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Full Download Book Unsaturated Polyester Resins Fundamentals Design Fabrication and Applications PDF
Full Download Book Unsaturated Polyester Resins Fundamentals Design Fabrication and Applications PDF
Edited by
Sabu Thomas
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, India
International and Interuniversity Centre for Nanoscience and Nanotechnology,
Mahatma Gandhi University, Kottayam, India
Mahesh Hosur
Department of Materials Science Engineering, Tuskegee University, Tuskegee,
AL, United States
Basim Abu-Jdayil
Chemical and Petroleum Engineering Department, United Arab Emirates University, Al Ain,
United Arab Emirates; Emirates Center for Energy and Environment Research, United Arab
Emirates University Al Ain, Abu Dhabi, United Arab Emirates
M. Alagar
Centre of Excellence for Advanced Materials, Manufacturing, Processing and Characterisation
(CoExAMMPC), Vignan’s Foundation for Science, Technology and Research (VFSTR),
Vadlamudi, India
Andrea C. Alexander
Center for Polymers and Advanced Composites, Auburn University, Auburn, AL, United States
Nima Alizadeh
Center for Polymers and Advanced Composites, Auburn University, Auburn, AL, United States;
Department of Chemical Engineering, Auburn University, Auburn, AL, United States
Sandro C. Amico
Post-Graduation Program in Mechanical Engineering, UFRGS, Porto Alegre, Brazil;
Post-Graduation Program in Mining, Metallurgical and Materials Engineering, UFRGS,
Porto Alegre, Brazil
M. Arous
Department of Physics, LaMaCoP, Faculty of Sciences of Sfax, University of Sfax, Tunisia
Anjali A. Athawale
Department of Chemistry, Savitribai Phule Pune University, Pune, India
Maria L. Auad
Center for Polymers and Advanced Composites, Auburn University, Auburn, AL, United States;
Department of Chemical Engineering, Auburn University, Auburn, AL, United States
D. Bachtiar
Structural Materials and Degradation Focus Group, Faculty of Mechanical and Manufacturing
Engineering, Universiti Malaysia Pahang, Pahang, Malaysia
Nil Ratan Bandyopadhyay
Dr. M. N. Dastur School of Materials Science and Engineering, Indian Institute of Engineering
Science and Technology, Shibpur, Howrah, India
Mattia Bartoli
Department of Applied Science and Technology (DISAT), Politecnico di Torino, Torino, Italy
Dibakar Behera
School of Applied Sciences (Chemistry), KIIT University, Bhubaneswar, India
Samantha A. Bird
Center for Polymers and Advanced Composites, Auburn University, Auburn, AL, United States
xix
xx List of Contributors
Bhabatosh Biswas
Dr. M. N. Dastur School of Materials Science and Engineering, Indian Institute of Engineering
Science and Technology, Shibpur, Howrah, India
Daniel H. Builes
Research and Development Center-Andercol, Andercol S.A.S, Medellı́n, Colombia
Shalini Chaturvedi
Samarpan Science and Commerce College, Gandhinagar, India
Cintil Jose Chirayil
Department of Chemistry, Newman College, Thodupuzha, India
Angélica Colpo
Post-Graduation Program in Mechanical Engineering, UFRGS, Porto Alegre, Brazil
Pragnesh N. Dave
Department of Chemistry, Sardar Patel University, Vallabh Vidyanagar, India
Virginia A. Davis
Department of Chemical Engineering, Auburn University, Auburn, AL, United States
Eduardo A.W. de Menezes
Post-Graduation Program in Mechanical Engineering, UFRGS, Porto Alegre, Brazil
S. Devaraju
Polymer Composites Lab, Division of Chemistry, Department of Science and Humanities,
Vignan’s Foundation for Science, Technology and Research (VFSTR), Vadlamudi, India
Hom Nath Dhakal
School of Mechanical and Design Engineering, Advanced Materials and Manufacturing (AMM)
Research Group, University of Portsmouth, Portsmouth, United Kingdom
John R. Ebdon
Institute for Materials Research and Innovation, University of Bolton, Bolton, United Kingdom
Marco Frediani
Department of Chemistry “Ugo Schiff”, University of Florence, Sesto Fiorentino, Florence, Italy
Leandro Friedrich
Post-Graduation Program in Mechanical Engineering, UFRGS, Porto Alegre, Brazil
Cincy George
Department of Chemistry, Newman College, Thodupuzha, India
Z.M. Hafizi
Advanced Structural Integrity and Vibration Research (ASIVR), Faculty of Mechanical and
Manufacturing Engineering, Universiti Malaysia Pahang, Pahang, Malaysia
M.H.M. Hamdan
Structural Materials and Degradation Focus Group, Faculty of Mechanical and Manufacturing
Engineering, Universiti Malaysia Pahang, Pahang, Malaysia
List of Contributors xxi
Sanjay K. Nayak
School for Advanced Research in Polymeric Materials (SARP) LARPM Central Institute of
Plastics Engineering & Technology (CIPET) - IPT, Bhubaneswar, India
Med Amin Omri
Department of Physics, LaMaCoP, Faculty of Sciences of Sfax, University of Sfax, Tunisia
Shivkumari Panda
School of Applied Sciences (Chemistry), KIIT University, Bhubaneswar, India
Jyoti A. Pandit
School of Chemistry, Dr. Vishwanath Karad MIT World Peace University, Pune, India
V. Ramamurthy
Department of Biotechnology, PSG College of Technology, Coimbatore, India
M.R.M. Rejab
Structural Materials and Degradation Focus Group, Faculty of Mechanical and Manufacturing
Engineering, Universiti Malaysia Pahang, Pahang, Malaysia
Emmanuel Richaud
PIMM, UMR 8006, ENSAM CNRS CNAM, HESAM Université, Paris, France
Luca Rosi
Department of Chemistry “Ugo Schiff”, University of Florence, Sesto Fiorentino, Florence, Italy
Sushanta K. Samal
School for Advanced Research in Polymeric Materials (SARP) LARPM Central Institute of
Plastics Engineering & Technology (CIPET) - IPT, Bhubaneswar, India
S.M. Sapuan
Department of Mechanical and Manufacturing Engineering, Universiti Putra Malaysia, Selangor,
Malaysia
N. Saranya
Department of Applied Science and Technology, A.C. Tech., Anna University, Chennai, India
Aruni Shajkumar
School for Advanced Research in Polymeric Materials (SARP) LARPM Central Institute of
Plastics Engineering & Technology (CIPET) - IPT, Bhubaneswar, India
Arijit Sinha
Dr. M. N. Dastur School of Materials Science and Engineering, Indian Institute of Engineering
Science and Technology, Shibpur, Howrah, India
J.P. Siregar
Structural Materials and Degradation Focus Group, Faculty of Mechanical and Manufacturing
Engineering, Universiti Malaysia Pahang, Pahang, Malaysia
Pavle M. Spasojevic
Faculty of Technical Sciences, University of Kragujevac, Cacak, Serbia; Innovation Center of
Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia
List of Contributors xxiii
Agnieszka Tercjak
Materials+Technologies Group (GMT), Department of Chemical and Environmental Engineering,
Faculty of Engineering Gipuzkoa, University of the Basque Country (UPV/EHU), Donostia-San
Sebastian, Spain
C. Tezara
Department of Mechanical Engineering, Faculty of Engineering and Quantity Surveying, INTI
International University, Negeri Sembilan, Malaysia
George V. Thomas
Department of Chemistry, St. Joseph’s College, Moolamattom, Idukki, India
Sabu Thomas
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, India; International and
Interuniversity Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University,
Kottayam, India
Hareesh V. Tippur
Department of Mechanical Engineering, Auburn University, Auburn, AL, United States
A. Triki
Department of Physics, LaMaCoP, Faculty of Sciences of Sfax, University of Sfax, Tunisia
Jacques Verdu
PIMM, UMR 8006, ENSAM CNRS CNAM, HESAM Université, Paris, France
Xiwei Xu
Key Laboratory of Bio-Based Polymeric Materials Technology and Application of Zhejiang
Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of
Sciences, Ningbo, P.R. China; School of Materials Science and Engineering, Zhejiang University
of Technology, Hangzhou, P.R. China
Jin Zhu
Key Laboratory of Bio-Based Polymeric Materials Technology and Application of Zhejiang
Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of
Sciences, Ningbo, P.R. China
CHAPTER
UNSATURATED POLYESTER
RESINS, BLENDS,
INTERPENETRATING POLYMER
NETWORKS, COMPOSITES, AND
1
NANOCOMPOSITES: STATE OF THE
ART AND NEW CHALLENGES
Anjali A. Athawale1 and Jyoti A. Pandit2
1
Department of Chemistry, Savitribai Phule Pune University, Pune, India 2School of Chemistry, Dr. Vishwanath
Karad MIT World Peace University, Pune, India
1.1 INTRODUCTION
Unsaturated polyesters (UPs) are synthetic copolymers having applications as fibers, plastics, com-
posites, and coatings. Depending on the choice of monomers, initiators, curing agents, additives,
and modifiers used, different varieties of products can be produced exhibiting a wide range of
chemical and mechanical properties. The low cost involved in their production makes them attrac-
tive. Their main application is as matrices in the composite industry. Among the composites, fiber
glassreinforced composites are of prime importance.
styrene). Neopentyl glycol or hydrogenated bisphenol A yields resins with high heat and chemical
resistance.
1.2.4 CHLORENDICS
Chlorine/bromine-containing anhydrides or phenols are used for preparing chlorendics. They
exhibit flame resistance along with good chemical and corrosion resistance. For example, the reac-
tion between chlorendic anhydride/chlorendic acid and MA/fumaric acid and glycol yields resin
with better flame retardancy than general-purpose UPR. Other monomers used include tetrachloro-
or tetrabromophthalic anhydride. The bromine content must be at least 12% in order to obtain a
self-extinguishing polyester.
was predicted on the basis of its fragility parameter (Mc). In the UPRMEKP system, the smaller
the Mc the larger the Tg and the better the heat resistance [12].
The curing behavior of UPR was studied using an experimental and theoretical model by Kosar
and Gomzi [13]. The kinetic behavior of the curing system was investigated using both dynamic
and isothermal measurements and a good agreement was established between the two (in terms of
presented kinetic parameters and reaction heat). Heat generated from the cure reaction was mea-
sured in molds of cylindrical shape. The difference in heat conductivity between glass and copper
was the main reason for the greater heat generated in the glass mold.
Control over resin shrinkage of residual monomers is an important concern in low-temperature
molding processes. The presence of low-profile additives (LPAs) can reduce the shrinkage of UPR/
styrene resins under proper processing conditions, but may increase the residual styrene content. A
systematic study was carried out to investigate the effect of the initiator system and reaction tem-
perature on the sample morphology, final resin conversion, and resin shrinkage of UPR with LPA.
The results showed that the final conversion of the resin system could be improved by dual initia-
tors, with the effect being prominent at low temperatures. The study on shrinkage control reported
that good LPA performances were achieved at low (35 C) and high (100 C) temperatures, but
worse performances were observed in the intermediate temperature range (e.g., 60 C75 C)
(Fig. 1.1). The final shrinkage is influenced by the effect of temperature on the morphology, the
relative reaction rate in the LPA-rich and UPR-rich phases, and microvoid formation [14]. The
sample morphology shows a two-phase cocontinuous structure at 35 C (Fig. 1.2). One is a particu-
late phase (LPA-rich) having loosely packed spherical particles with diameters ranging from 1 to
5 mm. The other phase is a flake-like region (UPR-rich) with domain sizes ranging from 10 to
20 mm. At a curing temperature of 60 C, a similar two-phase structure is observed, but it is no lon-
ger cocontinuous. The particulate region is smaller and becomes the dispersed phase with a domain
3
Volume shrinkage (%)
–1
–2
–3
35 60 75 100
Temperature (ºC)
FIGURE 1.1
Volume shrinkage of UP/St/LPA systems cured at different temperatures (3.5% LPA, 0.5% Co Oct., 1.3%
MEKP, 0.4% TBPB, 300 ppm BQ).
1.3 SYNTHESIS OF UNSATURATED POLYESTER RESINS 5
FIGURE 1.2
Morphology of St/UP/LPA samples cured at different temperatures (3.5% LPA, 0.5% Co Oct., 1.3% MEKP,
0.4% TBPB, 300 ppm BQ).
size of less than 20 mm, while the flake-like region forms the continuous phase. On increasing the
temperature to 75 C and 100 C, the size of the particulate region is further reduced. The various
morphological structures result in different interface areas, strongly affecting the shrinkage control.
Commercial UPRs contain 30%40% styrene by mass. The miscibility of resin and styrene
depends on the resin composition. Phase separation is reported with an increase in styrene concen-
tration. Thermal stability and mechanical properties are governed by the phase behavior of the mix-
ture and can, therefore, be controlled by styrene content [15]. Dynamic mechanical analysis (DMA)
tests have shown phase separation in cured resin with high styrene concentrations. Tg is also depen-
dent on styrene concentration together with thermal stability and mechanical behavior [16].
irritation. It is carcinogenic and also attacks the central nervous system on exposure over a long
period of time, leading to possible headaches and depression. The minimization of styrene volatili-
zation or its elimination using alternative monomers is being attempted to overcome these
problems.
The volatilization of styrene is reduced by paraffinic waxes which act as a barrier. However,
the wax layer needs prior removal to avoid problems of adhesion to other parts. The ambient con-
centration of styrene vapor can be reduced using spray guns that can monitor the amount of resin
sprayed. Since alternatives such as vinyl toluene, alpha-methylstyrene, and diallyl phthalate sug-
gested for styrene also involve health hazards, Poillucci and Hansen proposed the use of bio-
derived limonene oil and petroleum-derived vinyl neodecanoate and vinyl laurates as other substi-
tutes for styrene, but they exhibit limited chemical compatibility. The styrene content was reduced
by 50% using trimethylolpropane diallyl ether [17]. Mariani used various cross-linking agents such
as 2-hydroxyethyl acrylates (HEA) or a mixture constituted of diurethane diacrylate and styrene or
HEA for frontal curing of UPR derived from the reaction of MA and 1,2 propanediol [18]. Zang
et al. reported a benzyl end-cap-UP resin with low styrene emission using benzyl alcohol as the
end-capper [19].
For nonhalogenated resins, a marked restriction in styrene emission is achieved by including
long-chain alpha-olefins with 1840 carbon (C) atoms without the addition of wax. These olefins
on their own will not usually provide such a marked restriction in styrene emission, but will allow
for the incorporation of a waxy compound in an amount sufficiently large to achieve the desired
styrene emission restriction without incurring the expected disadvantages associated with the incor-
poration of such large amounts of waxy compound [20].
which are styrene-free and ultralow volatile organic compound (VOC) resins that provide matrix
materials to produce more ecologically friendly composites [26]. A styrene-free UPR forming a
stable dispersion in water has been reported. The modification was done by introducing polar
hydrophilic groups such as carboxylic and sulfonic groups (sodium 5-sulfonatoisophthalic acid)
into the resin molecule, which ensure good tolerance to water. Styrene has been replaced with the
glycerol monoethers of allyl alcohol and unsaturated fatty alcohols as reactive built-in cross-linking
monomers for resin modification [27].
Stable
viscosity Fiber
carrying Mold detail
reproducibility
Easy
handling Shrinkage and
dimentional
Pressure control
Fast Viscosity
thickening
I II III IV
Time
FIGURE 1.3
Ideal viscosity profile for SMCs or BMCs during molding: (I) thickening; (II) storage; (III) mold filling; and (IV)
curing.
8 CHAPTER 1 UNSATURATED POLYESTER RESINS, BLENDS
di- or multifunctional compound to the system which couples two or more polyester molecules
together via their terminal hydroxyl and/or carboxyl groups. As UPR molecules usually contain
more than two functional groups, the actual product formed is a complex network of interconnected
polymer chains rather than discrete individual chains. Compounds used for thickening UPRs are
known as “thickening agents” or “maturation agents.” Two types of compounds are used as thick-
ening agents. The first type comprises Group IIA metal oxides and hydroxides, for example, MgO
[29]. Maturation with this type of agent occurs via the formation of ionic bonds through the reac-
tion of MgO with the carboxylic acid end groups of polyester molecules. The other type of matura-
tion agent is diisocyanate [30]. Diisocyanates operate by forming covalent bonds, specifically
urethane linkages, with the terminal hydroxyl groups of polyester molecules. Each type of matura-
tion agent has its own advantages and disadvantages. The maturation process with MgO-type agents
is slow. They form ionic bonds which weaken at elevated temperatures encountered during mold-
ing. This results in a reduced compound viscosity and hence the desired material flow.
Diisocyanate maturation agents exhibit rapid thickening. The covalent bonds formed with
isocyanate-type thickeners do not weaken at molding temperatures and hence material flow is more
difficult. MgO-type maturation agents are highly sensitive to humidity after maturation, whereas
diisocyanates are not. A thermally breakable di-keto group can be introduced onto the UPR mole-
cule before curing through salt formation. This group, along with the salt, may break at elevated
temperature in most UPR molding operations and therefore reduce the compound viscosity upon
heating; hence the desired amount of material flow is realized. Modified resins are further thick-
ened with MgO or diphenyl diisocyanate. This exhibits a fast viscosity rise during molding and a
stable viscosity during room temperature storage [28].
Molded articles made with conventional UPRs often exhibit poor surface finishes. This is proba-
bly due to shrinkage of the UPR during the molding operation. LPAs are used to overcome this
problem. Along with LPAs, good material flow during molding is also necessary to obtain finishes
of the highest quality. The reduced material flow encountered when diisocyanates are used as thick-
eners reduces the effectiveness of LPA in these systems, which in turn may lead to significant fin-
ish problems. One proposal to overcome this limitation is to use a combination of both MgO-type
and diisocyanate-type thickeners in the same system [31].
curing by physical and chemical methods. When blends are formed by the physical mixing of two
or more polymers at least 5% of another polymer is necessary to form a blend. If the component
polymers are miscible, a single-phase blend is obtained. If they are immiscible, a multiphase blend
is formed. Even if rubber additives are soluble in uncured resin, phase separation during curing is
advantageous since these blends are tougher than homogeneous blends [33,34]. The presence of
elastomeric domains increases the absorption and dissipation of mechanical energy. Various
mechanisms proposed for toughening by blending with rubber include the debonding of the rubber
matrix interphase, energy absorption by rubber particles, matrix crazing, shear yielding, and com-
bining shear yielding and crazing [32,33].
Essential characteristics of elastomers for toughening are [35]:
1. The presence of a sufficient number of polar groups to enhance solubility in the resin.
2. The elastomer should have a slow rate of cross-linking compared to the UPR used to facilitate
the distribution of discrete elastomeric particles during cross-linking.
3. The weight of the elastomer should be relatively high.
4. The major part of the elastomer should be thermodynamically incompatible with resin.
FIGURE 1.4
Impact strength of pure UPR and UPR/NRL blends using different dispersion aids: (A) using SLS as a dispersion
aid; (B) using toluene as a dispersion aid; and (C) using liquid ammonia as a dispersion aid.
1.4 UNSATURATED POLYESTERS RESIN BLENDS 11
properties, except for their strain rates which were higher. The wear rates of the blends were found
to decrease with increasing NBR content [39]. Cherian and Thachil prepared blends of UPR with
elastomers bearing reactive functional groups such as hydroxy-terminated polybutadiene, epoxi-
dized natural rubber, hydroxy-terminated natural rubber, and maleated nitrile rubber. These elasto-
mers show better compatibility with resin and impart superior toughness, fracture resistance, and
impact resistance as compared to unmodified elastomers [34]. The authors also synthesized UPR
blends using two different strategies for incorporating rubber. The first method involves the dissolu-
tion of masticated elastomers such as natural rubber (NR), styrene butadiene rubber (SBR), NBR,
butyl rubber (IIR), and chloroprene rubber (CR) in styrene followed by blending with UPR, while
in the second method, elastomers are modified with MA and then dissolved in styrene and blended
with UPR to get maleated elastomers. Blends having elastomers modified with MA show improved
mechanical properties (toughness, impact resistance, and tensile strength) compared to unmodified
rubbers (Tables 1.1 and 1.2). The performance of nitrile rubber is found to be far superior in
Table 1.2 Summary of Properties of UPR Modified With 0%5% Maleated Elastomers
Maximum Improvement Achieved (%)/Maleated Elastomer
Concentration (%)
Drittes Kapitel.
Eine mißglückte Autofahrt.