Thesis - ADDING VALUE TO RECYCLED POLYETHYLENE THROUGH THE ADDITION OF MULTI-SCALE REINFORCEMENTS - 2005 - USA

ADDING VALUE TO RECYCLED POLYETHYLENE THROUGH
THE ADDITION OF MULTI-SCALE REINFORCEMENTS
A Thesis
Presented to
The Graduate Faculty of The University of Akron
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
Meagan E. Hill
August, 2005
ADDING VALUE TO RECYCLED POLYETHYLENE THROUGH
THE ADDITION OF MULTI-SCALE REINFORCEMENTS
Meagan E. Hill
Thesis
Approved: Accepted:
_______________________________ __________________________________
Advisor Dean of College
Dr. Lloyd Goettler Dr. Frank N. Kelley
_______________________________ __________________________________
Department Chair Dean of Graduate School
Dr. Sadhan C. Jana Dr. George K. Newkome
_______________________________ __________________________________
Faculty Reader Date
Dr. Mark D. Soucek
ii
ABSTRACT
As a result of the degradation experienced by polymers during their use and the
impurities acquired during the recycling process, recycled polymers tend to have weaker
mechanical properties than their virgin counterparts. Efforts have been made to upgrade
recycled high-density polyethylene so that it may compete with virgin material, both
economically and performance wise.
This study focuses on the improvement of the mechanical properties of recycled
high-density polyethylene (RHDPE) through the addition of multi-scale reinforcements.
RHDPE composites reinforced with nanoclay, cellulose fibers, and a combination of the
two were made. The effects of the reinforcements on the mechanical properties of the
composites as well as the effect of compatibilization on the composite properties are
highlighted.
To address the economic objective of this study, bentonite is investigated as a
possible alternative to montmorillonite as the nanofiller in the hybrid system. Bentonite
is the ore from which montmorillonite is refined. So, it is less expensive than
montmorillonite, but possesses the same layered silicate structure.
In this study, a hybrid composite was made and shown to have increased tensile
strength and elastic modulus compared to that of virgin HDPE. The nanoscale clay
reinforcement was found to provide effective stiffening to the composite, while the
microscale cellulose reinforcement was found to have effective strengthening.
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AKNOWLEDGEMENTS
I would like to thank Dr. Lloyd Goettler for his caring and supportive attitude
throughout the duration of my work. I would also like to thank my family and friends for
their support and understanding.
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TABLE OF CONTENTS
Page
LIST OF TABLES………………………………………………………………………..xi
LIST OF FIGURES……………………………………………………………….……..xii
CHAPTER
I. INTRODUCTION….……………………………………………………………...1
II. BACKGROUND…………...…………………………………………………….4
2.1 Materials...……..…….………………………………………………………..4
2.1.1 Nanoclays….……………….……………………………………………….4
2.1.1.1 Monmorillonite Clays…………..…………………………………...…..4
2.1.1.2 Bentonite Clays……………..………………………………………...…6
2.1.2 Cellulose Fibers……………………………………………………….……7
2.1.3 High-Density Polyethylene………………………………………………....7
2.2 Recycling of Polyethylene………………..……………………………………8
2.3 Polymer/Clay Nanocomposites………...……..……………………………..…9
2.3.1 Current Market for Polymer/Clay Nanocomposites……...……………….11
2.3.2 Polyethylene/Clay Nanocomposites…………………...………………….12
2.3.3 Preparation of Polyolefin Nanocomposites………………………………..13
2.4 Polymer/Cellulose Microcomposites…………………...…………………....15
2.4.1 Market for Polymer/Cellulose Microcomposites…………….……………15
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2.4.2 Use of Recycled Materials in Polymer/Cellulose Composites…………....16
2.4.3 Polyethylene/Cellulose Microcomposites…………………………...…….17
III. EXPERIMENTAL……………………………………………………………..19
3.1 Materials………………………………………………………………...……19
3.1.1 Polyethylene Matrix……..………………………………………...………19
3.1.1.1 Recycled Polyethylene…..………………………………………..……19
3.1.1.2 Virgin Polyethylene………..…………………………………………..19
3.1.2 Compatibilizer……………………………………………………………..20
3.1.3 Nanoclays…………………………………………………………….……20
3.1.3.1 Montmorillonites…………………………………………………….....20
3.1.3.2 Bentonite Clays……………………………………………………..….22
3.1.3.3 Ammonium Salt for Clay Treatment……………………………..……22
3.1.4 Cellulose Fibers………………………………………………………..….23
3.2 Hybrid Composite Development……...……………………………………...23
3.2.1 Introduction………………………………………………………………..23
3.2.2 Preparation of Polymer/Clay Nanocomposites………………………...….24
3.2.2.1 Study of Mixing Schemes……………………...……………………....24
3.2.2.2 Clay Treatment…………………………………………………………25
3.2.2.3 Experimental Test Matrices………………………………………..…..26
3.2.3 Preparation of Polymer/Cellulose Microcomposites……...………………28
3.2.4 Preparation of Hybrid Composites…………………………………...……29
3.2.5 Preparation of Compounds for Probing Studies…………………………..30
3.2.5.1 Treatment of Clay During Compounding……………………………...30
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3.2.5.2 Compatibilization of RHDPE via Reactive Compounding…………....31
3.2.6 Specimen Preparation………………………………………………..……32
3.3 Characterization………………………………………………………………33
3.3.1 Mechanical Testing…………………………………………………….….33
3.3.2 Wide Angle X-ray Diffraction (WAXD)………………………………….33
3.3.3 Scanning Electron Microscopy (SEM)…..…………..……………………33
3.3.4 Differential Scanning Calorimetry (DSC)………………………..……….34
IV. RESULTS……………………………………………………………………...35
4.1 Introduction……………………………………………………………...……35
4.2 Polymer/Clay Nanocomposites……………………………………………….35
4.2.1 Mixing Scheme Analysis…………………………………………….……35
4.2.1.1 Tensile Strength……………………...………………………………...36
4.2.1.2 Elastic Modulus……………………...………………………………...36
4.2.1.3 Percent Elongation……………………...………………………...……37
4.2.1.4 Summary of Mixing Scheme Analysis for Polymer/Clay

Nanocomposites…………………………………………...………..….38
4.2.2 Treatment of Bentonite Clay………………………………………………38
4.2.2.1 Mechanical Properties………………………………………………….38
4.2.2.2 Morphology……………………………………………………….……40
4.2.3 Mechanical Properties of Polymer/Clay Nanocomposites………………..42
4.2.3.1 Stress-Strain Curve……………………………………………….……42
4.2.3.2 Tensile Strength…………………………………………………..……43
4.2.3.2.1 Tensile Strength Dependence on Clay Treatment and Clay

Loading……………………………………………………………..43
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4.2.3.2.2 Tensile Strength Dependence on Clay Loading and MA-g-PE
Loading.………………………………………………………...….44
4.2.3.3 Elastic Modulus…………………………………………………….….45
4.2.3.3.1 Elastic Modulus Dependence on Clay Treatment and Clay

Loading…………………………………………………….....…….45
4.2.3.3.2 Elastic Modulus Dependence on Clay Loading and MA-g-PE

Loading……………………………………………………………..46
4.2.3.4 Percent Elongation…………………………………………………..…47
4.2.3.4.1 Percent Elongation Dependence on Clay Treatment and Clay

Loading………………………………………………………….….48
4.2.3.4.2 Percent Elongation Dependence on Clay Loading and MA-g-PE

Loading.……………………………………………………………....….49
4.3 Polymer/Cellulose Nanocomposites…………………………………………..50
4.3.1 Mechanical Properties of Polymer/Cellulose Nanocomposites…………...50
4.3.1.1 Stress-Strain Curve………………………………………………….....50
4.3.1.2 Mechanical Property Dependence on Cellulose Type and Presence of

Lubricant…………...…..………………………………………………51
4.3.1.2.1 Summary of Effects of Cellulose Type and Presence of

Lubricant………………………………………………………...….55
4.3.1.3 Mechanical Property Dependence on Cellulose Loading and MA-g-PE

Loading………………………...……………………………………....56
4.3.1.4 Percent Elongation……………………………………………………..58
4.4 Hybrid Composites………………………………………………………..….59
4.4.1 Mechanical Properties of Hybrid Composites………………………….....59
4.4.1.1 Stress-Strain Curve………………………………………………….....60
4.4.1.2 Mechanical Property Dependence on Reinforcement Loading…..……60
4.4.1.3 Mechanical Property Dependence on MA-g-PE Loading………..……63
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4.4.2 Morphology…………………………………………………………….….67
4.4.2.1 Wide Angle X-ray Diffraction………………………………………....67
4.4.2.2 Scanning Electron Microscopy…………………………………...……68
4.4.2.3 Crystallization Effects in the Hybrid System………………………..…68
4.5 Probing Studies……………………………………………………………….71
4.5.1 Clay Treatment During Compounding………………………………...….71
4.5.2 Compatibilization via Reactive Compounding…………….…………..….73
V. DISCUSSION……………………………………………………………….….76
5.1 Introduction……………………………………………………………….…..76
5.2 Mechanical Properties of Clay System……………………………………….76
5.2.1 Effect of Clay Treatment………………………………………………….76
5.2.2 Effect of Clay Types……………………………………………………....79
5.2.2.1 Mechanical Properties……………………………………………...…..79
5.2.2.2 Morphology………………………………………………………….....79
5.2.3 Effect of Clay Loading and MA-g-PE Content……………………...……80
5.3 Mechanical Properties of Cellulose System………………………………….82
5.3.1 Effect of Cellulose Type……………………………………………….….82
5.3.2 Effect of Cellulose and MA-g-PE Loading………………………...……..84
5.4 Mechanical Properties of Hybrid System……………………………….……86
5.4.1 Effect of MA-g-PE Loading…………………………………………...….86
5.4.2 Reinforcment Effects on Hybrid System………………………..…..…….88
5.4.3 Crystallization Effects on the Hybrid System……..……………………....88
5.5 Results from Probing Studies……………………………………………..….89
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5.5.1 Clay Treatment During Compounding……………………………………89
5.5.2 Compatibilization via Reactive Compounding…………………………....90
5.6 Economic Considerations…………………………………………….………90
VI. CONCLUSIONS……………...………………………………………….……93
REFERENCES……………………………………………………………………..96
APPENDIX…………………………………………………………………...…….99
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LIST OF TABLES
Table Page
3.1 Physical Properties for Alathon M 6210®43…………………………………………20
3.2 Reported Properties of Reported Properties of Cloisite® Na+, Cloisite® 20A,

Cloisite® 10A, and Cloisite® 25A44………………….……………………………...21
3.3 Properties of Neat Bentonite Clay…………...……………………………………...22
3.4 Properties of Arquad® 2HT-7545…………………………………………………….22
3.5 Properties of TC2500 and TC100446………………………………………………..23
3.6 Test Matrix for the Investigation of Clay Type and Loading……………………….27
3.7 Test Matrix for the Investigation of Clay and MA-g-PE Loading…………………..27
3.8 Test Matrix for the Comparison of Montmorillonite and Bentonite Clays………....28
3.9 Test Matrix for Investigation of the Cellulose System……………………………...29
3.10 Test Matrix for the Investigation of the Hybrid System…………………………....30
3.11 Test Matrix for Clay Treatment Study……………………………………………...31
3.12 Experimental Test Matrix for Reactive Compounding Study…………………...…32
5.1 Summary of Mechanical Testing Results for Hybrid System at 4 vol% Clay and/or
Cellulose…………………………………………………………………………....88
5.2 Cost of Raw Materials……………………………………………………………....91
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LIST OF FIGURES
Figure Page
1.1 Schematic of Hybrid System………...……………………………….………………2
2.1 Structure of Montmorillonite Clay………………………………….…...………...….5
2.2 Structure of Cellulose…………………………………………………………...……7
2.3 Schematic of Intercalated and Exfoliated Clay Structures………………………….10
2.4 Compatibilzation of HDPE nanocomposite………………………………………....13
3.1 Cloisite® 10A: dimethyl, benzyl, hydrogenatedtallow, quaternary ammonium44…..21
3.2 Cloisite® 20A: dimethyl, dihydrogenatedtallow, quaternary ammonium44…………21
3.3 Cloisite® 25A: dimethyl, hydrogenatedtallow, 2-ethylhexyl, quaternary

ammonium44……………………………………………………………………………...21
4.1 Tensile Strength Comparison for 3 Mixing Schemes………………………..……...36
4.2 Elastic Modulus Comparison for 3 Mixing Schemes………………………….……37
4.3 Percent Elongation Comparison for 3 Mixing Schemes………………………….....38
4.4 Comparison of Tensile Strength for Composites made with Treated and Untreated
Bentonite or Montmorillonite with 5 vol% MA-g-PE……………...…………….....39
4.5 Comparison of Elastic Modulus for Composites made with Treated and Untreated
Bentonite or Montmorillonite with 5 vol% MA-g-PE……………...…………….....40
4.6 WAXD for Nanoclays…………………………………………………………….…41
4.7 WAXD for Nanoclays (Low Intensity Magnification)…………...………………....42
4.8 Representative Stress-Strain Curve for Clay/Polymer System……………………...43
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4.9 Tensile Strength Dependence on Clay Treatment and Clay Loading at 1:1 vol%
ratio of silicate to MA-g-PE……………………………………...…………….....…44
4.10 Tensile Strength Dependence on Clay and MA-g-PE Loading at 1:1 vol% ratio of
silicate to MA-g-PE…………………………………………...………...……..……45
4.11 Elastic Modulus Dependence on Clay Treatment and Clay Loading at 1:1 vol%
ratio of silicate to MA-g-PE……………………………………...…………….....…46
4.12 Elastic Modulus Dependence on Clay and MA-g-PE Loading at 1:1 vol% ratio of
silicate to MA-g-PE…………………………………………...………...……..……47
4.13 Percent Elongation Dependence on Clay Treatment and Clay Loading at 1:1 vol%
ratio of silicate to MA-g-PE.………………………………………………..……….48
4.14 Percent Elongation Dependence on Clay and MA-g-PE Loading at 1:1 vol% ratio
of silicate to MA-g-PE……………………………………………..…..…………....50
4.15 Representative Stress-Strain Curve for Cellulose/Polymer System………………..51
4.16 Comparison of Tensile Strength with MA-g-PE Level for Softwood Cellulose
Fibers With and Without Lubricant. Triangles=Lubircation, Squares = No
Lubrication………………………………………………………………………......52
4.17 Comparison of Tensile Strength with MA-g-PE Level for Hardwood Cellulose
Fibers With and Without Lubricant. Triangles = Lubrication, Squares = No
Lubircation…………………………………………………………………………..53
4.18 Comparison of Elastic Modulus with MA-g-PE Level for Softwood Cellulose
Fibers With and Without Lubricant. Triangles=Lubircation, Squares = No
Lubrication………………………………………………………………………......54
4.19 Comparison of Elastic Modulus with MA-g-PE Level for Hardwood Cellulose
Fibers With and Without Lubricant. Triangles = Lubrication, Squares = No
Lubrication…………………………………………………………………………..55
4.20 Dependence of Tensile Strength on Cellulose and MA-g-PE Loading for Softwood
Cellulose Fiber Composite.……………………………………………..………...…57
4.21 Dependence of Elastic Modulus on Cellulose and MA-g-PE Loading for Softwood
Cellulose Fiber Composite.………………………………………………..…...……58
4.22 Percent Elongation Dependence on Cellulose Loading………………………….....59
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4.23 Representative Stress-Strain Curve for the Hybrid System………………………...60
4.24 Tensile Strength Dependence on Cellulose and Clay (Silicate) Loading ...….....….62
4.25 Elastic Modulus Dependence on Cellulose and Clay (Silicate) Loading for
Composites at 7.5 vol% MA-g-PE……………………………………..….………...63
4.26 Tensile Strength Dependence on MA-g-PE and Clay Loading at 7.5 vol%
Cellulose…………………………………….………………………………...…….65
4.27 Tensile Strength Dependence on MA-g-PE and Cellulose Loading at 1 vol%

Silicate…………………………….……………………………………………...….65
4.28 Elastic Modulus Dependence on MA-g-PE and Clay Loading at 7.5 vol%
Cellulose…………………….………………………………………………………66
4.29 Elastic Modulus Dependence on MA-g-PE and Cellulose Loading at 1 vol%

Silicate……………………….…………………………………………………...….66
4.30 WAXD for Hybrid System…………………………………………………………67
4.31 SEM for the Hyrbid System (a: left, b: right)……………………………………....68
4.32 DSC Curve for Neat RHDPE…………………………………………………….…69
4.33 DSC Curve for Polymer/Clay Composite with 3 vol% silicate (Closite® 20A) and
10 vol% MA-g-PE…….…………………………………………………………….70
4.34 DSC Curve for Hybrid Composite with 3 vol% silicate (Cloisite® 20A), 11 vol%
softwood cellulose fibers, and 10 vol% MA-g-PE………………...………………..70
4.35 Tensile Strength for Different Clay Treatment Methods for Bentonite
Composites…………………………………………………………………………..72
4.36 Elastic Modulus for Different Clay Treatment Methods for Bentonite
Composites…………………………………………………………………………..72
4.37 Percent Elongation for Different Clay Treatment Methods for Bentonite
Composites…………………………………………………………………………..73
4.38 Tensile Strengths for Comparison of Compatibilization Method………….….……74
4.39 Elastic Moduli for Comparison of Compatibilization Method………………….….75
4.40 Percent Elongation for Comparison of Compatibilization Method………………...75
xiv
5.1 Comparison of Tensile Strength for Various Clay Treatments……………..……....78
5.2 Comparison of Elastic Modulus for Various Clay Treatments……………………...78
5.3 Effects of Clay and MA-g-PE Loading on Tensile Strength…………………….….81
5.4 Effects of Clay and MA-g-PE Loading on Elastic Modulus……………………..…82
5.5 Comparison of Tensile Strength for Softwood and Hardwood Cellulose Fibers...…83
5.6 Comparison of Elastic Modulus for Softwood and Hardwood Cellulose Fibers…....83
5.7 Effects of Cellulose and MA-g-PE Loading on Tensile Strength………………...…85
5.8 Effects of Cellulose and MA-g-PE Loading on Elastic Modulus………………...…85
5.9 MA-g-PE Dependence on Tensile Strength in the Hybrid System………………….87
5.10 MA-g-PE Dependence on Elastic Modulus in the Hybrid System……………...….87
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CHAPTER I
INTRODUCTION
Plastics News listed high density polyethylene (HDPE) as the top material bought or
sold in the plastics recycling market in 2003.1 The abundance of recycled HDPE
(RHDPE) creates the need for new, innovative uses for this material.This project not only
focuses on developing a new use for RHDPE, but also brings together two hot topics in
the polymer industry. Polymer nanocomposites have commanded attention from the
polymer industry for the past two decades. Nanotechnology is one of the biggest things
to happen in the physical sciences in recent decades.2 The worldwide funding for
nanotechnology was estimated to have increased by seven times from 1997 to 2003.3
Wood-plastic composites have also made significant head-way in polymer markets as
plastic lumber. The wood-plastic composites market which is already at 1,3-billion-lb is
expected to grow 20% annually.4
The primary objective of this work was to add value to recycled polyethylene. In
completing this objective, two secondary objectives were also addressed. The secondary
objectives are: to do so in an economic and environmentally friendly way and to
investigate possible processing techniques that would serve to reduce the cost of the final
composite. Figure 1.1 shows a general schematic of the hybrid system created for this
work to meet the proposed objectives. It is expected that the nanoclay reinforcement will
stiffen the composite, while the cellulose reinforcement will strengthen the composite.
1
Cellulose Fibers
Nanoclay
Polymer Matrix
Figure 1.1: Schematic of Hybrid System
To achieve good dispersion in any composite system, there must exist a
compatibility between the fillers, which in this case are nanoscale clay and microscale
cellulose fibers, and the polymer matrix. For this hybrid system, one compatibilizer,
maleic anhydride treated polyethylene (MA-g-PE), is used to interact with both
reinforcements. The MA-g-PE serves two purposes, first to disperse the fillers in the
polymer matrix and second to strengthen the interface between the polymer and the
fillers. Studies have been done with both cellulose fibers and montmorillonite nanoclay,
which show improved mechanical properties with the addition of maleic anhydride
compatibilizers in polyolefin composites.5, 6
To address the economic objective of this study, bentonite is investigated as a
possible alternative to montmorillonite as the nanofiller in the hybrid system. Bentonite
is the ore from which montmorillonite is refined so it is less expensive than
montmorillonite, but possesses the same layered silicate structure. Bentonite is generally
not used as a nanofiller due to the impurities present, which are expected to decrease the
effectiveness of reinforcement of the silicate layers. However, for this system, where
2
recycled polymer is being used, the presence of impurities in the clay may not drastically
effect the properties of the final composite. The economic advantages as well as the
identical structure to montmorillonite make bentonite a logical choice for an alternative
nanofiller.
To complete this work, studies are conducted on three systems: clay/polymer
nanocomposites, cellulose/polymer microcomposites, and hybrid composites with both
clay and cellulose reinforcement. For these systems, the mechanical properties are
investigated, including the effects of reinforcement and compatibilization. For the hybrid
system, the morphology was studied using wide angle x-ray diffraction (WAXD) and
scanning electron microscopy (SEM). Finally, two probing studies were conducted to
briefly explore the viablility of treating clay during compounding and compatibilization
via reactive compounding.
3
CHAPTER II
BACKGROUND
2.1 Materials
2.1.1 Nanoclays
Nanosized clay platelets as fillers in polymers provide significant increases in
mechanical properties of the resulting composites at relatively low filler content.7,8 The
efficiency of these nanofillers is due to the high aspect ratio and large surface area of the
clay platelets dispersed at the nanoscale level. Many types of clays and clay treatments
are utilized depending upon the application and polymer system. The most common type
of clay currently used in nanocomposites is montmorillonite.
2.1.1.1 Montmorillonite Clays
Montmorillonite clay is a crystalline clay mineral with a three-layer structure. The
structure consists of a central alumina octahedral layer in between two silica tetrahedral
layers.9 The typical alumina to silica ratio in montmorillonite clay is 1 to 4. A single
clay sheet is approximately 10 Angstrom units or 1 nanometer thick and is usually several
micrometers long. Figure 2.1 shows the structure of montmorillonite clay10.
4
Figure 2.1: Structure of Montmorillonite Clay10
In nature, part of the aluminum in the octahedral layer is replaced by magnesium
causing a negative charge on the clay surface. In order to balance the negative charge,
the interlayer between the clay sheets contains exchangeable cations such as Na+ or Ca2+.
Water molecules are also present in the interlayer.
The exchangeable cations in the interlayer, specifically Na+, are a key part of the
clay treatment that is needed in order to make the polar clay layers compatible with non-
polar polymer matricies. In a simple reaction, the Na+ can be exchanged with an
5
ammonium cation, often having a long carbon chain.11 The bulky ammonium groups
used in cation exchange reactions for clay treatment are adsorbed onto the clay layers
causing the spacing between the clay layers to be increased. The increased space
between the clay layers makes it easier for the polymer chains to enter in between the
clay layers during a compounding process. A wide variety of ammonium groups can be
used for clay treatment to generate the highest enthalpic interaction with the polymer that
will be used to make the composite. In the case of polyethylene composites, protonated
amines with long, non-polar carbon chains are usually used.
2.1.1.2 Bentonite Clays
Bentonite is the name for the ore from which montmorillonite clay is derived.
Bentonite ore typically contain 65%-95% montmorillonite mineral.12 In addition to
montmorillonite mineral, bentonite contains cristobalite, quartz, mica, feldspar, and
carbonates, all of which can effect the reinforcing properties of the ore.12 This clay is
formed naturally from the chemical weathering of volcanic materials, including volcanic
ash. Bentonite has traditionally been used in drilling applications, waterproofing liners,
and wastewater treatment, to name a few. However, although bentonite is less pure than
montmorillonite, it still has potential as a reinforcement because it contains some
smectite clay, which has the same three layer crystalline structure as montmorillonite.
Also, bentonite clay is less expensive than pure montmorillonite clay, which makes it an
attractive option as a nanoscale reinforcement for low cost nanocomposites.
6
2.1.2 Cellulose Fibers
Cellulose is a natural polymer and the main component of the cell walls of more
highly developed plants. It is found in greatest quantity in wood, and in the fibers of
cotton, flax, etc. Figure 2.2 shows the general structure of cellulose.13
Figure 2.2: Structure of Cellulose13
Cellulose fibers have become an attractive option in recent years due partially to
the environmental benefits stemming from cellulose’s natural abundance. Other benefits
of cellulose fibers include high specific strength and good thermal stability14.
2.1.3 High-Density Polyethylene
Polyethylene (PE) is one of the most simple and inexpensive polymers available.
In forming this polymer, methane gas is first converted to ethylene. Then, upon addition
of heat and pressure, the double bond of the ethylene molecule is broken to allow
adjacent carbon atoms to connect through additional single bonds that form on the carbon
atom. The resulting structure is a long carbon chain with two hydrogen atoms attached to
each carbon atom.
This polymer has a wide range of uses including bottles, packaging, grocery bags,
and drainage pipes. It is used in so many applications because of the various attractive
properties it possesses such as: low price, good processability, excellent chemical
resistance, electrical insulation properties, toughness, and flexibility.

7
PE is available in several structural forms called: high-density PE, low-density PE,
and linear low-density PE. High-density PE (HDPE) has a density in the range of 0.941
to 0.965. PE is characterized as a semi-crystalline polymer containing both crystalline
and amporphous regions. The highly ordered crystalline regions occur when the chains
branching off of the side of the main chain are small in number. HDPE has a greater
crystallinity than the other grades of PE due to fewer branches present in the structure.
The size and distribution of the crystalline regions are determinants of the tensile strength
and the environmental stress cracking of the final polymer product.
2.2 Recycling of Polyethylene
By weight, plastic makes up about 7 percent of the waste stream according to the
EPA. By volume it is closer to 20 percent. The EPA estimates that in 2005, the amount of
plastics discarded in the U.S. will increase 55 percent from the early 1990's level.
Although plastic recycling has increased substantially, the EPA estimates that less than 1
percent of plastics are currently being recycled. HDPE is one of the main polymers
targeted for recycling due to its wide use and easy separation from other waste plastics.
PE is generally recycled via mechanical means, in which the plastics are ground,
melted, and remade into products with characteristics equivalent to original products or
products with less demanding performance requirements.
One main problem with recycling of plastics is the incompatibility between
polymers in the recycle stream and consequently the cost of separating polymer types
from each other as well as from the rest of the solid waste. Separation becomes a major
issue because the presence of impurities or other polymers affect the properties of the
recycled polymer. Also, most polymers suffer degradation during use due to exposure to
8
high temperature, UV-radiation, oxygen, and ozone, which leads to reduction in polymer
chain length and consequently polymer properties.
Even with these problems, PE is making its way through the recycling centers and
into consumer use. Recycled polyethylene is most commonly found as drums, pails,
agricultural drain tile, flowerpots, and plastic lumber. Of these uses, the plastic lumber
industry has been making great strides in the past several years and looks like a
promising market that will continue to demand recycled PE.
2.3 Polymer/Clay Nanocomposites
Polymer nanocomposites have been receiving a lot of attention for more than a
decade. This type of composite offers improved properties, which are different from
conventional composites due to the small size and the high surface-to-volume ratio of the
nanoscale fillers. Nanocomposites can enhance numerous polymer properties including:
thermo-mechanical properties, barrier properties, flame retardancy, heat resistance,
dimensional stability, and electrical conductivity. Currently, layered silicate nanoclays,
nano-talcs, carbon nanotubes, and graphite platelets are being studied for use in
nanocomposites. Of these fillers, nanoclays have been an attractive option because of
low cost, as compared to carbon nanotubes, and the many properties offered such as
increased stiffness, improved barrier properties, and dimensional stability. Currently, the
cost of nanoclay ranges from $2.25 to $3.25/lb15.
Since the properties of nanocomposites stem from high surface-to-volume ratio of
the clay reinforcement, it is important that the clay in the nanocomposite is well
dispersed. In order for an effective nanocomposite to be made the clay layers must be
either intercalated or exfoliated. Intercalation means that polymer is present in the clay
9
layers, but that the clay layers have maintained the initial relative position in relation to
the clay layers. In an exfoliated structure, the polymer has separated the clay layers and
caused them to be dispersed randomly in the polymer matrix. Figure 2.3 shows an
intercalated and exfoliated structure.
Figure 2.3: Schematic of Intercalated and Exfoliated Clay Structures.16
10
2.3.1 Current Market for Polymer/Clay Nanocomposites
In recent years, polymer nanocomposites have been present in the market place.
Two existing markets for polymer nanocomposites are automotive and packaging. Many
companies are developing products for these markets in order to gain acceptance in this
new industry.17 In 2003, the total market for polymer nanocomposites reached 24.5
billion pounds, which was valued at $90.8 million4. According to a study conducted by
Business Communications Co., Inc. in Norwalk, Connecticut, this market is expected to
grow 18.4% annually reaching an estimated $211.1 million in 20084.
This market existence is seen in the nanocomposite lines recently launched by
several well-known polymer companies. Noble Polymers has launched a polypropylene
nanocomposite with the trade name Forte PP®. Forte PP® provides lower density,
superior mechanical properties, improved surface quality and better recyclability
compared to glass-filled PP and was implemented in the seat backs of the Honda Acura
TL 20044, 18. PolyOne has also released a line of polypropylene/nanoclay compounds
called Maxxam® LS. This compound offers users high stiffness and impact resistance.
In addition to the Maxxam® LST line, PolyOne offers NanoblendTM concentrates, which
can be used to produce well-dispersed polymer nanocomposites19. Also, conventional
talc filled TPOs are being replaced by nano-talc TPOs in many automotive applications.
This offers more consistency of properties, retention of low temperature ductility,
improved colorability, reduced paint delamination, scratch and mar resistance, and
recyclability4.
11
2.3.2 Polyethylene/Clay Nanocomposites
In the area of nanocomposites, many polymer systems have been investigated
including polystyrene, polycaprolactone, polyamide, and epoxy resin20,21,22,23. It was
found that exfoliated/intercalated dispersion of the clay layers in the polymer matrix
could be achieved in certain polymers with polar functional groups that make the
polymer more compatible with the polar groups on the silicate clay layers. Polyolefins
have been an attractive choice for polymer nanocomposites because of its wide use and
low cost, but as non-polar polymers it is very difficult to disperse the nanoclay into the
polyolefin matrix to achieve a nanostructure.
Due to this challenge, much work has been done in the area of compatibilization of
these systems. Wang and coworkers reported an intercalated structure of
polypropylene(PP)/clay nanocomposites when compatibilized with maleic anhydride-
modified PP24. In another study, Wang and coworkers reported complete exfoliation of
PE/clay nanocomposites when the PE was grafted with maleic anhydride at levels above
0.1 wt% and the organic modifier on the clay had more than 16 methylene groups in the
alkylamine chain25. Ishida and coworkers reported intercalated and exfoliated structures
when preparing nanocomposites of PE and bentonite clay with the addition of epoxy or
poly(dimethylsiloxane) as swelling agents26. These studies, among others, have shown
that intercalated or even exfoliated structures of polyolefin nanocomposites are
achievable, but all note that compatibilization between the clay and the polymer matrix is
of great importance.
Although many compatibilization techniques have been studied, the most common
method for compatibilizing polyolefin nanocomposites is by grafting maleic anhydride to
12
the polymer chains. The maleic anhydride reacts with the polymer matrix to provide
polar groups, which will be attracted to the polar nature of the silicate clay layers. Figure
2.4 shows a representation of maleic anhydride compatibilization of PE/clay
nanocomposites. The three main interactions that occur are represented in the schematic:
1 shows the interaction between the polymer matrix and the polyethylene chain of the
compatibilizer, 2 two shows the interaction between the polar maleic anhydride group
and the polar silicate layer of the clay, and 3 and 4 show the interaction between the clay
treatment and the polymer matrix (3) or the polymer compatibilizer (4).
silicate
N+
2 MA
MA
HDPE 1 3
N+ compatibilizer
Figure 2.4: Compatibilzation of HDPE nanocomposite
2.3.3 Preparation of Polyolefin Nanocomposites
In addition to compatibilization, the processing technique used to make the
polyolefin/clay nanocomposites can have a notable effect on the dispersion and structure
13
of the composite. When preparing these composites, there are generally three approaches
that are taken including. First, the nanocomposite can be made by in-situ polymerization.
In this method, the clay layers are first intercalated by the monomer and the subsequently
polymerized. The polymerization that occurs between the clay layers provides force
from the expanding polymer chains, which results in further separation of the clay layers
and can lead to an exfoliated structure. Second, the nanocomposite could be made by
solution polymerization in which the polymerization reaction is conducted in a solvent or
the polymer intercalates the clay while in solution.27 Finally, the nanocomposite could be
made using direct melt intercalation. In this process, the nanoclay is added directly to the
polymer melt. The intercalation is caused by the migration of the polymer chains
between the clay layers, which must be driven by the compatibility between the polymer
matrix and the clay.28 This compatibility is most often achieved through polymer
modification and clay treatment. Also, the clay layers can be separated and dispersed as
a result of the shear force experienced during the mixing. Due to its low cost, high
productivity, and compatibility with current processing techniques melt intercalation is
currently the most attractive option for making polymer nanocomposites.
Many studies have been conducted, which look at the effectiveness of these
different processing methods. Jeon and coworkers reported an intercalated morphology
of HDPE nanocomposites prepared by solution blending of HDPE with sodium
montmorillonite cation-exchanged with protonated dodecylamine29. Others have shown
an exfoliated morphology when in-situ polymerization was performed on a
polyethylene/clay system30,31. Intercalated and exfoliated structures have also been
reported when using melt-intercalation for both PE and PP systems32,33,34.
14
2.4 Polymer/Cellulose Microcomposites
Due to heightened environmental awareness and ecological concerns surrounding
the polymer industry, interest in cellulose fibers has been growing over the past decades.
Currently, wood-plastic composites are challenging traditional composites, which are
reinforced with glass or carbon fibers. Wood fillers, such as cellulose fibers, are
expected to replace these synthetic materials in boat hulls, bathtubs, and archery bows to
name a few35. There are many reasons why cellulose fibers are becoming more attractive
than traditional fillers. In general, natural fibers are abundant, inexpensive, renewable,
recyclable, and biodegradable. As compared to glass fibers, cellulose fibers are non-
abrasive and offer a lower density while maintaining two-thirds to three-fourths of the
strength properties of glass fibers36. Other performance advantages of polymer/cellulose
composites are high stiffness, sound absorption, and good thermal stability.
2.4.1 Market for Polymer/Cellulose Microcomposites
Currently, cellulose fillers are priced in the mid $0.20/lb. range and are
commercially available in bulk with consistent properties and quality36. In 2004, the
market for wood-filled plastics was estimated to be around 1.3 billion pounds and said to
be growing at a rate of 20% annually37.
The major market to date for these composites is wood-plastic composite (WPC)
decking. The market share for WPC in decking has grown from less than 1% of the total
decking market in the mid-1990’s to over 10% in 200438. The market is expected to
continue growing to reach more than 20% by 201039. WPC decking manufacturers are
marketing their products as more environmentally safe than traditional treated wood
decking with higher performance properties. The projected growth of the WPC decking
15
industry is due to the public perceptions of greater durability and lower maintenance with
the WPC decking. In addition to the advantages offered by WPC decking, harsher EPA
restrictions on wood treatments are expected to drive the growth of the industry. In
January 2004, the EPA restricted residential use of chromated copper arsenate (CCA)
treated lumber38. Before this mandate, CCA was the most common and economical
treatment used. Using newer wood treatment technologies will cost more, which will
reduce the gap between the costs of WPC decking and traditional wood decking.
Other markets for WPC include siding, roofing, and automotive. Improvements
in WPC are currently being made in order to provide more duable siding and roofing
products. WPCs are just beginning to be introduced in the siding market, but trial
products have been introduced that promise to offer performance advantages over
traditional siding materials such as vinyl, aluminum, or wood38. In the early stages of
development, cellulose fibers were thought to be unsuitable for processing with high
temperature engineering plastics, such as those used in automotive applications.
However, Rayonier has found that purified cellulose can safely be melt compounded at
temperatures above 435°F38. This has opened the door for WPC to be used in
automotive-grade resins such as nylon 6 and polybutylene terephthalate.
2.4.2 Use of Recycled Materials in Polymer/Cellulose Composites
There is a significant opportunity for the use of both recycled polymer and wood
filler when making WPCs. Recycled wood fillers can be obtained from both post-
industrial and post-consumer sources. The most common wood filler used is wood flour,
which can be obtained from post-industrial wood shavings, chips or saw dust38. Many
companies are already using recycled wood fibers in their products. For example, Trex
16
decking uses about 50% recycled wood fiber and CorrectDeck uses 60% oak and pine
dust primarily from wood wastes generated in floor manufacturing 39,40,41. These
companies are also making use of recycled plastics in their decking products. In 2002,
Trex, the largest supplier of wood-plastic composite lumber, purchased over 227,000 kg
of plastic scrap each day41. CorrectDeck also makes use of recycled plastic by
incorporating recycled grocery bags and used pallet wrap into their decking material42.
These are only two of many companies making use of waste or scrap materials in their
products. Of all the polyolefins reclaimed from the post-consumer plastics stream, 38%
was used in wood-plastic composites, which helps to show the magnitude of plastic waste
being reused in this market.
2.4.3 Polyethylene/Cellulose Microcomposites
Polyolefin/cellulose composites and specifically composites made with PE have
shown a lot of promise in the wood-plastics composite industry. Currently, WPCs made
with PE account for 80% of the market37. WPCs made with PE are being used for many
applications including: decking, railing, fencing, doors, window frames, outdoor spas,
gazebos, siding, and roofing.
This combination looks to be ideal because PE is the most widely used synthetic
polymer, while cellulose is the most abundant natural polymer on the earth. Also, the
thermoplasticity of PE is expected to compensate for the poor processablility of cellulose
with rigid molecular chains. However, due to the naturally hydrophilic nature of the
cellulose fibers and the non-polar nature of PE, the two are incompatible without
modification. As with any composite, the compatibility of the components being mixed
is of key importance for dispersion of the filler as well as for creating strong interfaces in
17
the composite. Much work has been done in this area in order to effectively
compatibilize these composites. This is most commonly achieved by adding coupling
agents or compatibilizers to the polymer/cellulose system. These coupling agents will
serve to bond the wood fiber to the polymer matrix. In the case of PE/cellulose
composites, the most common coupling agent used is maleated PE. This compatibilizer
is made by grafting maleic anhydride onto PE. Another compatibilizer being considered
for this application is long-chain chlorinated paraffin from Dover Chemical.
Although WPCs with PE have been entering the market with success, there are
still many problems to be sorted out. A major problem is water absorption, which can
lead to warpage and splitting. In addition, staining and discoloration are often found to
occur due to the radiation from the sunlight that the decking and siding experience. In
the years to come, the main task for this industry will be addressing and fixing problems
such as these.
18
CHAPTER III
EXPERIMENTAL
3.1 Materials
Several materials were used as ingredients in formulating the hybrid compound
including: recycled and virgin polyethylene, compatibilizer, nanoclays, ammonium salts,
and cellulose fibers. The following is a list and description of those materials.
3.1.1 Polyethylene Matrix
3.1.1.1 Recycled Polyethylene
Recycled post consumer HDPE pellets (RHDPE) were obtained from CAPCO
Recycling, Inc. The HDPE comes from uses such as detergent bottles and milk cartons.
The material is washed and reground after one heat history. No additive or purification
steps are done on this material.
3.1.1.2 Virgin Polyethylene
Virgin HDPE used as a control for this work was Alathon M 6210® from Equistar
Chemicals. Alathon M 6210® is a medium molecular weight high-density homopolymer.
Typical physical properties reported by the manufacturer for this polymer are as follows.
19
Table 3.1: Physical Properties for Alathon M 6210®43
ASTM Test
Property Nominal Value Units Method
Melt Index 0.95 g/10 min D 1238
Density 0.958 g/cc D 1505
Elmendorf Tear Strength, MD (TD) 25 (1,100) G D 1922
Tensile Strength @ Yield, MD (TD) 3,900 (4,000) Psi D 882
Tensile Strength @ Break, MD (TD) 7,900 (3,400) Psi D 882
Elongation @ Break, MD (TD) 700 (750) % D 882
Secant Modulus, MD (TD) 136,000 (184,000) Psi E 111
3.1.2 Compatibilizer
Maleic anhydride grafted PE (MA-g-PE) was used to compatiblize the system by
providing a link between the non-polar polymer matrix and the polar clay and cellulose
reinforcements. The MA-g-PE used was Polybond 3009® from the Crompton
Corporation. According to the manufacturer, this particular grade of MA-g-PE has a
functionality of 1.0 wt% and a melt flow rate is 5g/10min at 190°C. The density of this
material is 0.95 g/cc at 23°C.
3.1.3 Nanoclays
3.1.3.1 Montmorillonites
Montmorillonites with various treatements were obtained from Southern Clay
Products Co. Cloisite® Na+, Cloisite® 10A, Cloisite® 20A, and Cloisite® 25A were used
in this study. Cloisite® Na+ is a purified natural montmorillonite clay, but is untreated
thus having only Na+ cations present in the clay galleries. Cloisite® 10A, Cloisite® 20A,
and Cloisite® 25A are also purified natural montmorillonite clays, but have been treated
by exchanging various ammonium salts for the Na+ cations initially present in the clay
galleries. The following figures show the treatments present on each clay type. In the
20
figures, HT signifies a hydrogenated tallow. The typical physical properties reported by
the manufacturer for each clay type are also shown.
Figure 3.1: Cloisite® 10A: dimethyl, benzyl, hydrogenatedtallow, quaternary

ammonium44
Figure 3.2: Cloisite® 20A: dimethyl, dihydrogenatedtallow, quaternary ammonium44
Figure 3.3: Cloisite® 25A: dimethyl, hydrogenatedtallow, 2-ethylhexyl, quaternary

Ammonium44
Table 3.2: Reported Properties of Cloisite® Na+, Cloisite® 20A, Cloisite® 10A, and
Cloisite® 25A44
Modifier % Weight
Concentration % Loss on Density d-Spacing
Treatment: (meq/ 100g clay) Moisture Ignition Color (g/cc) (Å)
Cloisite® Na+ NA <2 7 off white 2.86 11.7
Cloisite® 20A 95 <2 38 off white 1.77 24.2
21
3.1.3.2 Bentonite Clays
Bentonite clay was obtained from Tri State Packaging Company, Wooster, Ohio.
This grade of bentonite is used mostly as a pond liner or drilling mud. Initially, this
bentonite was in granular form, but was reduced to a powder form before use. The
following are typical properties for the raw bentonite.
Table 3.3: Properties of Neat Bentonite Clay

Interlayer
Treatment: Color
Spacing (Å)
Bentonite clay Gray 13.25
3.1.3.3 Ammonium Salt for Clay Treatment
The bentonite clay was treated with a di(hydrogenated tallow)dimethyl ammonium
chloride, the structure of which is shown as Figure 3.1 (Cloisite® 20A treatment). This
ammonium salt was obtained in paste form as Arquad® 2HT-75 from Akzo Nobel
Surface Chemistry, LLC. The typical alkyl distribution for this compound was 58% C18,
32% C16, 4% C14, and small traces of other carbon chains. Nominal properties for
Arquad® 2HT-75 are as follows.
Table 3.4: Properties of Arquad® 2HT-7545

Property Nominal Value Units
Boiling Point 80 ˚C
Melting Point 35 ˚C
Pour Point 40 ˚C
Density 0.859 g/cc
Vapor Pressure @ 20˚C 5.9 kPa
Color white NA
22
This treatment was used to synthesize organoclays with a treatment equivalent to
Cloisite® 20A.
3.1.4 Cellulose Fibers
Hardwood (TC 2500) and softwood (TC 1004) cellulose fibers obtained from
CreaFill Fibers Corp. were used in this study. CreaTech TC functional cellulose fibers
are highly pure fibers with a cellulose content of at least 99.5% in a dry state.46 The
following are nominal physical properties of these fibers.
Table 3.5: Properties of TC 2500 and TC 100446

Property TC 2500 TC 1004
Average Fiber Length (μm) 900 3028
Average Fiber Width (μm) 20 130
Bulk Density > 35 Need
Ash % 0.4 need
Moisture % < 7.5 need
The hardwood and softwood fibers are available from Creafill Fiber Solutions with
and without lubricant. Lubricated fibers are in the form of pellets and are lubricated with
a low molecular weight PE. Softwood fibers are produced with a lubrication level of 3
wt% while hardwood fibers have a lubrication level of 2 wt%.
3.2 Hybrid Composite Development
3.2.1 Introduction
The development of the hybrid composite consisted of three stages. Polymer/clay
nanocomposites, polymer/cellulose microcomposites, and dual-scale hybrid composites
containingboth clay and cellulose reinforcements were studied. In the course of these
three stages, various mixing schemes and processing conditions were considered in order
to optimize the properties of the different composites. Upon completion of the three
23
stages of experimentation, clay treatment during processing and compatibilization of the
polymer matrix via reactive compounding were investigated.
3.2.2 Preparation of Polymer/Clay Nanocomposites
In the first stage of this research, polymer/clay nanocomposites were made and
tested to determine the optimum clay treatment and optimum levels of clay and MA-g-PE
for the polymer system. Various mixing techniques were also studied.
3.2.2.1 Study of Mixing Schemes
Polymer/clay nanocomposites were made via three mixing schemes and then tested
to determine the optimum mixing scheme for the system. All mixing was done in a
Brabender Plasticorder at 160˚C and 60 rpm for a total mixing time of 15 minutes using
roller-style mixing rotors. Testing of the various mixing schemes was done with 1 vol%
nanoclay and 5 wt% MA-g-PE in the polymer matrix.
For mixing scheme one, the recycled polyethylene (RHDPE) was first added and
allowed to melt for 2 minutes. Next, the MA-g-PE was added all at once and mixed with
the RHDPE for 1 minute. Finally, the nanoclay was added over a two-minute interval
and the mixture was allowed to mix for an additional 10 minutes. In this scheme, the
MA-g-PE was already well dispersed in the polymer matrix when the clay was added.
This was expected to help in the dispersion of the clay because the dispersed
compatibilizer would attract the clay.
In mixing scheme two, the MA-g-PE and nanoclay were first combined together in
a powder premix. The powder premix was made by grinding the MA-g-PE pellets in a
strand granulator and then combining the MA-g-PE powder with the nanoclay by dry
mixing. Once the powder premix was prepared, the RHDPE was added to the mixer and
24
allowed to melt for 2 minutes. The MA-g-PE/nanoclay powder premix was then added
over a two-minute interval and the mixture was mixed for an additional 11 minutes. This
mixing scheme was choose to determine if there would be a benefit to having the MA-g-
PE and clay in close proximity during mixing. It was thought that if the MA-g-PE was
already close to the clay, the compatibilization might be more effective.
For mixing scheme three, the nanoclay was added over a two-minute interval to the
RHDPE after it had been allowed to melt 2 minutes. The RPE/nanoclay mixture was
allowed to mix for 2 minutes and then the MA-g-PE was added. The final mixture was
mixed for an additional 9 minutes. This mixing scheme was added as a control. It was
expected that no benefit would be observed to adding the clay to the polymer matrix
before the compatibilizer.
As a result of the mixing study, all subsequent compounds were prepared using
mixing scheme one.
3.2.2.2 Clay Treatment
Clay treatment was done in order to modify bentonite clay with an organic cation
equivalent to that of Cloisite® 20A. A simple ion exchange procedure was followed and
used to treat the unpurified bentonite.
The ion-exchange reaction was carried out in a borosilicate glass jar. An OMNI
GLH homogenizer with a 20 mm-diameter flat bottom generator probe was used to
provide mixing for the clay suspensions. A 1” PTFE baffle was used to prevent vortex
formation in the mixing jar that would otherwise be present and prevent homogeneous
mixing. A thermometer, placed in the mixing jar, along with a hot plate, which was
25
placed underneath the mixing jar, were used to control the temperature during the
procedure.
The following procedure was used to produce treated Cloisite® Na+ and bentonite.
A 0.5 wt% solution of clay was made with deionized water and maintained a between 75-
85°C. To this suspension the desired amount of ammonium chloride, which was
described previously, was added. The solution was then subjected to homogenization for
15 minutes at 13500 rpm.
Following homogenization, the solution was vacuum filtered and washed to remove
excess water and chloride ions from the treated clay. The filtration was done using a
Buchner funnel and washed with at least 2.5L of deionized water.
Once filtration was complete, the thick, wet cake of clay remaining was air dried
for 24 hours at 80°C. This removed most of the remaining water. The material was then
ground into powder form using an IKA Works A 11 basic handheld mill. Finally, the
powder was vacuum dried at 80°C for approximately 12 hours.
3.2.2.3 Experimental Test Matrices
In order to evaluate optimum montmorillonite clay type and loading as well as
compatibilizer loading, various compounds were prepared with different clay treatments,
clay content and MA-g-PE content. First, three different clay treatments with two levels
of clay loading were tested. For this system, MA-g-PE was added at a 1:1 ratio to the
clay by weight. Controls for this system were also prepared at this time. The
compositions for each of these nanocomposites are as follows.
26
Table 3.6 Test Matrix for the Investigation of Clay Type and Loading
Experiment Clay Type vol% Silicate wt% MA-g-PE
1 none 0 0
2 none 0 5
3 none 0 100
4 Cloisite® 10A 1 4.7
5 Cloisite® 10A 3 14
As a result of this study, Cloisite® 20A was used in all subsequent composites.
In order to determine an optimum loading of montmorillonite clay and MA-g-PE, a
central composite design was used, which varied both the amount of clay and the amount
of MA-g-PE over five levels. The composition of each of these nanocomposites are as
follows.
Table 3.7: Test Matrix for the Investigation of Clay and MA-g-PE Loading
Experiment vol% Silicate wt% MA-g-PE
1 2.6 6.8
2 1.5 4.0
3 1.5 4.0
4 0.4 1.2
5 2.6 1.2
6 0.4 6.8
7 3.0 4.0
8 0.0 4.0
9 1.5 0.0
10 1.5 4.0
11 1.5 4.0
12 1.5 8.0
Finally, composites were made in order to compare the performance of
montmorillonite and bentonite clays. Montmorillonite with the 20A treatment was
compared with untreated bentonites and bentonites with a 20A equivalent treatment. The
compositions of these nanocomposites are as follows.

27
Table 3.8: Test Matrix for Comparison of Montmorillonite and Bentonite Clays
Experiment Clay Type vol% Silicate wt% MA-g-PE
2 Bentolite-L 3 10
3 untreated bentonite 3 10
4 treated bentonite 3 10
5 Cloisite® Na+ 3 10
3.2.3 Preparation of Polymer/Cellulose Microcomposites
In the second stage of the research, polymer/cellulose microcomposites were
prepared in order to study the effect of cellulose type, cellulose loading, and MA-g-PE
loading on the composite properties.
The cellulose composites were prepared following mixing scheme one, which was
outlined in Section 3.2.2.1. Compounding was done in a Brabender Plasticorder at
160°C, 60 rpm, with a total mixing time of 15 minutes using roller-style mixing rotors.
In order to evaluate optimum cellulose type and loading as well as
compatibilizer loading, various compounds were prepared with different cellulose type,
cellulose content and MA-g-PE content. Four types of cellulose fibers were tested:
softwood and hardwood cellulose fibers with and without lubricant. A two level factorial
experimental design was used to study this system. The compositions of each of the
microcomposites prepared are as follows.
28
Table 3.9: Test Matrix for Investigation of the Cellulose System
wt%
Experiment vol% Cellulose wt% MA-g-PE Lubricant Type of Cellulose
1 11 2 0 softwood
2 22 2 3 softwood
3 22 2 0 hardwood
4 11 4 3 softwood
5 11 4 0 hardwood
6 22 4 2 hardwood
7 22 4 0 softwood
8 11 2 2 hardwood
9 22 0 0 softwood
10 22 0 0 hardwood
11 22 0 3 softwood
12 22 0 2 hardwood
3.2.4 Preparation of Hybrid Composites
In the third stage of this research, polymer/clay/cellulose multi-scale composites
were prepared in order to study the interactions of variables in this complex system such
as: reinforcement loading and MA-g-PE loading. The effects of processing conditions on
the mechanical properties of the hybrid composites were also studied for this system.
The hybrid composites were prepared in a Brabender Plasticorder. Compounding
was done at 160°C, 60 rpm, with a total mixing time of 15 minutes using roller-style
mixing rotors. First, the RHDPE was added and allowed to melt for two minutes. Then,
the MA-g-PE was added all at once and allowed to mix with the RHDPE for one minute.
Next the nanoclay was added followed immediately by the addition of the cellulose
fibers. The addition of reinforcements was carried out over a two-minute interval.
Finally, the composite was mixed for an additional 10 minutes.
In order to determine the interaction in this system, various compounds were
prepared with different clay, cellulose and MA-g-PE loadings. For this system, Cloisite
29
20A nanoclay was used along with non-lubricated soft wood cellulose fibers. The
compositions of the multi-scale composites are as follows.
Table 3.10: Test Matrix for the Investigation of the Hybrid System
Experiment vol% Silicate vol% Cellulose wt% MA-g-PE
1 2 8 5.3
2 2 8 10.5
3 4 14 10.5
4 4 8 5.3
5 2 14 5.3
6 2 14 10.5
7 4 8 10.5
8 4 14 5.3
3.2.5 Preparation of Compounds for Probing Studies
3.2.5.1 Treatment of Clay During Compounding
In an effort to reduce the cost of processing the hybrid compound, treatment of the
clay during compounding was investigated. This method would reduce cost by
eliminating additional process steps, which would be needed for clay treatment. For the
purposes of this study, the method was only briefly explored in order to determine
whether or not it is a viable method that would warrant further research.
For these experiments, bentonite clay was used and was treated with
di(hydrogenated tallow)dimethyl ammonium chloride, the same treatment found on
Cloisite® 20A. First, the desired amount of clay and treatment were combined with
enough water to make a wet cake mixture. This mixture was allowed to sit in a closed
container overnight at room temperature. When compounding, approximately 50% of the
total RHDPE was added to the Brabender and allowed to melt. The MA-g-PE was then
added and mixed for approximately one minute. Next, the wet clay/treatment mixture
was added to the molten polymer. Once the clay was incorporated, the rest of the
30
RHDPE was added to the mixture. At this time, if the composite was to contain cellulose
fibers, they were added. The total mixing time for each compound was 15 minutes. The
wet cake was added to a half full Brabender in order to reduce the splattering of the water
from the cake upon contact with the molten polymer.
The following table shows the test matrix used for this investigative study. Two
levels of temperature were used to determine the effect of temperature on the reaction
between the clay and the clay treatment during compounding.
Table 3.11: Test Matrix for Clay Treatment Study

Temperature wt% vol% vol% wt%
Experiment
(C) Treatment Silicate Cellulose MA-g-PE
1 170 9 4 0 10
2 170 9 4 11 10
3 140 9 4 0 10
4 140 9 4 11 10
3.2.5.2 Compatibilization of RHDPE via Reactive Compounding
Grafting of maleic anhydride onto RHDPE during compounding was also
investigated. This method of compatibilization was looked at briefly in order to
determine whether it is a viable method that warrants further study. If this method were
to provide adequate compatibilization, it would reduce the overall cost of the composite
as the raw materials used to make the compatibilized matrix are less expensive than the
MA-g-PE used. This method would add no processing costs as the reaction could be
incorporated into the already existing process for producing the hybrid composite.
The compounds for this portion of the study were made in a Brabender Plasticorder
at 60 rpm, 160°C, and a total mixing time of 15 minutes. First the RHDPE was added to
the mixer and melted. This was followed by the addition of maleic anhydride, which was
31
mixed for 2 minutes before the addition of the peroxide, which was added dropwise via a
plastic syringe. Finally, the reinforcement was added and the mixture was allowed to mix
for the remainder of the mixing time.
The following table shows the experimental test matrix used for this probing study.
Table 3.12: Experimental Test Matrix for Reactive Compounding Study

wt% MA-g- MA:Peroxide vol% vol%
Experiment Description PE Ratio silicate TC1004
1 low MA/low ratio 5 1:0.03 0 0
2 low MA/high ratio 5 1:0.06 0 0
3 high MA/low ratio 10 1:0.03 0 0
4 with clay 4 1:0.03 3 0
5 with cellulose 4 1:0.03 0 22
3.2.6 Specimen Preparation
The above composites obtained from mixing in the Brabender Plasticorder were
granulated using a Weima granulator. These granules were either injection molded into
tensile bars or compression molded into thin films.
The injection molded specimens were made using a DSM Research Micro-
Injection Molding Machine, with a cylinder temperature of 220˚C with a mold
temperature of 55˚C and an injection pressure of 6 bar. The tensile bars were made with
a gauge length of 7.6 mm.
The compression molded films were pressed using a Carver press at a temperature
of 160°C. Each film had a final thickness of less than 1 mm.
32
3.3 Characterization
3.3.1 Mechanical Testing
Tensile testing was performed on the injection molded specimens using an Instron
4204 mechanical testing machine. ASTM D638 Type II specimens were pulled at room
temperature and a rate of 12.5 mm/min.
The data from testing was used to calculate the elastic modulus, tensile strength,
and percent elongation for each sample. The elastic modulus was calculated using the
initial tangent line on the stress-strain curve, the tensile strength was calculated using the
maximum load for the test run, and the percent elongation was reported using the
elongation at break for each sample.
3.3.2 Wide Angle X-ray Diffraction (WAXD)
In order to conduct WAXD experiments, square specimens were cut out of
compression molded samples, which were less than 1 mm thick. The samples were
mounted on the sample hold such that the x-ray beam was perpendicular to the
compression molded surface. For this reason, reflection mode was used when testing the
molded samples, while transmission mode was used to test the neat clay powders.
Experiments were conducted using the Rigaku X-ray generator over a range of 1.5 to 10
2θ values. Intensity vs. 2θ data were obtained and used along with Bragg’s law to
calculate the interlayer spacing of the individual clay types and the clay in the hybrid
composites.
3.3.3 Scanning Electron Microscopy (SEM)
In order to obtain SEM pictures, fracture surface specimens were prepared. For
preparation, tensile bars were submerged in liquid nitrogen for 5 minutes and then
33
fractured at the center of the tensile bar. These fracture surfaces were then mounted on
SEM sample holders using conductive tape.
Before the SEM pictures were taken, all samples were coated in silver using an
Emitech K575x Turbo Sputter Coater. Following coating, SEM pictures were obtained
using a Hitachi S-2150 SEM.
3.3.4 Differential Scanning Calorimetry (DSC)
DSC curves were obtained for neat RHDPE, an RHDPE/clay composite containing
3 vol% silicate made with Cloisite® 20A, and a hybrid composite with 3 vol% silicate and
11 vol% cellulose. Each composite was made with 10 vol% MA-g-PE compatibilizer.
The DSC was conducted on a TA Instruments Differential Scanning Calorimeter. The
test was setup increased the temperature of the 12 mg sample from room temperature to
190°C at a rate of 10°C/min. The heat of crystallinity for 100% crystallized HDPE used
for calculating percent crystallinity was 293 J/g47.
34
CHAPTER IV
RESULTS
4.1 Introduction
In this section, the results from the three systems studied as well as summaries of
two probing studies conducted are presented.
In most cases, Design Expert software was used to analyze the experimental data
and produce models to predict the behavior of the mechanical properties of the various
composite systems. These models were then used to create contour plots so that the
effect of the experimental variables on the mechanical properties could be observed. The
contour data presented in the following sections represent predictions based on these
models. Actual experimental values are in the Appendix.
4.2 Polymer/Clay Nanocomposites
4.2.1 Mixing Scheme Analysis
In order to determine which of the mixing schemes discussed in Section 3.2.2.1
was the optimal way to compound the nanocomposites, tensile testing was performed on
specimens from each of the three mixing schemes. The results obtained from this testing
are presented in the following sections. All values for tensile strength and elastic
modulus are reported in MPa.
35
4.2.1.1 Tensile Strength
The variation of the tensile strength for the three mixing schemes is shown in
Figure 4.1. Mixing scheme two shows a higher tensile strength than the other mixing
schemes suggesting more positive interactions between the clay and the matrix.
However, in each case, the tensile strength is increased by less than 4% as compared to
the original polymer matrix showing that the presence of clay in the matrix did not
significantly improved the tensile strength of the composite.
35
30
Tensile Strength (MPa)
25
20
15
10
0
PE - MA-g-PE - 20A MA-g-PE/20A mix - PE PE - 20A - MA-g-PE
Mixing Scheme 1 Mixing Scheme 2 Mixing Scheme 3
Note: Standard deviation is included for each data point, b ut may

b e too small to b e seen.
Figure 4.1: Tensile Strength Comparison for 3 Mixing Schemes
4.2.1.2 Elastic Modulus
The variation of the elastic modulus for the three mixing schemes is shown in
Figure 4.2. Mixing scheme one shows the highest increase in modulus, with a 60%
increase as compared to the virgin polymer matrix. Mixing scheme two shows a 30%
increase in modulus, while mixing scheme three shows only a 15% increase in modulus.
The higher increase observed with mixing scheme one can be attributed to the uniform
36
distribution of the MA-g-PE in the polymer matrix before clay addition. This aided in the
dispersion of the clay throughout the polymer matrix resulting in a higher modulus.
1400
Elastic Modulus (MPa)
1200
1000
800
600
400
200
0
Figure 4.2: Elastic Modulus Comparison for 3 Mixing Schemes
4.2.1.3 Percent Elongation
The variation of the percent elongation for the three mixing schemes is shown in
Figure 4.3. The results show that mixing scheme three resulted in the highest percent
elongation. Mixing scheme one showed the lowest percent elongation of the three.
37
1200
1000
% Elongation
800
600
400
200
0
Figure 4.3: Percent Elongation Comparsion for 3 Mixing Schemes
4.2.1.4 Summary of Mixing Scheme Analysis for Polymer/Clay Nanocomposites
Analysis of both the elastic moduli and tensile strengths of the compounds from the
various mixing schemes proved that mixing scheme one is the most beneficial mixing
scheme. This mixing scheme resulted in a 60% increase in modulus and a 3.6% increase
in tensile strength. Therefore, mixing scheme one was used to make all subsequent
composites for this work, unless otherwise stated.
4.2.2 Treatment of Bentonite Clay
4.2.2.1 Mechanical Properties
Two clay types were studied, montmorillonite and bentonite. Both clays have the
same layered structure, which allows polymer to intercalate into the galleries, since
bentonite is the ore from which montmorillonite is refined. Figures 4.4 and 4.5 show the
mechanical properties for these two types of clays in composites of 3 vol% silicate. In
the untreated form, the bentonite yields a significantly lower tensile strength and a
38
slightly lower modulus than the montmorillonite (Cloisite® Na+). However, when
comparing the properties of the clays after treatment, the tensile strength of the treated
bentonite is only slightly lower than that of the treated montmorillonite (Cloisite® 20A)
and the modulus values for the two composites are statistically the same.
40
35
3 vol% silicate
30
25
20
15
10
0
RHDPE Cloisite® Na+ Cloisite® 20A Untreated Betonite Treated Bentonite
Figure 4.4: Comparison of Tensile Strength for Composites made with Treated and
Untreated Bentonite or Montmorillonite with 5 vol% MA-g-PE
39
2000
1800
3 vol% silicate
1600
1400
1200
1000
800
600
400
200
0
RHDPE Cloisite® Na+ Cloisite® 20A Untreated Betonite Treated Bentonite
Figure 4.5: Comparison of Elastic Modulus for Composites of Treated and Untreated
Bentonite or Montmorillonite with 5 vol% MA-g-PE
4.2.2.2 Morphology
WAXD was conducted on the Cloisite® Na+, Cloisite® 20A, untreated bentonite
and treated bentonite. Figures 4.6 shows the x-ray results obtained. As expected, the
untreated bentonite and montmorillonite (Cloisite® Na+) have lower d-spacings that the
other clays tested. Once treated, both the bentonite and montmorillonite (Cloisite® 20A)
have increased d-spacing. Interestingly, the less pure treated bentonite has a higher d-
spacing than the more refined treated montmorillonite (Cloisite® 20A).
40
3000
treated bentonite Cloisite® 20A
d =37.7 Å d = 29.2 Å
2500
Cloisite® Na+ Cloisite® 20A
2000 untreated bentonite treated bentonite
scotch tape control

Intensity
1500
Cloisite® Na+
d = 19.0 Å
1000
untreated
500 bentonite
d 12 8 Å
0
0 1 2 3 4 5 6 7 8 9 10
2θ
Figure 4.6: WAXD for Nanoclays
Figure 4.7 shows the same results as in Figure 4.6, but with an emphasis on the low
intensity portion of the curve. You can see that in addition to the main peaks shown by
Cloisite® 20A and the treated bentonite are lower intensity peaks existing around the d-
spacing range of approximately 13.
41
700
Cloisite® Na+ Cloisite® 20A
untreated bentonite treated bentonite

600
scotch tape control
500
400 treated bentonite

Intensity
d =13.57 Å
Cloisite® 20A
300 d = 12.35 Å
200
untreated bentonite
100 d = 12.8 Å
0
0 1 2 3 4 5 6 7 8 9 10
2θ
Figure 4.7: WAXD for Nanoclays (Low Intensity Magnification)
4.2.3 Mechanical Properties of Polymer/Clay Nanocomposites
Results from all mechanical property testing are as listed below. All values for
tensile strength and elastic modulus are reported in MPa.
4.2.3.1 Stress-Strain Curve
Figure 4.8 show a representative stress-strain curve for the polymer/clay
nanocomposite system. The figure shows that debonding of the clay with the polymer
matrix is occurring in the system.
42
35
30
25
Engineering Stress (MPa)
20
15
10
0
0 2 4 6 8 10 12
Engineering Strain
Figure 4.8: Representative Stress-Strain Curve for Clay/Polymer System
4.2.3.2 Tensile Strength
The effects of clay type, clay loading, and MA-g-PE loading on the tensile strength
are presented in the following sections.
4.2.3.2.1 Tensile Strength Dependence on Clay Treatment and Clay Loading
The tensile strength of composites made with Cloisite® 10A, Cloisite® 20A, and
Cloisite® 25A at clay loadings of 1 and 3 vol% silicate are shown in Figure 4.9. For all
clay types, the tensile strength increases slightly with an increased clay content. The
level of MA-g-PE was held contant at a 1:1 weight ratio with the amount of clay in the
composite. The highest increase in tensile strength is observed with the 20A composite.
This increase in strength is attributed to the compatibility of the clay treatment with the
polymer matrix.
43
40
35
Tensile Strength (MPa) 30
25 10A
20 25A
15 20A
10
5
0
0 0.5 1 1.5 2 2.5 3 3.5
vol % Silicate
Figure 4.9: Tensile Strength Dependence on Clay Treatment and Clay Loading at 1:1
vol% ratio of silicate to MA-g-PE
4.2.3.2.2 Tensile Strength Dependence on Clay Loading and MA-g-PE Loading
The tensile strength of composites made with Cloisite® 20A at various levels of
clay and MA-g-PE are shown in Figure 4.10. Figure 4.10 was made using the following
equation fitted to experimental data:
Tensile Strength =
+28.41
+2.04 * Silicate (vol%)
+0.136 * MA-g-PE (vol%) (4.1)
-0.297 * Silicate (vol%)2
-0.015 * MA-g-PE (vol%)2
+0.068 * Silicate (vol%) * MA-g-PE (vol%)
The R2 value of the model is 0.97. According to t-tests, this model can correctly predict
all of the experimental points. The tensile strength is shown to increase as the level of
clay in the composite increases. At low levels of clay (<1.5 vol% silicate), the tensile
strength is independent of the amount of MA-g-PE in the system. However, as the level
of clay is increased (>1.5 vol% silicate), the effects of MA-g-PE in the system become
44
more significant. At these higher clay levels, increasing the amount of MA-g-PE in the
system results in higher tensile strength.
8 .0 1
T e n s i le S tr e n g th
33.5
6 .0 1 33
B: MA-g-PE (vol%)
32.5
4 .0 0
29 29.5 30 4
30.5 31.5
31 32
2 .0 0
0 .0 0
0 .0 0 0 .7 5 1 .5 0 2 .2 5 3 .0 0
A : S i l i c a te ( v o l % )
Figure 4.10: Tensile Strength Dependence on Clay and MA-g-PE Loading at 1:1 vol%
ratio of silicate to MA-g-PE
4.2.3.3 Elastic Modulus
The effects of clay type, clay loading, and MA-g-PE loading on the elastic modulus
are analyzed in the following sections.
4.2.3.3.1 Elastic Modulus Dependence on Clay Treatement and Clay Loading
The elastic modulus of composites made with Cloisite® 20A, Cloisite® 10A, and
Cloisite® 25A at clay loadings of 1 and 3 vol% silicate are shown in Figure 4.11. The
composite. For all clay types, an increase in modulus is observed with the addition of 1
45
vol% clay. However, only the 20A shows an increase in modulus with the addition of
more clay in the system.
2500
2000
1500
10A
1000 25A
20A
500
0
0 1 2 3 4
vol % Silicate
Figure 4.11: Elastic Modulus Dependence on Clay Treatment and Clay Loading at 1:1
4.2.3.3.2 Elastic Modulus Dependence on Clay Loading and MA-g-PE Loading
The elastic modulus of composites made with Cloisite® 20A at various levels of
clay and MA-g-PE are shown as Figure 4.12. Figure 4.12 was made using the following
equation fitted to the experimental data:
Elastic Modulus =
+925.68
-6.17 * MA-g-PE (vol%) (4.2)
+2.56 * MA-g-PE (vol%)2
+9.17 * Silicate (vol%) * MA-g-PE (vol%)
all of the experimental points. The results show the dependence of the modulus on the
46
clay and MA-g-PE levels in the composites as well as the presence of interactions
between the clay and MA-g-PE themselves. This is exhibited in the trends observed in
Figure 4.6. At low clay levels (below 1 vol% silicate) the elastic modulus is independent
on the amount of MA-g-PE in the system and is increased with the addition of clay. As
clay levels increase, the elastic modulus becomes more dependent upon the amount of
MA-g-PE in the system with a higher modulus resulting from a higher amount of MA-g-
PE.
8.00
E la s tic M o d ulus
1500
6.00 1400
B: MA-g-PE (vol%)
1300
4.00
1100 1200 4
1000
2.00
0.00
0.00 0.75 1.50 2.25 3.00
A: S ilic a te (vo l% )
Figure 4.12: Elastic Modulus Dependence on Clay and MA-g-PE Loading at 1:1 vol%
The effects of clay type, clay loading, and MA-g-PE loading on the percent
elongation are analyzed in the following sections.

47
4.2.3.4.1 Percent Elongation Dependence on Clay Treatment and Clay Loading
The percent elongation of composites made with Cloisite® 20A, Cloisite® 10A, and
Cloisite® 25A at clay loadings of 1 and 3 vol% silicate are shown in Figure 4.13. The
composite. The percent elongation is found to increase for all clay types with the
addition of 1 vol% silicate. The increase is the greatest for 10A, followed by 20A, and
finally 25A with the smallest increase. The trends become more complex however with
the addition of 3 vol% silicate. Both the 10A and 20A composites experience a decrease
in elongation, which returns the elongation value to that of the polymer matrix without
clay. Conversely, the elongation of the 25A composite continues to increase with the
addition of more clay.
1400
1200
% Elongation
1000
10A
800
25A
600 20A
400
200
0
0 1 2 3 4
vol % Silicate
Figure 4.13: Percent Elongation Dependence on Clay Treatment and Clay Loading at 1:1
48
4.2.3.4.2 Percent Elongation Dependence on Clay Loading and MA-g-PE Loading
The percent elongation of composites made with Cloisite® 20A at various levels of
clay and MA-g-PE are shown as Figure 4.14. Figure 4.14 was made using the following
equation fitted to the experimental data:
% Elongation =
-42.53
+58.97 * MA-g-PE (vol%) (4.3)
-4.91 * MA-g-PE (vol%)2
-2.54 * Silicate (vol%) * MA-g-PE (vol%)
all of the experimental points. As shown in the figure, the trends vary depending upon
the level of clay in the system. At low clay levels (0-1.5 vol% silicate), additional clay in
the system causes the elongation to increase. Conversely, at high clay levels (1.5-3 vol%
silicate), additional clay results in a decrease in elongation. An interesting dependence of
MA-g-PE is also observed for this system at clay levels approaching 1.5 vol% silicate.
At this point, the elongation is most strongly affected by the MA-g-PE level and shows
an increase in elongation with the addition of MA-g-PE up to 4 vol% silicate.
49
8 .0 0
% E lo n g a ti o n
6 .0 0
B: MA-g-PE (vol%)
250
4 .0 0
200 4 300
150 300 250
200
2 .0 0
100
400
150
50
350
0 .0 0
0 .0 0 0 .7 5 1 .5 0 2 .2 5 3 .0 0
A : S i l i c a te ( vo l % )
Figure 4.14: Percent Elongation Dependence on Clay and MA-g-PE Loading at 1:1 vol%
4.3 Polymer/Cellulose Nanocomposites
4.3.1 Mechanical Properties of Polymer/Cellulose Nanocomposites
Results from all mechanical property testing are as listed below. All values for
tensile strength and elastic modulus are reported in MPa.
Figure 4.15 shows a representative stress-strain curve for the cellulose system. The
curve is characteristic of a high strength composite.
50
50
45
Engineering Stress (MPa) 40
35
30
25
20
15
10
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
Engineering Strain
Figure 4.15: Representative Stress-Strain Curve for Cellulose/Polymer System
4.3.1.2 Mechanical Property Dependence on Cellulose Type and Presence of

Lubricant
The tensile strength data for composites made with softwood cellulose fibers with
and without lubricant are shown in Figure 4.16. The data obtained for hardwood
cellulose fiber composites are shown in Figure 4.17. These figures both show composites
loaded at 16.8 vol% cellulose. Equation 4.4 shows the model equation represented in
Figures 4.16 and 4.17. This model is not fully numeric and therefore cannot be translated
into actual values. The R2 value for this model is 0.93. According to t-tests, this model
can correctly predict all of the experimental points.
Tensile Strength =
+39.89
+6.29 * Cellulose (vol%)
-1.07 * MA-g-PE (vol%)
-2.83 * Lubricant Level (4.4)
+5.02 * Cellulose (vol%) * MA-g-PE (vol%)
-8.18 * Lubricant Level * Type of Cellulose
-1.90 * MA-g-PE (vol%) * Lubricant Level * Type of Cellulose
51
As shown in the two figures, the effect of lubricant is very different when comparing soft
and hardwood fibers. In the case of softwood cellulose fibers, the presence of lubricant
has a negative effect resulting in a significantly lower tensile strength. The hardwood
cellulose fibers, however, show a positive effect of lubricant with an increased tensile
strength upon the addition of lubricant to the composite system.
In te r a c ti o n G r a p h
C : L u b r i c a n t L e ve l
70
58
Tensile Strength
C -
45
33
C +
20
2 .0 2 .5 3 .0 3 .5 4 .0
B : M A - g - P E (vo l% )
Figure 4.16: Comparison of Tensile Strength with MA-g-PE Level for Softwood
Cellulose Fibers With and Without Lubricant. Triangles = Lubrication, Squares = No
Lubrication.
52
In te r a c ti o n G r a p h
C : L u b r i c a n t L e ve l
70
58
Tensile Strength
45
C+
C-
33
20
2 .0 2 .5 3 .0 3 .5 4 .0
B : M A - g - P E ( vo l % )
Figure 4.17: Comparison of Tensile Strength with MA-g-PE Level for Hardwood
Lubrication.
The elastic modulus data for composites made with softwood and hardwood
cellulose fibers with and without lubricant are shown in Figures 4.18 and 4.19. Equation
4.5 shows the model equation represented in these figures. This model is not fully
numerical and therefore cannot be translated into actual values. The R2 value for this
model is 0.86. According to t-tests, this model can correctly predict all of the
experimental points.
Elastic Modulus =
+2053.51
+744.78 * Cellulose (vol%) (4.5)
+413.51 * Cellulose (vol%) * MA-g-PE (vol%)
-617.08 * Lubricant Level * Type of Cellulose
-229.44 * MA-g-PE (vol%) * Lubricant Level * Type of Cellulose
53
In these figures, the composites are loaded with 18.5 vol% cellulose. As observed with
the tensile strength data, the lubricant effect is different for hardwood and softwood
fibers. The lubricant has a positive effect on the elastic modulus in the hardwood
cellulose composites, but a negative effect in the softwood cellulose composites.
In t e r a c t i o n G r a p h
C : L u b ric a n t L e ve l
3 1 7 7 .0 6
2 6 1 9 .1 9
C -
Elastic Modulus
2 0 6 1 .3 2
C +
1 5 0 3 .4 5
9 4 5 .5 8 4
2 .0 0 2 .5 0 3 .0 0 3 .5 0 4 .0 0
B : M A -g -P E (vo l% )
Figure 4.18: Comparison of Elastic Modulus with MA-g-PE Level for Softwood
Lubrication.
54
In t e r a c t i o n G r a p h
C : L u b r ic a n t L e ve l
3 1 7 7 .0 6
2 6 1 9 .1 9
C +
Elastic Modulus
2 0 6 1 .3 2
C -
1 5 0 3 .4 5
9 4 5 .5 8 4
2 .0 0 2 .5 0 3 .0 0 3 .5 0 4 .0 0
B : M A -g -P E (vo l% )
Figure 4.19: Comparison of Elastic Modulus with MA-g-PE Level for Hardwood
Lubrication.
4.3.1.2.1 Summary of Effects of Cellulose Type and Presence of Lubricant
The results from this portion of the study were used as a factor in determining
which cellulose fiber to use in further testing for this system and for the hybrid system.
The softwood cellulose fibers were chosen for further testing for the following reasons:
softwood fibers are more economical than hardwood fibers, softwood fibers are effective
reinforcement without lubricant, which adds additional economic incentive, and the
softwood fibers used in this study are made from recycled materials, which offers an
environmental incentive for choosing them. For these reasons, the data from the
“softwood fibers without lubricant” experiments will be further analyzed in the following
sections. Consequently, softwood fibers without lubricant were also used in the hybrid
system.
55
4.3.1.3 Mechanical Property Dependence on Cellulose Loading and MA-g-PE
Loading
The tensile strengths of composites made with softwood cellulose fibers without
lubricant at various levels of cellulose and MA-g-PE are shown in Figure 4.20. This
figure was made using the model given Equation 4.4. The data show that the dependence
of tensile strength on MA-g-PE level is affected by the amount of cellulose in the
composite. At low levels of cellulose (below 19 vol%) the addition of MA-g-PE results
in a decrease in tensile strength. However, at higher levels of cellulose, the addition of
MA-g-PE causes an increase in tensile strength. These results show that the effectiveness
of the MA-g-PE as a compatibilizer is a function of the amount of cellulose in the
composite. As expected, at a constant level of MA-g-PE, the addition of more cellulose
reinforcement resulted in an increased tensile strength.
56
4 .0 0
24
3 .5 0 28
B: MA-g-PE (vol%)
40
32
3 .0 0
36
2 .5 0
2 .0 0
1 1 .0 0 1 3 .7 5 1 6 .5 0 1 9 .2 5 2 2 .0 0
A : C e l l u l o s e L e ve l ( vo l % )
Figure 4.20: Dependence of Tensile Strength on Cellulose and MA-g-PE Loading for
Softwood Cellulose Fiber Composite
The elastic moduli of composites made with softwood cellulose fibers without
lubricant at various levels of cellulose and MA-g-PE are shown in Figure 4.21. This
figure was made using the model shown in Equation 4.5. The figure shows that the
addition of more cellulose in the composite results in an increased elastic modulus. Also,
the presence of MA-g-PE in the experimental range of 18.5-22 vol% cellulose is not
highly significant. However, the effects of the MA-g-PE can be observed below 14 vol%
where additional MA-g-PE in the system results in a lower elastic modulus value.
57
4 .0 0
E la s ti c M o d u lu s
400
3 .5 0
750
2150
B: MA-g-PE (vol%)
1100 1800
3 .0 0
1450
2 .5 0
2 .0 0
1 1 .0 0 1 3 .7 5 1 6 .5 0 1 9 .2 5 2 2 .0 0
A : C e llu lo s e L e ve l ( vo l% )
Figure 4.21: Dependence of Elastic Modulus on Cellulose and MA-g-PE Loading for
Softwood Cellulose Fiber Composite
The percent elongation was found to be soley dependent upon the cellulose loading
for this system. The type of cellulose, presence of lubricant, and MA-g-PE loading were
found to have no significant effect on the elongation of the composites. Figure 4.22
shows the variation of percent elongation with cellulose loading. As expected, more
cellulose present in the system results in a lower elongation. The model equation shown
in the figure represents four data point of varied cellulose type and lubrication level at
each of the two cellulose levels. The points shown in the figure represents the mean of
these data points. Consequently, the model shown does not have an R2 value of 1, even
though it represents a straight line.
58
O n e F a c to r P lo t
2 2 .0 8
% Elongation = -6.8*Cellulose (vol%) + 11.4

1 7 .2 5 9 1 R2 = 0.87
% Elongation
1 2 .4 3 8 1
7 .6 1 7 2 1
2 .7 9 6 2 8
1 1 .0 0 1 3 .7 5 1 6 .5 0 1 9 .2 5 2 2 .0 0
A : C e llu lo s e L e ve l ( vo l% )
Figure 4.22: Percent Elongation Dependence on Cellulose Loading
4.4 Hybrid Composites
Hybrid composites were made using Cloisite 20A® nanoclay as the nanoscale
reinforcement and TC1004 softwood cellulose fibers as the microscale reinforcement.
4.4.1 Mechanical Properties of Hybrid Composites
Results from all mechanical testing property testing are as listed below. The scatter
in the percent elongation data for the hybrid system was such that differences in
elongation between the various composites was not correlatable. It is suspected that the
trend in the percent elongation should follow that of the individual systems where the
addition of reinforcement results in a decreased percent elongation. The tensile strength
and elastic modulus values are shown as MPa.
59
Figure 4.23 shows a representative stress-strain curve for the hybrid system. The
curve shows no signs of the debonding observed in the clay/polymer system.
35
30
Engineering Stress (MPa)
25
20
15
10
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Engineering Strain
Figure 4.23: Representative Stress-Strain Curve for the Hybrid System
4.4.1.2 Mechanical Property Dependence on Reinforcement Loading
Figure 4.24 shows the tensile strength for varied levels of cellulose and clay in the
hybrid composite. This analysis assumes 7.50 vol% of MA-g-PE in the system and was
represented by the model equation below, which was fitted to the experimental data. The
R2 for this model is 0.96. According to t-tests, this model can correctly predict all of the
experimental points.
60
Tensile Strength =
+28.55
-0.308 * MA-g-PE (vol%)
+0.287 * Cellulose (vol%) (4.6)
-0.041 * MA-g-PE (vol%) * Silicate (vol%)
+0.061 * MA-g-PE (vol%) * Cellulose (vol%)
-0.225 * Silicate (vol%) * Cellulose (vol%)
The results show that the dependence on tensile strength is affected by the amount of
reinforcement in the system. At low levels of clay (below 2.5 vol% silicate) and
cellulose (below 5 vol%), the tensile modulus is increased at a similar rate with the
addition of both clay and cellulose. At the same clay levels and high cellulose (above 5
vol%), a different trend is observed. In this range, the strength is still increased by
adding cellulose, but the addition of clay causes a reduction in strength. At high levels of
clay (above 2.5 vol% silicate), the trend is reversed. For this region, higher amounts of
cellulose in the system cause a decrease in the tensile strength, while increased levels of
clay cause the tensile strength to be increased. For all regions, the effect of cellulose in
the tensile strength is more prevalent than the effect of clay.
61
1 0 .0 0
38.5
37
35.5
7 .5 0
32.5
34
C: Cellulose (vol%)
5 .0 0
32.5
31
2 .5 0
29.5
28
0 .0 0
0 .0 0 1 .0 0 2 .0 0 3 .0 0 4 .0 0
B : S i l i c a te ( v o l % )
Figure 4.24: Tensile Strength Dependence on Cellulose and Clay (Silicate) Loading
Figure 4.25 shows the elastic moduli for varied levels of cellulose and clay in the
hybrid composite. The following equation shows the model used to create the figure.
The R2 for this model is 0.94. According to t-tests, this model can correctly predict all of
the experimental points.
Elastic Modulus =
+816.22
+9.23 * MA-g-PE (vol%)
+333.26 * Silicate (vol%) (4.7)
+23.71 * Cellulose (vol%)
-19.08 * MA-g-PE (vol%) * Silicate (vol%)
+5.71 * MA-g-PE (vol%) * Cellulose (vol%)
-6.78 * Silicate (vol%) * Cellulose (vol%)
The modulus shows an expected trend where the addition of any reinforcement, whether
cellulose or clay causes an increase in the property.
62
1 0 .0 0
E la s ti c M o d u lu s
2200
7 .5 0
2000
C: Cellulose (vol%)
1800
5 .0 0
1600
2 .5 0
1400
1200
1000
0 .0 0
0 .0 0 1 .0 0 2 .0 0 3 .0 0 4 .0 0
Figure 4.25: Elastic Modulus Dependence on Cellulose and Clay (Silicate) Loading for
Composites at 7.5 vol% MA-g-PE
4.4.1.3 Mechanical Property Dependence on MA-g-PE Loading
Figures 4.26 and 4.27 show the effect of MA-g-PE loading on the tensile strength
in relation to both clay and cellulose loading. Figure 4.26 assumes a constant cellulose
level of 7.5 vol% and Figure 4.27 assumes a constant clay level of 1 vol% silicate. The
figures were made using the model from Equation 4.6. The variation of clay at constant
cellulose (Figure 4.26) shows that additional MA-g-PE in the system causes an increase
in tensile strength at constant clay level. The rate of increase of tensile strength is greater
at lower clay levels and decreases at higher clay levels. The level of MA-g-PE was found
to have a positive effect on tensile strength at all cellulose levels when clay loading is
constant. (Figure 4.27).
63
Figure 4.28 and 4.29 show the effects of MA-g-PE loading on the elastic modulus.
Figure 4.28 assumes a constant cellulose level of 7.5 vol% and Figure 4.29 assumes a
constant clay level of 2 vol% silicate. These figures were made using the model
presented in Equation 4.7. In the case of varied clay loading (Figure 4.28), the addition
of MA-g-PE is found to increase the elastic modulus in all cases, though the rate of
increase is greater at lower clay levels. In the case of varied cellulose levels (Figure
4.29), the MA-g-PE is found to be ineffective in increasing the modulus in certain cases.
The MA-g-PE shows more effectiveness at higher cellulose loadings, but even then
reaches a threshold above which a further increase in modulus is not observed.
64
1 0 .0 0
37
36
7 .5 0
35
A: MA-g-PA (vol%)
34
33
5 .0 0
32
2 .5 0
31
30
0 .0 0
0 .0 0 1 .0 0 2 .0 0 3 .0 0 4 .0 0
Figure 4.26: Tensile Strength Dependence on MA-g-PE and Clay Loading at 7.5 vol%
Cellulose
1 0 .0 0
38
8 .7 5
A: MA-g-PA (vol%)
37
36
7 .5 0 34
35
33
6 .2 5
5 .0 0
5 .0 0 6 .2 5 7 .5 0 8 .7 5 1 0 .0 0
C : C e llu lo s e ( vo l% )
Figure 4.27: Tensile Strength Dependence on MA-g-PE and Cellulose Loading at 1 vol%
Silicate
65
1 0 .0 0
E la s t i c M o d u lu s
7 .5 0
2000
A: MA-g-PA (vol%)
2100
1900
5 .0 0
1800
1700
1600
2 .5 0 1500
1400
1300
1200
0 .0 0
0 .0 0 1 .0 0 2 .0 0 3 .0 0 4 .0 0
B : S i l i c a te ( vo l % )
Figure 4.28: Elastic Modulus Dependence on MA-g-PE and Clay Loading at 7.5 vol%
Cellulose
1 0 .0 0
E la s t i c M o d u lu s
2200
2050
7 .5 0
1900
A: MA-g-PA (vol%)
1750
5 .0 0
1150 1600
1300
1450
2 .5 0
0 .0 0
0 .0 0 2 .5 0 5 .0 0 7 .5 0 1 0 .0 0
C : C e llu lo s e ( vo l% )
Figure 4.29: Elastic Modulus Dependence on MA-g-PE and Cellulose Loading at 1 vol%
Silicate
66
4.4.2 Morphology
The morphology of the hybrid composites was investigated using WAXD and
SEM. The results from the study are presented in the following sections.
4.4.2.1 Wide Angle X-ray Diffraction
Figure 4.30 shows WAXD results comparing the d-spacing of the treated clay with
the d-spacing of the clay in the hybrid compound. The d-spacing of the peaks for the clay
and the composite are labeled in the figure. The d-spacing of the hybrid composite is
observed to be similar to that of the treated clay, but the peak shown is very broad,
suggesting clay structures at higher d-spacings are also present in the composite.
3000
2500
2000
Hyrbid Composite
Cloisite 20A
Intensity
1500
1000
500
0
0 2 4 6 8 10 12
2θ
Figure 4.30: WAXD for the Hybrid System
67
4.4.2.2 Scanning Electron Microscopy
SEM pictures were obtained in order to further characterize the dispersion of the
clay and cellulose in the hybrid composites. Figure 4.31a shows cellulose fibers coated
in the RHDPE. The fact that the fibers are coated suggests that the compatibilization
provided by the MA-g-PE is effective. Otherwise, upon fracture, bare cellulose fibers
would be present showing that the failure was caused by poor compatibilization. Figure
4.31b shows the clay dispersion. The specks of clay dispersed evenly throughout the
polymer provide evidence of adequate clay dispersion in the hybrid composite.
Figure 4.31: SEM for the Hybrid System (a: left, b: right)
4.2.2.3 Crystallization Effects in the Hybrid System
DSC was used to determine the percent crystallinity for neat RHDPE, a
clay/polymer composite, and a hybrid composite. Figures 32, 33, and 34 show the DSC
curves obtained. The crystallinity for the clay and hybrid systems needed to be corrected
due to the presence of materials other than HDPE in the composite. After these
68
corrections were accounted for, the actual crystallinity for the sample of 3 vol% silicate
(Cloisite® 20A) is 55.5%. The actual crystallinity of the hybrid composite with 3 vol%
silicate (Cloisite® 20A) is 53.8%.
The crystallinity of the polymer matrix is decreased slightly with the addition of
reinforcements for both the clay and hybrid system.
123.28°C
177.0J/g
-1 60.42 % crystallized
Heat Flow (W/g)
-2
-3
132.61°C
-4
40 60 80 100 120 140 160 180
Exo Up Temperature (°C) Universal V3.9A TA Instrum ents
Figure 4.32: DSC Curve for Neat RHDPE
69
0 .0
1 2 2 .5 6 °C
1 4 0 .3 J /g
4 7 .9 0 % c rys ta lliz e d
-0 .5
-1 .0
Heat Flow (W/g)
-1 .5
-2 .0
-2 .5
1 3 1 .1 1 °C
-3 .0
40 60 80 100 120 140 160 180 200
E xo U p T e m p e ra tu re (°C ) U n iv e rs a l V 3 .9 A T A In s tru m e n ts
Figure 4.33: DSC Curve for Polymer/Clay Composite with 3 vol% silicate (Cloisite®
20A) and 10 vol% MA-g-PE
0 .5
0 .0
122.17°C
104.4J /g
35.65 % crystalliz ed
-0 .5
Heat Flow (W/g)
-1 .0
-1 .5
-2 .0
130.07°C
-2 .5
40 60 80 10 0 120 14 0 160 18 0 2 00
E xo U p Tem perature (°C ) U niversal V 3.9 A T A In strum ents
Figure 4.34: DSC Curve for Hybrid Composite with 3 vol% silicate (Cloisite® 20A), 11
vol% softwood cellulose fibers, and 10 vol% MA-g-PE
70
4.5 Probing Studies
4.5.1 Clay Treatment During Compounding
Figure 4.32 shows the tensile strength of the various composites made with clay
treatment during compounding. For the clay/polymer composites, a reduction in tensile
strength is observed when treatment during compounding is employed. However, in the
hybrid composite, when the clay is treated during compounding, the tensile strength is
higher than that with conventional ion exchange.
Figure 4.33 shows the elastic modulus of the various composites made with clay
treatment during compounding. When considering the clay/polymer composites, there is
statistically no difference in elastic modulus between treatment methods and
temperatures. The hybrid composites show a substantial increase in modulus with clay
treatment during compounding compared with conventional ion exchange. The elastic
modulus is statistically the same for both temperatures studied.
Figure 4.34 shows the percent elongation of the composites. The hybrid system
exhibits a much lower percent elongation, which is a result of the presence of cellulose in
the system.
71
40
35
30
25
20
15
10
0
Untreated Betonite Conventional Ion Treated During Treated During Conventional Ion Treated During Treated During
Exchange Compounding @ Compounding @ Exchange Compounding @ Compounding @
170C 140C 170C 140C
Composites with 3 vol% silicate and 15.4

Composites with 3 vol% silicate. vol% cellulose
Figure 4.35: Tensile Strength for Different Clay Treatment Methods for Bentonite
Composites
2500
2000
1500
1000
500
0
Exchange Compounding @ 170C Compounding @ 140C Exchange Compounding @ 170C Compounding @ 140C

Figure 4.36: Elastic Modulus for Different Clay Treatment Methods for Bentonite
Composites
72
300
250
200
% Elongation
150
100
50
0
Exchange Compounding @ Compounding @ Exchange Compounding @ Compounding @
170C 140C 170C 140C

Figure 4.34: Percent Elongation for Different Clay Treatment Methods on Bentonite
Composites
4.5.2 Compatibilization via Reactive Compounding
Figures 4.35, 4.36 and 4.37 show the tensile strength, elastic modulus, and percent
elongation, respectively, for the various composites made utilizing reactive
compounding. The clay/polymer composite shows a slight increase in tensile strength
when comparing reactive compounding versus conventional compatibilization. The
cellulose/polymer composite, however, shows a decrease in tensile strength when making
the same comparison. The elastic modulus is shown to increase in the clay/polymer
composite when utilizing reactive compounding while no change is observed in the
cellulose/polymer system. The percent elongation is decreased in the clay/polymer
composite when the compatibilization is done using reactive compounding, while again
73
there is no change in the cellulose/polymer system. The percent elongation is
significantly lower for the cellulose composites compared to the clay composites.
50
45
40
35
30
25
20
15
10
0
Conventional Compatibilizer Reactive Compounding Conventional Compatibilizer Reactive Compounding
3 vol% Silicate 31 vol% Cellulose
Figure 4.35: Tensile Strength for Comparison of Compatibilization Method
74
3000
2500
2000
1500
1000
500
0
Figure 4.36: Elastic Moduli for Comparison of Compatibilization Method
1200
1000
800
% Elongation
600
400
200
6.74 8.27
0
Figure 4.37: Percent Elongation for Comparison of Compatibilization Method
75
CHAPTER V
DISCUSSION
5.1 Introduction
The studies conducted to characterize the clay, cellulose, and hybrid systems have
yielded a wide range of results for analysis. These studies included variables such as clay
type, cellulose type, reinforcement loading and compatibilizer loading. The tensile
property data reflect the reinforcing ability of the clay and/or cellulose along with the
compatibility that exists between the reinforcement and the matrix. Observing the
variation of the tensile properties with MA-g-PE level helps in understanding the
dispersion of the clay and/or cellulose in the system and the interactions that take place at
the polymer/reinforcement interface. WAXD patterns and SEM pictures provide
complementary information to aid in the study of the hybrid system morphology.
5.2 Mechanical Properties of Clay System
5.2.1 Effect of Clay Treatment
Figures 5.1 and 5.2 show the comparisons of mechanical properties for composites
made with clays of varying surface treatment. The treatment present on an organoclay
plays an important role in the interactions that take place between the clay and the
polymer matrix. In the case of polyolefins, it is advantageous to use clays that have been
treated to reduce the hydrophilicity. This allows them to interact more positively with the
hydrophobic polymer matrix. The clays used in order of increasing hydrophobicity are:
76
Cloisite® 10A, Cloisite® 25A, and Cloisite® 20A. As shown in the figures, Cloisite® 20A
gives the best mechanical properties, especially when considering the 3 vol% silicate
composites. The properties are improved with this clay because of the greater
hydrophobicity of the clay as compared to the other clays tested. This provided more
compatibility between the polymer and the clay making dispersion with this type of clay
more thermodynamically favorable and thus resulting in higher mechanical properties.
77
35
10A
Tensile Strength (MPa) 30 25A
25 20A
20
15
10
0
1 vol% silicate 3 vol% silicate
Figure 5.1: Comparison of Tensile Strength for Various Clay Treatments
2500
10A
2000 25A
20A
1500
1000
500
0
1 vol% silicate 3 vol% silicate
Figure 5.2: Comparison of Elastic Modulus for Various Clay Treatments
78
5.2.2 Effect of Clay Types
Two clay types were studied, montmorillonite and bentonite. Both clays have the
same layered structure, which allows polymer to intercalate into the galleries, since
bentonite is the ore from which montmorillonite is refined.
5.2.2.1 Mechanical Properties
Figures 4.4 and 4.5 show the mechanical properties for the two types of clays in
composites of 3 vol% silicate. The lower tensile strength and slightly lower modulus of
the untreated bentonite are attributed to impurities present in the unrefined ore. After
treatment, the bentonite clay shows improvement in both mechanical properties. One
possibility is that some of the impurities present in the bentonite were washed away
during the clay treatment process, leaving a more pure treated bentonite whose properties
are similar to treated montmorillonite. Another possible explanation is that the effects of
the treatments, which make both clay types more effective reinforcements, are masking
the effects of the impurities in the clay and causing less of a difference to be observed
between the more and less pure clays.
5.2.2.2 Morphology
Figures 4.6 and 4.7 show the results from the WAXD performed on the bentonite
and montmorillonite clays. When untreated, the montmorillonite shows a higher d-
spacing that the bentonite, which is possibly a result of the refinement and purification of
the montmorillonite. After treatement, the d-spacing of both clay types are increased
significantly and the bentonite d-spacing is found to be higher than that of the
montmorillonite. This shows that the impurities in the unrefined bentonite do not
negatively effect the clay treatment process.
79
At lower intensities, and higher 2θ values, smaller peaks can be observed in both
the treated bentonite and the Cloisite® 20A. The peak in the Cloisite® 20A is
approximately half of the larger peak signifying that it is present as a harmonic peak.
This is not the case for the bentonite peak. It is expected that this peak is showing that
some of the clay is still present at a d-spacing close to that of the original untreated
bentonite peak. There is a slight shift to the left, showing that this clay has been
intercalated by the treatment to a small degree. In any case, the higher intensity peak
shown at a 2θ of approximately 2.5 proves the clay treatment for the bentonite was
successful in increasing the spacing of the silicate layers.
5.2.3 Effect of Clay Loading and MA-g-PE Content
Figures 5.3 and 5.4 show the effects of clay and MA-g-PE loading on the
mechanical properties of the clay system. These two variables will be discussed together
as each show effects, which are dependent upon the other. For the levels of
compatibilization in this study, the MA-g-PE itself was found to have no significant
effects on the mechanical properties of polymer matrix.
The tensile strength is shown to increase with both clay and MA-g-PE loading.
However, when adding MA-g-PE at levels above 4 vol%, the increase in tensile strength
is not observed at lower clay loadings. The decrease in the rate of increase of the tensile
strength with additional MA-g-PE infers that the additional MA-g-PE in the system is not
providing compatibilization at the interface, but simply existing as excess in the polymer
matrix. These results suggest that, in order to optimize the tensile strength for the clay
system, it would be preferred to keep the MA-g-PE level at or below this threshold,
which is dependent upon the clay loading.

80
The elastic modulus is found to increase initially with clay loading, but to begin to
either decrease or level off as the clay loading is further increased. The rate of decrease
of the modulus with clay loading is higher when no MA-g-PE is present. The rate of
decrease becomes less as the amount of MA-g-PE in the system is raised. This shows
that the clay utilizes the compatibilization provided by the MA-g-PE for dispersion and
interaction with the matrix. The concavity of the curves shows that this compatibilization
is most effective at intermediate clay loadings and reaches a threshold above which the
rate of increase of modulus decreases.
34
33
32
31
30
29
28
27
0 0.5 1 1.5 2 2.5 3 3.5
vol% Silicate
0 vol% MA-g-PE 2 vol% MA-g-PE 4 vol% MA-g-PE
6 vol% MA-g-PE 8 vol% MA-g-PE
Figure 5.3: Effects of Clay and MA-g-PE Loading on Tensile Strength
81
1800
1600
Elastic Modulus (MPa) 1400
1200
1000
800
600
400
200
0
0 0.5 1 1.5 2 2.5 3 3.5
vol% Silicate
0 vol% MA-g-PE 2 vol% MA-g-PE 4 vol% MA-g-PE
Figure 5.4: Effects of Clay and MA-g-PE Loading on Elastic Modulus
5.3 Mechanical Properties of Cellulose System
5.3.1 Effect of Cellulose Type
Four types of cellulose were used in this study: softwood and hardwood fibers with
and without lubricant. Figures 5.5 and 5.6 show a comparison of the mechanical
properties for these four types of cellulose fibers. Similar results are observed for the
tensile strength and the elastic modulus. The softwood fibers are more effective without
lubricant, while the hardwood fibers are more effective with lubricant present. This
shows that the hardwood fibers are either more difficult to disperse in the composite or
that the properties of the hardwood composites are more dependent on the dispersion.
The softwood fibers show a hinderance in reinforcement with the presence of lubricant.
In this case, the lubricant may be reducing the fibers’ interactions with the compatibilizer
and thus reducing the mechanical properties of the final composite.
82
60
50 softwood fibers
hardwood fibers
40
30
20
10
0
without lubricant lubricated
Figure 5.5: Comparison of Tensile Strength for Softwood and Hardwood Cellulose Fibers
3000
softwood fibers
2500
hardwood fibers
2000
1500
1000
500
0
without lubricant lubricated
Figure 5.6: Comparison of Elastic Modulus for Softwood and Hardwood Cellulose Fibers
83
5.3.2 Effect of Cellulose and MA-g-PE Loading
Figures 5.7 and 5.8 shows the effects of cellulose and MA-g-PE loading on the
cellulose system. These two variables will be discussed together because of the
interactions that exist.
In the case of cellulose loading, two different behaviors can be observed. When
little or no MA-g-PE is present in the system, the addition of cellulose results in a
decrease in both tensile strength and elastic modulus. This infers weak interaction
between the cellulose and the matrix causing weak interfaces and poor dispersion. When
more MA-g-PE is added, the addition of cellulose causes an increase in both mechanical
properties. This shows that the MA-g-PE is effectively compatibilizing the system and
aiding in dispersion and strengthening of the cellulose/polymer interface at these levels.
The performance of the MA-g-PE shifts from ineffective to effective somewhere in the
range of 1-2 vol% MA-g-PE. The highest properties are observed at high levels of both
MA-g-PE and cellulose. At these levels, enough MA-g-PE is present to compatibilize the
system and allow the cellulose to provide effective reinforcement to the compound.
84
70
60
50
40
30
20
10
0
0 5 10 15 20 25
vol% Cellulose
Figure 5.7: Effects of Cellulose and MA-g-PE Loading on Tensile Strength
4500
4000
3500
3000
2500
2000
1500
1000
500
0
0 5 10 15 20 25
vol% Cellulose

Figure 5.8: Effects of Cellulose and MA-g-PE Loading on Elastic Modulus
85
5.4 Mechanical Properties of Hybrid System
5.4.1 Effect of MA-g-PE Loading
Figure 5.9 and 5.10 show the variation of tensile strength and elastic modulus
with MA-g-PE loading, respectively. The lines in each figure represent at constant clay:
cellulose ratios. A similar trend can be observed for both the tensile strength and elastic
modulus, although the trend is more pronounced in the elastic modulus data. At lower
levels of MA-g-PE, the mechanicals properties show an increase in value as more clay is
in the system. For example, at 2 wt% MA-g-PE, a higher modulus is observed for the 4:1
line than for the 1:4 line. At higher levels of MA-g-PE, the trend is reversed showing
higher mechanical properties with the presence of more cellulose in the composite. The
crossover where the trend is reversed, occurs at approximately 6 wt% MA-g-PE for the
elastic modulus and over a wider range of MA-g-PE values (approximately 4-8 wt%) for
the tensile strength. This change in effectiveness of the MA-g-PE is attributed to the
different compatibilities of the MA-g-PE with clay and cellulose. It is expected that the
clay, due to the non-polar treatment, is less attracted to the polar groups on the MA-g-PE
than the cellulose fibers. This would explain the observance of higher properties in
composites of high MA-g-PE level with more cellulose present.
86
50
clay:cellulose loading
1:1 1:2 1:3 1:4
45
2:1 3:1 4:1

40
35
30
25
0 2 4 6 8 10 12 14 16
PEMA Level (vol%)
Figure 5.9: MA-g-PE Dependence on Tensile Strength in the Hybrid System
3500
clay:cellulose loading
3300 1:1 1:2 1:3
3100 1:4 2:1 3:1
2900 4:1
2700
2500
2300
2100
1900
1700
1500
0 2 4 6 8 10 12 14 16
PEMA Level (vol%)
Figure 5.10: MA-g-PE Dependence on Elastic Modulus in the Hybrid System
87
5.4.2 Reinforcement Effects on Hybrid System
Table 5.1 highlights the results obtained from mechanical testing of the hybrid
system. This table shows predicted data from the experimentally obtained models. In
each case the level of each component other than the polymer matrix is 4 vol%. The clay
only composite shows a significant increase in elastic modulus with a smaller increase in
tensile strength. The cellulose only composite shows a smaller increase in elastic
modulus as compared to the clay only composite and a greater increase in the tensile
strength. The hybrid composite shows an increase in modulus exceeding that of both
individual systems and an increase in strength equal to that of the cellulose only system.
It can then be concluded by comparison of the three systems that the increase in modulus
for the hybrid system is occurring mostly by clay reinforcement and the increase strength
is a result of the cellulose reinforcement. The hybrid system effectively provides an
increase in both modulus and strength where the individual systems can each provide an
increase in only one of the properties.
Table 5.1: Summary of Mechanical Testing Results for Hybrid System at 4 vol% Clay
and/or Cellulose
Elastic Tensile
% %
Type of System Modulus Strength
Increase Increase
(MPa) (MPa)
RHDPE 900 0 27 0
RHDPE + MA-g-PE + 20A 1600 78 29 7.4
RHDPE + MA-g-PE + CF 1200 33 34 26
RHDPE + MA-g-PE + 20A + CF 1800 100 34 26
5.4.3 Crystallization Effects on the Hybrid System
Figure 4.32, 4.33, and 4.34 show the results from the crystallization study
conducted. The resulting decrease in crystallinity in for the clay and hybrid composites
88
indicates that the reinforcement effects observed for those systems are a result of the
reinforcing properties of the clay and cellulose rather than a consequence of added
crystallinity.
5.5 Results from Probing Studies
5.5.1 Clay Treatment During Compounding
The results presented in Section 4.5.1 show clay treatment during compounding to
be a viable method for treating the clay for the systems studied in this work. Figure 4.32
shows little change in tensile strength with the various clay treatment methods
investigated. In both cases (clay and hybrid system), the treatment during compounding
produced better results at the lower temperature level (140°C). The lower temperature is
expected to slow the evaporation of the water from the clay/treatment cake, which allows
more reaction time for the aqueous system.
Figure 4.33 shows no statistical change in the elastic modulus for the clay/polymer
system with the various treatment methods. In the hybrid system, the modulus is
increased with treatment during compounding.
Both the tensile strength and elastic modulus show significant increase in the
hybrid system with compounding treatment at 140°C. It is possible that in the case of the
hybrid system, some of the treatment added is being reacted to the cellulose fibers
causing them to be more compatible with the polymer matrix and resulting in increased
mechanical properties. These results suggest that the treatment of cellulose fibers is an
important variable, which should be considered in future studies involving this system.
In addition, the results confirm that the method of treating the clay during
compound is competitive with the conventional ion exchange method due to its high
89
effectiveness and low cost. It is suggested that further studied be conducted in this area
in order to optimize this method.
5.5.2 Compatibilization via Reactive Compounding
The results presented in Section 4.5.2 suggest that this method of compatibilization
is a viable method that is worthy of further study. The main area of concern observed
from the data is the decrease in strength observed in the cellulose/polymer composite
when using reactive compounding (Figure 4.35). The loss of strength in the cellulose
composite is important as the cellulose is relied on to impart strength in the hybrid
composites studied in this work. However, a benefit can be observed in the increase in
elastic modulus observed in the clay/polymer system (Figure 4.36). This increase is
especially advantageous as the clay is expected to stiffen the hybrid composites looked at
in this work.
It is suggested that this method of compatibilization be further studied, optimized
and applied to the hybrid system. For example, the reacting time allowed before
introduction of the cellulose may be critical to prevent cellulose degredation. The aim of
the study should be to maintain the elastic modulus increase and improving the tensile
strength property as the method is transferred from the individual systems (clay and
cellulose) to the hybrid system.
5.6 Economic Considerations
For this research, the objective was not only to make a composite with superior
properties but also to do so at the lowest cost possible. When modifying inexpensive
materials, such as recycled polyethylene, it is important to recognize the cost that is
added with modification. The modifications in this work included: clay, cellulose, and
90
compatibilization. Table 5.2 shows the cost of the components used to make the various
hybrid composites.
Table 5.2: Cost of Raw Materials
Material Description Cost

Polymers:
HDPE Virgin HDPE $0.50/lb.43
RHDPE Post Consumer Regrind HDPE $0.38/lb.48
Nanoclays:
Cloisite 20A Sodium Montmorillonite $3.50/lb44
Bentonite Sodium Bentonite $0.18/lb.49
Clay Treatment:
Arquad 2HT-75 Dimethyl Dihydrogenated Tallow $1.27/lb.45
Cellulose Fibers:
TC1004 Soft Wood Cellulose Fibers $0.2046
TC2500 Hard Wood Cellulose Fibers $0.2046
Compatibilizers:
Polybond 3009 1% maleic anhydride grafted HDPE $1.92/lb50
Hydrogen Peroxide 2,5-dimethyl-2,5-di(tert-butylperoxyl) hexane $12.84/lb51
Maleic Anhydride maleic anhydride $10.13/lb51
The first cost comparison is the cost of the hybrid composite versus virgin HDPE.
The price of HDPE over the last year averaged $0.50/lb. To make a hybrid composite
with RHDPE, 2 vol% silicate from treated bentonite, 11 vol% cellulose, with 10 vol%
MA-g-PE compatibilizer costs only $0.53/lb. The mechanical property data for this
hybrid show more than 30% increase in tensile strength and a 200% increase in elastic
modulus for a cost of only $0.03/lb. The compounding cost of the hybrid composite was
not included in this cost estimate. In order to resell recycled resin, the polymer must be
reprocessed and pelletized. Therefore, it would be possible to make the hybrid composite
by modifying the already existing process will little added cost. This cost comparison
shows that the use of RHDPE in these composites is not only beneficial mechanically,
but also cost effective.
91
Another cost comparison is between the bentonite and montmorillonite clays.
Treated bentonite made with an equivalent treatment to Closite® 20A costs only $0.85/lb.
compared to $3.50/lb for Cloisite® 20A. The cost of the treated bentonite includes only
raw material costs and not the cost of actually treating the clay. However, clay treatment
costs would only need to remain below $2.00-$2.50/lb. for the bentonite clay to remain
competitive with the Cloisite® 20A as each clay showed very similar mechanical property
data in the clay and hybrid systems. It would likely be closer to $1.00/lb for the
treatment, which would result in significant cost benefits for using bentonite versus
Cloisite® 20A. In addition, efforts have been made in this study to provide a cost
effective alternative to the clay treatment step. As discussed previously, clay treatment
during compounding offers similar mechanical properties while eliminating the need for
a separate clay treatment process. More research in this area could further aid in reducing
the cost of nanoclays as polymer reinforcements.
Another alternative method briefly studied was using reactive compounding to
compatbilize the system instead of using pre-made compatibilizer. When considering
only raw material costs, reactive compounding reduces the cost of the final composite by
$0.05/lb. as compared to the cost of using the pre-made MA-g-PE. Much work has
already been done in the area of reactive compounding and more specifically reactive
extrusion, which helps to make it an attractive option as a cost reducer for this system.
These cost comparisons, along with the mechanical data presented throughout this
work support the conclusion that the hybrid system not only offers a method of
improving the mechanical properties of RHDPE but a method which is also cost effective
when compared with virgin HDPE and with traditional reinforcements.
92
CHAPTER VI
CONCLUSIONS
The synthesis and characterization of various RHDPE composites with various
reinforcements (clay and/or cellulose) has provided understanding of the effects of
reinforcement type, reinforcement loading, and compatibilizer concentration on
mechanical properties. Specific conclusions of this study are as follows, broken down
according to the three systems studied:
Clay/Polymer Nanocomposites
1. Cloisite® 20A is the most compatible clay of those tested for this system.
2. The interactions between the MA-g-PE and the clay are such that the MA-g-PE
becomes a more effective compatibilizing agent at higher clay loadings.
3. The effect of clay is more prevalent in the elastic modulus compared to the tensile
strength.
4. Bentonite is effective as a nanofiller and can compete with the mechanical
properties imparted by conventional nanoclays (Cloisite® 20A).
Cellulose/Polymer Nanocomposites
1. The interactions between the cellulose fibers and the MA-g-PE are such that the
MA-g-PE is less effective at lower cellulose concentrations.
2. To maximize the effectiveness of the compatibilizer a constant ratio of MA-g-PE
to cellulose should be used.
93
3. Cellulose serves as an effective reinforcement by increasing both tensile strength
and elastic modulus as sufficiently low loading, although the stiffening effects of
the cellulose are not as effective as clay stiffening.
Clay/Cellulose/Polymer Hybrid Composites
1. A significant interaction occurs between the level of MA-g-PE and the
concentration of clay and cellulose in the hybrid system, which is attributed to the
different compatibilities of the clay and cellulose with the MA-g-PE.
2. For this system, the clay reinforcement provides effective stiffening, while the
cellulose reinforcement provides effective strengthening.
3. The hybrid system is an effective way to achieve high modulus and high strength
simultaneously.
4. Reasonable levels of clay and cellulose dispersion were achieved in the hybrid
system.
Clay Treatment During Compounding
1. The treatment of clay during compounding is a viable method of treatment, which
results in mechanical properties comparable to that imparted by clays with
traditional ion exchange treatment.
2. Clay treatment during compounding is more effective at lower temperatures.
3. Crystallinity in the hybrid system does not significantly effect the mechanical
properties of the hybrid composites.
Compounding via Reactive Extrusion
1. Compatibilization via reactive compounding is an acceptable method of
compatibilization for both the clay and cellulose systems.
94
2. In order for reactive compounding to be a viable method of compatibilization for
the cellulose system (and possibly the hybrid system), the decrease in tensile
strength caused by this method would need to be addressed and corrected.
Overall conclusions
1. The hypothesis made in this work was confirmed by producing a RHDPE
reinforced system that is competitive with virgin HDPE both economically and
performance-wise.
2. The process to make the hybrid system is economical and can be made more cost
effective with further work in the areas discussed in the probing studies.
3. For the systems studied, increased crystallinity was not a factor in increasing the
mechanical properties of the composites.
4. The hybrid system is capable of producing a RHDPE composites with tensile
strengths approaching 40 MPa and elastic moduli of over 2000 MPa.
95
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98
APPENDIX
Experimental Data for Clay/Polymer System

vol% Elastic Modulus Tensile Strength
Run vol% Silicate % Elongation
MA-g-PE (MPa) (MPa)
1 2.6 6.8 1540 32.7 301
2 1.5 4.0 1462 31.6 410
3 1.5 4.0 1218 31.5 511
4 0.4 1.2 1117 29.7 192
5 2.6 1.2 1156 31.9 308
6 0.4 6.8 1247 29.7 216
7 3.0 4.0 1122 33.3 165
8 0.0 4.0 832 28.5 169
9 1.5 0.0 1158 30.7 291
10 1.5 4.0 1226 31.6 512
11 1.5 4.0 1198 31.4 460
12 1.5 8.0 1347 32.0 534
Experimental Data for Cellulose System

vol% vol% Lubricant Elastic Modulus Tensile Strength
Run Cellulose Type % Elongation
Cellulose MA-g-PE Level (MPa) (MPa)
1 11 2 No Lubricant TC 2500 1569 35.9 22.1
2 22 2 Lubricant TC 2500 2682 44.7 4.8
3 22 2 No Lubricant TC 1004 3068 52.4 4.0
4 11 4 Lubricant TC 2500 1509 36.6 15.9
5 11 4 No Lubricant TC 1004 1770 38.6 21.8
6 22 4 Lubricant TC 1004 2054 35.1 5.5
7 22 4 No Lubricant TC 2500 2472 45.1 6.7
8 11 2 Lubricant TC 1004 1305 30.9 12.8
9 22 0 No Lubricant TC 2500 1364 36.0 4.4
10 22 0 No Lubricant TC 1004 1328 37.3 3.4
11 22 0 Lubricant TC 2500 1645 36.4 4.0
12 22 0 Lubricant TC 1004 1894 27.7 4.1
99
Experimental Data for Hybrid System
vol% vol% vol% Elastic Modulus Tensile Strength
Run % Elongation
MA-g-PE Silicate Cellulose (MPa) (MPa)
1 5.3 2 4.4 1615 32.6 37
2 10.5 2 4.4 1590 32.3 27
3 10.5 4 7.8 2330 33.6 6
4 5.3 4 4.4 1923 32.4 11
5 5.3 2 7.8 1966 33.6 11
6 10.5 2 7.8 2006 34.0 12
7 10.5 4 4.4 1745 32.7 10
8 5.3 4 7.8 2307 31.9 6
100

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ADDING VALUE TO RECYCLED POLYETHYLENE THROUGH

THE ADDITION OF MULTI-SCALE REINFORCEMENTS

The Graduate Faculty of The University of Akron

of the Requirements for the Degree

THE ADDITION OF MULTI-SCALE REINFORCEMENTS

economically and performance wise.

This study focuses on the improvement of the mechanical properties of recycled

high-density polyethylene (RHDPE) through the addition of multi-scale reinforcements.

composites as well as the effect of compatibilization on the composite properties are

To address the economic objective of this study, bentonite is investigated as a

possible alternative to montmorillonite as the nanofiller in the hybrid system. Bentonite

montmorillonite, but possesses the same layered silicate structure.

microscale cellulose reinforcement was found to have effective strengthening.

their support and understanding.

2.1.1.1 Monmorillonite Clays…………..…………………………………...…..4

2.1.1.2 Bentonite Clays……………..………………………………………...…6

2.1.2 Cellulose Fibers……………………………………………………….……7

2.1.3 High-Density Polyethylene………………………………………………....7

2.2 Recycling of Polyethylene………………..……………………………………8

2.3 Polymer/Clay Nanocomposites………...……..……………………………..…9

2.3.1 Current Market for Polymer/Clay Nanocomposites……...……………….11

2.3.2 Polyethylene/Clay Nanocomposites…………………...………………….12

2.3.3 Preparation of Polyolefin Nanocomposites………………………………..13

2.4 Polymer/Cellulose Microcomposites…………………...…………………....15

2.4.1 Market for Polymer/Cellulose Microcomposites…………….……………15

2.4.3 Polyethylene/Cellulose Microcomposites…………………………...…….17

3.1.1 Polyethylene Matrix……..………………………………………...………19

3.1.1.1 Recycled Polyethylene…..………………………………………..……19

3.1.1.2 Virgin Polyethylene………..…………………………………………..19

3.1.3.2 Bentonite Clays……………………………………………………..….22

3.1.3.3 Ammonium Salt for Clay Treatment……………………………..……22

3.1.4 Cellulose Fibers………………………………………………………..….23

3.2 Hybrid Composite Development……...……………………………………...23

3.2.2 Preparation of Polymer/Clay Nanocomposites………………………...….24

3.2.2.1 Study of Mixing Schemes……………………...……………………....24

3.2.2.2 Clay Treatment…………………………………………………………25

3.2.2.3 Experimental Test Matrices………………………………………..…..26

3.2.3 Preparation of Polymer/Cellulose Microcomposites……...………………28

3.2.4 Preparation of Hybrid Composites…………………………………...……29

3.2.5 Preparation of Compounds for Probing Studies…………………………..30

3.2.5.1 Treatment of Clay During Compounding……………………………...30

3.2.6 Specimen Preparation………………………………………………..……32

3.3.1 Mechanical Testing…………………………………………………….….33

3.3.2 Wide Angle X-ray Diffraction (WAXD)………………………………….33

3.3.3 Scanning Electron Microscopy (SEM)…..…………..……………………33

3.3.4 Differential Scanning Calorimetry (DSC)………………………..……….34

4.2 Polymer/Clay Nanocomposites……………………………………………….35

4.2.1 Mixing Scheme Analysis…………………………………………….……35

4.2.1.1 Tensile Strength……………………...………………………………...36

4.2.1.2 Elastic Modulus……………………...………………………………...36

4.2.1.3 Percent Elongation……………………...………………………...……37

4.2.1.4 Summary of Mixing Scheme Analysis for Polymer/Clay

4.2.2 Treatment of Bentonite Clay………………………………………………38

4.2.2.1 Mechanical Properties………………………………………………….38

4.2.3 Mechanical Properties of Polymer/Clay Nanocomposites………………..42

4.2.3.1 Stress-Strain Curve……………………………………………….……42

4.2.3.2 Tensile Strength…………………………………………………..……43

4.2.3.2.1 Tensile Strength Dependence on Clay Treatment and Clay

4.2.3.3 Elastic Modulus…………………………………………………….….45

4.2.3.3.1 Elastic Modulus Dependence on Clay Treatment and Clay

4.2.3.3.2 Elastic Modulus Dependence on Clay Loading and MA-g-PE

4.2.3.4 Percent Elongation…………………………………………………..…47

4.2.3.4.1 Percent Elongation Dependence on Clay Treatment and Clay