The degradation study of PVC/ABS and PVC/ABS/Carbon blends during repeated extrusion on mechanical and thermal properties.

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UNIVERSITI TEKNIKAL MALAYSIA MELAKA

Faculty of Manufacturing Engineering

THE DEGRADATION STUDY OF PVC/ABS AND

PVC/ABS/CARBON BLENDS DURING REPEATED EXTRUSION

ON MECHANICAL AND THERMAL PROPERTIES

Muhyiaddin Abdul Qadir bin Abu Bakar

Master of Manufacturing Engineering (Industrial Engineering)

2014

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THE DEGRADATION STUDY OF PVC/ABS ａｾｄ＠ｐｖｃＯａｂｓＯｃａｒｂｏｾ＠ BLENDS DURING REPEATED ｅｘｔｒｌＧｓｉｏｾ＠

ON MECHANICAL AND THER'1AL PROPERTIES

MUHYIADDIN ABDUL QADIR BIN ABL' BAKAR

A thesis submitted

in fulfillment of the requirements for the degree of Master of Manufacturing Engineering (Industrial Engineering)

Faculty of Manufacturing Engineering

UNIVERSITI TEKNIKAL MALAYSIA :WELAKA

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DECLARATION

I hereby, declared that this report entitled ' The Degradation Study of PVC/ABS and

PVC/ABS/Carbon Blends During Repeated Extrusion on Mechanical and Thennal Properties'

is the results of my own research except as cited in the references.

0

Signature

Name : Muhyiaddin Abdul Qadir Bin Abu Bakar

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APPROVAL

I hereby declare that I have read this thesis and in my opinion this thesis is sufficient in terms

of scope and quality for the award of Master of Manufacturing Engineering (Industrial

Engineering).

Signature

Supervisor Name : Dr. Zaleha Binti Mustafa

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ABSTRACT

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ABSTRAK

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ACKNOWLEDGEMENTS

First and foremost, I would like to take this opportunity to express my sincere acknowledgement to my supervisor Dr. Zaleha Mustafa from the Faculty of Manufacturing Engineering Universiti Teknikal Malaysia Melaka (UTeM) for her essential supervision, support and encouragement towards the completion of this Master Project 2.

Particularly, I would also like to express my deepest gratitude to Mr. Azhar and Mr. Hairul Hisham, the technicians from material laboratory Faculty of Manufacturing Engineering, for their assistance and efforts in the lab and analysis works.

Special thanks to all my peers, my mother, beloved father and siblings for their moral support in completing this Master Project 2. Lastly, thank you to everyone whom had been to the crucial parts of realization of this project.

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4 RESULT AND DISCUSSION

4.1

Introduction

66

4.2

66

4.2.1

Analysis of variance (ANOVA)

68

4.2.2

Ultimate Tensile Strength

71

4.2.3

Strain at Ultimate Tensile Strength

73

4.2.4

Elastic Modulus

74

4.2.5

Strain at Failure

75

4.3

Thermal properties 77

4.4

Fracture Morphology

81

5 CONCLUSION & RECOMMENDATION

5.1

Conclusion

91

5.2

Recommendation

93

REFERENCES

94

APPENDICES

104

v

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LIST OFT ABLES

TABLE TITLE PAGE

2.1 Mechanical & thermal properties of PVC 18

3.1 Design of experiment (DOE) 55

3.2 Properties of PVC 57

3.3 Properties of ABS 57

3.4 Properties of Carbon 57

3.5 Blend composition 58

3.6 Temperature zones of extrusion profile 58

3.7 Numbers of specimens required 60

Specification of Universal Testing Machine 5kN (Computer Servo 62 3.8

Control)

3.9 Zeiss Stemi 2000 Stereomicroscope specification 65 3.10 Zeiss EVO 50 XVP Electron scanning microscope specification 65 Effect of numbers of extrusion to the mechanical properties of PVC 67 4.1

and PVC blends

Effect of numbers of extrusion to the glass transition temperature of 77 4.2

PVC, ABS and PVC blends

[image:10.511.39.458.187.540.2]

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LIST OF FIGURES

FIGURE TITLE

2.l Thermal dehydrochlorination of PVC. C: Carbon. H: Hydrogen. Cl :

Chlorine. ｾＺ＠ Heat. x,y: Integers

2.2 Scanning Electron Micrograph for (a)-(i) unexposed film of only

PVC (a)-(ii) only PVC film exposed to solar radiation (a)-(iii) only

PVC film exposed to artificial UV radiation. (b )-(i) Unexposed

composite film of PVC- ZnO (b )-(ii) PVC- ZnO composite film

exposed to solar radiation (b )-(iii) PVC- ZnO composite film exposed

to artificial UV radiation

2.3 Laser microscopic image of the fading section around the surface

after weathering test: (a) 0 h (the obvious inorganic particles are

pointed by arrows), and (b) 3000 h (the obvious voids are pointed by

arrows)

2.4 Laser microscopic image of the section around the surface after

thermal aging test: (a) 0 h, and (b) 240 h. The obvious inorganic

particles are pointed by arrows

2.5 Molecular structure for (a) vinyl chloride and (b) polyvinyl chloride,

PVC

2.6 Dependence of tensile strength ( crM) of the extrudate obtained from

the mixture of A/B (0 % gel/I 00% gel) granulated products on the

processing temperature (T): 1- 0/ 100 % gel; 2- 25/75 % gel; 3- 50/50

% gel ; 4- 75/25 % gel ; 5- 100/0 % gel

2.7 Dependence of relative elongation at failure ( c8 ) of the extrudate

obtained from the mixture of A/B (0% gel/ 100% gel) granulated

products on the processing temperature (T): 1- 0/100 % gel; 2- 25/75

% gel; 3- 50/50 % gel ; 4- 75/25 % gel; 5- 100/0 % gel

2.8 DSC Curve of uPVC Gelation Test

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PAGE

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13

14

15

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2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2 .21 2.22 2.23

Molecular structure of ABS monomer

Molecular structure of ABS

The change in Izod impact strength with the increase of injection

cycles

The change in stress at yield point with the increase of injection

cycles

External surface of ABS sewer pipe after UV exposure

Notched impact strength of composites as a function of nano-CaC03

content

Yield strength and elongation at failure of the composites as a

function of nano-CaC03 content

Impact strength as a function of the PVC:ABS ratio

Impact properties of the PVC/ ABS blends at various mass blending

ratios

Scanning electron micrographs of tensile-tested PVC/ ABS (70:30)

blend

TE M images; left=l5nm CB sample " good dispersion"; right= l5nm

CB sample " bad dispersion"

The relation between the Modulus of elasticity of HDPE sample with

weight fraction of Ti02-C.B.fillers at different wt.% of C.B and

constant Ti02 content (15% wt) and. at different wt.% of Ti02and

constant C.B content

Mass throughput at screw speeds of 50 and 90 rpm and Energy

consumption at screw speeds of 50 and 90 rpm

The extrusion pressure and elongation at failure, as a function of

number of extrusions

The elongation at failure for ABS vs the number of cycles in the

extrusion series, the series involving ageing steps of 72 h at 90°C and

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2.24 2.25 2.26 2.27 2.28 2.29 2.30 2.31 2.32 2.33 2.34 2.35 2.36

the combined extrusion and ageing series. The data point at 0 cycles

represent elongation at failure for samples of ABS after the first

extrusion

Tensile strength of ABS subjected to multiple reprocessing

The effect of the number of injection mouldings of ABS on tensile

strength (1) and tensile stress at failure (2)

Elongation at failure of ABS subjected to multiple reprocessing

The effect of the number of injection mouldings of ABS on tensile

strain at ultimate tensile (1) and tensile strain at failure (2)

The effect of the number of injection mouldings of ABS on modulus

of elasticity

The effect of the number of injection mouldings of PC on tensile

strength (I) and tensile stress at failure (2)

Fracture surface of PS in SEM: a, overview with brittle fracture

edges; b, larger magnification of ruptured crazes with domain-like

hills, revealing broken and relaxed craze fibrils

Scheme showing differences between homogeneous (a) and

fibrillated crazes (b) in relation to the entanglement network: top,

view as in electron micrographs; bottom, entanglement network with

stretched meshes. a, Dense pattern of small stretched meshes in homogeneous crazes; b, coarse pattern with voiding and fibrillation in

large meshes in fibrillated crazes

SEM micrographs of ABS in shear deformation fracture level

Shear deformation of 100 wt% ABS

'Black Box' Process Model Schematic

Half-Normal Probability Plot

Normal Probability Plot

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3.1 Design schematic for DOE of the study 55

3.2 Flow chart of the experiments 56

3.3 ASTM D638-I-mm units 60

3.4 GOTECH Universal Testing Machine 61

3.5 Perkin Elmer DSC 4000 63

3.6 Zeiss Stemi 2000 Stereomicroscope 64

3.7 Zeiss EVO 50 XVP Scanning Electron Microscope 65

4.1 Half normal% probability graph; (a) Ultimate tensile ｳｴｲ･ｮｧｴｨｾ＠ (b) 69

Strain at ultimate tensile, (c) Elastic Modulus, (d) Strain at failure

4.2 Normal probability plot ofresidual; (a) Ultimate tensile ｳｴｲ･ｮｾ＠ (b) 70

Strain at Ultimate Tensile, (c) Elastic Modulus, (d) Strain at failure

4.3 Interaction plot between materials and number of extrusion; effect of 72

numbers of extrusion to ultimate tensile strength.

numbers of extrusion to strain at ultimate tensile

numbers of extrusion to elastic modulus.

4.6 Interaction plot between materials and number of extrusion; (a) effect 75

of different materials to strain at failure, (b) effect of number of

extrusions to strain at failure.

4.7 DSC thermograms of PVC with different numbers of extrusion 78

4.8 DSC thermograms of PVC/ ABS 70/30 wt°/o with different numbers 78

of extrusion

4.9 DSC thennograms of PVC/ ABS/Carbon 70/23/7 wt°/o with different 79

numbers of extrusion

4.10 Optical and Scanning electron micrographs of tensile tested 1st 81

extrusion PVC (a) PVC drawing at the crack path;(b) pores at the

crack ;( c) --{ d) crack path propagation

4.11 Scanning electron micrographs of tensile tested 2°d extrusion PVC. 82 (a) optical micrograph on the start of crack formation path;(b) jagged

fracture surface;( c )-( d) smooth fracture surface.

4.12 Scanning electron micrographs of tensile tested 3rd extrusion PVC. 83

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4. 13

4.14

4.15

4.16

4.17

4.18

crack path propagation.

Scanning electron micrographs of tensile tested 1 st extrusion 70/30

wt% PVC/ABS blend. (a) jelly fish surface;(b) coexisted deformation;( c) crack from the top view; ( d) crack from side view Scanning electron micrographs of tensile tested 2°d extrusion 70/30 wt% PVC/ABS blend. (a) microvoids on shear deformation surface;(b) coexisted deformation;( c) shear deformation region; ( d) fibril from side view

Scanning electron micrographs of tensile tested 3rd extrusion 70/30 wt% PVC/ABS blend. (a) fibrillated deformation surface;(b) -{c) shear deformation or homogeneous region;( d) crack from side view Scanning electron micrographs of tensile tested 1 st extrusion 70/23/7

wt% PVC/ABS/Carbon blend. (a) shear deformation surface;(b) relaxed craze fibril ;(c) not homogeneous dispersion of carbon;(d) crack at with massive shear deformation

Tensile fracture surface of 70/23/7 wt% PVC/ ABS/Carbon blends after 2rd extrusion. (a) shear or homogeneous deformation surface;(b) coexisted deformation surface;( c) fibrillated deformation surface;( d) dispersion of carbon

Tensile fracture surface of 70/23/7 wt% PVC/ ABS/Carbon blend after 3rd cycle of extrusion process.(a) brittle region (b) homogeneous region, ( c) crack, ( d) more refine dispersion of carbon.

xi

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84

85

86

87

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ABS ASA AMS-ABS ANOVA ASTM V-0

BR

DOE CaC03 CB

oc

DSC OMA CPE EVA EPDM ft GPC Tg HCI HDT HOPE h in J kg

LIST OF ABBREVEATIONS

Acrylonitrile butadiene styrene

Acrylonitrile Styrene Acrylate

a-methylstyrene-acrylonitrile- butadiene-styrene copolymer

Analysis of Variances

American Society for Testing and Materials

Burning stops within 60 seconds on a vertical specimen

Butadiene rubber

Design of Experiments

Calcium carbonate

Carbon black

Degree of centigrade

Differential scanning calorimetry

Dynamic Mechanical Analysis

Chlorinated polyethylene

Elongation at failure

Ethylene vinyl acetate

Ethylene propylene diene monomer

Foot

Gel permeation chromatography

Glass transition temperature

Hydrogen chloride

Heat distortion temperature

High-density polyethylene

hour

Inch

Joule

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LDPE Low density polyethylene LOI Loss on ignition

MAH Maleic anhydride grafted

MAStVA Maleic anhydride-styrene-vinyl acetate Wt% Mass fraction

m Meter

Tm Melting temperature

mm Milimeter MPa Megapascal

NBR Nitrile butadiene rubber Tonset,m Onset melting temperature

% Percent

PC Polycarbonate

PMMA Poly(methyl methacrylate)

pp Polypropylene PPE Polyphenyl ethers PVC Polyvinyl chloride PS Polystyrene

lbs Pound

psi pound per square inch

RH Relative humidity rpm Revolutions per minute T Temperature

CTM Tensile strength

Ti02 Titanium dioxide K-value Thermal conductivity TGA Thermogravimetric TP Thermoplastic TS Thermo set

TEM Transmission electron microscopy SEM Scanning electron microscope SD Standard deviation

SAN Styrene Acrylonitrile

xiii

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SMA

UL94

UV VCM

XRF

w

ZnO

Styrene-maleic anhydride

Standard for Safety of Flammability of Plastic Materials

Ultraviolet

Vinyl Chloride Monomer

X-ray Fluorescence

Weight fraction

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NO

A

LIST OF APPENDICES

TITLE

Overall ANOV A Report

xv

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Page

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CHAPTER!

INTRODUCTION

1.1 Background

Plastics can be divided into two groups which are thermoplastic (TP) and thermoset

(TS). Thermoplastic is the type of plastic that can be repeatedly softened by heating and

then solidified by cooling. Molecules

iri

a thermoplastic are held together by relatively

weak intermolecular forces. Thermoplastic can be processed several times and makes these

kinds of plastics suitable for recycling. Thermosets in a soft solid or viscous state that

changes irreversibly into an infusible, insoluble polymer network by curing. Curing can be

induced by the action of heat or suitable radiation or both. A cured thermosetting polymer

is called a thermoset.

Polyvinyl chloride (PVC) is a thermoplastic polymer. PVC is primarily an

amorphous material with good durability, fire retardant, oil and chemical resistant and

good mechanical properties. Many commercial polyvinyl chloride (PVC) resins contain

crystalline regions ranging from 5 to I 0 % of the polymer. The polymer will remain intact

at temperatures well over 200 °C. The region of crystallinity with relatively narrow

molecular weight distribution will help impart superior melt strength during extrusion.

Another unique characteristic of polyvinyl chloride (PVC) is the amorphous nature of the

polymer promotes cost effective fabrication of clear articles in thickness exceeding 0.25 in

(lOmm) if proper addictive selection used (Grossman, 2008).

Polyvinyl chloride (PVC) contains approximately 57 % chlorine by weight. The

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wide range of additives. No other commercial polymer can have its properties modified in

so many ways compare to polyvinyl chloride (PVC). Beside of that, the chlorine in

polyvinyl chloride (PVC) will also make the polymer flame resistance.

PVC has been use in wide range of short life and long life product application. In short life product, PVC have been processed in packaging material use in food, cleansing

materials, textile, beverage packaging bottles and medical devices. In long life product, PVC have been processes into pipes, window frames, cable insulation, floors coverings

and roofing sheets (Sadat-Shojai and Bakhshandeh, 2011).

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1.2 Problem Statements

Every product has specific cycle time. There is a time when the product will come

to their end life and the product need to be properly disposed. PVC with a wide range of

products, their waste will increase with time. Thus will become a problem to the

community. Today, PVC waste is dispose in landfill. However, using landfill to cater the

problem is not a good solution because the area required for landfilling will increase with

increasing of the waste. Beside of that, using landfilling to dispose PVC waste have

potential environmental hazard because of the chlorine content of the polymer.

Another route to solve the increment of PVC waste is by recycle the PVC waste

into another product. Thus, recycling of the PVC has gain interest for researcher in order to

produce secondary materials (Sadat-Shojai and Bakhshandeh, 2011). However, recycle the

PVC into similar or another product is not a straight path. Recycle PVC showed to have

inferior mechanical properties (Yarahmadi et al., 2001). The recycle PVC with low

mechanical properties however can be process into a low strength requirement type of

product with cost conscious production. But, if the recycle PVC need to be use in another

requirement type of products, the molecule properties of the material need to be alter.

One of the most popular methods to retain and increase the properties of the

material is by blending the polymer with another polymer. Polymer blending has become

an important field in polymer research. ln this research the target was to reduce the polymer waste problem by blending the PVC with other type of polymer and make sure

that the recycle blends polymer still retains an identical properties compare to the first

cycle of the blends. With identical properties of the blends compare to the virgin and the

recycle of the virgin, it will make the blends as an ideal replacement material to be used for

consumer products. Then, by showing a slightly decrease in properties after a few recycle

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will fulfil the purpose to retain the properties of the material and can be used for several

times in processing. It will give a huge profit for recycle industries because the scrap from

the blends can be recycle to be made into the same or different product that meet the

requirement base on their properties whereas the recycle from the copolymer cannot

sustain the same properties.

Beside of improving physical properties of the material, polymer blends will also

benefit in low investment cost in a new material design. In this case, a cheaper material

like PVC will be dilute with expensive polymer material in hope to retaining some of the

high performance properties. The blends maybe homogeneous (true thermodynamic

miscibility of components) or heterogeneous (phase-separated). In heterogeneous blends, components maybe thermodynamically immiscible but mechanically compatible (Elias,

2003). Many researches have blend PVC with other polymer materials such as

PVC/PMMA, PVC/NBR, PVC/EVA and PVC/CPE (Grossman, 2008). Thus, the objective

to minimize the cost for a new material design with improves material properties can be

achieved.

Polystyrene (PS) is amorphous region material with good impact resistance high

heat resistance. In theory, blending PVC with PS will improve thermal and mechanical

properties of the material. But, does the properties can be retain if the blends were recycles

for several times? The assumption can be made that the recycle of PVC/PS blends will

give the identical outcome with slightly reduce number compare to the first cycle. Another

famous amorphous region material is acrylonitrile butadiene styrene (ABS) with good

impact resistance, toughness and weather ability. In theory, blends PVC with ABS will improve impact resistance, toughness and weather ability of the material (Rimdusit et al. ,

2012). But, does the properties can be retain if the blends were recycles for several times?

Same as PVC/PS blends, assumption can be made that the recycle of PVC/ABS blends will

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give the identical outcome with slightly reduce number compare to the first cycle. There

are very limited knowledge about the properties either PVC/PS or PVC/ABS biends when

there were recycles for several times.

Blends of polyvinyl chloride (PVC) with a-methylstyrene-acrylonitrile-

butadiene-styrene copolymer (AMS-ABS) show a single glass transition temperature (Tg) when

observed by differential scanning calorimetry (DSC). This result indicates that PVC is

miscible with AMS-ABS (Zhang et al. , 2013). The research suggest that the most

interesting area for further investigation is the region containing 15 - 30 wt% of

AMS-ABS because within these compositions, the heat distortion temperature (HDT) and the

impact strength have improved effectively without losses in tensile and flexural properties.

The impact strength show gradually increase when the PVC/ ABS blends below 30 wt% of

ABS content and the drastic increase observed when the ABS content range from 30 to 50

wt% (Rimdusit et al. , 2012). Pavan et al. (1980) show that 30 wt% of PVC/ABS blends

will give the identical impact strength compare to Rimdusit et al. (2012). Thus, for this

degradation study, 30 wt% of ABS will be choose to blend with 70 wt% of PVC. Although

using 30 wt°lo of ABS will not give the highest mechanical properties compare to 50 wt%

of ABS, the composition of 30 wt% of ABS is more economical to the highest

composition. Then, comparison between 15 to 30 wt°lo of ABS show that 30 wt°/o will

result in the highest mechanical properties. So, by choosing 30 wt°lo of ABS, it is the best

composition to use in term of material properties and economic scale.

Effect of repeated extrusion on the properties and durability of rigid PVC scrap

have been studied previously (Yarahmadi et al. , 2001). The PVC scrap has been extruded

for five times without adding new additives. The result shows that PVC scrap is suitable

for mechanical recycling for up to three times only. The fourth recycle show the decrease

The degradation study of PVC/ABS and PVC/ABS/Carbon blends during repeated extrusion on mechanical and thermal properties.

UNIVERSITI TEKNIKAL MALAYSIA MELAKA

Faculty of Manufacturing Engineering

ON MECHANICAL AND THER'1AL PROPERTIES

APPROVAL

ACKNOWLEDGEMENTS

TABLE OF CONTENTS

3 METHODOLOGY

4 RESULT AND DISCUSSION

LIST OF FIGURES

ABS ASA AMS-ABS ANOVA ASTM V-0

LIST OF ABBREVEATIONS

UV VCM

CHAPTER!

1.1 Background