiffness, rigidity and viscosity and
improves the productivity of PP. Vakili et al. [70], study the effect of
nanostructured CaCO3addition on the thermal conductivity of PP, have a good
nanoparticles dispersion CaCO3. However, in spite of using stearic acid for
preventing the coalescence of nanoparticles, partial coalescence was
unavoidable. The dispersion of nanofillers within the PP matrix could enhance

the TC of the nanocomposites even at lower nanofiller loadings owing to

enhanced filler-matrix interaction. This is because of the intrinsic TC of the
inorganic nanofillers. In the nanocomposite with 0.03 volume fraction of
CaCO3 nanoparticles TC increased by 23% compared to that of pure PP while
at 0.045 volume fraction, this increase was almost 64%. This result is higher
than that of carbon nanofibers in a PP matrix [71]. This fact can be attributed
to the intrinsic TC of the CaCO3 nanoparticles and their large surface area,
such that even at lower loadings of nanofillers they are effective to transfer the
heat through the samples [71]. At a higher volume fraction, this effect
becomes stronger. However, a slight increase in melting temperature is
observed for 20 wt% fillers. Indeed, melting temperatures are affected by the
flexibility of matrix chains. It is clear that higher content of fillers causes less
flexibility of chains and leads to increased melting temperatures. Aggregates
have a bad influenceon mechanical properties [72]. Thio et al. [73] and
Zuiderduin et al. [66] showed that with calcium carbonate fillers of diameter70
nm, Izod impact strength is not improved, whereas Chan et al. [74] succeeded
to toughen PP with particles of only 44 nm in size. The higher surface energy
of nanoparticles induces more interactions between particles and so more
agglomerates and aggregates and hence an increase in the nanocomposite
viscosity. The decrease in viscosity noticed in case of coated particle may be
because of a reduction of the immobilized polymer fraction because of the
lower interfacial tension between the solid particles and surrounding liquid
phase [75]. Microcomposites show a higher increase in crystallinity than
nanocomposites. It may be that nanoparticles of CaCO3 with the same weight
content as microparticles are so huge that only a small fraction served as
nucleating sites; most particles restrict molecular movements and hinder
orderly packing of molecular segment [76]. We can say that CaCO3has a very
weak nucleating effect on the crystallization of PP, and that the increase in
crystallinity percents depends on physical and topological factors.
Elloumi et al. [77] study the effect of nanoparticle treatment and particle
size of calcium carbonate on the mechanical, rheological, and morphological
properties to calcium carbonate (CaCO3) reinforced polypropylene/ethylene
propylene rubber (PP/EPR) copolymer composites. Particle size have indirect
effects on the elastic properties by influencing the state distribution on the
matrix. Moreover, in the case of treated particles, the formation of core-shell
morphology reduces the rigidity of particles and increases the effective volume
of soft particles. SEM micrographs of fracture surfaces across the tensile
specimen on the necking zone show many voids surrounding calcium
carbonate particles due the debonding of fillers that is considered beneficial

for increasing toughness of many semi-crystalline polymers [78]. Visual

observations of deforming specimens of modified particle shows that yield and
plastic flow are accompanied by strong whitening of the blend in the necking
zone. This suggests extensive debonding of the particles from the matrix. The
debonded particles facilitate both plastic deformation and shear yielding
behavior.
Untreated particles exhibit a good adhesion to the matrix, even at higher
plastic deformation. In fact, stretched fibrils could be a sign of plastic
deformation. Fibrils surrounded by untreated particles indicated good adhesion
of calcium carbonate with the polymer matrix.
In fact, the debonding favored by coating agent, creates more voids on the
matrix, and reduces the sensitivity towards crazing. The shear yielding
becomes operative and composite become able to absorb large quantities of
energy up to fracture.
Nanocomposites based on clays are in wide use owing to their high
mechanical strength and good thermal resistance. The type of clay and its
pretreatment method, the selection of the polymer component, and the method
of incorporation of clay have significant effects on nanocomposite properties.
The purity and dispersion of clay also affect nanocomposite properties.
Polymers and clays are non miscible due to the difference in their polarity.
Clay polarity needs to be changed to organophilic to successfully form
polymer clay composites, and this can be carried out using swelling agents
such as surfactants, which increase the interlayer distance of the clay structure
before it is mixed with the monomeric material then polymerized in the
presence of clay to form nanocomposites. A clay-based nanocomposite can be
produced in form of an intercalated or exfoliated structure. In intercalated
nanocomposites, the organic component is inserted between layers of clay
such that the interlayer spacing is expanded, but layers still bear a well-defined
spatial relationship to each other. In an exfoliated structure, the layers of clay
are completely separated and individual layers are distributed throughout the
organic matrix. Nanomer and Cloisite are the popular nanoclays available in
the market, and 0.5% to 10% of these nanoclays can be used [79]. The
superior properties of these materials can match metal, glass, and wood.
Addition of small quantities of nanoclay improves the gaseous barrier
property. The flame-retardant behavior of PP is improved with 2% nanoclay
loading. The heat release rate diminishes substantially by nanoclay addition.
Nanoclay incorporation causes a significant reduction of water absorption in
the polymer. Improvement in clarity, stiffness, thermal stability, barrier
properties (moisture, solvents, vapors, gases, and flavors), chemical properties,

flame resistance, scratch resistance, and dimensional stability is noted. Nam et

al. [80], prepared polypropylene nanoclay (PPNC) composites using maleic
anhydride polypropylene (MAPP) and organophilic clay. It was revealed that
with higher clay loading, more MAPP chains were intercalated in the
nanocomposites. The intercalation capability of the compatibilizers in clay
layers and the composition of the compatibilizer in PP/clay composites helped
in the exfoliation and homogeneous dispersion of clay layers. The formation of
complete hybrids took place when the intercalation capability of MAPP has a
MAPP/clay weight ratio > 3:1.
Rousseaux et al. [81], used carboxyl at clays to synthesize PPNC.
Carboxylate salts partially neutralized the MA groups of MAPP, and the
resultant ionicgroups of the partially neutralized polymer have a good
interaction with clay. The three carboxylate salts used were sodium acetate,
sodium propionate, and sodium butyrate. A higher basal spacing was obtained
while intercalating sodium acetate into the silicate layers. Nanocomposites,
with the addition of clay and trihydrated sodium acetate, exhibited the best
thermal and rheological properties owing to good dispersion.
The impact behavior of PP clay nanocomposites was studied by Yuan and
Misra [82]. Higher impact strength was reported in the 0°C–70°C range, but
impact strength remains unaffected below 0°C using clay. Crystal structure,
dispersion state, and interfacial interaction were the factors responsible for the
change in impact behavior of PPNC. Bureau et al. [83], reinforced PP with
organo-modified clays using different MAPPs. Tensile strength improved
significantly due to the reinforcing effect of the nanoparticle. Improvement in
toughness was due to improved matrix resistance attributed to finer, more
oriented clay nanoparticles. No change in melting temperature (Tm) and
degree of crystallinity of composites was found with the addition of clay and
MAPP, but thermal stability, heat deflection temperature was higher [79].
However, recent advances in polymer/clay and polymer/silicate
nanocomposite materials, have inspired efforts to disperse montmorillonite-
based (mmt) fillers in PP. First, the report of a nylon 6/montmorillonite
material from Toyota research [84], where very moderate inorganic loadings
resulted in concurrent and remarkable enhancements of thermal and
mechanical properties.
The mmt crystal lattice consists of 1-nmthinlayers, with a central
octahedral sheet of alumina fused between two external silica tetrahedral
sheets (in such a way that the oxygens from the octahedral sheet also belong to
the silica tetrahedra). Isomorphic substitution within the layers (for example,
Al3+ replaced byMg2+ or Fe2+) generates a negative charges defined through

the charge exchange capacity (CEC)sand for mmt is typically 0.9-1.2

mequiv/g depending on the mineral origin. These layers organize themselves
in a parallel fashion to form stacks with a regular van der Waals gap between
them, called interlayer or gallery. In their pristine form their excess negative
charge is balanced by cations (Na+, Li++, Ca2+) which exist hydrated in the
interlayer. Obviously, in this pristine statemmt is only miscible with
hydrophilic polymers [85], torender mmt miscible with polymers, one must
exchange the alkali counterions with cationic-organic surfactants, such as alkyl
ammoniums [86]. Thus, the “challenge” with PP is to design systems where
the polymer/mmt interactions are more favorable than the surfactant/mmt
interactions. There are two ways to overcome this challenge:
1. Improve the interactions between the polymer and the mmt to become
more favorable than the alkyl surfactant/mmt interactions. This can be
achieved by PP “functionalization”, that is, introducing polar or
polarizable groups in the polymer.
2. Decrease the enthalpic interactions between thesurfactant and the
mmt, which effectively will render the PP/mmt contacts favorable.
This second route is more challenging, as the alkyl-surfactant/mmt
interactions are already very poor (that is exactly the reason these
surfactants work so well in dispersing most non aliphatic polymers).
However, semi-fluorinated surfactants do have more unfavorable
interactions than the hydrogenated polyolefins, and if used
appropriately to organically modify the mmt, they will promote
PP/organo-mmt miscibility.
Synthesis of PP/o-mmt nanocomposites, with a coexisting intercalated and

exfoliated structure, was realized in two ways by Manias et al. [87]: (i)
introducing functional groups in PP and using common alkylammonium
montmorillonites and (ii) by using neat/unmodified PP and a semifluorinated
surfactant modification for the mmt. As is typical in most polymer/silicate
nanocomposites, PP/mmt hybrids exhibit concurrent improvements in several
materials properties, for very moderate inorganic cloadings (typically less than
6 wt% of mmt). Enhanced properties include improved tensile characteristics,
higher heat deflection temperature, high barrier properties, better scratch
resistance, and increased flame retardancy. Because these PP/mmt
nanocomposite matrixes are amenable to common processing techniques and
can be further reinforced by traditional fillers, such as fibers, these hybrid
materials hold high promise for new potential applications.

Obtaining the optimum properties for nanocomposites will usually require

excellent dispersion of the nanoparticles. The tendency for nanoparticles
(including platelets and fibers of nanoscale dimensions) to coalesce into
macrosize agglomerates can seriously impact the achievable properties. The
advantages that nanocomposites offer far outweigh the costs and concerns and
with time the technology will be further refined and processes more
developed. Research continues into many types of nanofillers, allowing new
nanocomposite structures with different improved properties that will further
advance nanocomposite use in many diverse applications. The synthesis of
polymer nanocomposites is an integral aspect of polymer nanotechnology. By
inserting the nanometric compounds, the properties of polymers improve and
hence this has a lot of applications depending upon the material present in the
polymers. The improvements obtained in nanocomposite structure can make
this commercial thermoplastic polymer more suitable for automotive,
construction and packaging applications. The synthesis of polymer
nanocomposites is an integral aspect of polymer nanotechnology.
4. POLYPROPYLENE DEGRADATION
4.1. Main Aspects of Photodegradation of Polyolefins
Degradation of polymeric materials typically occurs in a wide variety of

environments and service conditions, limiting the service lifetime. It occurs as
a consequence of environment-dependent chemical or physical attack, caused
by a combination of degradation agents, and involves several chemical
mechanisms and mechanical processes [88-89].
Polymer degradation is recognized by its effects. Typical effects:
discoloration, embrittlement, tackiness, loss of surface gloss, and
crazing/chalking of the surface [90].
Low degrees of chain scissioning of the high polymers, which have the
highest probability for chain scissioning, are sufficient to cause severe losses
in the material’s physical properties. As the polymer industry evolved, an
extensive area of research has been made to understand, at a molecular level,
the degradation of polymers during weathering, and means were found to
retard it [91]. Polymer Degradation can be considered to be an irreversible
change in some properties that is detrimental to their usefulness. During

processing the following modifications can occur: thermal cleavage, oxidative

decomposition, and hydrolytic degradation.
One of the most severe service environments is the outdoors due the vast
amount of degradation agents present. The degradation process typically starts
at the outer surface and penetrates gradually into the bulk of the material [88].
Polymer degradation can be caused by heat (termal degradation), light
(photodegradation), ionizing radiation (radiodegradation), mechanical action,
or by fungi, bacteria, yeasts, algae, and their enzymes (biodegradation).
The overall process of the interaction between light and the material in the
presence of oxygen generally is referred to as oxidative photodegradation or
photo-oxidation. There are a few ways to mantain degradation at its minimum,
as examples given [92] through the use of stabilizers, by avoiding unnecessary
thermal exposure, and by excluding oxygen and water as much as possible.
Because of joint action of radiation and oxygen, UV absorbers and
antioxidants are generally supplied to plastics designed for exterior use.
In terms of photostability, polymers can be divided as follows [93]:
1. Highly photostable polymers: tipically used without any

photostabilizer added, e.g., poly(tetrafluoroethylene) and
poly(methylmethacrylate), and have an service life of many years.
2. Moderately photostable polymers: can be used outdoors without any
photostabilizer, e.g., poly(ethylene terephthalate), polycarbonate,
poly(vinyl fluoride), and poly(vinylidene fluoride), and have an
service life of a few years.
3. Poorly photostable polymers: need extensive photostabilization for
outdoor use, e.g., polyolefins, poly(vinyl chloride) (PVC), polystyrene
(PS), aliphatic and aromatic polyamides, polyurethanes, diene
rubbers, and polymeric coatings, and have an service lifetime of less
than a year when compounded without any photostabilizer added.
Commercial synthetic polymers suffer from chemical modification upon

irradiation with UV light (a component of solar spectrum) because they tend to
have impurities or the additives employed have chromophoric groups attached
to their inner structure. Light absorption in a molecule consists of a specific
interaction of a certain chromophoric group with a photon of given energy.
Light is absorbed statistically by the chromophore groups it contains.
Compounds with saturated bonds such as C–C, C–H, O–H, and C–Cl
absorb light at λ < 200 nm. Carbonyl groups and conjugated double bonds
have absorption maxima between 200 and 300 nm. However, plastics tend to

have impurities or additives that can absorb in this wavelength range. This
explains in most cases the instability of polymers, which, according to their
chemical structure, should be resistant to solar radiation. The chance of an
absorbed photon to induce a chemical change in a molecule depends mainly on
the photophysical processes following the absorption. The physical processes
involved in photodegradation include absorption of light by the material;
electrical excitation of the molecules; and deactivation by radiative or
radiation-less energy transitions, or by energy transfer to some acceptor.
The energy absorption produces two excited states of the molecule, such
as the singlet state (S), in which the spins of electrons remain paired, and the
triplet state (T), in which the spins are unpaired. The ground state (S0) is
almost always a singlet state. The excitation of a molecule from the ground
state to the first excited (S1) singlet state is represented as follows:
In order to lose its excess energy, the molecule has a vibrational relaxation
and emission (fluorescence), and the emission of light by the
transition is called phosphorescence [94].
The ground state of oxygen molecules is a triplet state in which two
unpaired electrons are present. Oxygen usually participates in degradation
reactions of polymers as a free radical species. Although an oxidative
degradation reaction can occur at normal temperatures and in the absence of
UV light, the most common effects result from the combined action of
oxidation and thermal degradation or photodegradation. The oxidative chain
mechanism is of prime importance whenever there is a source of free radicals:
In the second step, RH can be a polymer. Because of the chain nature of
this reaction, even small concentrations of free radicals can result in significant
amounts of oxidative degradation. The primary oxidation product, the
hydroperoxide ROOH, is thermally and photolytically unstable. It decomposes
to produce two radicals, each of which can participate as R* in the chain
process:
In a further step of degradation caused by oxygen arises when, in the

presence of a photo sensitizer able of absorbing UV rays, energy transfer

occurs to produce an excited state of the oxygen molecule, singlet oxygen

(1O2) [90, 93].
The degradation of polymers in the outdoors usually involves a very
complex reaction sequence. As an example given, the photo degradation
process can be initiated by light propagated by oxidative reactions; thermal
effects induce subsequent steps, the rates of which can be affected by the
presence of moisture or participation of pollutants.
Oxidation can occur in conjunction with UV or nuclear radiation or in air
alone. Photooxidation forms carbonyl, carboxyl, hydroxyl, or peroxide groups
into the polymer chain. For all cases, the reaction rate is favoured by higher
temperatures and under mechanical stress. It also works in opposite direction;
i.e., once oxidation has occurred in elastomers, light is absorbed because
hydroperoxide absorbs UV radiation 300–500 times more strongly than pure
elastomers.
The presence of carbonyl groups in a degraded polymer indicates that
oxidation has taken place and also means that the material is vulnerable to
further deterioration due to the photolability of these groups. Common
products are aldehyde/ketone carbonyl groups during processing and the effect
on the subsequent degradation behavior is significant [89].
In addition to the polymer oxidation initiation by the photolysis of
hydroperoxide groups, a second major contributor to the photodegradation of
polymers is ketone photolysis, which proceeds through two major reactions
called Norrish I (free radical generation without chain cleavage) and Norrish II
(chain cleavage), as shown below. Ketones are introduced onto the backbones
of polymers by photo-oxidation. On exposure to light, these ketone groups
absorb photons of appropriate energy, break carbon–carbon bonds, and
scission the polymer backbone.
Photodegradation that occurs outdoor under the action of light in the
presence of air depends on the chemical structure of the polymer, the
wavelength of the incident light, the radiation intensity, among several factors
such as temperature and metallic traces. The absorbed UV light causes bond
dissociation (commonly C–C and C–H) in molecules of one or more of the
constituents of a polymeric material by a homolytic process producing free
radicals as the primary photochemical products. This event can lead
subsequently to one or more of the following chemical phenomena: chain
scission, cross-linking, separation of small molecules (H2O, CO, CO2, etc.),
formation of double bonds in the main chain, depolymerization, and
photohydrolysis (photolysis) [88]. Photolysis is caused by UV irradiation at
high temperatures causing depolymerization with monomer evolution.

Figure 3. Typical photodegradation mechanism.
Photo-oxidation produces embrittlement at the surface of polymers

(caused mainly by cross-linking), which is a major cause of surface crazing
and fracture in polymers. The photons that make up the UV component of
sunlight have enough energy to split intra- and intermolecular bonds and thus
set off a chain reaction in which the surface layer becomes embrittled to a
depth of more than 100 mm. The brittle surface layer rapidly generates cracks
at low strains that propagate into and through the unaffected material. Not all
polymers are equally affected by this outdoor aging.
Resistance to oxidation increases with increasing density of the
polyolefins because a less branched polymer has a diminished permeability to
gases and a smaller number of tertiary carbon atoms in the macromolecule
(which constitute sensitive points of attack). Traces of metals (catalysts)
enhance the oxidation process [95].

Many applications of polyolefins, such as packaging materials, garden

equipment, horticultural films, crates, and stadium seating, require a degree of
outdoor stability. Although low-density PE (LDPE), high-density PE (HDPE),
and PP are intrinsically unsuitable for outdoor applications because they are
prone to photo-oxidation, their attractive properties, combined with their
relatively low cost, has ensured that stabilization of these polymers has
received a great deal of attention. The continuous research of adequate
additives for these systems is the pilar of a growing polymer stabilization
industry. So, the improvements achieved in the outdoor stability of polyolefins
are directly attached to the advances made in stabilizers [96].
Polyolefins and some other polymers ought to be transparent to terrestrial
sunlight, i.e., to wavelengths of ~290 nm. Because photodegradation, as
manifested by embrittlement, does occur in use, the early stages of
photoinitiation must involve the absorption of photons by chromophoric
groups or impurities.
Light-absorbing groups implicated in photo-oxidation of PP include
hydroperoxide, peroxide, catalyst residue (e.g., TiO2), intrachain ketone,
methyl ketone end groups, and oxygen–hydrocarbon charge transfer
complexes. There is an increasing accord that PP hydroperoxides are the
dominant group the photochemistry of this polymer during outdoor exposition,
however some researchers are still convinced that carbonyl impurities also
play an important role.
In a recent study by Butler et al. Volatile peroxides are detected at low but
measurable levels from the earliest times of exposure, but after an induction
period of about 100 h, the volatile peroxides are emitted at an increasing rate
that begins to level-off after about 500 h. The volatile peroxides that are
generated during the oxidation of a hydrocarbon polymer, and peroxides
remained in the sample may indeed be the identity of an agent previously
observed to be infectious within a polymer and to nearby polymers [97].
The end of the induction period of the oxidation of PP is characterized by
a diminishing of the g relaxation intensity, together with other effects such as
the decrease of the molecular weight. This decrease of the g relaxation
intensity occurs no matter the nature of the oxidation agent; this same effect is
seen during also during thermal oxidation [98].
Gel permeation chromatography (GPC) has been used to monitor the
molecular weight changes that occur when polymers are degraded by photo-
oxidation. Examples are given of applications to studies of PP, glass fiber rein
ethyl forced PP and PS exposed to UV irradiation in the laboratory. The results
show that the degradation rate is faster near the exposed surface, but in PP,

degradation is much faster at the unexposed surface than in the center where
the UV intensity is greater than at the unexposed surface. From these results, it
is deduced that degradation at the center is slowed due to a shortage of oxygen
[99]. Scission and crosslink concentrations have been determined using
computer analysis of molecular weight distributions obtained from gel
permeation chromatography. The results confirmed that scission dominated
cross-linking at all depths. Comparison of results obtained with bars exposed
unstressed and under an uniaxial tensile stress (of 10 MN m-2) indicates that a
tensile (applied) stress accelerated macromolecular scission near the surface
[100].
To avoid degradation, some coatings have been used with silica, alumina
and hindered amine light stabilizers (HALS). High efficiency HALS (the
amine and amino ether derivatives 2,2,6,6-tetramethylpiperidine), as inhibitors
of polymer photooxidation, are considered to be determined primarily by a
complex set of reactions involving compaction active alkyl and peroxy
radicals, formed during oxidation [101].
After a quick overview of the photodegradation phenomenom here
discussed there have been two main paths towards this phenomenon:
One that avoids the photodegradation as much as possible and the other
one complete opposite to this that favor it. We are going to focus in
prodegradant systems since there have been a great effort in order to get rid of
all the polymer pollution.
4.2. Oxo-Degradable Polypropylene
Degradable polyolefin systems are typically designed to oxo-degrade

undergoing changes in chemical structure as a result of oxidation in air,
causing the breakdown of the molecules into small fragments that are then
bioassimilated [102].
4.2.1. Oxo-Biodegradation
As Ammala et al. defined, Oxo-biodegradation is a term used to describe a
two stage process of polyolefin degradation. The first stage involves the
reaction of oxygen in the air with the polymer [102].
An oxidation occurs to the carbon backbone of the polymer resulting in
the chain scission. This first stage of oxo-degradation is an abiotic process.
The incorporation of oxygen into the carbon chain polymer backbone results
in the formation of functional groups such as carboxylic or hydro-carboxylic

acids, esters as well as aldehydes and alcohols. The polyolefins change their
behaviour from hydrophobic to hydrophilic thereby allowing the fragmented
polymer to absorb water.
The second stage is the biodegradation of these oxidation products by
microorganisms (bacteria, fungi and algae) that consume the oxidized carbon
backbone fragments to form CO2, H2O and biomass [102].
In the first stage of oxo-biodegradation, the oxidative degradation of the
polymer can be accelerated by either ultraviolet (UV) light (photodegradation)
or thermal degradation using heat over time. This stage is an important as it
determines the rate of the entire process. The process of thermal degradation is
described in more detail below.
Thermal Degradation
The mechanism and products from oxidation initiated by heat are similar
to those resulting from photo-oxidation as represented in Figure x. One
difference between oxidation initiated by heat and by light is that ketone
products are stable to heat but not to light [103].
The rate of thermal degradation directly depends upon the temperature,
with higher values achievable at higher temperatures [104].
As stated before with both photo and thermal degradation of polyolefins,
the resistance to oxidation increases with increasing density of the polymer.
This is decrease is caused because a less branched polymer having a
diminished permeability to gases and a smaller number of tertiary carbon
atoms, which constitute sensitive points of attack is less possible in terms of a
high density material [88, 104]. Chain defects, such as unsaturation, also,
influence the rate of degradation. The oxidation susceptibility of the most
common polyolefins can be the following: iPP (isotactic polypropylene) >
LDPE (low density polyethylene) > LLDPE (linear low density polyethylene)
>HDPE (high density polyethylene) [104]. Oxidative degradation in
polypropylene leads primarily to chain scission [105].
4.3. Mechanical Stress Degradation
Although less studied compared to the other two most common types of
degradation (photodegradation and thermal degradation), the application of
mechanical stress can promotes the degradation of polymers. This is because
the degradation mechanisms are morphology dependent and stress causes
changes in the polymer morphology. The influence of mechanical action alone

has been reported to cause degradation, examples given shear forces in an

extruder or mill [106]. The influence of mechanical forces over
photodegradation has also been reported with stress accelerating
photodegradation [106].
4.4. Biodegradation
During the microbial degradation stage, most of the abiotic oxidation

products (low molecular weight compounds) are utilized by the microbes. An
important aspect during this stage is that the growth of microorganisms should
be sustained. It has been reported elsewhere that in order obtain significant
biodegradation in a reasonable time period, the average molecular weight of
oxidized polyolefin should be under 5000 Da [107].
It has been observed a decrease in the number of carbonyl groups during
the biodegradation stage. This decrease of carbonyl groups from the original
oxidation products such as ketones, esters and lactones indicates that the
microorganisms population is increasing. Eventually the microorganisms
degrade the smaller segments of the polyolefin chains to form carbon dioxide
and water as final products.
4.5. Prodegradant Technology
Although polyolefins such as PE and PP will eventually degrade naturally,

the process is usually long (over many decades to achieve completely). The
convenience of plastic packaging and increasing demand for these polymers
has forced the need to convert them into biodegradable materials in
significantly shorter time. A possible solution is to use an additive capable of
accelerating the degradation of the polymer with atmospheric oxygen and
incorporating oxygen atoms into the polymer chains. The additives that
accelerate this process and promote biodegradation are called prodegradants
and their use shall be briefly reviewed ahead. The prodegradants will be
classified as follows
4.5.1. Transition Metal Salts

Transition metal ions are the most widely used prodegradant additives
nowadays. The appealing of these additives is due to their capacity to catalyse
the decomposition of hydroperoxides into free radicals (Table 1) [105].

The most commonly used transition metals include iron, cobalt and
manganese. Iron is highly effective in photodegradation while manganese and
cobalt are to thermal degradation. The metal ions are generally employed as
organic complex. As given examples are:
4.5.2. Salts of Fatty Acid Esters, Amides and Dithiocarbamates

One of the earliest reports of Newland et al. that use of transition metal
ions as prodegradant was about 1966, that work relates to controlled
degradation rates of agricultural films and includes the use of additives such as
acetyl acetonates of manganese, cobalt, chromium, copper and vanadium
[108]. Preferred examples of prodegradants also include manganese stearate,
oleate, acetate, cobalt acetate, stearate, cupric oleate and ferric acetate. Besides
to the prodegradant additives, this invention describes the use of pigments or
dyes, for reducing the transmission of sunlight and hence control the
degradation rates.
Another patent of Scott et al. reported that the metal complexes were
activated by light (and optionally heat) to accelerate degradation. After
photodegradation had begun by the action of UV light a rapid oxidative
degradation of the polymer continued even if there isn’t any source of light
present. The transition metal complexes were found to act as photoactivators
even in polymers containing antioxidants and stabilizers [109].
Iron was reported as the preferred metal ion; however, cobalt, nickel,
manganese, silver, palladium, molybdenum, chromium, tungsten and cerium
are also mentioned. The patent also reports of a better performance if a
mixture of zinc and iron is used. The patent gives many examples and claims
that sulphur ligands are preferred over nitrogen, oxygen or phosphorus.
Dibutylthiocarbamate is an example of a sulphur containing complexing anion.
Another patent from EPI Environmental Products Inc. [110] reveals the
combination of a metal carboxylate and an aliphatic poly hydroxylcarboxyl
acid as the prodegradant system. The main metal carboxylates used in the
patent are cobalt, cerium and iron stearate. The aliphatic polyhydroxylcarboxyl
acid is described as an aliphatic acid having either more than one hydroxyl
(–OH) or more than one carboxyl (–COOH) group in the acid structure.
A patent assigned to Gain Mark Technology [111] describes the use of
fatty acid amides in order to improve the rate of the degradation of
prodegradant systems based on transition metal ions. The preferred amides
contain between 8 and 20 carbon atoms and the example given is oleamide or
9-octadecenamide. As well as the transition metal salt (preferably cobalt
chloride or cobalt nitrate) and fatty acid amide, the composition also consists

of a carboxylic acid (lauric, stearic, palmitic, oleic, and linoleic) and a base
(sodium hydroxide).
4.6. Metal Oxides
Metal oxide polymer additives such as TiO2 and ZnO are well known as
UV absorbers and white dyes. The photostability of the metal oxides relays
strongly on surface treatment, particle size and crystalline form. While the the
behavior as UV stabilizer of ZnO in polyolefins is well known [102, 112],
controling the photoactivity via dopping with metal ions has also been
reported by several reports by Casey et al. [113, 114]. The rate of
photodegradation can be reduced using coated TiO2 particles or TiO2 doped
with Cr or Mn ions. Inversely the rate increased on adding TiO2 doped with V
and Mo or W ions.
This behavior is described on another patent [115]. The use of a transition
metal coating on fillers such as the anatase or rutile form of titanium dioxide
offers improved performance. Other typical fillers may been calcium
carbonate, talc and clay. The most used transition metals are iron and
manganese. The process of coating the fillers is described and involves the
dispersion of a fatty acid transition metal ion salt and filler in an alcohol
solvent followed by a calcination step to obtain the final transition metal oxide
coating on the filler. One or more transition metals may be used on the same
filler. An example illustrated in the patent is TiO2 coated with FeO and MnO.
The addition of TiO2 with other metal stearate prodegradants has been
reported [102]. A rare earth modified TiO2 photocatalyst is also reported in
other patent [102].
On the other hand, the addition of lanthanide complexes to polymers is of
importance as limit the degradation of polymers under UV radiations and also
allows their identification by UV fluorescence spectrometry facilitating the
sorting and recycling of end-of-life products as reported by Massardier et al.
[116]

Table 1. Typical organic groups present in a transition metal

prodegradant system
Name Chemical Formula

Fatty ester salts M = Iron,
cobalt, nickel,
manganese, silver,
palladium,
molybdenum,
chromium, tungsten
and cerium
Acetylacetonates M = copper,
vanadium, chromium,
manganese, cobalt,
iron, nickel and zinc
Dithiocarbamates
Oleamides R = 8-20
4.6.1. TiO2 as a Prodegradant System

We are going to make an little review over the TiO2 because is one of the
most important inorganic white pigment in the industry and is heavily
employed as a pigment in polymer applications

Titanium oxide (TiO2) is the most studied crystalline system in the area of
metallic oxide surfaces, with rutile and anatase being the most important
forms. This material is very important in society because of its multiple uses.
For example, it is used in heterogeneous catalysis, photocatalysis, solar cells
for hydrogen and electric power, for gases sensors, white pigments, corrosion
protective coatings, optical coatings, ceramics and electronic devices like
varistors. Also, it has an important role in the biocompatibility of osseous
implants and it is studied for door insulating in the new generation of
MOSFET transistors and spacer materials in magnetic spin valve systems
[117]. It also used in the nanostructured form for lithium batteries and
electronic devices [117-118].
The defects of titania crystals have an important role in many surface
phenomena [117]. Water is the most important adsorbent in the TiO2 surface.
Many of its applications, for example, almost all of its photocatalytic
processes, are carried out in aqueous environments. Steam from the
environment interacts with the TiO2 surfaces and superficial hydroxyls can
easily affect adsorption and the reaction processes. For further information, we
highly suggest the work of Henderson, in which details regarding water
adsorption in the crystalline surfaces of TiO2 are given [119]. Results from
different spectroscopic methods have shown that water adsorbs in a
dissociative and molecular way [119].
Wang et al. have shown that water dissociation which occurs in free
oxygen produces a macroscopic effect in the wet capacity of the water.
Generally, the surfaces of TiO2 are oleophilic and hydrophobic, however,
when TiO2 is exposed to UV radiation, the contact angle of water drops to
zero. By keeping them in darkness, these amphiphilic surfaces restore the
hydrophobicity of the original surface. This is because new free surfaces
appear which dissociate the water and generate hydrophilic microscopic sites
[117, 119].
Recently, TiO2 has found new applications in the area of nanomaterials,
this is because of the various techniques used to obtain it, such as the sol-gel
method, hydrothermal method, sol method, chemical deposition steam method
and direct oxidation. These materials have mainly found usage in
photocatalytic applications, photovoltaics and electronic devices [120].
Commonly is found in the plastic used for agricultural padded, which is
used to protect crops and soil from the action of atmospheric agents. For the
development of bright white plastic films, TiO2 particles can be used, where
the crystalline structure consists mainly of rutile, for a pigment with a higher
refractive index (2.73), in all white pigments scale. TiO2 particles are not

chemically stable, so when they are used in plastic which is exposed to the
environment, the TiO2 particles have to be coated with alumina (Al2O3), silica
(SiO2), zirconia (ZrO2) or a mix of these materials to prevent photocatalytic
activity. This is because, TiO2 behaves like a semiconductor, which with UV
radiation (less than 400 nm) means the electrons have the capacity to exceed
the band gap of 3 eV, which produces free radicals that cause plastic
degradation [117, 119]. Due to the previously described behavior, it is
necessary to gain insight into the role of the coatings (silica and alumina) in
influencing the decreased catalytic activity of TiO2. Also, is very important to
know the role that water plays when it is in contact with the plastic film which
contains TiO2, as this is an essential part of polymer degradation.
Taking advantage of its surface properties several studies had been made.
As an example given; Miyazaki et al. have found that the addition of Poly
(ethylene oxide) (PEO) microcapsule containing TiO2 to PP is an easy way to
prepare the novel photo-degradable PP [121]. The adsorbed H2O in the PEO
phase and the TiO2 photocatalytically reacted forming hydroxyl radicals (OH),
which initiated the PEO degradation. The degraded PEO produced the acid
and the aldehyde, which facilitate PP degradation. The addition of the
PEO/TiO2 microcapsule brought about the facilitative effect of the PP
degradation. In another study the TiO2 was added to PP by the use of a PEO
microcapsule [122]. There was no reported the absence of any difference
between the degradation rates of the PP/PEO/TiO2 and of the
PP/PEO/modified TiO2 with the hydrogenophosphate, the calcium compound
and the dicalcium phosphate dehydrate (DCPD) covering materials. Whereas,
the Octacalcium phosphate intercalated with dicarboxylate ions (OCPC)
covering material brought about the higher PP degradation rate. Since the
severer degradation behavior of the PP/PEO/modified TiO2 with the OCPC
covering material was observed, it was confirmed that the dissolution of the
OCPC released the acid species (dicarboxylate ion) facilitating PP degradation
[122].
In a similar study by Miyazaki et al., as the other two cited before the role
of PP/PEO/TiO2 during biodegradation was studied. In this report the
biodegradation behavior of the PP/PEO/TiO2 and PP/PEO/TiO2/OCPC
samples was studied with the respirometric test [123]. The mineralization rate
of photodegraded the PP/PEO/TiO2 samples reached up to ca. 10% at the 80
days test. The molecular weight and distribution of molecular weight were
decreased by the biodegradation. By 1H NMR, the authors showed that the
anaerobic metabolization was performed. The results suggested that the OCPC
existence initiated the aerobic metabolic reaction of the PP part [123].

Opposite case, it was reported elsewhere that the presence of rutile-type

titanium dioxide (CST) nanorods in the PP matrix can help to reduce the
extent of photo-oxidation and constrain the degradation in a thinner surface
region with respect to the organic UV absorber Tinuvin® 328 (T328) [124].
The anti-aging mechanism of CST mainly thanks to its UV-shielding ability
when it is well dispersed.
The present work demonstrated the great potential of the rutile-type TiO2
nanorods in the photostabilization of polymers. As inorganic nanoparticles, the
CST nanorods are more stable than the conventional organic UV absorbers
and resistant to migration [124].
Similar stabilizing degradation effect of TiO2 was present in other report
describing that during photooxidation the rutile pigment is synergistic in
stabilization activity with phenolic antioxidants and hindered piperidine
stabilisers (HAS) but antagonistic with benzotriazole and benzophenone
absorbers anatase, on the other hand exhibits a marked autocatalytic oxidation
effect on the polymer giving strong antagonistic effects. With mixed
antioxidant/stabilizer combinations, synergistic stabilization is not
significantly influenced by rutile but markedly antagonized by the presence of
the anatase pigment. In that report it was found that the most effective light
stabilizer in retarding the catalytic oxidative effect of anatase is the polymeric
HAS, Chimassorb 944 [125]. During thermal oxidation the polymeric HAS
exhibit strong thermal antioxidant activity compared with the non-polymeric
HAS. Both antioxidants and the benzophenone absorber are found to be
strongly antagonistic with rutile while the HAS and benzotriazole stabilisers
displayed weak synergism. The anatase strongly accelerates and catalyses the
thermal stabilisation effects with all the stabilisers and antioxidants when used
alone.
Finally a recent study showed that modified TiO2 nanoparticles, with
pimelic acid, which is a common nucleating agent, exhibit the following
features: high thermal stability, since calcium pimelates being used as a β-
nucleating agent promotes an improved thermal stability and also promotes
degradation by increasing the number of carbonyl groups present in the
composite once the material has been exposed to radiation [126]. This material
was a β-nucleating agent [127] and could be useful especially in oxo-
degradable polypropylene, promoting a possible β-phase polypropylene and
aiding the degradation of the material.
Another filler used as a support of prodegradant additives is the use of
clays which will be discussed ahead

4.7. Clays as Prodegradants
Several studies have been made through the years that describe the use of
clays. As an example, it was reported by Morlat et al. that the mechanism of
polypropylene photo-oxidation is not modified by the interactions with the
nanoclay and the compatibilizing agent [128]. The photo-oxidation of an
organo-modified montmorillonite reveals that the alkylammonium cations can
be degraded and that the presence of iron species in the clay playing a further
role in the degradation mechanism. It was found that the presence of the clay
and of the compatibilizer modifies dramatically the kinetics of oxidation,
leading to a shortening of the induction period. This behavior can be attributed
to an initiation of the photo-oxidation by active species generated by
photolysis or photooxidation of the organoclay and/or by interactions between
the antioxidant, montmorillonite, and maleic anhydride.
Other study by Mailhot et al. described that photo-oxidation at long
wavelengths of polypropylene based nanocomposites produces the same
photoproducts as those of the pristine polypropylene and in the same quantities
[129]. The maleic anhydride grafted PP used as compatibilizer and the
organically modified nanoclay do not significantly modify the rate of
photooxidation of the samples, but the efficiency of the additives is
considerably reduced. This could result from the location of the additives close
to the organoclay due to the spreading of these polar species onto the
hydrophilic nanoplatelets. It was found that the additive nature and
composition can be tailored for the case of nanocomposites in which the
quantity of interface between the nanofiller and the polymer matrix plays an
important role [129].
Aslanzadeh et al. studied the photo-oxidative rate of a PP/Polypropylene
grafted with maleic anhydride (PPgMA)/organic modified montmorillonite
OMMT composite. In that study it was found that the rate depends strongly on
the melt processing conditions [130]. The rate increases with residence time
during melt processing and exposure of the melt to air during cooling. The
photo-oxidation of PP/PPgMA/OMMT composite becomes more agressive if
polar groups are introduced during melt processing. These polar groups were
supposed to be formed by thermal degradation of PP, PPgMA and organic
modifier of OMMT.
The presence of the structural elements in the clay, such as Fe2+ and Fe3+
accelerate the photo-oxidative rate of the composite [130].

4.8. Non Transition Metal Prodegradants
While the majority of research on oxo-biodegradation include transition

metal salts, there are also a few reports of other prodegradant additives that do
not contain any transition metals.
Common polyolefins will undergo chemical changes under UV light
because they contain impurities or additives that possess chromophoric groups.
These chromophores are the ones that will absorb the light or photon of given
energy. Photodegradation as depicted before shows the importance of the
presence of carbonyl groups in the overall degradation mechanism. The
deliberate introduction of these groups into the polymer to accelerate the
degradation is illustrated in the following sections.
4.9. Ketone Copolymers
Use of copolymers which included a carbonyl group alpha to the main

chain, known as the Ecolyte process were the first attempts in this field [103,
131]. Vinyl ketones were copolymerized with the specific vinyl monomers to
produce polyolefins with a much improved sensitivity to sunlight than those
without ketone groups. Similarly, photosensitive condensation polymers have
been synthesised with ethylene–carbon monoxide copolymers (ECO). Most
common applications include loop carriers for beverage can 6 packs [103] as
well as for containers, closures and food trays [102].
4.10. 1, 2-Oxo-Hydroxy Groups
In a Patent assigned to DSM, they describe how the oxo-biodegradation of

polyolefins can be achieved through the addition of additives containing at
least one 1,2-oxo-hydroxy-moiety according to the structure below [132]
(Table 2).
The key point in this patent is that the metal M+ is not a transition metal,
but instead, an alkaline earth metal cation or an ammonium ion. Some of the
additives include citric acid and tartaric acid combined with alkaline
carboxylates. Other alkaline or alkaline earth metal salts include those from
fatty acids, e.g., stearates, palmitates, linolates and oleates. The patent also
describes the addition of stabilisers to control the processability and lifetime of
the polymer.

Montagna et al. reported that the influence of an organic pro-degradant on

PP under the two different environmental conditions (abiotic and biotic),
verifying that samples of modified PP subjected to abiotic and biotic
degradation showed a decrease in molecular weight and increase in the degree
of crystallinity [133]. Also, changes in the surface morphology were observed
with increasing exposure time, this being more pronounced after exposure to
natural weathering. In that study the use of an 1, 2-oxo-hydroxy additive was
found to be effective in enhancing the PP degradation when exposed to natural
weathering and soil conditions.
4.11. Unsaturated Alcohols or Esters
In a patent assigned to Owens-Illinois [134] discloses the employment of

an ethylenically unsaturated alcohol or ester to degrade polyolefins. A carbon
hydrogen bond is activated with respect to hydrogen atom abstraction by an
adjacent C-C double bond, fastening thermal or photooxidation to
hydroperoxides and subsequently free radicals. Some of the alcohol structures
are presente below on Table examples of alcohol structures listed include
geraniol, linalool, citronellol, allyl alcohol and furfuryl alcohol.
Common esters employed as prodegradants include geranyl acetate,
linalyl acetate and furfuryl acetate (Table 2). In an invention assigned to
Techmer [102] describes similar unsaturated ethylene structures to that
described above. The additive is described as containing at least one
alkoxylated ethylenically unsaturated or saturated compound as prodegradant.
4.12. Benzophenones
Additives which active compound are benzophenone accelerate the

degradation of polymers in the presence of air and UV light. As an illustrative
example in a patent it is described the use of benzophenone and anthraquinone
additives as prodegradants in polyolefins and gives examples of activity both
alone and together with other additives such as iron stearate and coloured
pigments [135]. The typical structures are shown on Table 2. Systems
containing both the benzophenone additive and transition metal stearate were
found to be most effective for promoting the degradation of polyolefins. This
prodegradant effect is enhanced by the addition of certain coloured pigments
(presumably iron salts present in the pigment).

Other invention assigned to ICI also discloses the use of benzophenones to

degrade polyolefins [102]. In this patent the additives employed are
plaurylacetophenone and p-laurylbenzophenone (Table 2).
Benzophenones are also used in two more patents: one of Sekisui
Chemical Co. where they are used together with transition metal compounds
[136] and the last one assigned to Ecostar International which discloses the use
of two transition metal compounds, iron and copper stearate and
benzophenone [137].
Finally a last invention describes the use of arylketones together with a
borate or phosphate ester of an alkanolamine for greater control of strength
prior to degradation [102].
4.13. γ-Pyrones
Organic compounds as chromone, flavone or xanthone whose contain a γ-

pyrone ring have been used to promote photodegradation of polyolefins [102].
The degradation rates can be controlled by varying the additive amount. It is
noteworthy that these compounds can migrate to the polymer film surface at
higher concentrations and they can form a protective UV screening layer.
Lower concentrations are preferred for increased polymer degradation.
Typical structures are shown on Table 2.
4.14. β-Diketones
The use of β-diketones (or 1,3-diones) as prodegradant additives in

polyolefins has been reported elsewhere [138]. In that patent it is described the
synthesis of some aryl substituted additives and shows the degradation of these
additives in the presence of calcium stearate. The structure is shown in Table 2
and can also exhibit keto-enol tautomerism.
Polyisobutylene
In a patent assigned to Chevron is another example whereby no transition
metal prodegradant is used [139]. This patent describes the use of
polyisobutylene to improve the rate of the photodegradation of polyolefins.

4.15. Amines
Various amine structures have been also reported to act as prodegradants

in polyolefins. The patent assigned to Chisso Corp. describes the use of
hexmethylene tetramine [140] (Table 2). In another patent assigned to the
same company (Chisso Corp.) it is disclosed that the amine guanidine and/or
phenyl naphthyl amine have prodegradant activity [141] (Table 2). The patent
assigned to Owens-Illinois also describes the use of amines as examples of
additives used together with ketones to photodegrade polyolefins [142].
4.16. Peroxides
A patent assigned to Clariant, describes the use of a peroxide based

additive for targeted scission or cross linking reactions in plastics [143]. The
masterbatch comprises a peroxide (15–85%) and polyolefin waxes. The
peroxide in question is di-t-butyl peroxide, dicumyl peroxide or diacetyl
peroxide. In another patent assigned to Ciba, it is discussed the preparation of
degradable polymers triggered by light and/or heat and/or humidity [102].
Finally organic peroxides and hydroperoxides are used in a patent
assigned to Owens-Illinois as examples of photosensitizers, effective as
prodegradants when used together with other oxidizable additives [142].
(Table 2).
Finally is worth to mention that there have been studies that focus on the
type of biodegradation. In a recent study by Contat the oxo-degradation
process of PP samples containing prooxidant/pro-degradant additive was
investigated by monitoring their morphological and thermal properties under
abiotic and biotic accelerated degradative conditions [144].
On the basis of the results obtained, the prooxidant/pro-degradant additive
can promote the abiotic oxidation of polypropylene during UV-irradiation.
Photooxidation was found to lead to a reduction of crystallinity and a drop of
the melting temperature that are accompanied by the formation and subsequent
predominance of thinner crystalline entities.
It was also shown a significant lowering of the thermal stability of these
materials during exposure to UV radiation. Moreover, the level of oxidation
observed in UV-aged samples seems to be dependent on the additive load.

Table 2. Typical organic groups present in a free transition metal

prodegradant system

1,2-oxy- X = OR, SR, NR1R2,
hydroxy R OM
compounds Y = OR, NR1R2, R in
which R, R1, R2 = H,
C1–C20 alkyl group,
C6 – C20 aryl group,
C7 – C20 alkylaryl
group, and C7 – C20
arylalkyl group.
Insaturated Geraniol,
alcohols
Linalool,
Citronellol,
allyl alcohol
Furfuryl alcohol
Maleic
Anhydride
Insaturated Geranyl
esters acetate
Linalyl acetate

Table 2. (Continued)

Furfuryl acetate.
Benzophenones Benzophenone
Anthraquinone
p-laurylbenzophenone.
(R = 12)
p-laurylacetophenone
(R = 12)
γ-Pyrones Xanthone
Flavone


Chromone
β-Diketones
Polyisobutylene
Amines Hexamine
Phenyl naphthylamine
Guanidine
Peroxides Dicumyl peroxide

Table 2. (Continued)

t-butyl hydroperoxide
On the other hand, changes in the morphological and thermal properties

were detected in previously photo-oxidized PP samples when subjected to a
subsequent soil burial test that can be associated with a certain progress of
oxidation. In general, both morphological and thermal properties were found
to exhibit a non-linear dependency with the incubation time in soil. Changes in
crystallinity suggest that although the degrading activity of the soil
microorganisms starts in the amorphous phase, this seems to later also affect
the crystalline phase, starting from thinner crystals.
Changes in thermal stability can be related to bioassimilation of the low
molecular weight polymer fractions generated during abiotic oxidation.
Furthermore, changes in both the morphological and thermal properties of the
polypropylene matrix during soil incubation were found to be proportional to
the additive load and the previous photo-oxidation extent.
It can then be concluded that the synergetic effect of abiotic degradation
(due to UV exposure) and biotic degradation (as a consequence of the
metabolic activity of the soil microorganisms) promotes the extent of the
whole degradation of the PP samples containing pro-oxidant/pro-degradant
additive studied in this work, confirming the potential of this additive in
producing environmentally degradable polypropylene via combination of
abiotic and biotic oxidizing agents [144].
CONCLUSION
We can conclude that Polypropylene will continue as an subject of study
due to its intense use in everyday activities whose have been made it an
excellent choice of material due to its outstanding properties, which continue
to be explored as it facility to be modified by several methods and fillers.

However one of its greatest disadvantages is their difficulty to be

degradaded to a point to be bio-assimilated by the environment. This problem
has been faced by the researchers through the entire world giving a variety of
solutions which partially have resolved this issue. But as far as we have
achieved an advance of this problem, we are far from solving this issue.
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Chapter 5
POLYPROPYLENE BIODEGRADATION
Celso Luis de Carvalho and Derval dos Santos Rosa

Universidade Federal do ABC, Santo André, São Paulo, Brasil
ABSTRACT
The difficulty of metabolism by living organisms does not give to
polypropylene the biodegradable characteristic as a function of the high
molar mass, which does not permeate through the cell membrane of
microorganisms. The biodegradation depends on to biotic phase, which
start the breaking reaction and remains on biotic reaction. To
understanding and research of different aspects of the abiotic degradation
of the polypropylene, this chapter proposes to show the degradation
caused by polyacetal (POM) and pro-oxidant additives. Some analysis of
the polypropylene in the natural life cycle - "cradle to cradle" was
realized. The concentration of 3% by weight of the POM can enhance the
thermal stability of the PP in the conditions investigated, however, above
3% wt. of the POM caused oxidation of the polyolefin and the synergistic
effect of degradation maximized the miscibility of POM with PP (in the
interface region). The oxidative degradation of the polypropylene with
d2w® agent evolves the formation of new areas arranged in the structure
of the PP. The oxidation caused with the incorporation of POM leads to
increased structural disorder thus allowing diffusion of new agents
decomposition during the life cycle of the PP.

142 Celso Luis de Carvalho and Derval dos Santos Rosa
ENVIRONMENTAL CONSIDERATIONS
Population growth and the extension of human life are interfering with the
speed of environmental changes; climate change and biodiversity loss are clear
indications of this phenomenon [1]. The introduction of substances or energy
by man into the environment has caused imbalances in ecosystems and living
beings. Increased pollution is generated from processing natural resources that
are useful to man in the development of civilization, survival, and societal
comfort in general.
The continuous removal of environmental materials and the possibility of
exhaustion led society to question the extraction limit of natural resources and
the impact of pollution generated from the extraction of natural resources, such
as the improper disposal of waste generated during commodity extraction.
The Life Cycle Assessment (LCA) is a tool that allows a paradigm shift
from a fragmented view of the environment, with emphasis on one phase of
the life cycle, for a holistic approach to the life cycle; Figure 1 shows an
example LCA.
Figure 1. Holistic view of a material’s life cycle.

Polypropylene Biodegradation 143
The knowledge of a product's life cycle is the first step in the pursuit of
sustainable development. From the point of view of this analysis, the life cycle
begins when resources are removed from their origin, the cradle, and ends up
when the material returns to the earth, the grave.
The continuous line in Figure 1 represents the potential performance of
the material in the environment with respect to time of use. Sustainability of
materials is only reached at the end of the period of biodegradation, i.e., with
the mineralization process of the material. In the biodegradation step, the
elapsed time should be much less than the time of human existence; otherwise,
the environmental liabilities identified as rejected are transferred to the next
generation. Although the LCA ends with the final disposal of the waste, it is
necessary to investigate the evolution of the biodegradation process in order to
propose solutions that reduce disposal time.
As shown in Figure 1, synthesis or biosynthesis of the material can reduce
power consumption and additives by applying engineering synthesis and
genes, respectively; however, this strategy can reduce the performance of the
material in the environment, and therefore, one must know the maximum
requested product performance during use.
BIODEGRADABLE POLYMERS
Currently, the search for functionality in "new" materials on a nanometric
scale, and the proximity of this scale in biological materials, produces new
phenomena in materials that are unique to biology; in effect, the use of the
“Bio” prefix in naming new materials has been registered in the literature. This
understanding cannot be applied to all names found in the market; for
example, while it is common to associate the Bioplastics or Biopolymers
denomination with biodegradation properties, Figure 2 shows that some
Biopolymers are non-degradable. The 1st quadrant of Figure 2 contains
conventional polymer fossil fuels (oil, gas, and coal), which are considered
non-biodegradable, i.e., during the degradation process only the physical and
chemical phenomena remain after a long period of depolymerization and only
in the final step is the material biodegradable by the action of living
organisms, thereby raising the total decomposition time. The vast majority of
synthetic polymers are considered non-biodegradable, highlighting the
commodities (polyethylene (PE), polypropylene (PP), polyvinyl chloride
(PVC), polystyrene (PS), and ethylene-PET terephthalate) present in high
concentrations in domestic solid waste [2]. The 2nd quadrant classifies

Biopolymers that also come from fossil sources but are biodegradable.
Generally, linear polyesters, such as poly (ɛ-crapolactona) (PCL) and poly
(vinyl alcohol) (PVOH), are synthetic biodegradable polymers; in this case,
the initial depolymerization is governed by abiotic hydrolysis of the ester
group for PCL and by dissolution in water for PVOH. In the 3rd quadrant,
biopolymers are classified as base-Bio (bio-based) of renewable origin,
derived from plants, that is, polymerization synthesis occurs from monomers
obtained from renewable sources, such as synthesized PP polymerization
monomers produced from glycerin (e.g., a by-product of biodiesel) or PE
obtained from monomers produced from alcohol derived from sugar cane. The
degradation behavior of these biopolymers is equivalent to conventional
polymers; however, beyond the inherent sustainability, these biopolymers have
favorable carbon content to control the greenhouse effect. Biopolymers located
in the 4th quadrant are biodegradable, but differ from others by being
obtainable via biosynthesis, either directly from plants by microbial action or a
combination of plants and fermentation biotechnology. Currently, the main
biopolymers of industrial interest of this group are the polysaccharides,
especially those obtained from the starch of tubers and various cereals, and the
potential for obtaining plant waste from industrial processing [3]: poly (lactic
acid) (PLA), obtained by biotechnology, and poly (3-hydroxybutyrate) (PHB)
and poly (3-hydroxybutyrate-3-valerate) (PHBV), obtained by microbial
action.
Figure 2. Diagram illustrating the different groups of biopolymers and their ratings
regarding degradability [4].

Although the science and technology of new polymer materials, from the
point of view of sustainability, has inherited all the knowledge generated in the
development of conventional polymers, there is still a long way to go,
especially in new applications, whose performance coexists with that of
materials of fossil origin.
Biodegradable polymers are relatively new and began to emerge in the
1960s, first in the medical applications, such as surgical sutures of aliphatic
polyesters made from monomers that are normally present in the human body,
such as glycolic acid and lactic acid [5-7].
THEORETICAL ASPECTS OF BIODEGRADATION

The biodegradation of materials has been defined by researchers in several
ways. It can be understood from changes of the surface and mechanical
properties of the material, carried out by the action of microorganisms by
cleavage of the main chain and the consequent reduction of the molar mass-
derived enzymatic activity [8, 9].
According to ASTM D-5488-94d, biodegradation is defined as "a process
capable of decomposing carbon dioxide materials, methane, water, inorganic
compounds, and biomass, or the predominant mechanism is the enzymatic
action of microorganisms which can be measured by standard tests in a given
period of time, reflecting the existing flow conditions" [10]. Abiotic
degradation of the material is degradation without the presence of a living
organism; degradation due to the presence of living organisms is biotic. The
analysis is done separately for better understanding of the phenomena
involved, although often the evolution of the biotic phase depends on the start
and continuity of the reactions that occur in the abiotic phase [11].
Regardless of the environment of the (bio) degradation in vitro (soil,
landfill, composting and water), Figure 3 outlines the steps involved in the
evolution of the material changes caused by degradation and biodegradation.
Figure 3 shows the threshold between the two conditions, abiotic and biotic,
from the fixation of microorganisms to the material. It should be noted that the
beginning of the transition between abiotic and biotic conditions is difficult to
identify when the process occurs in vivo. Another consideration is the reversal
of (bio) degradation, or when a change in property caused by abiotic induction
(e.g., mechanical) can be reversible or irreversible; the change caused by
chemical change is always irreversible, independent of abiotic or biotic phases.

Figure 3. Schematic representation of the degradation processes and degradation of

material.
The two stages of degradation presented are also useful for understanding
the biodegradation of plastics, called oxy-biodegradation. According to the
Oxo-Biodegradable Plastics Association (2010), "oxy-degradation is defined
as degradation resulting from oxidative cleavage of macromolecules oxo-
biodegradation and as a result degradation of cell-mediated oxidation,
simultaneously or successively" [12]. Oxo-biodegradable plastic consists of a
polymer that contains an additive that accelerates oxidative degradation in the
presence of light or heat. These additives are compounds of transition metals,
specifically Iron, Nickel, or Cobalt. Therefore, considering that the photo-
oxidation and heat in the abiotic phase cause the physical disintegration of the
polymer, and this increases the surface area for microbial colonization [8], we
can infer that for oxy-biodegradable material, the rate of biodegradation
depends on the abiotic degradation of history; this dependence is not checked
in biodegradable polymers.

BIODEGRADATION OF POLYPROPYLENE
PP is a difficult substrate for biodegradation by microorganisms because,
due to its high molar mass, the polymer does not permeate the cell membrane
of microorganisms; however, some investigators described an extracellular
fungal enzyme that can degrade polyolefins [13]. Several studies [14-17]
investigated the abiotic degradation of PP by photobleaching and
thermodegradation.
Cacciari et al. [18] concluded that aerobic and anaerobic species with
different catabolic abilities (fermentation, cell respiration, and aerobic
respiration) can work in close cooperation to degrade isotactic PP films (PPi).
The evidence that biodegradation occurred was increasing concentrations of
product removed with methylene chloride (a solvent suitable for removing
nonpolar products and slightly polar residues from polymeric structures) and a
45% loss of PPi mass after 175 days of incubation with different micro-
organisms, glucose, and starch PE [18]. Conventional sources of carbon
(carbohydrates, starch, and organic acids) support microbial growth and help
in the process of degradation, especially under anaerobic conditions [19].
Morancho et al. [20] studied biodegradability in soil PP films mixed with
starch compounds (50% ethylene vinyl alcohol (EVOH)/50% starch) by
differential scanning calorimetry (DSC) and thermogravimetric analysis
(TGA) after exposure to ultraviolet radiation and compared samples with and
without exposure to UV. They observed changes in crystallinity and the
crystallization kinetics using the Avrami equation. The process of
photodegradation decreased crystallinity, which increased biodegradation in
the soil after various degradation times (up to 6 months). The PP thermal
stability decreased after irradiation and increased ground, as observed by
TGA, in samples exposed for different times (20 days, 4 months, and 6
months).
Pandey and Singh [21] studied the extent of the effect of short-term photo-
irradiation on the biodegradability of PP, low-density PE (LDPE), and
ethylene-propylene copolymers. They concluded that the carbonyl and
hydroxyl groups formed upon irradiation, indicated by the intrinsic viscosity
and chain scission, were more susceptible to biodegradation, especially PP, as
indicated by the weight loss of the incubated samples at different exposure
times (up to 6 months). The photo-oxidation is a precursor to bioassimilation.
Kaczmarek et al. [22] studied the aging of PP with the addition of 5-30%
cellulose after UV irradiation and aging garden soil for 6 months, taken at
intervals of 30 days, and the samples were evaluated by electron microscopy

(SEM), infrared Fourier transform attenuated total reflectance (ATR-FTIR),

and their mechanical properties (PM). The SEM observations in the irradiated
and aged samples of soil revealed that no changes occurred on the PP surface;
however, cracks and depressions formed in the compositions formed by
removing PP cellulose. Samples with pre-irradiation prior to aging in soil were
measured by ATR-FTIR and revealed the formation of carbonyl groups
favoring (bio) fragmentation.
Alariqi et al. [23] studied the effect of biomedical γ-sterilization on the
biodegradation of high density PE (HDPE), PP, and ethylene propylene
copolymer (EP) in composting and culture microorganisms. The increases in
carbonyl and hydroxyl indices were observed by FTIR after exposure to
different doses of ɣ-sterilization. Overall, there was a decrease in intrinsic
viscosity due to the increase of the breakup of the chains after exposure to
different doses of ɣ-sterilization and incubation times in the compound. PP
was more susceptible to microbial attack than the other materials tested, and
the degradation and biodegradation of the EP depends on the composition and
distribution of the monomers in the polymer chain. The ɣ-sterilization
pretreatment may accelerate the biotic biodegradation in the environment.
DEGRADATION OF POLYPROPYLENE
PP is a thermoplastic material obtained from propylene monomers. The
most commonly used catalysts in PP polymerization produce a semi-
crystalline polymer. The byproduct of this synthesis is characterized by a
smaller crystallization, which gives the material a set of properties that are not
usable in commonly injected and extruded products, but a soft product used in
the sealing and adhesives industry. The above-mentioned products are called
isotactic PP (iPP), atactic PP, and crystallizable aPP. The two major
occurrences of PP are due to geometrically asymmetric monomer, which
enables different spatial distributions of the same polymer, a property called
tacticity [24].
Suzuki at al. [25, 26] investigated and quantified the effect of tacticity on
PP thermal autoxidation by TGA and activation energy (Ea). They concluded
that the smallest fraction pentane meso (mmm) - measured as obtained from
nuclear magnetic resonance (NMR) that quantifies the tacticity disorder -
increases the thermal stability of PP in reference to the PP syndiotactic (PPs),
where mmm = 0. The change competition between the unimolecular and
bimolecular decomposition of hydroperoxides, provided by the helical

conformation (molecular dynamics), was suggested as a factor in the thermal

stability of PP [25, 26]. Nakatami [26] showed that the unimolecular
decomposition of POOH predominates, which takes more energy than the
bimolecular mechanism. He et al. [27] compared the thermal stability of iPP
with the syndiotactic PP (PPs) using FTIR, TGA, DSC, and kinetic parameters
(activation energy), and concluded that, due to the high flexibility of the PPs
chain, the PPs thermal stability is much higher than that of iPP.
Hoyos et al. [27] investigated the effect of microstructure on iPP thermo-
oxidation via C13-NMR of the solid ethylene-propylene copolymer; they
discovered a reduction of the activation energy and thermal stability of the
copolymerized PP produced from 30 iPP units that was associated with short
interruption.
At this time, after the reported dependence of PP autoxidation on PP’s
configuration and microstructure, one can relate the architecture of the PP
structure of interest to the performance and (bio) degradation. The lower
tacticity disorder favors crystallization and specific thermal and mechanical
properties are dependent on this microstructure, thus achieving the higher
softening temperature required in the performance of long-life products,
although this increases the consumption of antioxidants, based on the reported
results; on the other hand, this increases the time for biodegradation and
therefore increases waste. Therefore, there is a conflict of interest between
service and waste performance. Currently, part of the energy content of the PP
stored in the crystalline order and antioxidants is forwarded without a distinct
market application, which leads us to conclude that the energy content of PP in
disposable products is above performance requested product.
PP degrades very similarly to PE [28] (Figure 4), but due to the presence
of lateral methyl groups on the chains (tertiary carbon), the transfer of the
intramolecular hydrogen is more likely in the PP degradation than for PE [28,
29]. The removal of the hydrogen atom can occur from direct attack of
molecular oxygen or by decomposition of the peroxides and hydroperoxides
present in the polymer formed during synthesis, storage, or processing [30].
According to Agnelli [30], the practical stabilization of PP can be
described from the thermo-oxidation and photo-oxidation in the molten state
and solid, respectively. The most important aspects that differentiate the two
processes are:

 Above the polymer melting temperature, the mobility of the radicals

produced in the different steps involved in the thermo-oxidation is
high enough to reduce the probability of recombination and thus the
above cycle, in Figure 4, can be repeated many times until
termination;
 Increased autocatalytic photo-oxidation (since hydroperoxides,
responsible for this characteristic, are the results of the synthesis step,
storage, and processing) and the lowest number of cycles of the
formed radicals to the terminator, since the solid mobility of these
radicals is much smaller and therefore the probability of
recombination is higher;
 Heterogeneity of the degree of oxidation that occurs in semi-
crystalline polymers, such as PP. In the solid state, these processes
occur in highly reactive sites on amorphous regions of the polymer,
since the molecular oxygen diffusion coefficient is low in the
crystalline regions.
Figure 4. General representation of polyolefin degradation, and PH is a polyolefin and

P· an alkyl macroradical.

DEGRADATION OF POLYMER MIXTURES

According to the International Union of Pure and Applied Chemistry
(IUPAC), the blend is "a homogeneous mixture of two or more different
species of polymer." Generally, blends produce different properties of the pure
materials. In this work, although they use a mixture of different polymer
techniques, the term blend is not used for mixtures of PP with polyacetal,
because the purpose of increasing the performance in service, and therefore the
longevity of the material, is not pursued so directly.
Commercially, mixtures are prepared by a mechanical process in the
extruder; however, the investigation of degradation mechanisms and stability
of mixtures did not follow during development due to the large number of
variables involved in the process and because it was often difficult to control
the preparation conditions, composition of the mixture, additives, and
environmental exposure.
What can be said with some certainty is that the component degradation
products in the mixture, which degrades at temperatures lower than the mixing
process temperature, will accelerate the degradation of another component.
According to De Paoli [29], the start of degradation by thermal and
chemical processes can be summarized in three forms, specifically the
interaction effects between the components of a blend, in relation to the
degradation reactions:
 Migration of molecules or low molecular weight free radicals of a

blend component to another blend component;
 Migration of additives or their breakdown products of a blend
component to another blend component;
 Power of a state transfer (electronic or vibrational) located in a
chemical group of one of the blend components to a state (electronic
or vibrational) of a chemical group located in another component of
the blend.
The three forms can occur in isolation, in stages, or simultaneously,

depending on the variables already mentioned; however, the action of the
degradation products will strongly depend on the level of miscibility of the
blend components. In the miscible region, migration of degradation products is
direct, whereas in blends with phase formation, migration depends on the
surface / volume ratio of the formed domains.

Waldman and De Paoli [31] reported the thermomechanical degradation of

iPP and LDPE and the effect of specific degradation processes of each
polymer in the 1:1 mixture of the polymers, mixed using a double co-rotating
twin-screw extruder coupled to a torque rheometer. The products were
characterized by FTIR and TGA under inert and oxidative atmospheres. LDPE
showed three to four times the carbonyl content of PPi processing conditions
used in preparing the mixtures. The main reason for this difference was the
addition of stabilizers to PPi by the producer before granulation. The mixture
with LDPE stabilizes PPi, even at temperatures above their melting point.
Miyazaki and Nakatani [32] prepared a blend of PP with poly (ethylene
oxide) (PEO) in the form of a microcapsule containing TiO2, in order to induce
PP photodegradation from the water by PEO adsorption. TiO2 encapsulated by
PEO undergoes photodegradation and catalyzes the formation of OH from
water adsorbed on PEO, i.e., it becomes a pro-oxidant. The acidic compounds
and aldehydes are formed from the degradation of PEO, promoting the
decomposition of hydroperoxides present in the PP. The additive effect of the
microcapsule on the PP degradation rate was assessed by FTIR, the tensile
test, and optical microscopy. In addition, a control on the rate of degradation
was investigated by Hindered Amine Light Stabilizers (HALSs) and a
phenolic antioxidant. The researchers concluded that the PEO/TiO2
microcapsule facilitated PP degradation. Furthermore, the addition of HALSs
retarded the degradation of PP initiated by the microcapsule, although the
retarding effect was increased by the simultaneous addition of the phenolic
antioxidant in the initial stage of PP degradation. However, simultaneous
addition otherwise showed effects after 4 h of degradation.
POLYACETAL DEGRADATION
Polyacetal or polyoxymethylene (POM) is an important engineering
plastic characterized by the chain formed by alternating carbons and oxygens,
that is, it consists of oxymethylene units (OCH2). POM offers an excellent
balance of high strength and stiffness, as well as good chemical resistance.
While POM has desirable properties, it is inherently unstable and undergoes
thermal degradation with the prompt release of formaldehyde. To reduce the
tendency toward thermal degradation, a copolymerization approach with
occasional incorporation of C-C bonds in the main chain was developed. For
additional stability, commercial PMS copolymers are heat-treated to modify
the end of an unstable hemiformal group (OOCH2OH) to a stable ether

hydroxyethyl (OCH2CH2OH), and some necessary additives, such as thermal

stabilizers, are also in use to ensure greater stabilization [33].
Cottin et al. [34] studied the mechanisms involved in POM
photodegradation in wavelengths emitted at 122, 147, and 193 nm. The
researchers were motivated to investigate the quantitative determination of
photochemical degradation due to the presence of organic molecules present in
comets, and formaldehyde (H2CO), one detected in Halley’s Comet. The
identification of the major degradation products of gaseous PMS by
photodegradation in the absence of molecular oxygen was obtained by
production quantum yields. The products were H2CO (formaldehyde), CO
(carbon monoxide), HCOOH (formic acid), CO2 (carbon dioxide), CH3 OH
(methanol), CH3OCHO (methyl formate), and C3H6O3 (trioxane). The
estimated production was higher amounts of formaldehyde (Ф122 nm = 0.75 ±
0.21), Ф147 nm = 0.96 ± 0.19) and formic acid (Ф122 nm = 0.13 ± 0.05, Ф147
= 0.26 ± 0.10 nm). POM H2CO production by photodegradation is 37% of the
total weight loss of grain through this process; the remaining 63% contributes
to the production of CO, CO2, and HCOOH.
Archodoulaki et al. [35] investigated the thermo-oxidative stability of both
types of polyoxymethylene in various conditions of aging and oxidative
induction time (OIT). The results revealed that the proposed method is suitable
for the characterization of the use of POM stabilizers during thermal aging.
The OIT event is predominantly based on endothermic processes under
experimental conditions, which is in clear contrast to polyolefins. An
extrapolation of the OIT data at high temperatures (molten state) to room
temperature (solid) does not reflect the performance of an effective
antioxidant. Therefore, the measurements of crystalline melting temperature
(Tm) are representative for the solid state but unsuitable for reliable estimates
of lifetime.
Ping et al. [36] investigated the thermal aging rate for the POM melt index
test (IF) and tensile strength (RT) to determine a thermal decomposition
model. The surface morphology and type of POM surface chemical function
were observed and analyzed by SEM and X-ray photoelectron spectroscopy.
The value of the IF increased with aging time. After 120 days of aging, SEM
identified cracks that were dispersed in the POM surface; 20 days of aging did
not significantly alter the tensile strength. The oxygen content in the surface
POM increased by 16% after heat aging and oxidative aging mainly consists of
the C-C bond breaking.

DEGRADATION WITH PRO-OXIDANT

The pro-oxidation inhibiting polymer consists of antioxidant systems and
the creation of reactive oxygen species by the presence of oxygen and
transition metals, such as iron (Fe), cobalt (Co), and nickel (Ni). Oxygen has
two unshared electrons on the last layer, and therefore it is expected that
oxygen reacts spontaneously and rapidly with any free radical that is present,
forming a peroxyl radical.
The release cations of the transition metals can initiate oxidative
degradation reactions in two ways [37], oxidation (1) and reduction (2):
Mn+ + O2 PH → [Mn+1 + (OOH-)]n+ + P. (1)
Mn+1 + PH → P + H+ + Mn+ (2)
Hydroperoxide decomposition, oxidation (3), and reduction (4):
POOH + Mn+ → PO + [Mn+1 + (OH-)]n+ + R (3)
POOH + Mn+1 → POOH + Mn + H+ (4)
Oxo-biodegradable plastic consists of a polymer containing an additive

(pro-oxidant) that accelerates their oxidative degradation in the presence of
light or heat. The products additivated with pro-oxidant are "grounded" on the
following principles:
 The life of control or use of the material can vary from a few months
to several years, depending on the additive formulation;
 The resulting products of the degradation of polyolefins are
biodegradable;
 The combination of abiotic oxidation and biodegradation determines
the time of storage and use of the product;
 The by-products arising from the abiotic and biotic degradation must
be nontoxic.
Although the additivated polymer with pro-oxidant "stipulates" control of

the abiotic degradation of plastics, these materials cannot be regarded as

functional materials, since the control of degradation is dependent on external

parameters (the environment) unrelated to human control.
Muthukumar and co-workers [38] investigated the degradation percentage
of HDPE films and PP mixed with starch and pro-oxidant that were exposed to
three different environments: soil, underwater, and direct sunlight.
Degradation was measured by counting colonies in films, weight loss, TGA,
contact angle measurement, SEM, FTIR, and X-ray fluorescence. The most
relevant results showed a greater degradation of PP mixed with starch under
direct light exposure (mass loss of 10% in 60 days of exposure), compared to
PP/HDPE mixed with pro-oxidant. There was a direct correlation between
reductions of the contact angle with weight loss, indicating a quality criterion
in the evaluation of degradation.
Pablos et al. [39] studied the effects of metal and calcium stearate in
LDPE and linear LDPE (LLDPE) under natural and artificial exposure. The
stearate activity was evaluated by chemiluminescence (CL) and FTIR. Gas
chromatography-mass spectrometry (GC-MS) determined changes in
molecular weight and degradation product content. We observed the
decomposition of hydroperoxides with the incorporation of the stearate-Fe
complex CL shown. For the samples containing calcium stearate (Ca-East), we
observed a shift of the peak peroxides to a lower temperature, which
corroborates the TGA results. The degraded samples in an artificial
environment followed the same trend described for samples exposed to the
natural environment. The concentrations of the products taken and identified
by GC-MS, as well as the reduction of the molar mass, was more significant in
PEs containing the Fe-stearate complex than PE containing the Ca-stearate and
pure PE, respectively.
Burman and Albertsson [40] evaluated the stabilizing effect of different
antioxidants on low-temperature polymers. In a relatively short time, the
evaluation was performed using the incorporation of pro-oxidants for catalytic
oxidation. Comparisons were made between PP films stabilized with primary
antioxidants, with and without manganese stearate (pro-oxidant), at different
temperatures. At the end of the aging time, the amount of residual antioxidant
was removed by microwave-assisted extraction (MAE). It was concluded that
in less time, it is possible to compare the efficiency of the primary antioxidant
in PP films, when the films containing such a pro-oxidant catalyst were aged at
40°C. Moreover, a better correlation was obtained in the consumption of
antioxidants and hydroperoxide accumulation, compared with the traditional
accelerated test, at 120-150°C.

CONTROLLED DEGRADATION
The controlled degradation of PP is a post-reactor method used for the
production of resins with predetermined properties [41, 42]. This method,
which can also be termed reactive extrusion, describes a special process in
extrusion technology in which the individual components participate in
chemical reactions within the extruder: polymerization reactions, grafting,
compatibility, and rheology control can be conducted by reactive extrusion.
In this method, PP and organic peroxide are fed to an extruder (mono-
screw or twin-screw) in which the degradation reaction occurs, giving a
product with low molar mass and a narrow molar mass distribution known as
PP with controlled rheology [41].
According to Janssen [43], a good understanding of the factors that
determine the stability of the reactive extrusion process is important to control
the reaction. The most important factor in the instability is the change in the
length of the screw and the barrel of the extruder, indicating a complex
interaction involving the residence time, conversion, and viscosity of the
materials. Other thermal or chemical origin factors also influence these
interactions as well, including the inherent characteristics of the materials,
such as molar mass, molar mass distribution, and concentration of additives.
The melt flow index (MFI) is a characterization method that can be used
to evaluate the controlled degradation process of PP by reactive extrusion;
however, correlating this parameter with the polymer properties must be done
carefully, because the MFI is affected by a large number of variables [44].
EXPERIMENTAL METHODS
Materials
The iPP H603 (density 0.905 g.cm-3 and MFI 1.5 g.10 min-1) was used in
granulated form, as supplied by Braskem (Triunfo/RS, Brazil). Polyacetal
copolymer (density 1.41 g.cm-3 and MFI of 14.0 g.10 min-1) was used in
powder form, as supplied by Ticona (São Paulo/SP, Brazil). The pro-oxidant
additive brand d2w® was supplied by RES Brazil (Valinhos/SP, Brazil).

Preparation and Characterization of Compositions
POM and d2w® were incorporated into PP by mixing the compounds

together in a kinetic type K-mixer (model MH-100, MH Equipment Ltda.,
Guarulhos, SP, Brazil). Table 1 summarizes the PP/POM and PP/d2w® blends
used in this investigation. The blends were prepared in a single-screw extruder
that consisted of a 25-mm-diameter screw heating cylinder with an L/D ratio
of 25:1 and four metal screens in series (one 60 mesh, one 100 mesh, and two
150 mesh) to maximize homogenization. The extrusion conditions were 220
°C, 250 °C, and 250 °C for the first, second, and third zones, respectively, to
wire and die (exit orifice  = 3 mm). The screw rotation speed was 66 rpm (28
Hz) and the handle/shredder was operated at 720 rpm (240 Hz). The materials
were extruded once only.
Table 1. The polymer/additive blends used in this study
Code Polypropylene * Polyacetal* d2w* Total mass/g

PP1 100 0 0 2000
PP2 100 1 0 2020
PP3 100 0 1 2020
PP4 100 2 0 2040
PP5 100 0 2 2040
PP6 100 3 0 2060
PP7 100 0 3 2060
PP8 100 10 0 2200
* Amount expressed in pph/part per hundred 100 pph = 2,000 g
Thermogravimetric Analysis (TGA) and Activation Energy (Ea)
TGA was performed on TGA equipment (TA Instruments) in a nitrogen

atmosphere at a heating rate of 5 °C min-1, 10 °C min-1, 20 °C min-1, and 40 °C
min-1 over a temperature range of 25-550 °C. The nitrogen flow was 50 ml
min-1. The average mass of sample used was 10.0 ± 0.1 mg. The results were
used to calculate the change in activation energy (Ea) as described in ASTM
E1641 [45].

OIT
The OIT was determined in a universal V4.OC (TA Instruments,

Campinas, SP, Brazil) using ~10 mg of sample, under the following
experimental conditions: nitrogen flow = 50 ml min-1, heating rate = 20 °C
min-1, oxygen flow = 50 ml min-1, and temperature switching from nitrogen to
oxygen at 200°C.
Nuclear Magnetic Resonance (NMR)
For NMR, the ultra-23 MARAN equipment manufactured by Oxford

Instruments was used. The application of low magnetic field was measured
and the 0.54T time longitudinal spin-lattice relaxation of hydrogen was
determined directly by traditional pulse inversion recovery sequence (180° - τ
- 90°) and 90° pulse 7.6 µs, calibrated automatically by the instrument
software. The time interval between pulses range (τ) was 100-5e6 μs and the
waiting time of each measurement was 1s. The number of scans for each
measure was 4 scans, repeated twice for each sample, at 28°C. The distribution
of longitudinal relaxation domains were obtained ranging from 0.1 to 10000
ms (T1H). The relaxation values and intensities were obtained by adjusting the
exponential data with the help of the program.
RESULTS AND DISCUSSION
TGA
Thermogravimetry (TG) is a thermal analysis method in which the weight

loss of a sample subjected to a controlled temperature program is measured.
Figure 5 shows the thermogravimetric curves for pure PP, POM, and d2w®.
There were differences in the relative thermal stabilities of POM and d2w®
compared to PP. POM had the lowest thermal stability of the materials, while
d2w® showed the greatest stability, but only after losing about 10% of its mass;
the latter finding indicated that one component of d2w® underwent thermal
degradation. Although this analysis considered only the early products of
degradation, the results nevertheless indicate that POM had a lower thermal
stability than PP at all stages of degradation.

Figure 5. Thermogravimetric curves of pure PP, POM, and d2w®.
The kinetics of the thermal decomposition of carbonaceous materials is

complex and the decomposition of these materials involves a large number of
reactions in parallel and in series. TGA provides general information that can
elucidate the kinetics of the overall reaction instead of individual reactions;
TGA can be used as a tool to compare the kinetic data of various reaction
parameters, such as temperature and heating rate.
According to De Paoli [29], the polymer blend degradation evaluation can
have two different behaviors: additive or non-additive. In additive degradation,
if the mass loss of the components were added in proportion to its
concentration in the mixture, then the mass loss curve will be the weighted
average of the weight loss curves of the mixture components, i.e., the thermal
decomposition process of a component does not affect the thermal
decomposition of the other. Thus, in non-additive degradation, the mass loss
curve’s behavior does not correspond to the weighted average of the weight
loss curves of the components, showing interactions between the thermal
degradation processes of the blend components that may be synergistic or
antagonistic.

Figure 6 shows the change in mass as a function of temperature for blend

PP8 and for the pure materials (PP1 and POM); a theoretical curve calculated
curve calculated based on the weighted average of the experimental curves of
the pure materials (PP and POM) is also shown. The region of the curve for
blend PP8 close to the experimental curve of pure PP (PP1) may reflect a
greater stabilizing effect of PP. The stabilizing effect decreases as the loss of
mass increases and the theoretical curve approximates the observed curve,
probably because of competition with degradation reactions. The region
beyond the point where the theoretical and observed curves cross corresponds
to additional degradation by shifting the equilibrium of the degradation
reactions of the matrix phase (PP) induced by the dispersed phase (POM).
Figure 6. Experimental curves for changes in mass versus time for blend PP8 and pure
materials (PP and POM). The theoretical (calculated) for blend PP8 is also shown.
Activation Energy (Ea)
Predicting the lifetime of polymeric materials depends on the conditions

they are submitted to, and when thinking of thermal degradation, thermal
aging due to exposure in the use of the material is an extremely important tool.

The time to failure or degradation rate is determined by measuring at high

temperatures (when compared with the usage conditions) and the data are used
to extrapolate the performance of the material at room temperature; the most
important methodology for these extrapolations is based on the Arrhenius
relationship.
Extrapolations of Arrhenius consider that a chemical degradation process
is controlled by a reaction rate (k) proportional to the exponential (-Ea/RT),
where Ea is the Arrhenius activation energy, R is the gas constant
(8.314 J.K-1.mol-1), T is the absolute temperature, and A is the pre-exponential
factor (Eq. 1). Consequently, the logarithm of the reaction rate (k) or
degradation times (1/k) versus the reciprocal of temperature (1/T) should yield
a straight line and allow simple extrapolations (Figure 7). This can be
expressed as:
d 2W
PP
1,6 POM
Log Heating Rate (K/min)
1,4
1,2
1,0
0,8
0,6
1,45 1,50 1,55 1,60 1,65 1,70 1,75 1,80 1,85 1,90 1,95
1000/Temperature (K)
a) Pure materials
Figure 7. (Continued)

PP2
1,6 PP4
PP6
PP8
1,4
1,2
1,0
0,8
0,6
1,45 1,50 1,55 1,60 1,65
b) Blends of PP/POM
PP3
PP5
1,6 PP7
1,4
1,2
1,0
0,8
0,6
1,44 1,46 1,48 1,50 1,52 1,54 1,56 1,58 1,60
c) Blends of PP/d2w®
Figure 7. Arrhenius plots for pure materials and their blends.

The Ea values for the pure materials and their blends are shown in Table 2
and Figure 8. As can be seen, d2w® and POM had opposite effects on the Ea of
PP as a function of their concentration; the high Ea resulted in a relatively
small diffusion coefficient [46]. The low mobility of elements of d2w®
attached to a polymeric carrier probably contributed to the rise in Ea as the
concentration of additive increased. For PP/POM blends, the formation of
volatile low molecular weight products derived primarily from formaldehyde
could explain the decrease in Ea with increasing POM concentration. Previous
studies have shown that the propagation of high-temperature oxidation in
stabilized PP occurs via the gas phase [47, 48, 49]. Although other products,
such as water, ethylene, isobutylene, and acetic acid, are formed during the
degradation of PP, formaldehyde is the product most likely to be involved in
the propagation of oxidation by the gas phase in stabilized PP [47]. This
conclusion agrees with the marked decrease in the Ea for PP8 shown in Figure
6. A synergistic effect on degradation was suggested by the fact that the Ea of
PP8 was lower than that for POM alone.
180 180
Activation energy (kJ.mol )
-1
160 160
140 140
PP
120 120
d2w
100 100
Pure materials
80 PP/POM 80
PP/d2W
POM
60 60
PP2 PP3 PP4 PP5 PP6 PP7 PP8 PP1 POM d2W --
Blends and pure materials
Figure 8. Energy of activation (Ea) for pure materials (PP, POM, and d2w®) and blends
of PP/POM and PP/d2w®.

Table 2. Activation energy (Ea) and correlation coefficients for pure

materials and blends
Blends PP2 PP3 PP4 PP5 PP6 PP7 PP8

Ea (kJ.mol-1) 152,6 110,3 145,5 175,9 128,8 182,8 58,2
r -0.985 - 0.750 - 0.831 -0.996 -0.958 -0.985 -0.988
Pure materials PP POM d2w®
Ea (kJ.mol-1) 123,4 66,6 110,9
r -0,937 -0,880 -0,995
OIT
The OIT is an accelerated aging test that allows the comparison of the
relative resistance of materials to thermal oxidation. Table 3 and Figure 9
provide the OIT values for the pure materials and blends studied. The additive
d2w® accelerated the oxidation of PP in the presence of oxygen; however,
there was little change in the OIT values of the blends containing different
amounts of d2w® (PP3, PP5, and PP7), i.e., the OIT values essentially reflected
the amount of pure additive (d2w®) present in the mixtures. This finding
indicates that there is little margin for controlling the thermo-oxidation of PP
during processing, since all samples were processed under the same condition.
In addition, changes in morphology arising from processing interfere with the
diffusion of volatile degradation products. In PP/POM blends, there was a
marked decrease in the OIT values from blend PP6 onwards. In contrast, there
was an increase in the OIT values of blends PP2 and PP4, i.e., a stabilizing
(antioxidant) effect. The OIT and TGA results indicated that d2w®
concentrations ≥2% increased the thermal stability of the blends. In the case of
POM, there was a decrease in the stabilizing synergistic effect at
concentrations up to 3%; at higher concentrations, POM had an oxidizing
effect on PP.
The oxidation of a polymer involves a complex chain of reactions that
involves many steps, such that the overall Ea is the sum of the energies of
activation of individual stages. In this chain of reactions, there may be
temperature ranges in which deviations from Arrhenius’ law can be neglected,
e.g., with blends PP2 and PP4. The oxidation of PP (in powder form) has been
referred to as having non-homogeneous (heterogeneous) kinetics that are
characterized by chemiluminescence [50]. This oxidation is based on a model
containing small numbers of localized zones (amorphous regions) in which

oxidation occurs at a high rate and from where it spreads to other regions. The
presence of stabilizers retards the diffusion of volatile degradation products for
a short period of time, known as the induction period. Even using sensitive
techniques involving photon emission, such as chemiluminescence, the
investigation of this phenomenon over such a short timescale is a difficult task,
even though the Ea is higher in this period [51]. Several studies [52, 53, 54,
55] have shown that the decomposition of hydroperoxides in PP leads to the
formation of volatile products and that water is a major product of
degradation, but water does not interfere with the spread of oxidation. During
this period, generally only a decrease in polymer molecular mass is observed,
along with the formation of volatile, low molecular mass products. Eriksson
[47] suggested that following the formation of peracids by the oxidation of
formaldehyde, the spreading of oxidation is favored by the gas phase and that
the relatively low reactivity of formaldehyde allows greater diffusion to more
distant regions.
6 6
Oxidation induction time (min)
PP
5 5
4,55
4 4
3 Pure materials 3
PP/d2W
PP/POM
2 2
1 d2W 1
1,27
0 0
PP2 PP3 PP4 PP5 PP6 PP7 PP8 PP1 d2W
Blends
Figure 9. Oxidation induction time for pure materials and blends.

Table 3. Oxidation induction time for pure materials and blends
Pure materials and blends

PP 1 PP 2 PP 3 PP 4 PP 5 PP 6 PP 7 PP 8 d2w® POM
Time (min) 4.55 5.47 1.09 5.58 1.04 4.52 1.03 1.67 1.27 <1
Controlled Degradation of PP/POM
For this study, we can suggest the combination and coexistence of two
autoxidation reactions in PP from the formaldehyde-released peracid
formation in POM degradation (Figure 10):
a) In low POM concentrations (<3%), the terminal PP oxidation reaction

is predominant, combining the peracid formed in the radical decomposition of
formaldehyde with the PP macroradical.
b) In POM concentrations > 3%, the PP propagation oxidation reaction is
favored with increasing concentration of peracid.
PP Oxidation Degradation Formaldehyde
Initiation
Propagation
Termination
a) reaction proposed <3% of POM in PP
Reaction PP termination oxidation with formaldehyde reaction product

b) reaction proposed >3% of POM in PP
Reaction PP propagation oxidation with formaldehyde reaction product
Figure 10. Proposal reactions of POM/PP in different concentrations.

NMR
The time of spin-lattice relaxation or longitudinal time constant (T1)

occurs along the Z axis (magnetic field direction) by releasing heat energy.
This, in general, occurs due to the interaction between the cores of interest and
not-excited nuclei in the middle as well, with electric fields in the environment
(referred generically as a "network"). Therefore, T1 is measured as the time
required for the magnetization vector M to retrieve a value equal to 63% of its
initial magnitude; its value varies with the magnetic field density. The average
time T1(1H) is an average value of all the relaxation times of the protons in the
sample, including many that are in the amorphous phase or the rigid crystalline
phase. The values of T1(1H) of PP1 (neat PP) and compositions are shown in
Table 4. Figures 11 and 12 show the distribution curve domains of T1 values
(1H), comparing PP1 and PP3 compositions with PP8, respectively. The areas of
the distribution curves are the breakdown of T1 relaxation times (1H), showing
the organization of the array. The domain is a region where the chains are
organized in a characteristic way. Areas in less time (X axis) are regions of
greater molecular mobility (relax faster). Areas in longer times are regions of
greater stiffness (relax more slowly); closer base relaxation time domain
curves indicate a smaller number of different conformations (more
homogeneous material), whereas broader bases indicate a greater number of
different conformations (more heterogeneous materials).
Table 4. Average time (T1 (1H)) of longitudinal relaxation
Code T1(1H) (µs)

PP1 263
PP2 261
PP3 252
PP5 258
PP6 264
PP7 263
PP8 251
It is observed in Figure 11 that the relaxation time of the domain PP3 has a
smaller amplitude than pure PP and little modification order of the areas of
greatest amplitude. Most likely there was a decrease in the "connections"
between regions of different relaxation times (for example, amorphous and
crystalline regions). There has also been a narrowing of the curves with less
relaxation time, indicating increasing order (recrystallization) of these regions

after acquiring greater mobility, caused by the additive d2w®. In Figure 12,
there is an enlargement of the bases of the different areas and small reductions
of the relaxation time in areas of lesser amplitude. The chemical modifications
of the chains caused by incorporating PP/POM increased the mobility of the
chains in the areas of lesser extent and areas where different relaxation times
interface (amorphous and crystalline). The oxidative degradation of the PP
process incorporating the agent d2w® evolves to the formation of new areas
arranged in the structure of the PP, while the oxidation process with the
incorporation of POM leads to increased structural disorder, thus allowing the
diffusion of new agents’ decomposition during the life cycle of the PP.
100 PP1
PP3
Amplitude normalizada (M/M 0)
80
60
40
20
1 2 3 4 5 6 7 8
Tempo (ua)
Figure 11. Overlapping distribution curves of PP1 and PP3.
100
PP1
Amplitude normalizada (M/M 0)
80 PP8
60
40
20
1 2 3 4 5 6 7 8
Tempo (ua)
Figure 12. Overlapping distribution curves of PP1 and PP8.

CONCLUSION
The two "additives" (POM and d2w®) promoted the oxidative thermal
degradation of PP, and the POM presented controllable degradative induction
behavior through its concentration in PP. POM concentrations below 3% (by
weight of the POM) can enhance the thermal stability of the PP in the
conditions investigated; however, POM concentrations above 3% caused
oxidation of the PP, and the synergistic effect of degradation can be
maximized by increasing the miscibility of PP/POM in the interface region.
The oxidative degradation of the PP process incorporating the agent d2w®
evolves to the formation of new areas arranged in the structure of the PP,
while the oxidation process with the incorporation of POM leads to increased
structural disorder, thus allowing the diffusion of new agents’ decomposition
during the life cycle of the PP.
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Chapter 6
LIGNOCELLULOSIC BIOMASSES,
SUSTAINABLE PLATFORM FOR BIO-BASED
MATERIALS WITH POLYPROPYLENE
Tri-Dung Ngo1, and Thoi Ho2

*
1
Biomass Conversion and Processing Technologies,
Alberta Innovates-Technology Futures, Edmonton, Alberta, Canada
2Polymers Product Development TS&D, Flint Hills Resources,
LP, Longview, TX, US
ABSTRACT
Lignocellulosic biomasses are becoming very interesting for bio-
based materials development when they possess the advantages of their
environmental benefits, and renewability. Wood fibers have been used as
reinforcement for polymers for many years, the annual plant fibers
obtained from different sources, such as wheat, triticale, rice husk, sisal,
jute, coconut, hemp and flax, have good potential as a source of low-cost
reinforcements for polymers. Lignin is considered a natural polyol and
polyphenol in plant stem and the second most abundant natural polymers
coming only next to cellulose. Lignin is also an attractive biomass since it
is readily available and relatively inexpensive. Recently, nanotechnology
*
Corresponding Author address: Biomass Conversion and Processing Technologies, Alberta
Innovates-Technology Futures, 250 Karl Clark Road, Edmonton, Alberta, Canada T6N 1E4.
Email: tridung.ngo@albertainnovates.ca.

176 Tri-Dung Ngo and Thoi Ho
is helping improve products that we use every day and creating new,
exciting products for the future. To completely change the forest product
industry through nanotechnology, top-down approaches from bulk
cellulose have been used to generate cellulose at nanoscale
(nanocellulose) such as cellulose nanocrystals and cellulose nanofibrils.
As the demand for “green” materials and products is growing, the use of
renewable resources and recycled materials prove to be great attractions.
Thermoplastic biocomposites have appeared as low cost, light materials
for different applications, and have attracted much interest. Among the
thermoplastic, Polypropylene (PP) is used in various applications
including packaging, laboratory equipment, automotive component, etc.
This chapter addresses the potential utilization of different lignocellulosic
biomasses for the development of green materials based on PP, with the
objective to elucidate the possibility of using the bio based materials for
various industrial applications.
Keywords: green-product, biocomposite, lignocellulosic biomass,

polypropylene
INTRODUCTION
Applications of renewable and bio-degradable sources for preparation of
higher valued green chemicals and bio-based products have forced many
scientists to investigate the potential of utilization biomass for green bio-
materials. The global imperative to meet the challenges of environmental
destabilization begins with a recognition that human well-being depends on
the environment and adopting sustainable systems. The considerable
awareness to preserve environment, great efforts across the globe have been
pushed for the research of renewable and bio-degradable sources of material
available on the earth. Bio-products are a wide range of industrial and
consumer products that penetrate many sectors of the economy.
Lignocellulosic biomass and biomass derived materials have been pointed out
to be one of the most promising alternatives. These materials are generated
from available atmospheric CO2, water and sunlight through biological
photosynthesis [1, 2]. Environmental legislation as well as consumer demand
in many countries is increasing the pressure on manufacturers of materials and
end-products to consider the environmental impact of their products at all
stages of their life cycle, including recycling and ultimate disposal. Therefore,
lignocellulosic biomass has been considered to be the only sustainable source

Lignocellulosic Biomasses, Sustainable Platform … 177
of organic carbon in earth and the perfect equivalent to petroleum for the
production of fuels and fine chemicals with net zero carbon emission.
The use of fillers and reinforcements, in thermoplastics like PP, is a well-
known approach in industry. There is a wide variety of fillers and
reinforcements used in polypropylene, like calcium carbonate, talc, mica or
wollastonite [3]. Owing to the high stiffness of wood, wood-based fillers can
be used to increase the Young’s modulus and strength of general-purpose
thermoplastics such as PP. In addition, wood is the most abundant biomass
resource and has attracted considerable attention as reinforcement and filler for
plastics [4]. Recently, lignocellulosic biomasses have become very interesting
for bio-based materials development when they possess the advantages of their
environmental benefits, and renewability. Preparation of bio-based products
from PP with different biomass components such as cellulosic fibers (flax,
hemp, sisal, etc.), nanocelluloses (cellulose nanocrystals, cellulose
nanofibrils), and lignin, etc. has been considered to have substantial
environmental and economic benefits. However, the formulation as well as the
biomass sources including its form and interaction with other components in
the materials plays important roles to the performance of the bio-based
products. Much work is still needed to fully realize potentials of the biomasses
in production of bio-based materials, especially for enhancing their
performance. This chapter seeks to provide an overview of the science and
technology in relation to the potential of PP and lignocellulosic biomass
utilization for preparation of bio-based products, not just for the technical
challenges involved in material processing, and formulation, but also industrial
practice from the availability of such materials, and assess the environmental
benefits of the materials as well as the market forces impacting upon them.
SOURCES AND STRUCTURE OF

LIGNOCELLULOSIC BIOMASS
Lignocellulose refers to plant biomass. It is the most abundantly available
raw material on Earth. It is composed of carbohydrate polymers (cellulose and
hemicellulose) and an aromatic polymer (lignin) as illustrated in Figure 1. The
major component of lignocellulosic biomass is cellulose. Cellulose is the most
important and naturally abundant organic biopolymer in the biosphere. It is the
structural basis of plant cells produced from highly developed trees to

primitive organisms such as seaweeds, flagellates and bacteria. Cellulose is the

main constituent of wood (40-45%), cotton fiber (90%) and dried hemp (45%).
It is comprised of carbon, hydrogen, and oxygen bioengineered as a linear
homopolysaccharide chain with cellobiose as the repeating building blocks.
Each block is composed of two adjacent anhydro-glucose rings connected via
a β-1,4 glycosidic linkages as illustrated in Figure 2. This linkage motif
contrasts with that for α-1,4 glycosidic bonds present in starch, glycogen, and
other carbohydrates. Cellulose is a natural polymer, a long chain made by the
linking of sugar molecules that gives its remarkable strength. It is the main
component of plant cell walls, and the basic building block for many textiles
and for paper. The multiple hydroxyl groups on the glucose from one chain
form hydrogen bonds with oxygen atoms on the same or on a neighbor chain,
holding the chains firmly together side-by-side and forming microfibrils with
high tensile strength [5, 6].
Figure 1. Composition of the plant cell wall.

Figure 2. Schematic diagram of partial molecular structure of cellulose chain with

numbering for carbon atoms and n = number of cellobiose repeating unit.
Figure 3. Example for several forms of cellulose.

Cellulose is one of the most widely used natural substances and has
become one of the most important commercial raw materials. The major
sources of cellulose are plant fibers (cotton, hemp, flax, and jute are almost all
cellulose) and, of course, wood. Cellulose has no taste, is odorless, is
hydrophilic, is insoluble in water and most organic solvents, is chiral and is
biodegradable. Cellulose can be broken down chemically into its glucose units
by treating it with concentrated acids at high temperature. It is abundant and
renewable, and is therefore an almost inexhaustible raw material resource.
Cellulose is thus a potential replacement for many of the finite resources used
today. Cellulose and its derivatives can be found in many forms in nature and
is a valuable material for all manner of applications in industry. Cellulose is
found in both the crystalline and the non-crystalline structure. The coalescence
of several polymer chains leads to the formation of microfibrils, which in turn
are united to form fibers. In this way cellulose can obtain a crystalline
structure.
Cellulose fibers can be extracted from a wide variety of lignocellulosic
sources, such as bamboo, kenaf, banana, hemp, flax, sisal, pineapple, abaca,
oil palm, jute, kapok, etc. The principle of all methods to extract cellulose is to
remove the non-cellulosic components present in the fibers such as lignin,
hemicellulose and pectin as well as for the manufacture of fibers to produce
nanofibers. Many researchers studied the extraction of cellulose using
chemical, mechanical, chemo-mechanical treatments [7]. The retting process is
simplest extraction methods. It is a chemical process for removing non-
cellulosic material attached to fibers to release individual fiber. The fibers
have been used alone or in combination with other materials for various
applications. The main applications of cellulose fibers are in textile industry,
as chemical filter, and fiber-reinforcement composite, due to their similar
properties to engineered fibers, being another option for biocomposites and
polymer composites. Depending on the applications, cellulose fiber from
different lignocellulosic sources as well as forms of cellulose can be utilized.
Figure 3 shows examples of different cellulose forms including powder,
particle, short fiber, fiber mat, and fabric, etc.
Hemicellulose is the second most abundant polymer. Hemicellulose
belongs to a group of heterogeneous polysaccharides which are formed
through biosynthetic routes different from that of cellulose. Hemicellulose
found in the natural fibers is believed to be a compatibilizer between cellulose
and lignin. Hemicelluloses differ in composition too; hardwood hemicelluloses
contain mostly xylans, whereas softwood hemicelluloses contain mostly
glucomannans. Hemicellulose has a random and amorphous structure, which is

composed of several heteropolymers. The heteropolymers of hemicellulose are

composed of different 5- and 6-carbon monosaccharide units: pentoses
(xylose, arabinose), hexoses (mannose, glucose, galactose) and acetylated
sugars (Figure 4). Hemicelluloses are imbedded in the plant cell walls to form
a complex network of bonds that provide structural strength by linking
cellulose fibers into microfibrils and cross-linking with lignin [8].
Lignin is found in the cell walls of all vascular plants and can make up
between 20% and 40% of the content of these plants and acts as a water
transport system throughout the cell wall. Lignin is a large natural polymer
containing numerous aromatic moieties and plentiful hydroxyl groups,
extensively cross linked by ether bonds. It is the second most abundant
polymer on the planet after cellulose and the most abundant non-petroleum
source of aromatic compounds. Lignin has been known as a natural polyol and
also polyphenol in plant stem. Lignin also bonds plant cells together giving
plant stems rigidity and providing most of the material strength of the plant [9,
10, 11]. Lignin is an aromatic heteropolymer that is mainly deposited in the
walls of secondary-thickened cells. Lignin is an amorphous, highly branched
polyphenolic macromolecule of complex structure with high molecular
weight. The chemical structure of lignin polymer consists primarily of phenyl
propanoid units mainly p-coumaryl alcohol (H), coniferyl alcohol (G) and/or
sinapyl alcohol (S) as shown in Figure 5.
C5
Xylose Arabinose
C6
Glucose Mannose Galactose Rhamnose
Figure 4. Common C5 and C6 sugars found in Hemicellulose.

OCH3 CH3O OCH3
p-Coumaryl alcohol (H) Coniferyl alcohol (G) Sinapyl alcohol (S)
Figure 5. Chemical structure of lignin monomeric units.
Figure 6. Image of lignin powder.
The presence of lignin in the cell walls limits access to the cell wall
carbohydrates for enzymatic digestion by polysaccharidases. Therefore, there
is quite some interest in reducing the lignin amount in plants cell walls, or in
altering its composition such that the lignin polymer becomes easier to process
during biomass pretreatments. Lignin has historically been either burned for
energy or used as fillers in low margin, low value niche applications. There are
several types of lignin, defined by their sources (e.g., hardwood, softwood,
forestry, agriculture, etc.) and extraction processes (kraft, organosolv, soda,
steam explosion, etc.). They are lignosulfonate, kraft lignin, organosolv lignin,
hydrolysis lignin and alkali lignin. Lignin is an attractive biomass since it is
readily available and relatively inexpensive. Pulp and paper mills are
interested in creating applications development for their lignin waste as a
value added by product. Although lignin shows great promise as a starting
material for chemical synthesis, its heavily cross-linked nature makes it
difficult to process. Figure 6 shows the image of lignin powder.

Table 1. Types of lignocellulosic biomass and their chemical composition
Lignocellulosic biomass Cellulose (%) Hemicellulose (%) Lignin (%)

Wood fibers
Birch 41.0 32.0 22.0
Cedar 44.0 21.0 30.0
Douglas fir 44.0 11.0 27.0
Eucalyptus 54.1 18.4 21.5
Oak 40.4 35.9 24.1
Pine 42.0-50.0 24.0-29.0 20.0-28.0
Poplar 50.8-53.3 26.2-28.7 15.5-16.3
Spruce 45.5 22.9 27.9
Plant fibers, agricultural waste
Barley Hull 34.0 36.0 13.8-19.0
Barley Straw 36.0-43.0 24.0-33.0 6.3-9.8
Corn Cobs 33.7-41.2 31.9-36.0 6.1-15.9
Corn Stalks 35.0-39.6 16.8-35.0 7.0-18.4
Cotton 80.0-95.0 5.0-20.0 -
Flax 76.0 14.0 2.0
Hemp 63.0 10.0 6.0
Oat Straw 31.0-35.0 20.0-26.0 10.0-15.0
Ray Straw 36.2-47.0 19.0-24.5 9.9-24.0
Rice Husks 28.7-35.6 12.0-29.3 15.4-20.0
Rice Straw 29.2-34.7 23.0-25.9 17.0-19.0
Sugarcane Bagasse 25.0-45.0 28.0-32.0 15.0-25.0
Sorghum Straw 32.0-35.0 24.0-27.0 15.0-21.0
Wheat Straw 35.0-39.0 23.0-30.0 12.0-16.0
Grasses
Grasses 25.0-40.0 25.0-50.0 10.0-30.0
Switchgrass 35.0-40.0 25.0-30.0 15.0-20.0
Cellulose, hemicellulose and lignin are not uniformly distributed within

the cell walls. The structure and the quantity of these plant cell wall
components vary according to species, tissues and maturity of the plant cell
wall. Depending on the type of lignocellulosic biomass, these polymers are
organized into complex non-uniform three-dimensional structures to different
degrees and varying relative composition. Table 1 summarizes particular types
of lignocellulosic biomass and their chemical composition [12, 13, 14, 15, 16,
17, 18]. Nanotechnology is a rapidly evolving technology as science;
engineering and technology have merged to bring nanoscale materials that

much closer to reality. Nanofibers, nanotubes, nanoparticles, nanowhiskers,

nanoplates are examples of few substances that are within the nanoscale (less
than 100 nanometers) in at least one dimension [19, 20]. Nanotechnology is
helping improve products that we use every day and creating new, exciting
products for the future. To completely change the forest product industry
through nanotechnology, top-down approaches (chemical, physical, biological,
mechanical or combination of each of them) from bulk cellulose have been
used to generate cellulose at nanoscale such as cellulose nanocrystals (CNC)
or cellulose nanowhiskers (CNW) and cellulose nanofibrils (CNF). CNC and
CNF called nanocelluloses are typically processed as aqueous suspensions
because of their hydrophilic nature. The production and use of nanocellulose
such as cellulose CNC and CNF is an emerging technology that has gained
considerable interest from a range of industries that are working towards
greater utilization of bio-based materials. CNF and CNC are very attractive
because of their intriguing properties such as their high strength and stiffness
combined with low weight, biodegradability and renewability, low thermal
expansion, low toxicity and low cost. Depending on the process used, the
cellulose fibers then form into needle-like crystals (cellulose nanocrystals), or
a spaghetti-like structure of cellulose fibrils (Figure 7). Acid hydrolysis
process is often used to produce CNC and sulfuric acid hydrolysis is the most
well-known and efficient. By hydrolysis cellulose with concentrated acids, the
amorphous regions can be broken up, thereby producing nanocellulose
crystals. CNC are rod like pure cellulose crystals with 5-70 nm in diameters
and 100-300 nm in length. On the other hand, CNF can be prepared from
cellulose by using mechanical methods with or without cellulose pre-treatment.
CNF is composed of crystalline and amorphous regions with a high aspect
ratio (length to width). The diameters are 5-100 nm and the lengths are several
micrometers. Nanocellulose, unique and promising natural material extracted
from cellulose, has gained much attention for its use as biomaterial, because of
its remarkable physical properties, special surface chemistry and excellent
biological properties (biocompatibility, biodegradability and low toxicity). The
nanocellulose materials are being regarded as the next generation renewable
reinforcements for the production of high performance biocomposites.

Fibril Lignin,
Hemicellulose
Cell wall
Cellulose nanocrystal
Figure 7. Cellulose to nanocelluloses.
VALUABLE BIO-BASED MATERIALS FROM PP AND

LIGNOCELLULOSIC BIOMASS
Potential of Utilization of Lignocellulosic Biomass in PP
Over the last few years, great interest has been shown by researchers in
presenting alternative proposals for the design and fabrication of materials
with good mechanical properties and low cost for a variety of applications.
Materials based on lignocellulosic biomass constitute a relatively new and
promising class of composite materials. They are environmentally friendly,
and they offer good mechanical performance. Information about mechanical

properties of several cellulosic fibers are shown in the Table 2 and can be
compared to properties of commonly used fibers such glass fiber, aramid fiber,
and carbon fiber [21, 22, 23]. The influence of growth conditions and
processing treatments on the chemistry, ultrastructure and performance of
cellulose fibers is frequently considered to be one of the major disadvantages
of using cellulose fibers for reinforcement in composites. The cellulose fibers
are more variable properties as compared to synthetic fibers. Depending on the
intended application, one particular fiber type is more suitable than the other.
The relationship between length and diameter of the fibers is a determining
factor in the transfer of efforts to matrix. Another interesting point is the
irregular cross section of lignocellulosic fibers as well as their appearance
fibrillated, which exert a positive influence on the anchoring of the fibers with
the fragile matrix. In reinforced plastics, fiber are classified into two groups
based on the fiber aspect ratio (defined as the ratio of fiber length to diameter):
(1) short fibers, known as discontinuous fibers, with a general aspect ratio
between 20 and 60, and (2) long fibers, also known as continuous fibers, the
general aspect ratio is between 200 and 500. Normally, long fibers have higher
aspect ratio and better reinforcement potential as compared to short fibers.
Table 2. Properties of several biomass fibers and commonly used

synthetic fibers
Fiber Density Elongation Tensile strength Young’s modulus

(g/cm³) (%) (MPa) (GPa)
Coir 1.2 15.0-30.0 175-220 4.0-6.0
Cotton 1.5-1.6 3.0-10.0 287-597 5.5-12.6
Flax 1.4-1.5 1.2-3.2 345-1500 27.6-80.0
Hemp 1.48 1.6 550-900 70.0
Jute 1.3-1.5 1.5-1.8 393-800 10.0-30.0
Ramie 1.5 2.0-3.8 220-938 44.0-128.0
Sisal 1.33-1.5 2.0-14.0 400-700 9.0-38.0
Softwood kraft 1.5 - 1000 40.0
CNC 1.6 7500 120.0-220.0
CNF 1.5-1.6 2000 150.0
Carbon 1.4 1.4-1.8 1500-5500 230.0-240.0
E–glass 2.5 2.5-3.0 2000-3500 70.0
S–glass 2.5 2.8 4570 86.0
Kevlar 1.4 3.3-3.7 3000-3150 63.0-67.0
Steel wire 7.8 4100 210.0

Eco-friendly biocomposites from plant derived fiber and crop-derived

plastics would be the novel materials of the 21st century not only as a solution
to the growing environmental threat but also as a solution to alleviating the
uncertainty of the petroleum supply. Although unsaturated polyester resins
have been used broadly in bio-composite applications commercially, the non-
recyclable nature of this thermoset resin over the thermoplastic is hindering its
growing importance. As applications and services become more sophisticated,
it is frequently necessary to find new materials which can meet all the
expectations of the industry, especially when considering the cost, mechanical
properties and recyclability of the material. Among all the thermoplastic
matrix polymers; PP has attained much commercial success in biocomposites
for various applications.
Manufacture of PP-Lignocellulosic Materials
Due to lignocellulosic biomass’s great benefits (renewable, cheap,

recyclable, and biodegradable), the interest in biocomposites is rapidly
growing in terms of research and industrial applications (automobiles,
construction, packaging, railway coach, aerospace, and military applications).
Biocomposite is a composite material formed by a polymer matrix and
reinforcement such as lignocellulosic biomass fibers. The matrix phase is
formed by polymers derived from renewable and non-renewable resources.
The matrix is important to hold lignocellulosic biomasses together and to
transfer the loads on it, and to protect the lignocellulosic biomasses from
environmental degradation and mechanical damage. The reinforcements are
derived from biological origins, for example fibers from crops (cotton, flax or
hemp), recycled wood, crop processing by-products or regenerated cellulose
fiber (viscose/rayon), waste paper, nanocellulose and lignin, etc. These kinds
of material often mimic the structure of the living materials involved in the
process keeping the strengthening properties of the matrix that was used, but
always providing biocompatibility.
Polypropylene is a linear hydrocarbon polymer, expressed as CnH2n. PP is
made from the polymerization of propylene gas in the presence of a catalyst
system, usually Ziegler-Natta or metallocene catalyst. Polymerization
conditions (temperature, pressure and reactant concentrations) are set by the
polymer grade to be produced. Polypropylene is currently one of the fastest
growing polymers. PP, like polyethylene (PE) and polybutene (PB), is a
polyolefin or saturated polymer. PP is a thermoplastic polymer used in various

applications including packaging, laboratory equipment, automotive

components, and etc. PP is a tough, rigid plastic and produced in a variety of
molecular weights and crystallinities. It has a density ranging from 0.90 g/cm3
to 0.92 g/cm3. PP can be expected to have tensile strength between 26.0 and
41.4 MPa, tensile modulus of 0.95 to 1.78 GPa, and glass transition
temperature Tg between -23 and -10°C depending on its crystallinity [24]. The
melting point of homo-PP is between 160 to 176°C. PP can be processed by a
variety of fabrication techniques like film/sheet extrusion, multifilament, non-
wovens, injection molding, blow molding and profile extrusion. Three types of
polypropylene are currently available. Each suits particular specifications and
costing (although there is often some overlap). The first one is homopolymers,
a general purpose grade that can be used in a variety of different applications.
Homopolymers have the highest rigidity but the lowest toughness. The second
is an impact copolymer which is blend of homopolymer and ethylene
propylene rubbers (EPR). The impact copolymers can be prepared in situ by
mulitple reactors or it can be prepared by melt blend of homopolymer and
EPR. The ruber content is typically 7 to 20 wt% of EPR. This second type has
much improved impact resistance extending to temperatures below -20°C. The
third is random copolymers, in these materials, the incorporate co-monomer
units arranged randomly (as distinct from discrete blocks) along the
polypropylene long chain molecule. Such polymers typically containing 1-7%
ethylene are selected where a lower melting point, more flexibility and
enhanced clarity are advantageous. In addtion to the types of PP, different PP
grades are available dependent on the application and chosen processing
method. The blends of homopolymers and with lignocellulosic biofillers are
used for applications (rigid packaging) that require high rigidity while impact
coplymer are used for applications (automotive interiors and appliances) that
require high toughness. Typical mechanical properties of PP are showed in
Table 3.
Table 3. Typical mechincal properteis of PP
PP type Flexual Modulus (MPa) Notched Izod (kJ/m2)

Homopolymer 1379-2068 0.6-1.3
Radom copolymer 689-896 2.1-4.2
Impact copolymer 1034-1379 2.1-21.0
Information from Flint Hills Resources’ Techncial data sheet.

Figure 8. PP-lignocellulosic biomass materials design.
Over the last few years, great interest has been shown by researchers in
presenting alternative approaches for the designing and fabrication of
materials with good mechanical properties and low cost for a variety of
applications (Figure 8). The techniques used to fabricate biocomposites are
based largely on existing techniques for processing plastics and conventional
composite materials. The production of PP-lignocellulosic biomass materials
uses techniques that are currently used to manufacture plastics or composite
materials. These techniques include extrusion, injection molding, compression
molding, pultrusion, etc.
Blends of PP and lignocellulosic biomass can be prepared by an extrusion
process. If the total moisture content of the lignocellulosic bio-filler containing

composite is too high the material may need to be dried in a hot air or
dessicant dryer before use on typical processing equipment. The extrusion
temperature must be below 200°C to reduce the degradation of lignocellulosic
biomass that can generate odor and discoloration. In some cases, the
lignocellulosic biomass must be grinded to uniform particle size of 100-200
micron before processing. Extrusion process may result in decrease of aspect
ratio of lignocellulosic fiber. The fiber length is decreased from an initial 1.7
to 0.8mm after extrusion. The higher screw speed, higher fiber content not
only increased the shear energy, resulting in improved fiber dispersion but also
caused fiber breakage [25].
Figure 9. Compression molding of flax fabric and PP films.

Material selection and design are steps in the process of designing any
physical object. In the context of product design, the main goal of material
selection is to minimize cost while meeting product performance goals.
Material selection plays a critical role not only for human life but also for
engineering design of a successful sustainable product. Increasing demands for
special materials led to the conception of composites, since valuable properties
of different types of materials can be combined. With better reinforcement
potential as compared to short fibers, long cellulose fibers (flax, hemp, kenaf
and cotton) was often chosen for several applications such as automotive
industry, sporting goods. Generally comingled of these fibers and
thermoplastic polymer fiber was being used, which was subsequently hot
pressed to melt the thermoplastic fiber thereby forming the composite [26, 27].
Other alternative was used for long fiber was laminate compression moulding.
Compression molding of flax fabric and PP films has been utilized the PP-flax
fabric composites. The matrix films were placed with the flax fabrics to
fabricate the composites as shown in Figure 9 [28].
In PP matrix and lignocellulosic biomass composites, there appears to be
an optimum level of biomass-matrix adhesion to achieve best mechanical
properties. The main drawback of several lignocellulosic biomasses is their
hydrophilic nature that lowers their compatibility with comparatively
hydrophobic polymer PP matrix. The surface chemical modifications of
natural biomass such as cellulose fibers like dewaxing, alkali treatment, vinyl
grafting, cyanoethylation, acetylation, bleaching, peroxide treatment, sizing
with polymeric isocyanates, treatment with silane and other coupling agents
have achieved various levels of success in improving adhesion with polymer.
Triticale Spherulites
T melt T 119oC T 114oC T 108oC
100 µm
PP
Figure 10. Nucleating effect of triticale fiber on the crystallization of PP (Figure

adapted by authors from [29]).

Performance of PP-Lignocellulosic Materials
Lignocellulosic biomass thermoplastic composites have been developed

extensively for utilization in North America construction industries and have
been introduced into personal vehicles in Europe, South America, and Asia.
The introduction of lignocellulosic biomasses into Polypropylene has been
considered to have substantial environmental and economic benefits. In order
to increase its competitiveness, it is important for the composites industry to
reduce energy consumption and cost as well as to improve output and
performance. Cost reduction for blending and compounding the PP and
lignocellulosic biomass is essential. Ngo et al. reported the crystal growth of
PP in the presence of triticale fiber was very rapid and nearly completed at
108°C (about 35s from with the cooling rate of 20°C.min-1) [29]. This
phenomenon was similar to the flax fiber embedded in PP matrix where flax
also acted as a nucleating agent for the creation of spherulites [30]. In general,
the cellulose fiber played a role as the nucleating agent that facilitates the
crystallization of PP as shown in Figure 10. This could positive effect on the
processing time of the PP.
The mechanical properties of lignocellulosic biomass composites have
been extensively characterized and analyzed. Lignocellulosic fibers such as
flax, ramie and hemp possess excellent mechanical properties of breaking
length, as well as elastic moduli characteristics such as E-glass. Table 4
presents the tensile properties of several PP-lignocellulosic materials. The
selection of suitable fibers is determined by the required values of stiffness and
tensile strength of a composite. Burgstaller et al. studied the effect of fiber
diameter and shape of lignocellulosic fibers such as cotton, pulp fiber, sisal,
hemp, flax, abaca, and coir on mechanical properties such as tensile strength,
elastic modulus, and unnotched charpy impact strength for blend with PP. In
general, a lower diameter fiber provided better modulus and unnotched izod
[31]. A comparison of processing and performance for lignocellulosic
reinforced polypropylene for injection moulding applications reported that PP
composites with sisal fiber have better modulus and izod than composites with
wood particles which was better than composites with rice husk particles. The
smaller density fibers or particles in sisal fibers resulted in a composite with
better mechanical properties [32]. The effectiveness of filler reinforcement of
typical inorganic filler such as glass, CaCO3, and talc with varieties of
lignocellulosic biomasses were investigated. Lignocellulosic biomasses such
as sisal, flax, abaca, wood, hemp and cotton fibers improved both modulus and
toughness of the blends. Sometimes the mechanical properties of a blend with

typical inorganic fillers such as CaCO3 and talc can be matched with biofiller
blends [33].
Table 4. Tensile properties of PP with serveral lignocellulosic biomasses
Lignocellulosic biomass Biomass Tensile Young’s References

content (%) strength modulus
(MPa) (GPa)
PP - 25.6 1.3
PP/Cotton 30.0 58.5 4.1 [31, 33]
PP/CNW+coupling agent 5.0-10.0 25.0-39.0 1.5 [34]
MAgPP
PP/Curaua fibers 5.0-20.0 29.5-31.2 1.4-3.5 [35]
PP/Flax 40.0 96.9 7.9 [42]
PP/Flax+coupling agent 40.0 103.0 8.6 [42]
MAgPP
PP/Flax+coupling agent 40.0 109.0 10.1 [42]
MAgPP+CaO
PP/Flax fiber modified 30.0 39.0-40.0 4.9-5.0 [37]
with acetylation
PP/Jute-non woven mat 32.0 39.0 8.4 [36]
PP/Hemp 30.0 44.0 3.9 [31, 33]
PP/Rice husk 30.0 32.1 27.5 [31, 33]
PP/Sisal 30.0 45.5 3.9 [31, 33]
PP/Wood pulp 27.0 28.0 4.2 [37]
PP/Lignin 10.0-70.0 7.0-34.0 0.1-0.6 [38]
PP/Glass-chopped strand 20.0 77.0 5.4 [39]
mat
An essential requirement for a good fiber matrix adhesion is optimized

impregnation of the reinforcing system. Many attempts have been made to
modify the cellulosic fiber surface in order to enhance the adhesion with the
matrix through corona treatment, plasma treatment, graft copolymerization,
heat treatment, silane treatment, and other chemicals modifications [40, 41].
Treatment of the fiber not only affects the surface properties but also changes
both the physical and mechanical properties of single flax fibers. Although,
treatment could enhance the compatibility between the natural fibers and
matrix, it is disadvantageous due to time consuming, involving expensive
equipment, and chemicals. Treatment (2% NaOH solution for 2h at 80°C)
images of the fabric show the flax fiber’s outer surface to be quite smooth as
impurities and contaminants have been removed while the surface of fibers

before treatment seems not clean, with many lumps of contaminations seen on
the surface [42]. The alkali treatment of henequen fiber improves the
mechanical properties of the bio-composites. The alkali treatment leads to
fiber fibrillation and creates reactive bio-fiber [43]. Corona treatment
improved the mechanical properties of the cellulose PP composites. The
increasing on the mechanical properties depends on the treatment time [44].
The increase in the wetability of treated wood veneers might results mainly
from the oxidation of the high hydrophobic surface layer of the neutral fraction
substrates and reduction of the hydrophobicities [45]. Tensile strength of PP-
flax were found to increase with increasing degree of acetylation up to 18%
and then decreased with further increasing degree of acetylation. With the
addition of maleated polypropylene MAgPP, the same tendency was observed
and the tensile strength of 20 to 35% improvements was observed respect to
degree of acetylation. This is due to the formation of ester bonds between fiber
and polypropylene [46]. Enzymatic treatment of lignocellulosic biomass is an
alternative environment friendly method that can be implemented instead of
some toxic chemical treatment methods which are in many cases harmful to
the environment and health. For instant, the use of enzyme treatment is
expected to decompose the middle lamellae selectively and to separate
technical fibers into smaller bundles and single fiber cells. Pectinase treated
hemp fibers in reinforced PP significantly improved tensile and flexural
characteristics of the composite [47].
Acccording to Mieck et al., the alkyl functional silanes did not lead to
chemical bonds between the cellulose fibers and the PP matrix. However, the
long hydrocarbon chain of the silane influenced the wettability of the fiber.
Hydrogen bonds as well as covalent bonds can be found in the flax-silane.
They found 60% increase in shear strength of the system using the
vinyltrimethoxylane with dibutyl dilaurate of tin was added as catalyst [48,
49]. Bispo et al. reported that the incorporation of curaua fibers in composites
of PP resulted in an increase in the elastic modulus and tensile strength [35].
They suggested that it is feasible to use these materials in industry, facilitating
its recycling and improving its final mechanical properties. The addition of
coupling agent into the formulation caused noticcable improvement of the
performance of the PP-lignocellulosic biomass materials. However, the effect
depends on the fiber, matrix, and on the type of coupling agents used in the
formalation. The utilization of maleic acid modified PP improved the
properties of PP-flax composites due to an increased interaction between the
anhydride functions and the hydroxyl functions on the cellulose [50]. The
modification with MA-polypropylene copolymer Epolene E43 increased

tensile strength of PP-flax fiber composite [51]. Maleic anhydride-

polypropylene copolymer has showed to be a very effective compatibilizer for
lignocellulosic-PP composites [52, 53]. Laminated PP-flax fiber composites
can easily be fabricated using compression molding, achieving acceptable
performance. Ngo et al. reported that the addition of maleic anhydride grafted
PP and reactive additive CaO improved the interfacial adhesion between
hydrophilic flax and the hydrophobic PP matrix and thus the composites’
mechanical properties. The presence of both coupling agent and reactive
additive further improved interface interaction between the fiber and matrix
(Figure 11). Thus the formulation is very importance for fabricating a good
biocomposites [42].
The PP-maleated polypropylene-lalang fiber composites were prepared by
extrusion method using a twin-screw extruder between lalang fiber, PP and
maleated polypropylene at different compositions. The PP-maleated
polypropylene-lalang fiber composites were extruded twice to improve the
distribution of filler in their matrix. Bad wetting characteristic between lalang
fiber and PP leaded to decreasing in mechanical properties of PP-lalang fiber
composites. By introduction of 1% maleated PP give the higher mechanical
and thermal properties to PP-maleated polypropylene-lalang fiber composites
[54]. Leão et al. reported that the composites containing benzoylated fiber
could be adhering more to the polymer because of the presence of the polar
groups (benzoyl), which increased the values for tensile strength. Thus, the
values for tensile strength increased from 8.7% for 10 wt.%, 13% for 15 wt.%
and 9.3% for 20 wt.% for benzoylated fibers when compared to the non-
modified fibers [55]. Nordin et al. studied the modification of oil palm
mesocarp fiber (OPMF) characteristics using superheated steam (SHS)
treatment in order to modify its characteristics for biocomposite applications.
They reported that hemicellulose removal makes the fiber surface more
hydrophobic, whereby silica removal increases the surface roughness of the
fiber. They suggested that SHS is an effective treatment method for surface
modification and subsequently improving the characteristics of the natural
fiber [56]. Tran et al. studied the effect of Vietnamese rice husk flour (RHF)
on the mechanical properties of Polypropylene. They reported that the addition
of MAgPP to composites based on NaOH-treated RHF filler having size range
100 to 125µm and PP matrix improved tensile, flexural strength and toughness
of composites [57].

120.0 12.0
Tensile Strength
Tensile Modulus
Tensile Modulus (GPa)

Tensile Strength (MPa)
80.0 8.0
40.0 4.0
0.0 0.0
Figure 11. Tensile properties of PP-flax composites (Figure adapted by authors from
[42]).
Zhong et al. evaluated the physical properties of polypropylene blends

with alkylated lignin containing dodecyl groups [38]. They found that the
addition of bromododecane, as an alkylation agent, improved the compatibility
between lignin and PP. As a result, they could prepare a PP blend with very
high lignin content up to 70wt%. They also investigated the effect of adding
lignin on the flame retardancy of PP. The investigation suggested that there is
an optimal lignin content in this system for the best thermal degradation and
flame retardancy of PP. The incorporation of 5wt% of alkylated lignin
increased the thermal degradation temperature of pure PP at about 27°C and
the char yield at about 2wt%. In addition, both the temperature at which 50%
of the sample weight was lost, T50%, increased by almost 28°C in comparison
with neat PP. Pouteau et al. studied the antioxidant properties of lignin in
polypropylene [58]. Low molecular weight and low total OH content
(aliphatic+phenolic) of lignin tended to improve the compatibility (blend
morphology) and consequently the antioxidant activity. Lignin can be oxidized
at PP processing temperature resulting odor and color formation of
lignocellulosic composite. Therefore, the lignin removed wood fiber, and pulp

would be less sensitive to discoloration and odor generation at high processing

temperature of PP matrix.
Nowadays, engineering materials at the atomic and molecular levels are
creating a revolution in the field of materials and processing. The discovery of
new nanoscaled materials such as nanocelluloses significantly enhances
mechanical and physical properties of polymers. Incorporation of
nanocellulose in polyethylene and polypropylene, polystyrene, some of the
most widely used commercial hydrophobic synthetic polymers is a topical
subject. The addition of the nanocellulose in the formulation is either as a
reinforcement or to make the system rich in renewable material composition.
As seen in Table 4, adding MAgPP increased the adhesion between cellulose
nanowhiskers and PP and resulted in an increasing in the tensile strength and
modulus. The importance was to control the homogenous dispersion of the
nanocelluloses in the polymer matrix, leading to improvement in the tensile
strength and elastic modulus. The nanocelluloses can form a very strong
network, and furthermore bond well to polymer matrix materials with polar
groups. The hydrophilicity of the nanocellulose and the hydrophobicity of the
PP led to processing difficulties, since the nanocelluloses tended to aggregate.
The functional hydroxyl groups of the fibers can be modified to improve
dispersion and processability, although this is typically accompanied with
increased costs. The main challenges for nanocellulose composites are
probably to learn how to manufacture bulk composite components with
retained nanofiber slenderness and dispersion.
POTENTIAL APPLICATIONS OF
PP-LIGNOCELLULOSIC MATERIALS
With good chemical resistance, good fatigue resistance, better temperature
resistance than High-density polyethylene (HDPE) and lower density than
HDPE, PP can be utilized in different daily applications such as flexible and
rigid packaging, automotive, consumer products etc. A new Transparency
Market Research report states that the global polypropylene market was valued
at US$81.6 bn in 2014 and is predicted to reach US$133.3 bn by 2023. It is
expected to expand at a 5.7% compound annual growth rate (CAGR) in the
forecast period between 2015 and 2023. The rising demand for polypropylene
within the food and beverages packaging industry, along with the rising
demand for lightweight vehicles, is predicted to fuel the market for

polypropylene in the coming years. On the other hand, the rising concern
regarding the hazardous effects of plastics on the environment and the
unpredictable prices of raw materials may inhibit the growth of the market for
polypropylene in the coming years. To overcome this obstacle, manufacturers
of polypropylene are focusing on biobased polypropylene, which will bring in
new opportunities by the end of 2023 [59]. As a result of the ease of flow of
polypropylene materials they are often chosen for large area mouldings where
it is desirable to operate with minimum clamp forces. However for many
current polypropylene mouldings, especially where good surface finish is
required, it is common practice to use melt temperatures of 250°C combined
with high packing pressures (typically about 80MPa). Adding lignocellulosic
biomass has positive effect on the shrinkage of the molding parts and also
could introduce several different options for color selection for the materials in
various applications. Color match for rice husk (RH) blends are shown in
Figure 12. Although natural color of rice husk is lightly brown. Suitable
pigments can be used to difference colors such as beige, ivory, sand dune, and
black. These colors are typical colors for cars. The rice husk blend with granite
look alike color can be made using suitable color concentrate and different
sizes of rice husk particles [60]. However, the RH blend can have slight
burned odor after molding. The odor can dissipate in 24-72 hours if parts were
placed in open air. The odor can be masked with fragrances such as mint,
vanilla, and lemon. The odor reduced by molding at the temperature below
180°C. The odor issue can limit RH blend to the application where the odor is
critical.
Each year in North America, close to 12 million vehicles reach the end of
their useful lives and are taken out of service. A network of salvage and
shredder facilities process about 96 percent of these old cars, about 75% of old
car can be recycled, about 25 percent of the vehicles by weight, including
plastics, fibers, foams, glass and rubber, remains as waste [61]. A car made
mostly of heated, treated and molded bio-fiber would simply buried at its
lifetime, which would be consumed naturally by bacteria. In the automotive
sector, PP is utilised as a monomaterial solution for automotive interiors. The
monomaterial dashboard is becoming increasingly achievable, PP film
cushioning, film skins, and powder slush moulding and even blow moulded
parts with integral PP textile covers are emerging. Bumpers, cladding, and
exterior trim are also available manufactured from polypropylene.
Polypropylene developed for such applications provides low coefficient of
linear thermal expansion and specific gravity, high chemical resistance and
good weatherability, processability and impact/stiffness balance.

Improvements with colour-at-the-press and pre-coloured PP have also reduced

or eliminated the need for painting in some applications. The in-corporation of
lignocellulosic into PP for the automotives applications could bring the
advantage of renewable and degradable to the PP.
Figure 12. Color matched into different colors for PP-rice husk blends (Figure adapted
by authors from [60]).
The blend with 10% rice husk has acceptable processability for injection
molding with hot runner that is typically used in molding automotive parts. In
addition, within the particle size of rice used (50-300µm) particle size of RH
did not significantly affect the mechanical properties. However, the increasing

particle size reduced the gloss. Figure 13 shows and example of test door panel
made with PP and rice husk blends. It is demonstrated that door panels with
excellent surface appearance can be made using the 10wt% rice husk blend.
The biocomposites have better scratch resistant and lower density as compared
to talc filled PP. In addition to being bio filler, these lower weight and better
scratch resistant may increase the utility of biocomposite in the automotive
applications. To have acceptable toughness for several application such as
door panel only about 10-20wt% of bio-fillers can be added to the
polypropylene.
Mechanical properties some commercially available PP-lignocellulosic
biomass blends are shown in Table 5. The blends can be used in for injection
molding to make automotive parts, and packaging applications. AGPLAS
BF20H is the wheat straw filled PP that can be used in automotive interior.
Terraloy BP-1300A is a blend of thermoplastic starch with PP. Starch acts as a
plasticizer to reduce the stiffness of PP. Ademuwagun and Myers [62] has
developed a grinded coconut shell filled PP that can be used in automotive
heating-ventilation-air conditioning (HVAC). The blend has lower density
than talc filled PP, good processability, acceptable mechanical properties, and
good scratch resistance. The limitation of filler is about 10% to pass the odor
test automotive interiors. Rosen [63] reported that the cellulose fiber-reinforce
PP have stiffness equivalent to 20% glass filled composite, good mechanical
properties, and processibility for injection molding application. The material
has passed stringent automotives standard.
Table 5. Mechanical properties of some commercial available PP-

lignocellulosic biomass blends
Products Agrplas Terraloy BP- Ecogehr

BF20Ha 1300Ab WPC-30PPc
Lignocellulosic biomass Wheat Starch Wood fibers
straw
Melt flow rate (g/10 min) 3.0 N/A N/A
Notched Izod (kJ/m2) 3.4 2.5
Tensile strength (MPa) 27.5 21.0 29.8
Elongation at break (%) 3.0 75.0 1.8
Flexural modulus (MPa) 2300 1061
Heat deflection temperature at 0.45 MPa (°C) 125.0 N/A
Application AutomotiveInjection Open air
molding applications
Information from technical data sheets from A. Schulman (a), Teknor Apex (b), Gehr
Plastics Inc (c)

Figure 13. Pictures of door panel made with PP-rice husk blend on proction tool (non-
commercial parts) (Figure adapted by authors from [60]).
SUMMARY
After decades of developments of polymer, biocoposites with synthetic
materials, it is remarkable that biomasses have gained a renewed interest,
especially as substitutes in several industries such as automotive, construction,
etc. Alternative sources are sought to produce valuable materials from
renewable natural resources for decreasing the current dependence on fossil
resources as well as alleviating their corresponding environmental threats. In
this context, lignocellulosic biomass, being the most abundant bio-renewable
biomass on earth, has critical importance mainly owing to its worldwide
availability and non-competitiveness with food supplies. New environmental
regulations and societal concern have triggered the search for new products
and processes that are compatible to the environment. Biocomposites being
derived from renewable resources; the cost of the materials can be markedly
reduced with their large-scale usage. The combination of cellulosic fibers such
as flax, jute, hemp and sisal, as well as lignin and nanocelluloses with PP to
produce composite materials that are competitive with synthetic composites
requires special attention. PP biocomposites with different lignocellulosic

biomass components can be considered to have substantial environmental and

economic benefits. PP lignocellulosic biomass biocomposites have been
developed for applications such are automotive components, furniture,
appliance and household, and packaging. The blends have acceptable
mechanical properties, color, and processability. Suitable management of the
odor and high cost of the biocomposite issues may increase the utility of the
composite to many other applications. Establishing techniques to insure the
biocomposite is processed at a temperature below its degradation temperature
will improve properties and reduce odor in the final product.
Although the cost of lignocellulosic biomass as well as agricultural waste
such rice husk, wheat straw, and coconut shell is lower than cost of PP, the
compounding cost of the blend may make the overall cost of the blends
become more expensive than PP. While there is ample opportunity for the PP-
lignocellulosic biomass products to enter new markets and find new
application, it is essential that benefit in terms of cost saving is highlighted and
a stronger commercial case for these materials be made. It is currently difficult
to replace long established inorganic fillers with lignocellulosic biomass
unless a compelling case can be made either from a cost or mechanical
property standpoint. In many instances a suitable case cannot be made which
hinders there current widespread introduction. The cost saving of such low
percentage of the low cost materials cannot compensate for the compounding
cost. High cost of the blends could limit their use in cost sensitive applications
such as packaging. To reduce the compounding cost, polymer suppliers must
have in house capacity to make blends from reactor powder with the fillers. In
addition, promoting the use of these materials through more widespread
training and education is also needed if they are to be commercially
successful.
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BIOGRAPHICAL SKETCHES
TriDung Ngo
Affiliation: Research Scientist, Alberta Innovates-Technology Futures,

Alberta, Canada
Education:
 2007-2008: Post-Doctoral, National Research Council Canada-
Boucherville, Natural Sciences and Engineering Research
Council of Canada (NSERC) Fellowship

 2003-2007: PhD, Mechanical Engineering (Materials-

Nanocomposites), Concordia University, Montreal, QuéBec,
Canada. Dissertation: “Understanding the Effect of Adding
Nanoclays into Epoxies”
 1999-2001: M. Eng. Chemical Engineering (Polymer), University
of Technology, HoChiMinh, VietNam. Thesis: “High
Performance Materials for High Temperature Applications
(Graphite-Reinforced Polymers)”
 1992-1997: B. Eng. Chemical Engineering (Polymer), University
of Technology, HoChiMinh, VietNam. Thesis: “Development of
Self Lubricant Composite Materials for Textile Industries
Applications”
Research and Professional Experience: More than 18 years experiences

 Renewable sources and biomass (lignin, nanocelluloses, fibers,
etc.)
 Polymer (thermoset, thermoplastic, and rubber), polymers
synthesis, composites, nanocomposite, surface coating, bio-
polymers and bio-composites, from formulation, processing-
structure-performance relationships
 Teaching in chemical, material and mechanical engineering
Dr. Ngo received his Bachelor and Master in Chemical Engineering from
Polytechnic University, Vietnam. He obtained his Ph.D. in Mechanical
Engineering from Concordia University, Montreal, Canada in 2007.
Aftercompleting his NSERC post-doctoral fellowship in 2008, he joined
Industrial Materials Institute (IMI) of National Research Council of Canada
(NRC) as researcher. During his tenure, he had performed innovative R&D
activities on polymer, composite, nanocomposite, biopolymer, biocomposite,
biofoam from biomass, including synthesis, modification, formulation,
processing and performance for different industrial applications. Dr. Ngo is
currently working at Alberta Innovates Technology Futures (AITF) as research
scientist for Biomass Processing and Conversion-BioResources sector, a
position he has appointed since late 2014. His research focuses on biomass
processing and development of novel, eco-friendly applications using
renewable and sustainable biomaterials. Dr. Ngo also supervised
undergraduate and graduate students.

 Research Scientist Sep 2014-present
 Forestry/Biomass Processing and Biomaterials Applications,
Alberta Innovates-Technology Futures
 Research Officer Jul 2013-Aug 2014
 National Research Council Canada (NRC Boucherville)
 Researcher Jul 2008-Jun 2013
 National Research Council Canada (NRC Boucherville)
 Visiting Postdoctoral Fellowship Jun 2007-Jun 2008
 National Research Council Canada-Boucherville
 Fellowship from Natural Sciences and Engineering Research
Council of Canada (NSERC)
 Visiting Researcher Mar 2003-Jun 2007
 National Research Council Canada-Boucherville
 Research Assistant Jan 2003-Apr 2007
 Concordia Center for Composites
 Department of Mechanical and Industrial Engineering, Concordia
University, Montreal, Quebec, Canada
 Lecturer Jan 2001-Dec 2002
 Faculty of Materials Technology, University of Technology,
HoChiMinh, Vietnam
 Researcher Sep 1997-Dec 2002
 Polymer Research Center, University of Technology,
HoChiMinh, Vietnam
 Lecturer Sep 1997-Jan 2001
 Faculty of Chemical Engineering, University of Technology,
HoChiMinh, Vietnam
Publications:
Dr. Ngo has over 80 papers in international journals and conference
proceedings, book and book chapter, several inventions, many technical
reports, and presentations.

Thoi Ho
Affiliation: Flint Hills Resources
Education: PhD in Polymer Science (Tohoku University, Sendai, Japan)

Post Doctoral Fellowship at Columbia University, NY
Research and Professional Experience: Have been working more than

30 years in new product and process development, catalyst, and additives for
polycarbonate, polyethylene, and polypropylene.
Technical leader at Dow Chemical and Scientist at Flint Hill Resources
Honors:
Past Chairman of Polymer Modifier and Additives Division (PMAD) of
SPE
Honored Service Member of SPE
2004 Inventor of the Year Award (Dow Chemical)
Publications:
Inventor and Co-Inventor over 65 US patents and World Patents

INDEX
alkylation, 196
# alters, 10
aluminium, ix, 69, 71, 74
21st century, ix, 69, 187
amine, 109, 122, 136
amino, 109, 136
A ammonium, 119
amorphous phases, 26, 30, 54, 59
abstraction, 120 amplitude, 167
access, 182 anatase, 113, 115, 117
acetic acid, 163 angstroms, 88
acetylation, 191, 193, 194, 206 annealing, 38, 61
acid, 5, 8, 86, 92, 93, 94, 98, 112, 113, 116, annual review, 203
117, 119, 127, 128, 138, 145, 153, 194 antioxidant, 117, 118, 152, 153, 154, 155,
acidic, 152 164, 196
activated carbon, 128 aqueous suspension, 184
activation energy, 148, 149, 157, 161 aromatic compounds, 181
active compound, 120 aromatic rings, ix, 84, 92
additives, vii, x, xi, 84, 87, 104, 105, 108, Asia, 192
111, 112, 113, 117, 118, 119, 120, 121, atmosphere, 157
122, 141, 143, 146, 151, 153, 156, 169, atmospheric pressure, 90
172, 210 atoms, 86, 88, 107, 111, 178
adhesion, 14, 100, 191, 193, 197 automobiles, 187
adhesives, 148 automotive application, 200
adsorption, 91, 115, 152 automotive sector, 198
aerospace, 187 awareness, 176
agriculture, 182
air temperature, ix, 69, 70, 76, 78
B
alcohols, 86, 110, 123
aldehydes, 110, 152
bacteria, 104, 110, 178, 198
algae, 104, 110
Bahrain, 81
aliphatic polymers, 102

212 Index
band gap, 116

barium, 5
C
base, 113, 144, 167, 171
Ca2+, 5, 102
batteries, 115
calcium, x, 5, 84, 92, 93, 94, 95, 99, 100,
behaviors, 3, 51, 128, 159
113, 116, 117, 121, 131, 132, 134, 137,
benefits, xi, 3, 175, 177, 187, 192, 202
155, 177
beverages, 197
calcium carbonate, 93, 95, 99, 100, 113,
bio-based materials, xi, 175, 177, 184
131, 132, 134, 177
biocompatibility, 115, 184, 187
calibration, 40
biocomposite, 176, 187, 195, 200, 202, 208
calorimetric measurements, viii, 21
bioconversion, 203
caprolactam, 134
biodegradability, 138, 147, 170, 184
carbohydrate(s), 147, 177, 178, 182
biodegradable materials, 111
carbon, x, 25, 26, 27, 29, 50, 52, 54, 58, 84,
biodegradation, vii, xi, 104, 109, 110, 111,
86, 90, 94, 95, 97, 99, 106, 109, 110,
116, 119, 122, 137, 141, 143, 145, 146,
111, 112, 119, 120, 127, 128, 129, 130,
147, 148, 149, 154, 203
131, 132, 136, 144, 145, 147, 149, 153,
biodiesel, 144
170, 177, 178, 179, 181, 186
biodiversity, 142
carbon atoms, 86, 110, 112, 179
biomass, xi, 110, 145, 175, 176, 177, 182,
carbon dioxide, 111, 145, 153
183, 185, 186, 187, 189, 191, 192, 193,
carbon monoxide, 119, 153
194, 198, 200, 201, 202, 203, 208
carbon nanotube nanocomposites, 128, 132
biomass materials, 189, 194
carbon nanotubes, x, 84, 94, 97, 127, 128,
biomasses, v, vii, xi, 175, 176, 177, 187,
130, 131
191, 192, 193, 201
carbonyl groups, 106, 111, 117, 119, 148
biomaterials, 208
carboxyl, 93, 101, 106, 112
biopolymer(s), 144, 177, 203, 208
carboxylic acid, 91, 110, 113
biosphere, 177
catalyst, 22, 86, 87, 108, 155, 187, 194, 210
biosynthesis, 143, 144, 203
catalytic activity, 116
biotechnology, 144
cation, 5, 119
biotic, xi, 120, 122, 126, 141, 145, 148, 154
C-C, 25, 120, 152, 153
bleaching, 191
cellulose, xi, 72, 147, 171, 175, 177, 179,
blends, 6, 7, 9, 14, 133, 151, 157, 162, 163,
180, 181, 183, 184, 185, 186, 187, 191,
164, 165, 166, 188, 192, 196, 198, 199,
192, 194, 197, 200, 203, 204, 205, 206,
200, 202, 205, 207
207
bonding, 93, 206
cellulose fibre, 72
bonds, 104, 106, 107, 152, 178, 181, 194
cellulose nanocrystals, xi, 176, 177, 184
branching, 61
cellulose nanofibrils, xi, 176, 177, 184
Brazil, 156, 157, 158, 169, 171
cerium, 112, 114
breakdown, x, 84, 89, 109, 151, 167
chain scission, 103, 106, 109, 110, 147
brittleness, 89
challenges, 95, 176, 177, 197
building blocks, 178
charge exchange capacity (CEC), 102
by-products, 154
chemical, vii, ix, 1, 5, 7, 8, 10, 22, 25, 26,
52, 59, 81, 83, 85, 86, 90, 91, 93, 94, 96,
100, 103, 104, 105, 106, 109, 115, 119,
130, 143, 145, 151, 152, 153, 156, 161,

Index 213
168, 180, 181, 182, 183, 191, 194, 197, computer, 109
198, 208 conception, 191
chemical bonds, 93, 194 condensation, 119
chemical degradation, 86, 161 conditioning, 200
chemical deposition, 115 conductivity, 71, 72, 73, 81, 95, 96, 98, 133
chemical properties, 85, 100 conductors, 96
chemical reactions, 91, 156 conference, 209
chemical vapor deposition, 130 configuration, 3, 86, 87, 149
chemicals, 86, 176, 193, 202, 203 conflict, 149
chemiluminescence, 155, 164, 173 conflict of interest, 149
China, 1 Congress, 205
chromatography, 108, 155 constituents, 106
chromium, 112, 114 construction, 103, 187, 192, 201
civilization, 142 consumption, 143, 149, 155
cladding, 198 containers, 119
clarity, 100, 188 conventional composite, 189
cleavage, 104, 106, 145, 146 COOH, 112, 153
climate, 142 cooling, viii, 1, 6, 7, 12, 31, 32, 34, 48, 88,
climate change, 142 89, 118, 192
clusters, 3, 91 cooling process, 12
CO2, 106, 110, 153, 176 cooperation, 147
coal, 143 coordination, 5
coatings, 80, 104, 109, 115, 116 copolymerization, 152, 193
cobalt, 112, 114, 154 copolymer(s), 97, 99, 119, 128, 136, 148,
coconut, vii, ix, xi, 69, 70, 71, 72, 74, 77, 152, 156, 188, 194, 203
78, 80, 81, 175, 200, 202 copper, 71, 98, 112, 114, 121
colonization, 146 correlation, 8, 155, 164
color, 93, 196, 198, 202 correlation coefficient, 164
commercial, 103, 152, 180, 187, 197, 200, corrosion, 115
201, 202 cost, ix, xi, 69, 71, 72, 83, 94, 98, 108, 175,
commodity, 142, 202 176, 184, 185, 187, 189, 191, 192, 201,
compaction, 109 202
compatibility, 95, 156, 191, 193, 196 cost saving, 202
competition, 6, 148, 160 cotton, 72, 178, 180, 187, 191, 192
competitiveness, 192, 201 covalent bond, 23, 194
composites, ix, 14, 84, 94, 95, 96, 97, 99, covering, 92, 116
100, 101, 127, 128, 129, 131, 132, 133, cracks, 96, 107, 148, 153
138, 186, 191, 192, 194, 195, 196, 197, creep, 14, 15
201, 203, 204, 205, 206, 207, 208 Croatia, 169
composition, 5, 9, 90, 101, 112, 118, 139, crop(s), 115, 187
148, 151, 180, 182, 183, 197 crystal growth, 5, 88, 192
composting, 145, 148, 171 crystal structure, vii, viii, 2, 15, 88
compounds, 3, 103, 111, 121, 123, 145, 146, crystalline, vii, viii, ix, 1, 2, 3, 4, 5, 10, 13,
147, 152, 157 14, 21, 22, 23, 24, 25, 29, 30, 37, 42, 47,
compression, 10, 130, 189, 191, 195 50, 52, 53, 54, 57, 58, 60, 83, 86, 88, 89,

214 Index
90, 92, 94, 96, 113, 115, 122, 126, 127, depolymerization, 106, 143
148, 149, 150, 153, 167, 180, 184, 204 deposition, 93
crystalline lamellae, 42, 47 depression, viii, 22, 23, 31, 38, 40, 41, 55,
crystallinity, 3, 26, 30, 47, 54, 55, 59, 99, 58
122, 126, 131, 147, 188, 203 depth, 107, 136
crystallites, 3 derivatives, 92, 109, 180, 204
crystallization, vii, viii, ix, 1, 2, 3, 4, 6, 7, destruction, 14
10, 13, 14, 22, 38, 47, 48, 61, 83, 87, 88, deviation, 76
89, 92, 94, 96, 99, 127, 128, 129, 130, differential scanning, viii, 21, 24, 92, 147
131, 133, 147, 148, 149, 191, 192, 206 differential scanning calorimetry (DSC), 24,
crystallization kinetics, 97, 147, 206 30, 31, 32, 34, 35, 38, 40, 42, 44, 48, 49,
crystals, x, 2, 3, 4, 6, 7, 13, 14, 15, 84, 87, 55, 56, 59, 60, 92, 147, 149
88, 92, 93, 94, 115, 126, 138, 184 diffraction, 92
CST, 117 diffusion, xi, 141, 150, 163, 164, 165, 168,
culture, 148, 171 169
cycles, 23, 150 diffusivity, 71, 97, 133
Czech Republic, 205 digestion, 182, 203
disorder, xi, 141, 148, 149, 168, 169
dispersion, 6, 11, 91, 93, 94, 95, 96, 97, 98,
D 100, 101, 103, 113, 130, 190, 197, 204
dissociation, 7, 106, 115
decay, 50
distribution, 6, 91, 95, 98, 99, 116, 148, 156,
decomposition, xi, 92, 104, 111, 141, 143,
158, 167, 168, 195
148, 149, 152, 154, 155, 159, 165, 166,
DOI, 172
168, 169
dopants, 137
decoupling, 26
double bonds, 104, 106
defects, 6, 89, 110, 115
draft, 34
deforestation, 80
drawing, 22
deformation, 2, 14, 100, 129
drying, 34, 35, 36, 70
degradation, vii, x, xi, 84, 98, 103, 104, 105,
DSM, 138
106, 108, 109, 110, 111, 112, 113, 116,
dual task, 92
117, 118, 119, 120, 121, 122, 126, 135,
ductility, vii, 1, 2
136, 138, 139, 141, 143, 145, 146, 147,
dyes, 112, 113
148, 149, 150, 151, 152, 153, 154, 155,
156, 158, 159, 160, 161, 163, 164, 165,
166, 168, 169, 172,173, 190, 196, 202, E
204
degradation mechanism, 110, 118, 119, 151 education, 202
degradation process, 104, 106, 122, 143, elastomers, 106
146, 152, 156 electric field, 167
degradation rate, 108, 112, 116, 121, 152, electrical properties, 133
161 electricity, 70
degree of crystallinity, 86, 87, 101, 120 electrolyte, 130
dehydrate, 116 electron microscopy, 147
Denmark, 205 electron(s), 105, 116, 147, 154
density fluctuations, 3, 47 elongation, 14, 90, 95

Index 215
elucidation, 22 excitation, 105

emission, 105, 165, 177 experimental condition, 153, 158
endothermic, viii, 21, 23, 30, 32, 34, 35, 48, exposure, 104, 106, 108, 118, 120, 122, 126,
55, 153 147, 148, 151, 155, 160
energy, 2, 70, 76, 78, 81, 87, 90, 92, 98, extraction, 23, 142, 155, 180, 182
100, 104, 105, 106, 107, 119, 130, 142, extrusion, 13, 91, 92, 156, 157, 188, 189,
149, 164, 167, 182, 190, 192, 203, 206 195
energy consumption, 192
energy supply, 71
energy transfer, 105 F
engineering, x, 4, 81, 84, 143, 152, 183,
fabrication, x, 84, 185, 188, 189
191, 197, 202, 208
fatty acids, 119
enlargement, 168
fermentation, 144, 147
environmental change, 142
fiber content, 190
environmental conditions, 120
fiber(s), xi, 9, 11, 13, 14, 15, 81, 90, 91, 95,
environmental degradation, 187
96, 98, 102, 103, 108, 132, 175, 177,
environmental impact, 86, 176
178, 180, 183, 184, 186, 187, 190, 191,
environmental regulations, 201
192, 193, 194, 195, 196, 197, 198, 200,
environmental threats, 201
201, 203, 205, 208
environment(s), 26, 103, 104, 115, 116, 127,
fibrillation, 194
129, 142, 143, 145, 148, 155, 167, 169,
fillers, vii, x, 84, 95, 97, 98, 99, 101, 102,
171, 172, 176, 194, 198, 201
113, 126, 177, 182, 200, 202, 207
enzymatic activity, 145
films, 86, 108, 112, 115, 135, 138, 147, 155,
enzyme, 147, 194
170, 190, 191
enzymes, 104
fixation, 145
epitaxial growth, 6
flame, 100, 102, 132, 196
EPR, 99, 134, 188
flammability, 85
EPS, 73
flax, xi, 175, 177, 180, 183, 186, 187, 190,
equilibrium, 25, 160
191, 192, 193, 194, 196, 201, 204, 205,
equipment, xi, 86, 108, 157, 158, 176, 190,
206
193
flax fiber, 192, 193, 195, 204
ester, 91, 114, 120, 121, 144, 194
flexibility, 89, 99, 149, 188
ester bonds, 194
flour, 195, 206
ethanol, 204
flow field, 3
ethers, 136
fluid, 70, 87, 92
ethylene, 99, 116, 119, 120, 133, 136, 137,
fluorescence, 105, 113, 155
143, 147, 148, 149, 152, 163, 170, 171,
foams, 198
188, 203
food, 86, 90, 197, 201
ethylene oxide, 137, 152, 170, 171
force, 13, 92
ethylene-propylene copolymer, 147, 149
formaldehyde, 152, 153, 163, 165, 166, 206
Europe, 192
formation, viii, xi, 3, 4, 5, 6, 7, 9, 12, 13, 14,
evaporation, 35, 36
21, 23, 25, 30, 36, 49, 57, 87, 91, 93, 96,
evidence, 147
99, 101, 106, 109, 122, 141, 148, 151,
evolution, 8, 106, 143, 145
152, 163, 165, 166, 168, 169, 180, 194,
exchange rate, 70
196

216 Index
formula, 5, 76
fragments, x, 84, 109, 110
H
free radicals, x, 84, 105, 106, 111, 116, 120,
halogen, 5
151
HALS, 109, 136
freezing, viii, 21
hardness, ix, 84
friction, 70
health, 194
FTIR, 148, 149, 152, 155, 171
heat aging, 153
fuel cell, 130
heat capacity, 97, 98
functionalization, 91, 102
heat loss, 70, 74
fungi, 104, 110
heat release, 100
fusion, 128
heat transfer, 70, 72, 81
heating rate, 24, 157, 158, 159
G helical conformation, 149
hemicellulose, 177, 180, 181, 183, 195
gel, viii, 21, 22, 23, 24, 25, 27, 28, 29, 30, hemp, xi, 175, 177, 178, 180, 183, 186, 187,
31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 191, 192, 193, 194, 201
42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, hemp fiber, 194
53, 54, 55, 57, 58, 59, 61, 109 heptane, 23
gel formation, 49 heterogeneous catalysis, 115
gel permeation chromatography, 109 high density polyethylene (HDPE), 108,
gelation, viii, 21, 23, 30, 38, 39, 46, 48, 59, 110, 134, 148, 155, 197
60, 61, 62 high strength, 2, 152, 184
genes, 143 history, 146, 205
geometry, 70, 80 homolytic, 106
Germany, 66, 205 homopolymers, 188
glass transition, 188 human, 142, 143, 145, 155, 176, 191
glass transition temperature, 188 human body, 145
glow discharge, 132 human existence, 143
glucose, 147, 178, 180, 181 humidity, 122
glycerin, 144 hybrid, 11, 13, 15, 102, 133, 134
glycerol, 202 hybridization, 205
glycogen, 178 hydrocarbons, 86
GNP, 98 hydrogen, 5, 7, 23, 86, 115, 120, 149, 158,
governance, 130 178
GPC, 108 hydrogen bonds, 7, 178
grades, 188 hydrolysis, 144, 182, 184
graduate students, 208 hydroperoxides, 108, 111, 120, 122, 148,
graphene sheet, 130 149, 150, 152, 155, 165, 170
graphite, 95, 96, 133 hydrophilicity, 197
green, vii, xi, 176, 204 hydrophobicity, 91, 115, 197
greenhouse, 144 hydroxide, 95, 132
green-product, 176 hydroxyl, 5, 106, 112, 116, 147, 148, 178,
growth, ix, x, 3, 5, 6, 9, 61, 69, 84, 89, 111, 181, 194, 197
127, 142, 147, 186, 197 hydroxyl groups, 147, 178, 181, 197
growth rate, 197 hypothesis, 7

Index 217
ions, 93, 113, 116

I IR spectra, 53
iron, 112, 113, 114, 118, 120, 121, 154
identification, 113, 153
irradiation, 104, 147, 148, 171
identity, 108
isobutylene, 163
imbalances, 142
isolation, 151
impact energy, 134
isotactic polypropylene, vii, x, 6, 18, 84,
impact strength, 3, 13, 90, 99, 101, 192
110, 127, 128, 129, 130, 131, 134, 135,
implants, 115
138, 171
impregnation, 193
isothermal crystallization, 7
improvements, 85, 102, 103, 108, 194
issues, 10, 202
impurities, x, 84, 104, 105, 108, 119, 193
Italy, 66
in vitro, 145
in vivo, 145
incubation time, 126, 148 J
indirect effect, 99
indium, 24 Japan, 21, 24, 63, 66, 210
Indonesia, 81 jute, xi, 175, 180, 186, 193, 201, 205, 206
induction, 3, 4, 50, 108, 118, 145, 153, 165,
166, 169, 172
induction period, 108, 118, 165 K
induction time, 153, 165, 166, 172
industrial processing, 144 ketones, 111, 119, 122
industrialized countries, 90 kinetic parameters, 149, 204
industries, 85, 184, 192, 201 kinetics, 118, 159, 164
industry, xi, 3, 73, 85, 108, 114, 148, 176, Korea, 172
177, 180, 184, 187, 191, 192, 194, 197
infrared spectroscopy, viii, 7, 21, 94 L
initiation, 106, 118
inorganic fillers, 95, 98, 193, 202 lactic acid, 144, 145
insertion, 6, 90, 92 lamella, 11, 37, 89
insulation, vii, ix, 69, 70, 71, 72, 73, 74, 78, lanthanide, 113, 137
79, 80, 81 lanthanum, 5
insulators, 71 legislation, 176
integration, 70 life cycle, xi, 141, 142, 143, 168, 169, 176
integrity, 14 lifetime, 103, 104, 119, 153, 160, 198
interaction effect, 151 ligand, 5
interface, xi, 118, 141, 168, 169, 195, 206 light, x, xi, 84, 85, 88, 104, 105, 106, 109,
interfacial adhesion, 195 110, 112, 117, 119, 122, 136, 146, 154,
intermolecular interactions, 7 155, 176
interphase, 14, 50, 54, 59, 60 lignin, xi, 175, 177, 180, 181, 182, 183, 187,
intrinsic viscosity, 147, 148 193, 196, 201, 203, 205, 207, 208
inventions, 209 lignocellulosic, v, vii, xi, 175, 176, 177,
inversion, 158 180, 183, 185, 187, 188, 189, 191, 192,
inversion recovery, 158 193, 194, 196, 197, 198, 199, 200, 201,
ionizing radiation, 104 202, 203, 204, 205

218 Index
liquid phase, 99 134, 145, 148, 149, 175, 177, 185, 187,
lithium, 115 188, 189, 191, 192, 194, 195, 199, 200,
longevity, 151 202, 206, 207
low density polyethylene, 110 mechanical stress, 89, 106, 110
low temperatures, 8, 34 media, 204
low-cost reinforcements, xi, 175 medical, x, 84, 145
LTC, 172 medicine, 90
Luo, 3, 14, 16, 17 melt, viii, 1, 3, 6, 7, 22, 96, 97, 118, 129,
130, 138, 153, 156, 188, 191, 198
melt flow index, 156
M melting, viii, 6, 7, 9, 22, 23, 30, 31, 32, 33,
34, 36, 37, 38, 39, 40, 42, 43, 44, 48, 55,
macromolecules, 146
56, 58, 59, 60, 61, 87, 96, 99, 101, 122,
magnesium, 5
127, 135, 150, 152, 153, 188
magnetic field, 158, 167
melting temperature, viii, 6, 9, 22, 23, 30,
magnetization, 25, 50, 167
31, 33, 34, 36, 37, 38, 40, 42, 44, 49, 55,
magnitude, 76, 88, 167
56, 58, 87, 99, 101, 122, 150, 153
majority, 119, 143
membranes, 85
Malaysia, ix, 69, 74, 76
metabolism, x, 141
management, 202
metal complexes, 112
manganese, 112, 113, 114, 155
metal ion, 93, 111, 112, 113
manipulation, vii, viii, 2, 4, 7, 8, 15
metal oxides, ix, 83, 93, 94, 113, 127
manufacturing, 71, 133
metal salts, 93, 94, 119
MAS, 24, 26, 27, 29, 50, 51, 54, 58, 60, 61
metals, ix, 84, 107, 113, 119
mass, x, 71, 77, 78, 141, 145, 147, 155, 156,
meter, 74, 76
157, 158, 159, 160, 165
methanol, 153
mass loss, 155, 159
methodology, 161
mass spectrometry, 155
methyl group, 3, 25, 30, 86, 87, 149
materials, vii, xi, 2, 4, 11, 15, 71, 72, 73, 74,
methylene chloride, 147
76, 81, 85, 86, 90, 91, 92, 93, 95, 96, 97,
MFI, 156
98, 100, 101, 102, 108, 115, 116, 122,
microorganisms, xi, 110, 111, 126, 141,
131, 135, 142, 143, 145, 148, 151, 154,
145, 147, 148
156, 157, 158, 159, 160, 161, 162, 163,
microparticles, 99
164, 165, 166, 167, 170, 175, 176, 177,
microscope, 7, 36, 39, 61
180, 184, 185, 187, 188, 189, 191, 192,
microscopy, 88
194, 197, 198, 201, 202, 204, 206
microstructure, vii, 1, 96, 129, 149, 171
materials science, 131, 135
middle lamella, 194
matrix, 2, 7, 8, 13, 14, 15, 85, 91, 94, 95, 96,
migration, 117, 151
97, 98, 99, 100, 101, 117, 126, 129, 160,
military, 187
186, 187, 191, 192, 193, 194, 195, 197,
mineralization, 116, 143
205
mixing, 92, 96, 97, 151, 157
matrixes, 91, 102
modelling, 135
matter, 17, 90, 108
models, 2, 23, 63, 70
mechanical degradation, 171
modifications, vii, 1, 2, 18, 22, 85, 104, 137,
mechanical properties, vii, ix, xi, 14, 73, 83,
168, 191, 193
85, 95, 96, 98, 99, 101, 128, 130, 133,

Index 219
modulus, ix, 14, 70, 89, 91, 132, 177, 186, nanostructures, 91
188, 192, 193, 194, 197, 200 nanotechnology, xi, 85, 90, 103, 130, 131,
moisture, 100, 106, 189 175, 184, 204
moisture content, 189 nanotube, 127, 129, 130, 131, 132
mold, 97 National Research Council (NRC), 207,
molecular dynamics, 149 208, 209
molecular mass, 73, 165 natural polymers, xi, 175
molecular mobility, 25, 26, 50, 59, 167 natural resources, 142, 201
molecular oxygen, 149, 150, 153 Netherlands, 133
molecular structure, vii, 22, 23, 24, 25, 29, neutral, 194
48, 88, 179 next generation, 143, 184
molecular weight, 6, 23, 89, 108, 111, 116, nickel, 112, 114, 154
120, 126, 151, 155, 163, 181, 188, 196 nitrogen, 24, 81, 86, 112, 157, 158
molecular weight distribution, 109 noncrystalline regions, 55, 61
molecules, x, 4, 7, 8, 13, 59, 84, 86, 87, 92, non-polar, 93
105, 106, 109, 151, 153, 178 North America, 192, 198
molybdenum, 112, 114 novel materials, 187
monomers, 144, 145, 148 nuclear magnetic resonance (NMR), viii,
monosaccharide, 181 21, 24, 25, 27, 28, 29, 30, 50, 51, 52, 53,
morphology, viii, 2, 3, 4, 7, 8, 9, 10, 11, 13, 54, 58, 60, 61, 116, 148, 149, 158, 167
14, 15, 23, 32, 35, 36, 38, 46, 55, 57, 59, nucleating agent, vii, viii, ix, 1, 2, 4, 5, 12,
61, 85, 99, 110, 120, 128, 129, 153, 164, 13, 14, 15, 83, 88, 89, 90, 91, 92, 93, 94,
196, 206 117, 127, 128, 129, 192
motif, 178 nucleation, viii, 1, 4, 6, 61, 93, 94, 127, 128,
moulding, 191, 192, 198, 205 131
multiwalled carbon nanotubes, x, 84, 91, nuclei, 3, 4, 167
129, 130
O
N
o-dichlorobenzene, viii, 21, 24, 26, 27, 28,
Na+, 102, 135 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40,
naming, 143 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51,
nanocellulose, xi, 176, 184, 187, 197, 205 52, 53, 55, 56, 57, 60, 61, 62
nanocomposites, 85, 90, 95, 96, 97, 99, 100, oil, 143, 145, 180, 195, 203, 206, 207
101, 102, 103, 118, 129, 130, 131, 132, one dimension, 90, 184
133, 134, 135, 138 opportunities, 85, 198
nanocrystals, xi, 176, 177, 184 optical micrographs, 57, 62
nanofibers, 99, 180, 203 optical microscopy, 35, 152
nanolayers, 129 optimization, vii, 1, 2, 70
nanomaterials, 85, 90, 95, 115, 130, 137 organ, 86, 118, 129
nanometer(s), 37, 46, 55, 90, 184 organic peroxides, 122
nanoparticles, 85, 90, 95, 98, 101, 103, 117, organic solvents, 180
128, 132, 137, 138, 184 organism, 145
nanorods, 117, 138 organize, 102
nanoscale materials, 183 overlap, 188

220 Index
oxidation, x, xi, 84, 104, 105, 106, 107, 108, photosensitizers, 122
109, 110, 111, 115, 117, 118, 122, 126, photosynthesis, 176
135, 138, 141, 146, 147, 149, 150, 154, physical and mechanical properties, 193
155, 163, 164, 166, 168, 169, 170, 171, physical properties, 22, 71, 103, 133, 184,
172, 194 196, 197
oxidation products, 110, 111, 170 plants, 144, 181, 182
oxidative reaction, 106 plastic deformation, 100
oxide nanoparticles, 128 plasticizer, 200
oxygen, x, 84, 86, 104, 105, 108, 109, 111, plastics, 85, 91, 104, 122, 134, 135, 139,
112, 115, 153, 154, 158, 164, 178 146, 154, 170, 177, 186, 187, 189, 198
plastics processing, 135
platelets, 103
P platform, 203
playing, 118
palladium, 112, 114
PMS, 152, 153
paradigm shift, 142
polar, 8, 86, 93, 102, 118, 147, 195, 197
parallel, 12, 88, 89, 102, 159
polar groups, 118, 195, 197
patents, 121, 210
polarity, 100
PCM, 71, 80
polarization, 24
permeability, 107, 110, 127
pollutant(s), x, 84, 106
permeation, 108
pollution, 80, 109, 136, 142
permission, 5, 9, 10, 11, 12, 13, 63
poly(3-hydroxybutyrate), 66
peroxide, 106, 108, 122, 125, 156, 191
poly(ethylene terephthalate), 104
Peru, 81
poly(vinyl chloride), 104
PET, 143
polyamides, 104
petroleum, 177, 181, 187
polycarbonate, 104, 210
phase boundaries, 89
polyesters, 144, 145
phase diagram, 8
polyethylenes, 172
PHB, 144
polyisobutylene, 121
phenol, 206
polymer chain, 25, 32, 36, 88, 89, 106, 111,
phosphate, 116, 121, 137
148, 180
phosphorescence, 105
polymer composites, 130, 180, 204
phosphorus, 112
polymer industry, 103
photobleaching, 147
polymer materials, 85, 145
photocatalysis, 115
polymer matrix, 14, 15, 85, 88, 91, 95, 96,
photochemical degradation, 153
98, 100, 118, 187, 197
photodegradation, x, 84, 104, 105, 106, 107,
polymer molecule, 92
108, 109, 110, 112, 113, 121, 135, 138,
polymer nanocomposites, 98, 103, 130
147, 152, 153, 170, 171
polymer oxidation, 106, 170
photoelectron spectroscopy, 94
polymer properties, 156
photographs, 10, 36, 38
polymeric materials, 3, 91, 103, 160
photoinitiation, 108
polymeric melt, 7
photolysis, 106, 118
polymerization, 16, 86, 96, 131, 144, 148,
photons, 106, 107, 108
156, 187
photooxidation, 109, 117, 118, 120, 135,
138

Index 221
polyolefins, x, 84, 86, 102, 104, 107, 108, reactant, 187

110, 111, 113, 119, 120, 121, 122, 136, reaction mechanism, 87
137, 147, 153, 154, 171, 172 reaction rate, 106, 161
polysaccharides, 144, 180 reactions, 91, 105, 106, 109, 122, 135, 139,
polystyrene, 30, 73, 81, 86, 104, 129, 143, 145, 151, 154, 156, 159, 160, 164, 166
197 reactive groups, 96
polyurethanes, 104 reactive oxygen, 154
polyvinyl alcohol, 23 reactive sites, 150
polyvinyl chloride, 143 reactivity, 165
POOH, 149, 154 reality, 184
population, 111 recognition, 176
potassium, x, 84 recombination, 150
preparation, 2, 95, 122, 128, 135, 151, 176, recovery, 25, 28, 50, 51
177, 206 recrystallization, 6, 7, 13, 167
primary antioxidants, 155 recycled materials, xi, 176
principles, 8, 154, 172 recycling, 80, 113, 176, 194
probability, 103, 150 refractive index, 115
product design, 191 regenerated cellulose, 187
product performance, 143, 191 reinforcement, vii, xi, 1, 13, 14, 90, 91, 94,
propagation, 14, 163, 166 97, 129, 175, 177, 180, 186, 187, 191,
propylene, 22, 86, 87, 99, 132, 136, 148, 192, 197
187, 207 relaxation, 3, 13, 25, 28, 50, 52, 105, 108,
protective coating, 115 158, 167
protons, 167 relaxation process, 28
pulp, 192, 193, 196 relaxation times, 167
pultrusion, 189 renewability, xi, 175, 177, 184
purity, 89, 100 renewable energy, 70
PVA, 23, 31, 46 renewable resources, xi, 176, 187, 201
PVC, 104, 143 requirement(s), 91, 193
researchers, ix, 3, 7, 69, 74, 93, 94, 108,
127, 145, 152, 153, 180, 185, 189
Q residue(s), 108, 147
resins, 156, 187
quantum yields, 153
resistance, vii, ix, 1, 2, 13, 14, 15, 83, 85,
quartz, 24
86, 87, 89, 93, 101, 102, 110, 152, 164,
188, 197, 198, 200
R resolution, viii, 21, 24, 25
resources, xi, 142, 143, 176, 180, 187, 201
race, 23 respiration, 147
radiation, 70, 74, 76, 96, 104, 105, 106, 117, rheology, 156
147 rice husk, xi, 175, 192, 193, 195, 198, 199,
radicals, 105, 109, 116, 136, 150 201, 202, 207
radius, 23, 40, 41, 42, 43, 44, 46, 48, 55, 57, risks, 130
61, 62 ROOH, 105
raw materials, 180, 198 room temperature, 34, 48, 153, 161

222 Index
root, 14, 15 sol-gel, 115

roughness, 70, 80, 195 solid state, vii, viii, 8, 21, 23, 150, 153
routes, 85, 135, 180 solid surfaces, 137
rubber(s), 99, 104, 188, 198, 208 solid waste, 143
rutile, 113, 115, 117, 138 solubility, 3, 7, 8, 15
solution, 24, 38, 48, 59, 87, 111, 136, 187,
193, 198
S solvent molecules, 34, 37, 42, 55, 58
solvents, viii, 21, 23, 34, 37, 44, 55, 58, 86,
salts, ix, 83, 93, 101, 114, 119, 120
94, 100
SANS, 24, 43, 45, 46, 47, 48
South America, 192
saturation, 25, 28, 50, 51, 91
species, 7, 8, 53, 93, 94, 105, 116, 118, 147,
scaling, 94
151, 154, 173, 183
scattering, 24, 43, 44, 46, 47, 131
specific gravity, 198
scattering intensity, 24, 46
specific heat, 71, 97, 133
science, 85, 127, 133, 134, 135, 136, 137,
specific surface, 11, 98
145, 170, 177, 183
specifications, 188
scope, 22, 85, 93
spherulite, vii, viii, 1, 3, 11, 21, 36, 37, 38,
selectivity, 90, 92, 93
42, 47, 57, 61, 89
self-assembly, vii, viii, 2, 3, 7, 8, 9, 13, 14,
spin, 25, 28, 50, 115, 158, 167
15
spindle, 92
SEM micrographs, 99
stability, 96, 98, 101, 108, 117, 127, 135,
semiconductor, 116
136, 138, 149, 151, 152, 153, 156, 158
semi-crystalline polymers, 3, 94, 100, 150
stabilization, 108, 117, 135, 136, 149, 153
sensitivity, 100, 119
stabilizers, 104, 108, 109, 112, 136, 137,
sensor(s), 76, 115
152, 153, 165
services, 187
starch, 144, 147, 155, 170, 172, 178, 200
shape, 25, 29, 54, 70, 92, 192
state(s), viii, 7, 21, 24, 30, 32, 34, 42, 51,
shear, 9, 13, 92, 100, 111, 131, 190, 194
59, 71, 92, 97, 98, 99, 101, 105, 106,
shear strength, 194
149, 151, 153, 197
shortage, 109
storage, 14, 70, 80, 149, 150, 154
showing, 88, 94, 159, 167
stress, 13, 91, 92, 109, 110
signals, 26
strong interaction, 98
silane, 191, 193, 194
strontium, 5
silica, 40, 41, 101, 109, 116, 195
structure, vii, viii, x, xi, 1, 2, 3, 5, 7, 8, 9,
silver, 112, 114
10, 11, 13, 14, 15, 21, 22, 25, 29, 37, 49,
SiO2, 116
53, 54, 58, 71, 84, 85, 86, 87, 88, 89, 92,
sisal, xi, 175, 177, 180, 186, 192, 193, 201
100, 101, 102, 103, 104, 105, 106, 109,
sludge, 170
112, 115, 119, 121, 128, 129, 132, 133,
small-angle X-ray, 47
134, 141, 149, 168, 169, 180, 181, 182,
society, 5, 9, 10, 11, 115, 142
183, 187, 208
sodium, 92, 101, 113
substitutes, 201
sodium hydroxide, 113
substitution, 101
software, 158
substrate(s), x, 84, 94, 147, 194
solar cells, 115
sugarcane, 207
solar collectors, 70, 71, 75, 78

Index 223
sulfuric acid, 184 tensile strength, 2, 11, 13, 95, 153, 178, 188,
sulphur, 112 192, 194, 195, 197
Sun, 204 tension, 99
supermolecular structures, 10 tenure, 208
suppliers, 202 testing, 135, 205
surface area, 99, 146 textiles, 178
surface chemistry, 184 thermal aging, 153, 160
surface energy, 99 thermal analysis, viii, 21, 43, 46, 158
surface layer, 107, 194 thermal decomposition, 98, 153, 159
surface modification, 195, 206 thermal degradation, 105, 110, 112, 118,
surface properties, 116, 193 152, 158, 159, 160, 169, 172, 196, 204
surface region, 117 thermal energy, 70, 72
surface treatment, 113 thermal expansion, 184, 198
surfactant(s), 100, 102 thermal oxidation, 108, 117, 164, 173
survival, 142 thermal oxidative degradation, 171
susceptibility, 110 thermal properties, 72, 73, 97, 122, 126,
sustainability, 144, 145, 203 127, 133, 195, 203
sustainable development, 143 thermal resistance, 100
swelling, 86, 100 thermal stability, xi, 93, 96, 98, 100, 101,
symmetry, 53 117, 122, 126, 133, 141, 147, 148, 149,
synergistic effect, xi, 141, 163, 164, 169 158, 164, 169
synthesis, 85, 87, 103, 121, 137, 138, 143, thermograms, 56, 60
144, 148, 149, 150, 182, 208 thermogravimetric analysis (TGA), 147,
synthetic fiber, 186 148, 152, 155, 157, 158, 159, 164, 204
synthetic polymers, ix, 83, 104, 143, 170, thermoplastic, xi, 85, 86, 103, 148, 176,
197 187, 191, 192, 200, 204, 205, 208
thermoplastics, 177
thin films, 137
T tin, 194
titania, 115
tacticity, 89, 148, 149
titanium, 91, 113, 117, 137, 138
Taiwan, 19
top-down, xi, 176, 184
talc, 98, 113, 131, 177, 192, 200
topological structures, viii, 1
techniques, ix, 70, 92, 102, 115, 151, 165,
toxicity, 184
188, 189, 202
transformation, 44, 203
technologies, 90
transition metal, 112, 113, 114, 119, 120,
technology, 13, 103, 131, 145, 156, 170,
121, 123, 146, 154
177, 183
transition metal ions, 112
temperature, viii, ix, 2, 4, 6, 7, 8, 9, 12, 13,
translation, 93
14, 15, 22, 23, 24, 31, 33, 34, 35, 37, 38,
transmission, 98, 112
39, 40, 41, 43, 44, 46, 47, 49, 55, 58, 59,
transport, 96, 97, 98, 181
61, 62, 70, 71, 74, 77, 88, 94, 98, 101,
transportation, 202
102, 106, 110, 128, 129, 135, 149, 151,
treatment, 99, 134, 184, 191, 193, 195, 206,
155, 157, 158, 159, 160, 161, 163, 164,
207
180, 187,190, 196, 197, 200, 202
treatment methods, 194
temperature dependence, 71

224 Index
triggers, 7 waste, 142, 143, 144, 149, 182, 183, 187,

triticale, xi, 175, 191, 192, 204 198, 202, 203
tungsten, 112, 114 water, 22, 23, 24, 46, 70, 80, 81, 100, 104,
110, 111, 115, 116, 137, 144, 145, 152,
163, 165, 176, 180, 181
U water absorption, 100
water heater, 81
ultrasound, 89, 130
wavelengths, 108, 118, 153
ultrastructure, 186
weight loss, 147, 153, 155, 158, 159
UNFCCC, 169
weight ratio, 101
United Nations, 169
well-being, 176
United States (USA), 66, 76, 171, 172, 203,
wettability, 194
204, 205
wetting, 86, 195
UV irradiation, 106, 108, 122, 147
wheat, xi, 175, 183, 200, 202
UV light, x, 84, 104, 105, 106, 112, 119,
wood, 95, 100, 177, 178, 180, 187, 192,
120
194, 196, 203, 206
UV radiation, 106, 113, 115, 116, 122
wool, 71, 73, 74, 81
workers, 155
V worldwide, ix, 83, 201
valve, 115
X
vanadium, 112, 114
variables, 151, 156
X-ray photoelectron spectroscopy, 153
vector, 44, 167
vehicles, 192, 197, 198
ventilation, 200 Y
vibration, 89
Vietnam, 208, 209 yield, 13, 53, 95, 100, 161, 196
vinyl monomers, 119
vinylidene fluoride, 104
viscose, 187 Z
viscosity, 87, 92, 98, 156
zeolites, x, 84, 94
zinc, 5, 112, 114, 137
W zinc oxide, 137
zirconia, 116
wall temperature, 76 ZnO, 93, 113, 137
Washington, 136, 138, 139, 203

Polypropylene Uses and Benefits

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Polypropylene Uses and Benefits

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Additional books in this series can be found on Nova’s website

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NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

Published by Nova Science Publishers, Inc. † New York

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Polypropylene (PP) is a typical polymorphic polymer with α-form, β-

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enhancement via controlled crystallization. Polymer crystallization is

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Chapter 3 - As polypropylene undergoing phenomenal growth in

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microorganisms. The biodegradation depends on to biotic phase, which start

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SELF-ASSEMBLY β-NUCLEATING AGENTS

Yijun Li, Min Nie and Qi Wang

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crystal modification and morphology of PP. This chapter will

Keywords: controlled crystallization, polypropylene, β-nucleating agent, self-

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The high efficiency of selective induction of β-crystal and the designed

β-NUCLEATING AGENT AND ITS SELF-ASSEMBLING

β-Form Nucleating Agent

Addition of nucleating agent not only can accelerate the crystallization

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Table 1. β-form nucleating agent used in polypropylene

Name Chemical structure Activity

Linear trans γ- 72~84

The substituent groups of R1-8 are independently

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Impacts on the Nucleating Efficiency of the β-Form

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Another study on the isothermal crystallization of PP/TMB-5 blend

The Self-Assembly of β-Nucleating Agent

Many researchers have observed an interesting phenomenon by polarized

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The Morphological Manipulation of the Self-Assembling

Many efforts have been dedicated to achieve the subtle manipulation of

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detected in the intermedium range of the temperature gradient. This unique

Figure 2. Temperature/composition diagram of the PP/TMB-5 blends. In the diagrams,

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The self-assembled morphology of β-NA also influences the crystalline

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Figure 4. High-magnification SEM micrograph of PTC and the schematic diagram of

THE STRUCTURE-PROPERTIES RELATIONSHIP

The Reinforcing Effect of the Hybrid Shish-Kebabs

Since the performance of the semicrystalline polymer intensively relies on

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This cylindrical symmetrical architecture is constructed by two kinds of β-

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improvement of mechanical properties can be achieved at higher concentration

Enhanced Properties by Other Unique Morphologies

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 The β-form NAs are capable to achieve high fraction of β-crystals in