APPLICATION OF RESTAURANT WASTE LIPIDS (RWL) AS A BINDER
COMPONENT IN METAL INJECTION MOULDING
AZRISZUL BIN MOHD AMIN
A thesis submitted in
fulfillment of the requirement for the award of the
Doctor of Philosophy
Faculty of Mechanical and Manufacturing Engineering
Universiti Tun Hussein Onn Malaysia
APRIL 2017
iii
For my beloved mother PUAN HJH ZAMALIAH BTE SURATDI,
my loving wife SITI NURFAIZAH BINTI MOHSAN, my sons MUHAMMAD
AQEEL IFWAT, AHMAD AL-SHAREEF, my daughters KHAYRA ZAFIRAH,
AREEFA NAFEESAH, my only sister and her husband INTAN KARTINI BTE
MOHD AMIN, DR. HASMADI BIN HASSAN
“THANK YOU for your endless support”
iv
ACKNOWLEDGEMENT
In the name of ALLAH S.W.T, The Most Gracious and The Most Merciful,
Greeting and Blessing to Prophet Muhammad S.A.W
I would like to express my sincere appreciation to my supervisor; Associate Professor
Dr. Mohd Halim Irwan Bin Ibrahim and my co supervisor; Associate Professor Dr.
Md. Saidin Bin Wahab for his thoughtful insights, helpful suggestions and continued
support in the form of knowledge, enthusiasm and guidance throughout the duration
for this research.
My infinite gratitude also goes to our dedication technician members; Mr.
Fazlannuddin Hanur, Mr. Shahrul Mahadi, Mr. Anuar and Mr. Tarmizi for their
support and cooperation during completing the experimental and analysis process.
A millions thanks to my family for their constant encouragement and love I have
relied on throughout my studies. To my PhD colleagues; Dr. Mohd Yussni Hashim,
Mr. Suzairin Md Seri, Mr. Shazarel Shamsudin, Dr. Faizal Mohideen Batcha and Dr.
Zamri Noranai, thank a lot for your ideas, motivations, involvement and support during
my PhD journey. Finally, I would like to express my gratitude and appreciation to
Malaysian Government and Universiti Tun Hussein Onn Malaysia for the financial
support and facilities. THANK YOU.
v
ABSTRACT
Application of Restaurant Waste Lipids (RWL) is introduced as binder component in
metal injection moulding since it’s contains rich amounts of free fatty acids which is
suitable as secondary binder components. Different binder formulation of RWL and
Polypropylene (PP) were prepared as the binders and the mixture of these binders with
water atomized 316L powder were obtained. The suitability application of RWL as
binder component was monitored base on mixing condition, rheological characteristic,
injection moulding, debinding and sintering process. Mixing time of 90 minutes was
obtained as suitable mixing time for producing good homogenise feedstock base on
mixing the polypropylene (PP) and RWL. Binder ratio of 50/50 weight percentage
between PP and RWL was obtained to be good binder ratio although all binder ratio
of 60/40, 40/60 and 30/70 shows pseudoplastic behavior. Taguchi method was
successfully employed for optimizing the injection moulding parameters which
consists of injection temperature, mould temperature, pressure, packing time, injection
time, speed and cooling time. It was found that factors that contribute in injecting good
part density and strength were temperature, pressure and speed. Extraction process of
RWL using solvent debinding process indicates that hexane solution with temperature
of 60ºC and solvent to feeds ratio of 7:1 were better as compare to heptane with respect
to fastest time removal. Good thermal debinding process under air atmosphere
condition with temperature of 400ºC and heating rate of 30ºC/min was obtained.
Sintering of the thermal debound parts also shows good mechanical properties and
microstructure of 316L stainless steel parts.
vi
ABSTRAK
Penggunaan sisa buangan lemak dan minyak dari restoran makanan telah digunakan
sebagai komponen bahan pengikat dalam pembuatan pembentukan suntikan logam.
Nisbah percampuran yang berbeza antara RWL dan polimer polypropylene (PP)
dihasilkan dan nisbah percampuran bahan pengikat yang berbeza ini dicampurkan
bersama serbuk logam keluli tahan karat 316L. Kebolehan bahan ini sebagai
komponen bahan pengikat dalam menghasilkan bahan suapan serbuk logam 316L di
tunjukkan dari segi percampuran sekata, sifat reologi, pembentukan suntikan, proses
pembuangan bahan pengikat dan pensinteran. Masa adunan 90 minit menjadi pilihan
berdasarkan campuran yang sekata antara bahan pengikat. Nisbah 50/50 berat bahan
pengikat antara polimer dan minyak buangan dari restoran dipilih berdasarkan analisa
yang dilakukan walaupun semua nisbah yang terdiri dari 60/40, 40/60 dan 30/70
didapati boleh digunakan sebagai nisbah bahan pengikat. Dalam mencari parameter
acuan suntikan yang optimum bagi isipadu dan kekuatan komponen yang dihasilkan,
kaedah rekabentuk eksperimen Taguhi digunakan dan mendapati bahawa faktor suhu
suntikan, suhu acuan dan tekanan memainkan peranan utama bagi penghasilan
komponen suntikan yang mempunyai ketumpatan dan kekuatan yang baik.
Pengekstrakkan bahan buangan lemak dan minyak dari komponen menggunakan
pelarut hexane didapati lebih berkesan dari bahan pelarut heptane dengan suhu 60ºC
dengan nisbah berat pelarut dan komponen sebanyak 7:1 adalah lebih baik berdasarkan
faktor singkatan masa. Pembuangan bahan pengikat polimer menggunakan kaedah
haba dalam udara terbuka dengan suhu 400ºC dengan kadar 30ºC/min peningkatan
suhu adalah lebih baik tanpa sebarang kecacatan pada komponen berlaku. Proses
pensinteran terhadap bahan yang telah melalui proses pembuangan polimer
menghasilkan pembentukan komponen yang baik dari segi sifat mekanikal dan
mikrostruktur bahan 316L keluli tahan karat.
vii
CONTENTS
DECLARATION OF THESIS STATUS
EXAMINERS’ DECLARATION
TITLE i
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
CONTENTS vii
LISTS OF TABLES xiii
LISTS OF FIGURES xvi
LISTS OF SYMBOLS AND ABBREVIATIONS xxv
LISTS OF APPENDICES xxviii
CHAPTER ONE INTRODUCTION
1.1 Problems Statement 4
1.2 Objectives 5
1.3 Scopes 6
1.4 Research Methodology 7
CHAPTER TWO LITERATURE REVIEW
2.1 Powder Injection Moulding 9
2.2 Metal Injection Moulding 9
2.3 Binder 11
2.3.1 Backbone binder 12
2.3.1.1 Ethylene Vinyl Acetate (EVA) 13
viii
2.3.1.2 Polyethylene (PE) 14
2.3.1.3 Polymethyl Methacrylate (PMMA) 14
2.3.1.4 Polypropylene (PP) 15
2.3.2 Secondary binder 16
2.3.2.1 Polyethylene Glycol (PEG) 16
2.3.2.2 Paraffin wax (PW) 17
2.3.2.3 Carnauba wax 18
2.3.2.4 Palm kernel and stearin 19
2.3.3 Surfactants 20
2.4 Restaurant waste lipids as binder
(RWL)
21
2.5 Stainless steel 316L powder feedstock 24
2.5.1 Critical Powder Volume
Concentration (CPVC) of SS316L
powder
28
2.6 Feedstock formulation 31
2.6.1 Different binder components 32
2.6.2 Different weight or volume fraction of
binder component
33
2.7 Mixing 34
2.7.1 Mixing rotational speed and time 35
2.7.2 Mixing temperature 37
2.8 Rheology 38
2.8.1 Flow behaviour index, n 41
2.8.2 Activation energy analysis, 𝐸𝑎 44
2.8.3 Mouldability index, 𝛼𝑆𝑇𝑉 46
2.9 Injection moulding 47
2.9.1 Factorial design (DOE) 49
2.9.2 Taguchi design (DOE) 50
2.10 Debinding 51
2.10.1 Single step thermal debinding process 52
2.10.2 Two step debinding via wicking and
thermal debinding process 53
ix
2.10.3 Two step debinding via solvent and
thermal debinding process
53
2.10.4 Thermal debinding after solvent or
wicking peocess
57
2.11 Sintering 61
2.11.1 Sintering atmosphere 62
2.11.2 Heating rate 64
2.11.3 Sintering temperature 64
2.11.4 Cooling rate 65
CHAPTER THREE METHODOLOGY
. 3.1 Introduction 67
3.2 Stainless steel powder used for
feedstock
67
3.3 Binder components of feedstock 70
3.3.1 Polypropylene (PP) and Restaurant
Waste Lipids (RWL)
70
3.4 Mixing 73
3.5 Rheology experimental method 76
3.6 Optimising green density and strength
of the injection moulding processes
78
3.7 Solvent debinding process 82
3.8 Thermal debinding process 84
3.9 Sintering 87
CHAPTER FOUR RESULTS AND DISCUSSIONS: MIXING
AND RHEOLOGICAL
CHARACTERISTIC
4.1 Introduction 93
4.2 Characteristic of SS316L powder and
binder components
93
4.2.1 Characteristic of SS316L powder 93
4.2.2 Characteristic of binder components 94
x
4.3 Mixing homogeneity 95
4.3.1 Homogeneity mixing time 97
4.3.2 Characteristic of mixing binder
components
101
4.4 Effect of binder formulation on
rheological behaviour and
characterization of feedstock
106
4.4.1 Effects of temperature on viscosity
with different binder formulation 110
4.4.2 Effect of binder formulation on
activation energy, viscosity, flow
behaviour index of feedstock 113
4.5 Optimising powder loading 117
4.5.1 Effect of powder loading to
temperature variation with viscosity 121
4.5.2 Effect of powder loading on viscosity,
activation energy, mouldability index
and flow behaviour index of feedstock 125
CHAPTER FIVE OPTIMISING INJECTION MOULDING
FOR DENSITY/STRENGTH OF GREEN
PART
5.1 Introduction 129
5.2 Preliminary study of optimum density
of injected parts (green part) for
feedstock formulation of F1 with ISO
178 flexural bar shape 132
5.3 Optimising the green density of
injection moulded tensile bar shape of
F2 binder formulation 140
xi
5.4 Optimising the F2 binder formulation
for density and strength using L18
Taguchi method 147
5.5 Experimental Layout for Strength
Measurement 152
CHAPTER SIX RESULT AND DISCUSSION:
DEBINDING AND SINTERING
VARIABLES OF INJECTION
MOULDED 316L WITH RWL AS
BINDER
6.1 Introduction 156
6.2 Solvent Debinding 157
6.2.1 Effects of Solvents Temperature on
Weight Loss Percentage of Green
Compacts for F2 Feedstock During
Solvent Debinding 157
6.2.2 Effects of Solvents Temperature on
Diffusion Coefficient of Green
Compacts for F2 Feedstock 160
6.2.3 Effect of Solvent to Feed Ratio on
Solvent Debinding Time 164
6.2.4 Scanning Electron Microscopy
(SEM) and Energy Dispersive X-ray
Spectroscopy (EDS) on F2 Green
Compact Formulation
166
6.3 Thermal Debinding 169
6.3.1 Effect of Temperature in Degradation
of PP During Thermal Debinding 169
6.3.2 Effect of Heating/Cooling Rate on
Weight Loss During Thermal
Debinding 184
6.4 Sintering 185
xii
6.4.1 Surface Appearance Between Green,
After solvent, Brown and Sintered
Part 185
6.4.2 Linear Shrinkage and Density of
Sintered Part 186
6.4.3 Surface Morphology and Mechanical
Properties of Sintered Part 189
CHAPTER SEVEN CONCLUSION
Conclusion 194
REFERENCES 196
APPENDIX 219
xiii
LIST OF TABLES
Table 2 - 1 Fatty acid composition (%) of NIE, EIE and CIE 50:50
PO:PKO blend fractions
19
Table 2 - 2 Reported fatty acids present in grease trap 22
Table 2 - 3 % mass fatty acids profiles of cooking fats and oils 23
Table 2 - 4 Fatty acid and FFA profile of FOG samples and neat palm
oil
23
Table 2 - 5 Fatty acids composition of some vegetable oils and animal
fats
24
Table 2 - 6 Various debinding technique for binder 61
Table 3 - 1 Chemical composition of water atomised SS316L (source
of Epson Atmix Corp)
68
Table 3 - 2 Characteristic of water atomised SS316L 68
Table 3 - 3 Binder Formulation between PP and RWL with 60%
powder loading SS316L
74
Table 3 - 4 Table of selected Injection parameter 80
Table 3 - 5 Injection Moulding Factors and its Levels using Taguchi
L18
81
Table 3 - 6 Injection Moulding Factors and its Levels using Taguchi
L27
82
Table 3 - 7 Temperature of solvent (Hexane and Heptane) used with
time and temperature
84
Table 3 - 8 Experimental heating, cooling rate and temperature setup 86
Table 5 - 1 Injection parameters for optimised 130
Table 5 - 2 Binder components ratio and powder loading 131
xiv
Table 5 - 3 Level of Injection parameters for optimisation 133
Table 5 - 4 Experimental layout of the L16 and density measurement
of the part
134
Table 5 - 5 Analysis of Mean and Signal to Noise Ratio of each factor 134
Table 5 - 6 Response table of variability analysis of S/N ratio 135
Table 5 - 7 Response Table for variability analysis of Mean 137
Table 5 - 8 Confirmation optimised injected part 138
Table 5 – 9 Injection Moulding Factors and its Levels 141
Table 5 - 10 Experimental layout of the L27 and density measurement
of the part
142
Table 5 - 11 Analysis of Mean and Signal to Noise Ratio of each factor 142
Table 5 - 12 Response Table for variability analysis of S/N ratio 143
Table 5 - 13 Response Table for variability analysis of Mean 144
Table 5 - 14 Confirmation optimised injected part 146
Table 5 - 15 Injection Moulding Factors and its Levels 148
Table 5 - 16 Experimental layout of the L18 and density measurement
of the part
148
Table 5 - 17 Analysis of Mean and Signal to Noise Ratio of each factor 149
Table 5 - 18 Average S/N ratio table 149
Table 5 - 19 Average Mean table 150
Table 5 - 20 Confirmation optimised density of green part 152
Table 5 - 21 Experimental layout of the L18 and strength measurement
of the part
152
Table 5 - 22 Analysis of Mean and Signal to Noise Ratio of each factor 153
Table 5 - 23 Average S/N ratio table 153
Table 5 - 24 Average Mean ratio table 154
Table 5 - 25 Confirmation optimised strength of green part 155
xv
Table 6 - 1 Carbon and Oxygen contents before and after solvent
debinding process as compare to SS316L powder
167
Table 6 - 2 Weight loss/gain after thermal debound with different
temperature
170
Table 6 - 3 Chemical composition of water atomised SS316L powder
(Epson Atmix Corp.)
172
Table 6 - 4 Shrinkage percentage after sintering process 187
xvi
LIST OF FIGURES
Figure 1 -1 Examples of MIM process sequence 4
Figure 2 - 1 Production of metal powder by gas atomisation, centrifugal
and water atomisation
10
Figure 2 - 2 Examples of polymers used in different binder
formulations
12
Figure 2 - 3 Mean concentrations of fatty acids in the FOG deposits 22
Figure 2 - 4 Powder particle shape of SS316L (a) water atomised (b)
gas atomised
25
Figure 2 - 5 Critical powder loading by means of density measurement 26
Figure 2 - 6 Example of relative viscosity versus volume fraction at
different shear rates
27
Figure 2 - 7 Mixing torque of finding critical solid loading metal
powder
27
Figure 2 - 8 Example of powder particles shape 29
Figure 2 - 9 Brabender Plasti-Corder two screw mixer in open position 37
Figure 2 - 10 Typical (a) pseudoplastic, (b) Newtonian, (c) dilatant flow
behaviour of fluid subtances
39
Figure 2 - 11 Schematic diagram of capillary rheometer components 39
Figure 2 - 12 Examples of pseudoplastic (shear thinning), Newtonian
and dilatant (shear thickening) flow behaviour on viscosity
versus shear rate (force) profile
40
Figure 2 - 13 Examples of poor and well mixed of metal or ceramic
powder and binder on capillary rheometer pressure profile
40
xvii
Figure 2 - 14 Example of pseudoplastic behaviour of feedstock
relationship between viscosity and shear rate
41
Figure 2 - 15 Relationship of flow behavior index (n) or power law
exponent to temperature
42
Figure 2 - 16 Example of flow behavior with different particle size 43
Figure 2 - 17 Arrhenius-type plot for the OA, SA, and HSA suspensions;
different slopes indicate the suspension viscosity exhibiting
a different but specific temperature dependency
46
Figure 2 - 18 General moldability index vs. solid loading % 47
Figure 2 - 19 Moulding variables using factorial design 50
Figure 2 - 20 Effects of different heating rate on degradation temperature
of binder components
58
Figure 3 - 1 Particles analyser machine (Fritsch analysette 22 compact) 68
Figure 3 – 2 JEOL JSM-6380LA Scanning Electron Microscopy 69
Figure 3 - 3 Critical powder volume concentration (CPVC) of SS316L
powder
70
Figure 3 - 4 (a) Polypropylene (PP) and (b) RWL used in the
investigation
71
Figure 3 - 5 Auto Q20 differential scanning calorimeter (DSC) 71
Figure 3 - 6 Linseis Thermal gravimetric Analysis Equipment 72
Figure 3 - 7 Perkin Elmer FTIR equipment 73
Figure 3 - 8 Mattler Toledo density apparatus measurement 73
Figure 3 - 9 Brabender Plastograph EC mixer is used for compounding
SS316L powder, PP and RWL (b) RWL being heated using
hot plate heater
75
Figure 3 - 10 Mixing sequence of feedstock compound using mixer a) PP
into the mixing chamber, b) PP left for melting, c) SS316L
powder left for homogeneously mix with PP, d) RWL
going into chamber, e) feedstock being taken out, f)
feedstock being cooled at room temperature
75
Figure 3 - 11 (a) Crusher machine used in transforming the bulky
feedstock into (b) small pallet feedstock
76
xviii
Figure 3 - 12 Capillary rheometer used in determining the rheological
behaviour and characterization
77
Figure 3 - 13 Schematic diagram of capillary rheometer 77
Figure 3 - 14 Injection moulding machine unit used for green specimens 78
Figure 3 - 15 Mould of specimen ISO 178 flexural bar shape 79
Figure 3 - 16 Mould of specimen MPIF Standard 41 bar shape 80
Figure 3 - 17 Universal flexural/tensile machine 81
Figure 3 - 18 Mould of specimen ISO 527-2 tensile bar shape 82
Figure 3 - 19 Water bath used for solvent debinding process 83
Figure 3 - 20 Colourless heptane change to yellow/brown colour during
solvent debinding process of green compact
84
Figure 3 - 21 High temperature furnace and temperature profile of
thermal debinding process
85
Figure 3 - 22 Alumina crucible 85
Figure 3 - 23 X-ray diffraction Bruker D8 Advance machine 87
Figure 3 - 24 Vacuum Furnace at AMREC Kulim, Kedah 87
Figure 3 - 25 Mould sample holder 88
Figure 3 - 26 Grit size sequence of polishing sintered SS316L part 89
Figure 3 - 27 Grinding and polishing machine 89
Figure 3 - 28 Silicon carbide grinding paper 89
Figure 3 - 29 Polishing process 90
Figure 3 - 30 Samples test after being grinded and polished 90
Figure 3 - 31 Electro etching equipment setup for SS316L sintered part 91
Figure 3 - 32 Microhardness test equipment 91
Figure 3 - 33 Digital microscope used for detrmining the grain size 92
Figure 3 - 34 Tensile machine test of the sintered part 92
xix
Figure 4 - 1 (a) Powder size distribution of SS316L, (b) SS316L
powder morphology
94
Figure 4 - 2 Differential scanning calorimetry curve of RWL 95
Figure 4 - 3 Differential scanning calorimetry curve of PP 95
Figure 4 - 4 Thermalgravimetric analysis of the RWL 96
Figure 4 - 5 Thermalgravimetric analysis of the PP 96
Figure 4 - 6 Fourier Transform Infrared Spectrometry (FTIR) spectrum
of RWL
97
Figure 4 - 7 Surface morphology of the feedstock with binder
formulation (a) F1 (b) F2 (c) F3
98
Figure 4 - 8 TGA comparison of mixing time of Stainless steel powder
316L, RWL and PP for (a) 45 minutes (b) 90 minutes for
F2 binder formulation
99
Figure 4 - 9 TGA profiles of different binder formulation 101
Figure 4 - 10 DSC of F1 relatives to PP and RWL derivatives 103
Figure 4 - 11 DSC of F2 relatives to PP and RWL derivatives 103
Figure 4 - 12 DSC of F3 relatives to PP and RWL derivatives 104
Figure 4 - 13 DSC of F4 relatives to PP and RWL derivatives 104
Figure 4 - 14 DSC scans of the PP, RWL and feedstock formulation 105
Figure 4 - 15 Viscosity versus shear rate graph of binder F1 with 60%
powder loading
107
Figure 4 - 16 Viscosity versus shear rate graph of binder F2 with 60%
powder loading
108
Figure 4 - 17 Viscosity versus shear rate graph of binder F3 with 60%
powder loading
108
Figure 4 - 18 Viscosity versus shear rate graph of binder F4 with 60%
powder loading
109
Figure 4 - 19 Viscosities shear rate of all binder formulations at
temperature 190°C
110
Figure 4 - 20 Logarithmic viscosity against reciprocal temperature of F1
binder formulation at different shear rate
111
xx
Figure 4 - 21 Logarithmic viscosity against reciprocal temperature of F2
binder formulation at different shear rate
111
Figure 4 - 22 Logarithmic viscosity against reciprocal temperature of F3
binder formulation at different shear rate
112
Figure 4 - 23 Logarithmic viscosity against reciprocal temperature of F4
binder formulation at different shear rate
112
Figure 4 - 24 Comparison of logarithmic viscosity against reciprocal
temperature of all binder formulation at different shear rate
113
Figure 4 - 25 Activation Energy and flow behaviour index against binder
formulation profile at shear rate of 1000s-1
114
Figure 4 - 26 Viscosity and flow behaviour index against binder
formulation profile
115
Figure 4 - 27 Activation energy and mouldability index against binder
formulation profile
116
Figure 4 - 28 General moldability index vs. feedstock formulation 117
Figure 4 - 29 Viscosity versus shear rate graph of binder F2 with 60%
powder loading
118
Figure 4 - 30 Viscosity versus shear rate graph of binder F2 with 61%
powder loading
119
Figure 4 - 31 Viscosity versus shear rate graph of binder F2 with 62%
powder loading
119
Figure 4 - 32 Viscosity versus shear rate graph at 190°C for all Powder
loading
120
Figure 4 - 33 Viscosity and flow behaviour index against Volumetric
Powder Loading profile at 1000s-1 shear rate
121
Figure 4 - 34 Logarithmic viscosity against reciprocal temperature of
60% powder volume loading at different shear rate
122
Figure 4 - 35 Logarithmic viscosity against reciprocal temperature of
61% powder volume loading at different shear rate
123
Figure 4 - 36 Logarithmic viscosity against reciprocal temperature of
62% powder volume loading at different shear rate
123
xxi
Figure 4 - 37 Comparison of logarithmic viscosity against reciprocal
temperature of all powder volume loading at 1000 s-1 shear
rate
124
Figure 4 - 38 Viscosity and activation energy against Volumetric Powder
Loading profile at 190°C
125
Figure 4 - 39 Activation energy and flow behaviour index against
Volumetric Powder Loading profile
126
Figure 4 - 40 Activation energy and mouldability index against
Volumetric Powder Loading profile
127
Figure 4 - 41 Mouldability index and flow behaviour index against
Volumetric Powder Loading profile
127
Figure 4 - 42 Viscosity and mouldability index against Volumetric
Powder Loading profile
128
Figure 5 - 1 ISO 178 flexural bar shape 133
Figure 5 - 2 Schematic diagram dimension of ISO 178 flexural bar
shape
133
Figure 5 - 3 S/N ratios variations of green part density at various levels
of injection parameters
137
Figure 5 - 4 Mean variations of green part density at various levels of
injection parameters
137
Figure 5 - 5 Variations of density during the L16 Taguchi DOE
experiments
139
Figure 5 - 6 Injected part shape for solvent debinding (F2 feedstock) 140
Figure 5 - 7 S/N ratio of green part density at various levels of injection
parameters
144
Figure 5 - 8 Mean of green part density at various levels of injection
parameters
145
Figure 5 - 9 Tabulated density of green part density at various levels of
injection parameters
146
Figure 5 - 10 Bar shape injected moulded part 147
Figure 5 - 11 S/N Ratio main effect plot of the control factors 150
Figure 5 - 12 Mean main effect plot of the control factors 151
xxii
Figure 5 - 13 S/N Ratio main effect plot of the control factors 154
Figure 5 - 14 Mean main effect plot of the control factors 154
Figure 6 - 1 Schematic diagram of solvent debinding process inside the
green compact
156
Figure 6 - 2 Solubility of the RWL in (a) Hexane solution after 4 hrs (b)
Heptane solution after 2 hrs with solvent temperature of
50°C respectively
157
Figure 6 - 3 Weight loss percentage of RWL removed for F2 feedstock
during solvent debinding at different temperature using
hexane
158
Figure 6 - 4 Weight loss percentage of RWL removed for F2 feedstock
during solvent debinding at different temperature using
heptane
159
Figure 6 - 5 Injected test specimen of the F2 feedstock (a) green
compact (b) after extraction process
159
Figure 6 - 6 Effect of temperature on weight loss of the green compact
during the first hour for F2 feedstock with different organic
solvent
160
Figure 6 - 7 Diffusion coefficient of RWL for F2 feedstock during
solvent debinding at different temperature using hexane
161
Figure 6 - 8 Diffusion coefficient of RWL for F2 feedstock during
solvent debinding at different temperature using heptane
162
Figure 6 - 9 Effect of temperature on solvent debinding diffusion
coefficient during the first hour for F2 green compact with
different organic solvent
163
Figure 6 - 10 DSC profile of F2 green compact before and after first hour
solvent debinding process using hexane at 60°C taken from
the centre of the compact
163
Figure 6 - 11 Bar shape used for solvent debound process with different
solvent to feed ratio at 60°C
164
Figure 6 - 12 Weight loss percentage profile of different solvent to feed
ratio using hexane solution
165
Figure 6 - 13 Diffusion coefficient profile of different solvent to feed
ratio using hexane solution
165
xxiii
Figure 6 - 14 Evolution of pores from (a) green compact (b) solvent
debinding after 3 hrs (c) solvent debinding after 6 hrs
166
Figure 6 - 15 EDS analysis on solvent debound sample (a) area taken for
carbon analysis, (b) EDS element analysis of green
samples, (c) after solvent samples, (d) after thermal
samples
168
Figure 6 - 16 Comparison in dimension between brown part under
different temperature
170
Figure 6 - 17 TGA profiles of brown compact after solvent debound
process
171
Figure 6 - 18 XRD pattern of SS316L water atomised powder 171
Figure 6 - 19 Schaeffler diagram for determining phases formed upon
solidification, based on chemistry
172
Figure 6 - 20 XRD pattern for (a) part with 500°C (b) part with 600°C
thermal debound
173
Figure 6 - 21 XRD pattern of thermal debound part at 600°C indicates of
oxidation of SS316L brown compact
174
Figure 6 - 22 Example of XRD profile oxidation occurs on SS316L
powder during sintering under different atmosphere
174
Figure 6 - 23 Part sample that undergo temperature of (a) 500°C (c)
450°C (d) 400°C with heating rate of 10°C/min and (d)
swelling and crack of parts surface under 40°C/min at the
temperature of 400°C
175
Figure 6 - 24 Weight loss of thermal debound part with temperatures of
10 replications each
176
Figure 6 - 25 Effect of temperature in weight loss of part after thermal
debinding process
177
Figure 6 - 26 XRD pattern of part under 400°C thermal debound 178
Figure 6 - 27 Peaks of highlighted area from Figure 6-26 shows
increment of α- martensitic peak and decrease in γ-
austenite besides peak shifted
178
Figure 6 - 28 XRD pattern of part under 450°C thermal debound 179
xxiv
Figure 6 - 29 Peaks of highlighted area from Figure 6-28 shows
increment of α- martensitic peak and decrease in γ-
austenite besides peak shifted
180
Figure 6 - 30 XRD pattern of part under 500°C thermal debound 180
Figure 6 - 31 Peaks of highlighted area from Figure 8-18 shows
increment of α- martensitic peak and decrease in γ-
austenite besides peak shifted
181
Figure 6 - 32 SEM/EDS of water atomised SS316L 181
Figure 6 - 33 SEM of 400°C Thermal debound part morphology and
EDS analysis
182
Figure 6 - 34 SEM of 450°C Thermal debound part morphology and
EDS analysis
182
Figure 6 - 35 SEM of 500°C Thermal debound part morphology and
EDS analysis
182
Figure 6 - 36 Shrinkage value relatives to temperature of debinding
process
183
Figure 6 - 37 Effect of heating rate with 400°C temperature on
percentage of weight loss
184
Figure 6 - 38 Surface morphology of cross sectional (a) green part (b)
after solvent part (c) brown part (d) after sinter part
185
Figure 6 - 39 (a) comparison of part after each process (b) shrinkage
value after each MIM process
186
Figure 6 - 40 Density of part after each process 188
Figure 6 - 41 Density of part after each process in MIM relative to
theoretical density
189
Figure 6 - 42 Surface morphology of the sintered part (a) after polishing
and (b) after etching
189
Figure 6 - 43 Surface morphology of sintered part after etching 190
Figure 6 - 44 SEM and EDS analysis on the etched sintered sample 191
Figure 6 - 45 Section sketch of microhardness test on the sintered part 191
Figure 6 - 46 Hardness test for grip’s cross sectional area (A-A’) 192
Figure 6 - 47 Hardness test value on the surface of Grip area ‘B’ 192
xxv
Figure 6 - 48 Hardness test value on the surface of neck area ‘C’ 193
xxvi
LIST OF SYMBOLS AND ABBREVIATIONS
FOG - Fats, Oils and Grease
RWL - Restaurants Waste Lipids
PMMA - Poly(methyl methacrylate)
PP - Polypropylene
PE - Polyethylene
LDPE - Low Density Polyethylene
HDPE - High Density Polyethylene
CPVC - Critical Powder Volume
Concentration
TGA - Thermal gravimetric Analysis
DSC - Differential Scanning Calorimeter
ASTM - American Society for Testing and
Materials
MPIF - Metal Powder Industries Federation
SEM - Scanning Electron Microscope
XRD - X-Ray Diffraction
μMIM - Micro Metal Injection Molding
PIM - Powder Injection Molding
FCC - Face Center Cubic
BCC - Body Center Cubic
xxvii
PM - Powder Metal
𝐷10 - Distribution of powder at 10%
𝐷50 - Distribution of powder at 50%
𝐷90 - Distribution of powder at 90%
CHMA - Cyclohexyl Methacrylate
DMPT - Dimethylpara Toluidine
EVA - Ethylene-vinyl acetate
PEG - Polyethylene Glycol
PW - Paraffin Wax
PK/PS - Palm Kernel/Stearin
MW - Microcrystal paraffin wax
SA - Stearic acid
OA - Oleic acid
HSA - 12-hydroxystearic acid
𝑉𝑝 - Volume powder
𝑉𝐿 - Volume liquid
𝜂 - Viscosity, Pa.s
�̇� - Shear rate, 𝑠−1
𝑛 - Flow behavior index
𝐸𝑎 - Activation energy
𝑅 - Gas constant
T - Temperature
B - Reference viscosity
𝛼𝑆𝑇𝑉 - Mouldability index
DOE - Design of Exsperiment
xxviii
𝐷𝑒 - Interdiffusion coefficient
∅ - Removed fraction of soluble binder
A - Area
t - time
𝑁𝐴 - Avogadro constant
𝑁2 - Nitrogen gas
𝐻2 - Hidrogen gas
CIM - Ceramic Injection Moulding
DA - Dissociate Ammonia
Fe - Ferum
Cr - Chromium
Ni - Nickel
𝑆𝑊 - Distribution slope parameter
FTIR - Fourier transform infrared
spectroscopy
𝑊𝐵 - Weight of binder
𝑊𝑃 - Weight of powder
𝜌𝐵 - Density of binder
𝜌𝑃 - Pycnometry Density of powder
�̅� - Average S/N ratio
S/N - Signal to Noise
�̅� - Mean
𝛿𝑁−1 - Standard deviation
xxix
LIST OF APPENDICES
APPENDIX TITLE
PAGE
A Data of binder formulation calculation and rheology 219
B Data of stainless steel (SS316L) powder particle size,
Critical Powder Volume Concentration (CPVC) and
SEM/EDS analysis
230
C List of Publications
236
D Specification of stainless steel powder (SS316L),
Polypropylene, Restaurant waste lipids supplier 238
CHAPTER ONE
INTRODUCTION
Towards implementing the green technology, four pillars are being listed for
improvement, which are energy, which is seeking to attain energy independence and
promote efficient utilizations. Seconds is to enhance national economic development
through the usage of green technology while the third one is more concern on society
where to improve the quality of life for all generations. Finally, it is to conserve and
minimize the impact of development on environment. A sector, which is promising in
the usage of green technology, is identified to be in energy sectors, building, transports
and water waste management sectors. Sustainable Development will require major
changes with respect to production and consumption patterns in our societies,
including materials, energy sources and production processes used in industry, the
products and services offered, as well as the organisation and management of supply
chains and the governance of firms. Industry, and the manufacturing sector in
particular, is therefore one of the key addressees of the Sustainable Development
strategy since a more sustainable manufacturing sector can make significant
contributions to attain the objectives. This is stated in the Brundtland Report [1] about
the key concepts towards Sustainable Development " the idea of limitations imposed
by the state of technology and social organization on the environment's ability to meet
present and future needs" where here the technology is more towards the
manufacturing sectors to implementing the sustainable manufacturing with consuming
less materials resources and energy.
With rapid growth of human population, index of pollution results from RWL
also will increase. It is found that, the change of habits will also increase the solid
waste produce by the human [2]. Urbanisation also lead to change in diets where more
2
food with higher in fat, animal products, sugar and processed food become the priority
[3]. Due to these rapid changes of dietary more pollution is created results from fat, oil
and grease (FOG) to the water stream in sewage. This will results in high toxicity of
the wastewater [4] due to increasing use of oil and grease in high-demanded oil-
processed foods, establishment and expansion of oil mills and refineries worldwide,
as well as indiscriminate discharge of oil and grease into the water drains, domestically
and industrially. It will also increase the government expenditure due to pipe
blockages, pipe break excessive inflows and power failure. Clean up cost could rise
thousands of dollars to the municipalities as claimed by Hong Kong Drainage Service
Department [5]. The increasing of this source of food tend to increase the production
of cooking oil in factory and this is true through its export data of crude palm oil from
Malaysia palm Oil Council [6]. Besides the increasing of cooking oils demand, the
consumption of animal meat also increase which also contribute to the waste water
pollution. Reuse of such wastes as a sustainable construction material appears to be
viable solution not only to pollution problem but also to the problem of the land-filling
and high cost of building materials [7].
Powder injection moulding (PIM) which consists of metal injection moulding
(MIM) and ceramics injection moulding (CIM) is one of the major manufacturing
processes used to generate small parts with intricate geometries, thin walls and in large
production batches [8], [9]. It combines the flexibility and high productivity of the
plastics injection moulding with the powder metallurgy method of sintering.
Therefore, it has the capability to manufacture a wide range of components having
multifaceted shape, high performance, application areas are various ranging from
automotive (locking mechanisms, transmissions synchronisers, and airbag sensors),
electronics (computer hard disk drive magnet), defences and aerospace (rocket nozzle
guidance system, aircraft engine screw seal), to medical industry (orthodontic
brackets, medical forceps) and jewellery (wristwatches). A propose materials,
common metals, alloys, ceramics and carbides are frequently encountered [10].
Then, since the sintering of a compacted powder is similar for a part obtained
by injection or press moulding, the recipe points in MIM turned out to be how to make
the metal flow into the mould and how to retain the shape of the moulded part until it
begins the sintering. Dispersing the powdered metal into a binder to form a gloop that
flows at high temperature and becomes solid at room temperature commonly solves
3
this difficulty. As a result, the moulded part retains its shape after injection moulding
and may be handled and processed safely.
The research of binder is the heart of this technique in particular, the
binders in the feedstock strongly determine MIM quality [11]. The recipe points in
MIM binder turned out to be how to make the metal flow into the mould and how to
retain the shape of the moulded part until it begins the sintering. Dispersing the
powdered metal into a binder to form a gloop that flows at high temperature and
becomes solid at room temperature commonly solves this difficulty. They provide
adhesion among powdered particles and improve the mechanical properties of
feedstock and prevent separation phenomena among binders and powders. As a result,
the moulded part retains its shape after injection moulding and may be handled and
processed safely. cost reduction and less environmental issues of binder also plays
significant role in proper selection of binder besides to achieve low viscosity of the
feedstock [11], [12]. Usually binders are mixture of several organic compounds where
the main ingredients are waxes and synthetic polymers. The purpose of the polymer is
to convey rigidity to the part when cold, while the wax reduces the viscosity and flow
ability of the binder and the additives reduce particle severance and segregation [13].
It is usual to convert the powder-binder mix, the so-called feedstock, into solid pellets
by a granulation process. These feedstock pellets can be stored and fed into the
moulding machine as required.
Parts that are produce from the injection moulding machine are called
green parts where this parts contains of metal powder, polymer, wax and additives.
This is not a finalised part since it will go another process to get the finalized parts.
The green parts will then undergoes another process called debinding process where
the primer and secondary binder will be flowed out of the parts through solvent,
catalyst wicking or thermal debinding. Sometimes this thermal process will
simultaneously prepared with the sintering process since the sintering also required
certain temperature in bonding the metal powder in order to get the desired density,
strength and shape of final products. The full view of the process is shown in Figure
1-1;
4
Figure 1 - 1: Examples of MIM process sequence [14]
Due in promoting the sustainability development in this manufacturing area,
waste materials from the restaurants waste lipids (RWL) or fats, oils and grease (FOG)
derivatives from restaurants will be used here since it is believed that it can contribute
in some area of metal injection moulding process especially in preparing the binder
systems for powder metals feedstock. This abundant resource is increasing with the
increasing human population, which make it possible solution in reducing and
recycling waste as alternative for current binder in the markets for MIM.
1.1 Problems Statement
The use of RWL in MIM process is a new idea besides it’s used in the biodiesel sector.
It is the challenge how this waste can be used in the manufacturing area since it has
composition of different organic materials. It is found that this RWL contains high
energy and oil recovery which can be obtained from this abundant source of energy
[15]. In terms of MIM, process the RWL seems could be used in the production of
MIM feedstock since it has the mixture of animal fats, vegetable oils which compose
of several organic acids [16].
In MIM, the miscible issues of RWL and polymer will be analysed since the
mixing ability of the binder components is very important in providing good
5
interaction of metal powder and binder for flowability of the feedstock. Results of this
analysis could leads to better rheological characteristic of the feedstock.
Since RWL contains high fats and oils recovery which act as a lubricant in
feedstock during injection moulding process [17], other issues such as crack,
distortion, shot short, density and strength of the injected moulded parts or green parts
will be analysed [18]. It is expected that the binder components in MIM should not
retain in green parts and being removed before sintering processes. Therefore finding
the suitable extraction process of the binder need to be considered since improper
removal could results in several defect on the green parts which affect the sintering
process and the materials characteristic of the sintered parts [19].
1.2 Objectives
The main objective of the research is to evaluate the application of RWL in metal
injection moulding. In order to achieve the objective, several sub-objectives need to
be implemented, which are:
a) To investigate the mixing and rheological characterization of different
binder formulation between PP and RWL and optimum powder loading
for metal injection moulding feedstock.
b) Optimising the injection moulding parameters of metal injection
moulding process for highest green density and strength by means of
Taguchi method for RWL as binder component.
c) Determine the optimum effect of debinding conditions in removing
RWL binder component from the green compact.
d) Determine the mechanical and microstructure analysis of the sintered
part under graphite vacuum furnace.
6
1.3 Scopes
Scopes of this research focused on process ability of using novel binder system in order
to produce micro metal parts. In order to obtain this, this research will cover the
following scopes:
a) Feedstocks of the µMIM were prepared base on water atomised
Stainless Steel powder SS316L with mean size of 6µm, Polypropylene
and RWL as a backbone binder and lubrication/surfactant respectively.
b) Mixing homogeneity characteristic was based on mixing time between
45 minutes and 90 minutes. Homogeneity of the feedstock will be
monitored base on density and TGA and DSC analysis of the feedstock.
c) Characteristic of feedstock produced from the mixing were analysed on
rheological properties base on shear rate, shear stress, viscosity,
activation energy, flow index, mouldability index and temperature.
d) Optimization of the metal injection process were done base on Taguchi
Method where the parameter will be analysed are injection pressure,
injection temperature, mould temperature, injection time and holding
time.
e) Optimum solvent debinding was based on type of solvent (hexane and
heptane), solvent temperature, and time and diffusion rate. Optimum
thermal debinding was optimised base on the effect of heating rate and
temperature on oxidation of powder and other defects such as warping,
swelling and crack.
f) Mechanical properties and characteristic of the sintered parts under
heating rate of 5ºC/min, sintering temperature of 1360ºC, sintering
atmosphere under high vacuum furnace and dwell time of 100 minute
were investigated besides the carbon contents by means of SEM/EDS
and XRD.
7
1.4 Research methodology
In order to achieve the objectives of this study, the following methodologies were used
as a guideline during the course of the study.
a) Determination of critical powder volume concentration (CPVC) of
SS316L powder by means of ASTM D-281-31.
b) Determination of degradation and melting temperature of the binder
components which are polypropylene (PP) and restaurant waste lipids
(RWL) for mixing purposes.
c) Determining the optimum binder formulation and powder loading base
on rheological behaviour and characteristic using capillary rheometer
Instron CEAST SmartRHEO 10 (ISO 11443, ASTM D3835 and DIN
54811)
d) Optimizing the injection parameters for density and strength of green
compact by means of MPIF standard 15 and density of specimens
standard ISO 527-2 tensile bar for sintering.
e) After optimising the injection parameter has been done, green parts
were allowed to experience the solvent debound or extraction process
where optimising in terms of temperature, solvent’s type and time of
extraction were done. Effect of weight loss and diffusion coefficient of
RWL with respect to temperature, solvent’s type and extraction time
were analysed.
f) After solvent process, removing the polymer or backbone binder from
the brown compact was done by thermal pyrolysis/debound as suitable
heating rate and temperature. Selection of degradation temperature for
polymer were based on TGA results and temperature, which produced
high weight loss of the brown compact, will be selected without any
defect on the brown compacts.
g) Sintering process will be done base on the previous researchers such as
heating rate, temperature and dwelling time. Mechanical and
microstructure properties of the sintered part was done base on MPIF
standard 10/ASTM E8 for tensile strength, MPIF standard 51 for
8
microhardness properties and ASTM 112-13 for grain size properties
of the sintered parts.
CHAPTER TWO
LITERATURE REVIEW
2.1 Powder Injection Moulding
Powder injection moulding (PIM) process is the adoption process of plastic
injection moulding process. The difference is that the polymer is filled with disperse
metal and ceramic powder and transported into the mould cavity to form the mould
cavity shape. It is a process of capable in producing small intricate complex part shapes
with combining multiple parts into single one and at medium to high quantity
production [10], [20]. It has the ability to handle very fine metals or ceramics powder
that can be sintered to high densities near to its bulk metals or ceramics. Acceptable
ductility and strength could be produced using this technique. Besides its attractive
process, wide range of ceramics and metals could be processed with this technique
ranging from low alloy steels, stainless steel, magnetic alloys, nickel alloys, tool steels
and titanium alloys which become limitation for die casting process. Fine details such
as blind holes, recesses, sharp edges and internal or external threads which becomes
limited process for investment casting becomes much easier using PIM [21]. PIM
could divided into three categories which are ceramics [22]–[28], metals [17], [29],
[30] and cermets [31]–[33].
2.2 Metal Injection Moulding (MIM)
Metal injection moulding is subdivision of powder injection moulding process. The
composites fabricated by MIM can be divided into refractory metal based metal matrix
composites (MMC), titanium based, intermetallic based and steel based. The MIM
direction has enabled the fabrication of MMCs containing ingredient materials that are
10
not compatible in molten state and difficult to fabricate by conventional routes [21],
[34].
MIM relies on shaping metal particles and subsequently sintering those
particles. Hence MIM products are competitive with most other metal component
fabrication routes, and especially are successful in delivering higher strength compared
with die casting, improved tolerances compared with investment or sand casting, and
more shape complexity compared with most other forming routes [35].
MIM production involves several processing steps which are mixing of
binder and powder to form feedstock, injection of green part, debinding and sintering
[36]. Every steps of processing plays significant roles in producing good parts with
acceptable mechanical and dimensional properties. Mistakes could not be repaired in
subsequent process.
Various metals powder have been used ranging from stainless steel, titanium,
high speed steel, Inconel and Nickel Titanium alloy to form a feedstock [33], [37]–
[43]. Various powder particle shapes have been used in MIM process ranging from
sphere, rounded and flaky shapes. This particle shapes were depend on the types of
processing used in producing the metals powder such as air atomising particles which
results in sphere shape particles as compared water atomised which results in rounded
or irregular shapes as shown in Figure 2-1 [44].
Figure 2 - 1: Production of metal powder by gas atomisation, centrifugal and water
atomisation [44]
11
2.3 Binder
Binder plays significant role in transporting the metal powder to the mould cavity
during injection process. It should not interact chemically with the metal powder
during the subsequent process which may alter the composition of the final sintered
products. Many types of polymers range from thermoplastic and thermosetting can be
used as a backbone binder in MIM which hold the part retention during solvent,
wicking or thermal debinding [45]–[48]. Backbone binder itself is unable to produce
good flow in injection moldings process, which results in higher viscosity and shear
rate appreciated in the range of below 1000 Pa.s for viscosity and 102 to 105 s-1 for
shear rate. Therefore waxes in terms of vegetable oils, camphor, naphthalene, dish
soap and fish oil are common for lubrication in MIM feedstock to improve the
flowability of the feedstock.
Waxes commonly has low melting temperature which is an advantages during
debinding process in creating pores for the ease of thermal degradation of backbones
binder. With the help of pores after removing these waxes, quickest time possible for
removing backbone could be done which also reduced the possible defects on the part
in terms of part distortion, swelling and cracks. Waxes also serve as a good wetting
agent due to short molecular chain lengths low viscosities and decompose at low
temperature with small volume change compares to other polymers.
Fraction between polymer and waxes is roughly equal in its proportions. With
the aid of current research, this proportions evolved with just minimum by volume or
weight ratio of polymer is enough in holding the powder particles in place. Nowadays,
proportions of 20 to 80% by volume between polymer and waxes are possible with
appreciation of surfactants such as stearic acids (SA) and oleic acids (OA) [49]–[53].
These surfactants will increase the wettability of the binder constituents on powder
particles surface which results in reducing the amount of polymer in MIM feedstock
that can contribute in minimizing carburization on the sintered part during sintering
which could contributed to carbide formations which results in much brittle part [54]–
[56]. It is clear that the binder is the key that provides the rheological properties and
determines whether the resulting feedstock can be injection moulded without
introducing defects[57].
12
2.3.1 Backbone binder
Since polymer is the preferable backbone binder in producing acceptable feedstock,
many types of polymer have been used. Polymer from thermoplastic gives an
advantage among others type of polymer since the ability of recyclable of the feedstock
as compare to thermosetting which degrade upon reheating. This is due to the
thermosets polymer has the formation of chemical crosslinks by covalent bonds which
upon complete polymerization become infusible solids that will not soften when
reheated. Thermoplastics comprise essentially linear or lightly branched polymer
molecules, while thermosets are substantially crosslinked materials, consisting of an
extensive three-dimensional network of covalent chemical bonding [58]. Relative to
thermoplastic materials, it can be reheated several time, which likely become
favourable in the MIM feedstock. Only several polymers from thermosetting materials
being encountered for MIM feedstock, which is done by Castro et al., [45] where they
used cyclohexyl methacrylate (CHMA), ethylenglycol dimetacrylate (DMEG) and
dimethylpara toluidine (DMPT) for making AISI 316L feedstock in analysis of
mechanical properties and pitting corrosion resistance being explored although much
has been listed by Randall and Bose [59].
Various thermoplastic polymer have been encountered to be backbone
polymer for MIM such as polyethylene (HDPE, LDPE, LLDPE, MDPE),
polypropylene (PP), polystyrene (PS), ethylene vinyl acetate (EVA), polyethylene
glycol (PEG) and polymethyl methacrylate (PMMA) as shown in Figure 2-2 [22], [49],
[60]–[63].
Figure 2 - 2: Examples of polymers used in different binder formulations [62].
13
The selection of polymer usually base on the type of application. Although
polymer as binder in MIM should not dictate the final composition of the molded
materials, selection of the types of polymer also plays critical role in producing good
mechanical properties of the sintered materials due to residue produced from it through
thermal debinding. In some extent polymer selection need to consider environmental
issues due to its degradation has potential effects on human health such as styrene
monomers used in acrylonitrile-butadiene- styrene (ABS), and styrene-acrylonitrile
resins. Styrene is classied by International Agency for the Research on Cancer (IARC)
as possibly carcinogenic to humans[64]. Vinyl Chloride is used essentially to produce
polyvinyl chloride (PVC) resins also has some hazards potential such as halogen
acids[65].
Degrading these polymer during thermal debinding process could introduce
residual carbon on the sintered parts. Therefore such analysis in carbon contents have
become the interesting topic to be discussed. Carbon content after thermal debinding
was much influenced the degradation behaviour of the polymer, interaction of polymer
with the powder particles, chemistry of powder surfaces, thermal debinding
atmosphere and oxidation temperature of the powder [31].
2.3.1.1 Ethylene Vinyl Acetate (EVA)
EVA has low melting temperature which is approximately 86ºC with degradation
temperature of 520ºC [63]. It has some of the properties of a low density polyethylene
but increased gloss (useful for film) and being used as components of binder in MIM
because of its properties of non-toxic materials. It has been used widely ranging from
titanium [33], [36], [66], [67], stainless steel [12], [68]–[70], W–Cu alloys [71],
Inconel 718 Alloy [72]. It was used by Demers et al., [63] in analysing the segregation
measurement of powder injection molding feedstock using thermogravimetric
analysis, pycnometer density and differential scanning calorimetry techniques. Low
pressure MIM is possible with EVA as backbone binder since it has low melting
temperature. Fan et al., [49] used EVA in determining the effect of surfactant addition
on rheological behaviours of ultrafine 98W-1Ni-1Fe suspension feedstock and results
in better rheological properties with additional of surfactant. Youhua et al., [72] used
14
EVA with other components of binder in preparing the Inconel718 Alloy feedstock to
be used for MIM process in investigating the effects of sintering processes, hot
isostatic pressing and heat-treatment on the density, microstructure and mechanical
properties of the alloy for finding a proper way to prepare a high performance nickel
based alloy through MIM-sintering-HIP-heat treatment technology. Highest sintered
relative density of 98% can be achieved with superior mechanical properties was
achieved. Li et al., [73] used EVA in preparing the 17-4PH stainless steel for feedstock
preparation where low pressure injection moulding process was possible with the used
of paraffin wax (PW) and stearic acids. The lowest flow exponent for 68% powder
loading indicates that there is a best powder binder ratio for MIM feedstock to get
quick powder repacking and binder molecule orientation during moulding.
2.3.1.2 Polyethylene (PE)
Polyethylene polymer in MIM can be devided into low density polyethylene (LDPE),
high density polyethylene (HDPE) and medium density polyethylene (MDPE). It is
most common plastic used for packaging, toys and bullet proof vest. It consists of
nonpolar, saturated, high molecular weight hydrocarbons. In MIM, PE has been used
for binder in producing feedstock such as titanium feedstock [74]–[77], stainless steel
[52], [78], [79], zirconia [26], [80], cemented tungsten carbide [81] and among other
materials. The used of this binder shows good flowability of feedstock inside the
mould cavity and rheological characteristic. Subsequent process of the MIM showing
good part retention after solvent debinding without any parts defect such as swelling
or part cracks. The sintering condition with this type of binder shows good mechanical
properties.
2.3.1.3 Polymethyl Methacrylate (PMMA)
Using PMMA as binder in MIM was found in making the feedstock of stainless steel
[82], [83], titanium [84], tungsten carbide cobalt [85] and many other material
applications. The wide used of PMMA as backbone binder was due to its ability to
mix of powder with PMMA at room temperature with the help of acetone. Good part
shape retention also contributes to this wide usage of this polymer in MIM. Good
15
rheological characteristics and high powder loading on water atomised 316L powder
was determined by Ibrahim et al., [86]. Subsequent process of solvent, thermal
debinding and sintering also shows good mechanical properties and characteristic.
Table below shows application of PMMA as binder by other researchers in their
research.
2.3.1.4 Polypropylene (PP)
PP also known as polypropene, is a thermoplastic polymer used in a wide variety of
applications including packaging and labeling, textiles, stationery, plastic parts and
reusable containers of various types, laboratory equipment, loudspeakers, automotive
components, and polymer banknotes. An addition polymer made from the
monomer propylene, it is rugged and unusually resistant to many chemical solvents,
bases and acids. Kong et al., [37] did comprehensive study of determining the best
binder formulation between LDPE and PP as backbone binder. The PP and LDPE was
mixed with secondary binder of carnauba wax (CW) and paraffin wax (PW) with
addition of stearic acids (SA) as wetting and lubrication agents. Different molecular
weight of PP and LDPE have been tested with 60% powder loading of gas atomised
316L stainless steel powder (D50 = 3µm) . The best selection of binder were based on
mixing torque and rheological behaviour of the feedstock with different binder
composition. They found that, binder composition containing the PP with PW and SA
was better since it produced low mixing torque and low viscosity for rheological
behaviour. This binder formulation was then being further analysed for searching the
critical and optimum powder loading of stainless steel powder. From their results a
good sintered parts was obtained and optimal powder loading of 64 vol.% was
achieved. Other researchers also used PP as backbone binder in making their feedstock
for stainless steel powder and found that optimum powder loading were obtained
besides good rheological characteristics and sintered parts [87][88]. Other than that PP
was able to be mixed with other secondary binder like PEG, PW, palm kernel, palm
stearin and CW [10], [51].
Besides its usage in making the MIM feedstock, PP also being used in CIM
as binder in making the CIM feedstock. Onbattuvelli et al., [89] used PP as backbone
binder determining the effects of nanoparticle addition on binder removal of silicon
16
carbide injection moulded specimens. No defects were found for their debinding
analysis with the usage of PP as backbone binder. Aggarwal et al., [90] used PP in
their niobium feedstock for determining the master decomposition curve for binder
used in PIM where this method can predict the remaining amount of binder during the
debinding process, and such can help to optimize the binder composition without
additional experiments.
In making a feedstock of titanium, PP also has been used as backbone binder
by other researchers [91][74] and found that thermal debound and sintered of micro
parts shows no sign of defects. This indicates that the usage of PP as backbone binder
can be used as binder even for the difficult or critical powders such as titanium
feedstock.
2.3.2 Secondary binder
Secondary binder was name because of its ability to decrease the viscosity and increase
the wettability and miscibility of the feedstock during the injection moulding process.
It was not meant for powder particle holder since it has low molecular weight which
results in low melting temperature. Many types of polymer, waxes and plasticizers has
been encountered as secondary binder in MIM and CIM such as polyethylene glycol
(PEG), carnauba wax [92], paraffin wax [70], peanut oil, palm kernel and palm stearin.
2.3.2.1 Polyethylene Glycol (PEG)
PEG is a polyether compound with many applications from industrial manufacturing
to medicine. Due to its low melting temperature, PEG was used as secondary binder
in most MIM application related to feedstock. Unlike the polymer/wax binder systems
which used organic solvents frequently in solvent debinding process which are
flammable, carcinogenic and environmentally unacceptable, PEG is soluble in water.
This advantages contribute to very safe chemicals and are used quite extensively in
food industry and allowed from the local water authorities to dump the water/PEG
containing solvents into the drain after debinding [57], [93]. Yang et al., [57] use
different molecular weight of PEG in determining its effect on rheological behaviour
of injection moulding alumina feedstock. They found that PEG with highest molecular
17
weight (20K) was better as compare to low molecular weight (1K and 1.5K). The
backbone binder they used for their research was polyethylene wax. Chen et al., [77]
used PEG along with PMMA as backbone binder and stearic acid for wettability
agents. Analysis of PEG removal inside the water was increase with temperature and
diffusion of PEG was low at room temperature. Porosity increase with debinding time
base on the surface porosity of the green parts. This shows that PEG usage in MIM as
binder also shows good flowability in MIM. Krauss et al., [93] develop a model for
PEG removal in alumina injection moulded part. They found that the pore diameter
remain the same throughout the debinding time but the volume or number of pores
inside the specimens was increased. Hayat et al., [84] use the same experimental
method by Yang et al., [57] where the same molecular weight of PEG was used. They
conclude that the PEG with higher molecular weight shows good rheological
behaviour due to the interaction between powder and polymeric binder, as a result of
increased number of hydrogen bonds on the longer PEG molecule chains.
The used PEG with cellulose acetate butyrate (CAB) [84], [94], [95] as
backbone binder results in pseudoplastic behaviour and a global viscosity model
involving all of the dependent variables, including shear rate, temperature, solid
loading and particle sizes was achieved. Sharmin and Schoegl [23] used PEG (6000
molecular weight) along with EVA in analysing the two-step debinding and co-
extrusion of ceramic-filled polyethylene butyl acrylate (PEBA) and EVA blends. Good
rheological behaviour was achieved. Results of solvent debinidng of EVA-PEG was
better as compare to PEBA-PEG binder due to compatibilities between PEG and the
thermoplastic binder which in this case EVA shows better compatibility with PEG
than PEBA, and the slower removal rate and higher torque is attributed to a finer
dispersion of PEG within the blend. Thavanayagam et al., used PEG of 8000 molecular
weight as binder in titanium feedstock and good rheological behaviour was achieved.
2.3.2.2 Paraffin wax (PW)
Paraffin wax is a white or colourless soft solid derivable from petroleum, coal or oil
shale, which consists of a mixture of hydrocarbon molecules containing between
twenty and forty carbon atoms. Common applications for paraffin wax
include lubrication, electrical insulation, and candles.
18
Detail used of PW was elaborated by Zaky et al., [96] where they use different
molecular weight of PW ranging from 378 to 572 to investigate the influence of
paraffin wax characteristics on the formulation of wax-based binders and their
debinding from green moulded parts using two comparative techniques. The mixing
time and temperature were fixed at 150ºC and 30 minutes mixing time. Results of their
studies indicates that mixtures of EVA as backbone binder and PW of high molecular
weight was better since it has good compatibility and rheological properties as it has
viscosity below 10Pas which is suitable to fabricate homogenous feedstock during
compression or injection moulding process. They also conclude that solvent
immersion is a preferable technique as it saves the amount of solvent used as compared
with the evaporation–condensation technique.
You et al., [97] use PW as backbone binder in making low pressure injection
moulding in making micro gear. They used nano powder in making the feedstock and
successfully producing moulded gear which had a sound surface, uniform shape and
homogeneous microstructure even after thermal debinding process. The debound gear
of the micro-nano powder underwent isotropic shrinkage and near full densification
during sintering. Other application of PW as binder were shown by Sotomayor et al.,
[98] where they used PW with high density polyethylene (HDPE) as backbone binder
with formulation of 50/50 between secondary and primary binder for fremixed of
ferritic and austenitic stainless steel. Results shows that the PW was successfully
mixed with HDPE and solvent, thermal debinding and sintering process was
successfully being done without any defects. Four composition of binder was used by
Li et al., [99] in producing the molybdenum feedstock where PW as the major
components of the binder beside the HDPE, EVA and stearic acids. These types of
binder composition usually used for thermal debinding process only where solvent
debinding were not been used. All the injected parts were free from defects.
2.3.2.3 Carnauba wax
Carnauba wax is a wax from a plants which is obtained from the leaves of the carnauba
palm by collecting and drying them, beating them to loosen the wax, then refining and
bleaching the wax. Carnauba wax contains fatty acid which known to be good agent
for binder in MIM [100]. In MIM and CIM, carnauba wax has long been known for
19
its suitability as binder components. It has melting temperature of 84ºC which was
higher as compare to other types of waxes [92]. Supriadi et al., [12] used carnauba
wax for their wax binder systems and good mouldability shape was produced due to
its low heat capacity which in turns has high cooling rate and producing good shape
retention. Ahn et al., [101] has include carnauba wax in their analysis of determining
the effect of powders and binders on material properties and molding parameters in
iron and stainless steel powder injection molding process. All the properties of the
binder composition shows good pseudoplastic behaviour.
2.3.2.4 Palm kernel and stearin
Palm kernel and stearin was comes from palm oil plants which contains rich amounts
of fatty acids. The composition of fatty acids from palm kernel is shown in Table 2-1;
Table 2 - 1: Fatty acid composition (%) of NIE, EIE and CIE 50:50 PO:PKO blend
fractions [102]
As can be seen C18:0 and C18:1 were the carbon number of stearic acid and
oleic acid. This shows that this palm kernel were suitable to be used to replace the
function of wax and surfactant in a binder system to ensure good wetting of the powder
[51]. Omar et al., [51], [79], [103] quite intensively used palm kernel or stearin in their
research of producing 316L stainless steel powder feedstock. With this binder
composition, solvent and thermal debinding was successfully being done without any
20
defects. Sintering process of the parts also indicates good achievement where relative
density of 97% was achieved.
2.3.3 Surfactants
Polymeric surfactants are essential materials for preparation of many disperse systems,
of which we mention dyestuffs, paper coatings, inks, agrochemicals, pharmaceuticals,
personal care products, ceramics and detergents [50]. In PIM surfactants was used to
avoid particles agglomeration, wetting agents and lubrication. Surfactants such as oleic
and stearic acids was used to improve powder dispersion during mixing [104]. Several
analysis has been done in determining the influence of surfactant on suspension
structure and green microstructure of injection-moulded parts.
Fraction between polymer and waxes is roughly equal in its proportions. With
the aid of current research, this proportions evolved with just minimum by volume or
weight ratio of polymer is enough in holding the powder particles in place. Nowadays,
proportions of 20 to 80% by volume between polymer and waxes are possible with
appreciation of surfactants such as stearic acids (SA) and oleic acids (OA). The aims
to reduce the amount of polymer in MIM feedstock can contribute in minimizing
carburization on the sintered part during sintering which could contributed to carbide
formations which results in much brittle part. Stearic acids is known for low cost polar
molecule with molecular structure of CH3(CH2)16COOH and low melting temperature.
This wetting agent will improve wettability of the polymer and powder particles by
lowering the contact angle by decreasing the surface energy of the binder-powder
interface[59]. The ability of bridging the property of polymer could increase the
powder loading and results in lowering shrinkage value and reduces the parts from
slumping during thermal debinding and sintering. Surfactants also reacts as internal
lubricant (incorporated into the host resin during production or compounding), which
promotes fusion, and reduce melt viscosity and friction or increase slipperiness
between polymer particles before melting.
Tseng et al., [104] has tested several quantity of stearic acids on the zirconia
feedstock. The range of addition of stearic acid was between 3 vol.% to 17 vol.% and
was found that the pore size of the reduces with increasing the fraction of stearic acids.
This indicates good packing structure of the green parts and also leads to low viscosity
21
of the feedstock. They also found that although higher contents of stearic acid leads to
good viscosity and particles packing, too high fraction of stearic acid also leads to high
cracks during thermal debinding.
Comparison between oleic, stearic and 12-hydroxystearic acids on
rheological behaviour of alumina powders also been done by Tseng [104]. They
conclude that the viscosity of the suspension was lower for stearic acids and followed
by oleic and 12-hydroxystearic acids. Li et al., [105] did the analysis of different
fraction of stearic acids on making the 17-4PH stainless steel feedstock and found that
0.2% theoretical calculation was enough in producing single molecule layer of stearic
acid on the powder surface but higher fraction were needed for irregular shape
particles. They also found that as the fraction of stearic acid increase, the wetting angle
decrease. Fan et al., [49] have determining the influence of stearic acid during ball
milled the ultrafine 98W-1Ni-1Fe and found that it improves the particle sizes
distribution of the ball milled powder, reduce the mixing time for homogeneity of
feedstock, better rheology at lower temperature but opposite when higher temperature
were used and reduces the temperature required for injection moulding of 98W-1Ni-
1Fe powder. Therefore, the used of surfactant especially stearic acid for binder in MIM
becomes common such as in making the water atomised 316L stainless steel feedstock
[52], [106].
2.4 Restaurant waste lipids as binder
Domestic and commercial food establishments generate large volumes of wastewater,
in the form of grey water or sullage that contains significant amounts of fats, oil and
grease (FOG) or RWL. FOG must be separated from wastewater prior to entering the
sewage system, primarily because of its propensity to block municipal sewer lines and
disrupt the effective operation of downstream treatment processes [107]. RWL can be
recovered efficiently from grease interceptors for biodiesel production or other
cosmetics products. RWL is susceptible to hydrolysis because of its inherent high
moisture content and the presence of lipases associated with food residuals in the
grease interceptors. Since the evolved of engine diesel by Rudolf Diesel which tested
his engine with vegetable oils as fuel, many are drawback to see vegetable and animal
fats as biodiesel fuel for substituting the fossil fuel in minimizing the environmental
22
pollutions and reducing the dependence on fossil fuels [108]. The number of waste oils
and fats is expected to increase with urbanization, life style changes and nutrition
transition due to occupational which time consuming which also shifted the diets
towards fast foods [3].
Williams et al., [109] have characterized the FOG deposits in sewers on
several locations such as pumping station, sewers and sewage works. They found that
percentage of free fatty acids (FFA) were shown as Table 2-3 and Figure 2-3. They
also found that the majority of the deposits contain FFA of palmitic, oleic, stearic and
linoleic acid.
Table 2 - 2: % mass fatty acids profiles of cooking fats and oils [109]
Figure 2 - 3: Mean concentrations of fatty acids in the FOG deposits [109]
It is stated that RWL in restaurants sewers line are a major problem and can
cause sewer overflows, resulting in environmental damage and health risks [109]. It is
the challenge how this waste can be used in the manufacturing area since it has
composition of different organic materials. It is found that this RWL contains high
energy and oil recovery which can be obtained from this abundant source of energy
[15]. In terms of Metal Injection Moulding process the RWL seems could be used in
23
the production of feedstock since it has the mixture of animal, vegetable fats and
several organic acids. Table 2-2 shows the reported fatty acids present in restaurant
waste lipids.
Table 2 - 3: Reported fatty acids present in grease trap [110]
Montefrio et al., [107] also found the same FFA in their analysis of fats, oil
and grease from grease interceptors for biodiesel production. They found that higher
FFA in the grease interceptors and the results were compared with FFA contains in
palm oils, animal fats (tallow) and lards as shown in Table 2-4;
Table 2 - 4: Fatty acid and FFA profile of FOG samples and neat palm oil [107]
Since RWL contains of animal fats and vegetable oils, Banković-Ilić et al.,
[111] done some classification of FFA on several types of animal fats and vegetable
24
oil as shown in Table 2-5. All the vegetable oils and animal fats contains stearic acids
and oleic acid which useful as surfactant for dispersing metal powder in MIM
feedstock.
Table 2 - 5: Fatty acids composition of some vegetable oils and animal fats [111]
Although much discussion on FFA contain in RWL, much was concerning
its application on biodiesel [16], [110], [112], [113]. Therefore the use of RWL for
MIM binder seems suitable to replace the function of wax and surfactant in a binder
system to ensure good wetting of the powder since the RWL were either soft or waxy
in room temperature.
2.5 Stainless steel 316L feedstock
Stainless steel powder can be divided into of water atomised and gas atomised powder
particles. Water and gas is named based on its process for producing the powder
particles. Water atomised have round or irregular shapes as compared to gas atomised
which have the spherical shapes. Examples of water and gas atomised 316L stainless
steel powder is shown in Figure 2-4.
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