Study On The Effect of Filler Combination To The Cost and Quality of An Industrial Nitrile Glove

STUDY ON THE EFFECT OF FILLER COMBINATIONS TO THE
COST AND QUALITY OF AN INDUSTRIAL NITRILE GLOVE
A Dissertation
Presented to
The Faculty of Graduate Studies
University of Sri Jayewa rdenepura
Sri Lanka
In Partial Fulfillment
of the Requirements for the Degree
Master of Science in Polymer Science & Technology

DECLARATION
I hereby declare that this research project was conducted by me, under supervision of Dr.
Rajitha Gunarathne, Visiting Lecturer, Department of Chemistry, University of Sri
Jayewardenepura, Sri Lanka and Prof. Sudantha Liyanage, Dean, Department of
Chemistry, University of Sri Jayewardenepura, Sri Lanka. I also certify that this thesis
has not been submitted in whole or in part to any University or any other institute for
another Degree / Diploma.
........ . . ..
i.i1
Denzil Tennakoon Date
.........
Rajitha Gunarathne, Date

(Supervisor)
Visiting Lecturer,
Department of Chemistry,
University of Sri Jayewardenepura,
Sri Lanka.
. .. ,
Prof. Sudantha Liyanage, Date
(Supervisor)
Dean,
Department of Chemistry,
University of Sri Jayewardenepura,
Sri Lanka.
ACKNOWLEDGMENTS
I would like to express my deepest appreciation to all those who provided me the
possibility to complete this Research and project report successfully. A special gratitude
I must extend to my Research supervisors, Prof. Sudantha Liyanage, Dean, Department
of Chemistry, University of Sri Jayewardenepura, Sri Lanka and Dr. Rajitha Gunaratne,
Senior Lecturer. Department of Chemistry. University of Sri Jayewardenepura, Sri
Lanka whose contribution . encouragement and gLildance was enormous throughout the
whole process.
Furthermore I would like to extend my sincere gratitude to Dr. K.M.T.D Gunasekara,
Course coordinator of M,Sc. in Polymer Science and Technology for her generous
support and continuous encouragement to make this research a sLiccess. I would also
like to acknowledge with much appreciation the crucial role of the staff of Hands
International (Pvt) Ltd, a special thanks goes to my team mates Mr. Kasun Chanaka and
Mr. Harsha Kumara.
Last but not least I wish to thanks Dr. M.A.B Prasantha as well as the panel, especially
for the guidance had been given during my Pre-project presentation to improve my
presentation ski I Is.
ABSTRACT
Carboxylated acrylonitrile butadiene (XNBR) is vastly used synthetic latex for

industrial glove applications. In this project main intention was to make defects free,
cost competitive industrial glove with enhanced mechanical properties with the use of
XNBR latex compound and fillers. Hence three types of fillers and then their
combinations were incorporated into XNBR compound which contained XNBR latex
and other required curatives, to find out most suitable filler or filler combinations for the
XNBR latex which was used to dip gloves. Selected fillers were montrnorillonite
(MMT), kaolin and calcium carbonate. Initially fillers were added independently and
then as combinations. Mechanical properties such as abrasion resistance tear resistance,
cut resistance. puncture resistance and Clark stiffness were measured on cured gloves
and compared those properties with each other to identify the best filler or filler
combinations for the XNBR latex compound and visual inspection was carried out find
out faulty gloves prior to conduct mechanical tests.
The results of the study showed that all these three different fillers could be
incorporated with XNBR latex with different proportions and mechanical properties
were increased with the addition of fillers up to some extent and then it was decreased
with further addition. Cost of the XNBR compound was dropped with the incorporation
of calcium carbonate and kaolin. Compatibility of calcium carbonate with XNBR latex
was higher in comparison to others and at 18 parts of filler with XNBR gave balanced
properties as far as concern quality, cost and processing easiness. 15 parts of calcium
carbonate, 0.5 parts of montmorillonite (MMT) and 5 parts of kaolin mixture was
successful as three filler combination and cosmetic point of view. 20 parts of calcium
carbonate and 0.5phr MMT filler was also a good potential combination as far as
mechanical properties and cost were concerned. However as per current day prices of
fillers, availability and accessibility. 18 parts of calcium carbonate incorporation was
more economical than other two combinations where MMT was used. However MMT
has significant positive impacts on loading capability of other two fillers and also on the
physical properties.
Calcium carbonate was less defects creative than MMT and kaolin. Specially cracks
pinholes and lumps. Therefore it possessed highest loading ability in addition to
physical property enhancement.
Therefore it was obvious that calcium carbonate, kaolin and montmorillonite clay can
be used to improve mechanical properties of industrial nitrile gloves while enhancing its
profit margin and visual appearance.
II!A
TABLE OF CONTENTS
Topic Page
DECLARATION........................................................... . ........ . .................. I
ACKNOWLEDGRMENT................................. ... ......................... II
ABSTRACT. ............................................................................. III
TABLEOF CONTENTS ...................................... .... ....................... V
LISTOFTABLES .................................................................... XI
LISTOF FIGURES ....................................... ......................... XIII
CHAPTER 01 - INTRODUCTION........................................................ 1
1.1 General Description of the Nitrile Glove ..............................3
1 .2 Ideal Application.............................................................................3
1.3 EN Standard for Mechanical Protection ................................4
1.4 REACH Compliance (Hazardous Chemicals List).........................7
CHAPTER 02- LITERARTURE REVIEW. ......................................... 8
2.1 XNBR Latex................................................................8
2.1.1 Stability of Carboxylated NBR Latex ...................................9
2.2 Ammonia (25% Ammonium Hydroxide) .... .................................... 10
2.3 SABS (Sodium Alkyl Benzene Sulfonate)......................................11
2,4 Zinc Oxide....................................................................................... 11
is
2.5 SiiIphr 12
2.6 Organic Accelerator ZDBC............................................................. 13
2.7 Viscosity Modifier- Culminal MHPC 50..................................... 13
2.8 Hydrowax 215............................................................................... 14
2.9 Pigment Blue- Flexiverse BCD 9907........................................... 14
2.10 Calcium Carbonate Fille. ............................................................... 14
2.11 Clay Minerals................................................................................ 16
2.11.1 Kaolin Filler......................................................................... 17
2.12 Montmorillonite............................................................................ 18
CHAPTER 03- MATERIALS AND METHODS...............................22
3.1 Glove Formulations......................................................................22
3.2 Filler Matrix.....................................................................................23
3.3 Preparation of Blank Compound (added amounts)..........................25
3.4 Preparation of Dipped Gloves..........................................................27
3.4.1 Main Steps Involved in Blank Compound Dipping

Operation.........................................................................................27
3.5 Preparation of Calcium Carbonate Incorporated Compounds..........33
3.6 Preparation of Kaolin Filled Compounds .......................................... 34
3.7 Preparation of MMT Incorporated Compounds ................................ 34
3.8 Preparation of Kaolin &Calcium Carbonate Combination
Incorporated Compound..................................................................35
VI
3.9 Preparation of Kaolin & MMT Incorporated Gloves........................ 36
3. 10 Preparation of Calcium Carbonate& MMT Incorporated Gloves... 37
3.11 Preparation of Calcium Carbonate, Kaolin & MMT Incorporated

Gloves.............................................................................................. 37
3.12 Calculations.....................................................................................
38
3.13 Testing............................................................................
39
3.13.1 Martindale Abrasion Resistance Tester........................... 40
3.13.2 Universal Extension Tester (Puncture & Tear resistance),, 41
3.13.3 Circular Blade Cut resistance Tester.................................... 42
3.13.4 Clark Stiffness Teste. ........................................................... 43
CHAPTER 04- RESULTS & DISSCUSION......................................... 44
4.1 Calcium Carbonate Filler Incorporated Test Results.................. 44
4.1.1 Abrasion Resistance of Calcium Carbonate Incorporated

Samples.................................................................... 45
4. 1 .2 Blade Cut resistance of Calcium Carbonate Incorporated

Samples..................................................................... 46
4.1.3 Tear Resistance of Calcium Carbonate Incorporated

Samples.................................................................... 46
4.1.4 Puncture Resistance of Calcium Carbonate Samples.......... 47
4.1.5 Stiffness of Calcium Carbonate Samples........................ 47
4.2 Kaolin Filler Incorporated Test Results................................. 49
4.2.1 Abrasion Resistance of Kaolin Incorporated Samples......... 50
4.2.2 Cut Resistance of Kaolin Incorporated Samples............... 51
VII
4.2.3 Tear Resistance of Kaolin Incorporated Samples............... 51
4.2.4 Puncture Resistance of Kaolin Incorporated Samples........ 52
4.2.5 Stiffness of Kaolin Incorporated Samples....................... 53
4.3 MMT Filler Incorporated Sample Test Results............................... 55
4.3.1 Abrasion Resistance of MMT Incorporated Samples............. 56
4,3.2 Cut Resistance of MMT Incorporated samples...................... 56
4.3.3 Tear Resistance of MMT Incorporated Samples.................... 57
4.3.4 Puncture Resistance of MMT Incorporated Samples............. 58
4.3.5 Stiffness of MMT Incorporated Samples............................... 57
4.4 Kaolin & CaCO3 Filler Incorporated Sample Test Results........... 59
4.4. 1 Abrasion Resistance of Kaolin & CaCO3 Incorporated
Samples. ........................................................................................ 60
4.4.2 Cut Resistance of Kaolin & CaCO3 Incorporated

Samples........................................................................................... 61
4.4.3 Tear Resistance of Kaolin & CaCO3 Filler Incorporated

Samples.......................................................................................... 62
4.4.4 Puncture resistance of Kaolin &CaCO3 Filler Incorporated

Samples...................................................................... 63
4.4.5 Stiffness of Kaolin &CaCO3 Filler Incorporated

Samples....................................................................................... 63
4.5 MMT, CaCO3 and Kaolin Filler Incorporated Sample Test

Results....................................................................... 64
4.5.1 MMT& Calcium Carbonate Fillers Incorporated Sample

TestResult.............................................................................. 64
VIII
4.5.2 MMT & Kaolin Fillers Incorporated Samples Test
Results................................................................................... 65
4.5.3 Abrasion resistance of MMT in combination with Calcium

Carbonate or Kaolin............................................................... 66
4.5.4. Cut Resistance of MMT in Combination with Calcium

Carbonate and Kaolin .......................................................... 67
4.5.5 Tear Resistance of MMT. CaCO3 & Kaolin Incorporated

Samples..................................................................................
68
4.5.6 Puncture Resistance of MMT in Combinations with

Calcium Carbonate and Kaolin................................... 69
4.5.7 Stiffness of MMT in Combination with Calcium Carbonate

andKaolin.............................................................................. 69
4.6 MMT, Calcium Carbonate and Kaolin Incorporated Sample Test

Results..................................................................................... 70
4.6.1 Abrasion Resistance of MMT, Calcium Carbonate & Kaolin

Coni binations Incorporated Samples....................................... 72
4.6.2 Cut Resistance of MMT. Calcium Carbonate & Kaolin

Incorporated Samples.............................................................. 72
4.6.3 Tear Resistance of MMT, Calcium Carbonate & Kaolin

Incorporated Samples .................................................... 73
4.6.4 Puncture Resistance of MMT, Calcium Carbonate & Kaolin

Incorporated samples............................................................... 74
4.6.5 Stiffness of MMT, Calcium Carbonate & Kaolin

Incorporated Samples............................................................. 74
4.7 Tested Filler Combinations........................................................... 75
Ix
CHAPTER 05 -CONCLUSION AND FURTHER WORK ..............82
REFERENCES......................................................................................... 84
APPENDIX I.........................................................................85
APPENDIX II ........................................................................ 87
LIST OF TABLES
Table Page
Table 1.1 Mechanical properties 5
Table 1.2 Performance levels of existing glove ........................................... 5
Table 1.3 Dimensional & Weight parameters ............................ ........................ 6
Table 1.4 Hazardous Chemicals list with their availability details.................. 7
Table 2.1 Synthomer 6322 XNBR latex properties.......................................... 9
Table 2.2 Contents of Zinc Oxide.............................................................. 12
Table 2.3 Comparison of properties of Calcium carbonate grades................... 16
Table 2.4 Property comparison of kaolin grades............................................... 17
Table 2.5 properties of Del]ite 43B................................................................... 20
Table 3.1 Existing Standard Glove formulation ............................................. 22
Table 3.2 Formulation used for Experiments.................................................... 23
Table 3.3 Filler & filler combinations to be tested............................................ 24
Table 3.4 blank compound formulation ............................................................ 26
Table 3.5 Amounts of CaCO3 added.................................................................. 33
Table 3.6 Amounts of kaolin added................................................................... 34
Table 3.7 Amounts of MMT added................................................................... 35
Table 3.8 Kaolin &Calciurn carbonate combination......................................... 36
Table 3.9 Kaolin & MMT Combination............................................................ 37
Table 3.10 Calcium carbonate& MMT Combination........................................ 37
XI
Table 3.11 Calcium carbonate. Kaolin & MMT combination 38
Table 3.12 Features of Universal Extension Teste. ............................................ 41
Table 4.1 Calcium carbonate Filler Incorporated results................................... 44
Table 4.2Kaolin Filler Incorporated results........................................... 49
Table 4.3 Comparison of properties of CaCO3 and Kaolin glove samples...... 55
Table 4.4 MMT filler incorporated sample test results ..................................... 55
Table 4.5 Kaolin &CaCO3 Filler Incorporated sample test results ................. 60
Table 4.6 MMT &CaCO3 fillers incorporated sample's test results.................. 65
Table 4.7 MMT & Kaolin fillers incorporated sample's test results................... 67
Table 4.8 MMT, CaCO3 and kaolin Filler Incorporated sample test results 71
Table 4.9 Tested filler combinations................................................................. 75
Table 4.10 Selected filler Combinations.......................................................... 79
Table 4.11 EN 3 88:2003 Mechanical Properties comparison......................... 80
Table 4.12 Raw Materia] Prices........................................................................ 80
Table 4,13 Raw Material consumption ............................................................. 80
Table 4.14 Cost comparison of Selected combinations (cost/glove)................. 81
XII
LIST OF FIGURES
Figure page
Figure 2.1 Monomers of XNBR (Butadiene, Acrylonitrile and

Methacrylicacid)...................................................................... 6
Figure 2.2 Structure of Montmorillonite.............................................. 19
Figure 2.3 Exfoliation and intercalation...................................................... 19
Figure 3.1 overall process illListration ......................................................... 28
Figure 3.2 Fiberglass Formers ........................................................... 29
Figure 3.3 Dressing a forme................................................................ 29
Figure 3.4 Dressed formers........................................................... 30
Figure 3.5 Manual glove dipping step 01 .............................................. 30
Figure 3.6 Manual glove dipping step 02............................................ 31
Figure 3.7 Keeping for drain off....................................................... 31
Figure 3.8 Coagulant Dipping ...................................................... 32
Figure 3.9 Curing In Oven.......................................................... 32
Figure 3.10 Stripping............................................................... 33
Figure 3.11 Abrasion Tester.......................................................................... 40
Figure 3.12 Abraded Test pieces.................................................................. 40
Figure 3.13 Universal Extension teste. .......................................................... 41
Figure 3.14 Tear Resistance Test is performed............................................ 42
Figure 3.15 Puncture Resistance Test is performed..................................... 42
XIII
Figure 3.16 circular blade cut resistance tester............................................. 43
Figure 3.17 Cut Resistance test is performed.............................................. 43
Figure 3.18 Clark stiffness tester. 43
Figure 4.1 Abrasion Resistance of Calcium carbonate samples................... 45
Figure 4.2 Graph of Cut resistance of Calcium carbonate incorporated

Samples................................................................. 46
Figure 4.3 Graph of Tear Resistance of Calcium carbonate samples ........47
Figure 4.4 Graph of Puncture resistance of Calcium carbonate filled

samples.......................................................................................................... 47
Figure 4.5 Graph of Stiffness of Calcium carbonate Samples..................... 48
Figure 4.6 Graph of Abrasion resistance of Kaolin Filled Samples ......... 50
Figure 4.7 Graph of Cut resistance of kaolin filled samples .................. 51
Figure 4.8 Graph of Tear Resistance of Kaolin incorporated samples....... 52
Figure 4.9 Graph of Puncture resistance of kaolin incorporated samples... 53
Figure 4.10 Graph of Stiffliess oI'kaolin incorporated samples............... 54
Figure 4.11 Graph of Abrasion resistance of MMT incorporated samples.. 56
Figure 4.12 Graph of Cut resistances of MMT incorporated samples..........57
Figure 4.13 Graph of Tear resistance oIMMT incorporated samples..........57
Figure 4.14 Graph of Puncture resistance graph of MMT filled samples.... 58
Figure 4.15 Graph of Stiffness of MMT incorporated samples.................... 59
Figure 4.16 Graph of Abrasion resistance of Kaolin & CaCO3 filler

incorporated samples................................................................ 61
xlv
Figure 4.17 Graph of Cut resistance of Kaolin & CaCO3 or Kaolin
incorporated samples.................................................................62
Figure 4.18 Graph of Tear resistance of Kaolin & Calcium carbonate filler
Figure 4.19 Graph of Puncture resistance of Kaolin &Calcium carbonate

filler incorporated samples........................................................63
Figure 4.20 Graph of Stiffness of Kaolin & Calcium carbonate filler

incorporated samples............................................................... 64
Figure 4.21 Graph ofAbrasion resistance of MMT in combination with

Calcium carbonate or Kaolin......................................... 67
Figure 4.22 Graph of Cut resistance of MMT in combination with

Calcium carbonate or Kaolin..................................................... 68
Figure 4.23 Graph of Average Tear resistance of MMT in combination

with Calcium carbonate or Kaolin............................................. 68
Figure 4.24 Graph of Average puncture resistance of MMT, CaCO3&

Kaolin incorporated samples......................................... 69
Figure 4.25 Graph of Stiffness of MMT in combination with Calcium

carbonate or Kaolin................................................................... 70
Figure 4.26 Graph of Abrasion resistance of MMT, Calcium carbonate &

Kaolin....................................................................................... 72
Figure 4.27 Graph of Average cut resistance of MMT, Calcium carbonate

& Kaolin incorporated samples................................................. 73
Figure 4.28 Graph of Tear resistance of MMT, Calcium carbonate&

Kaolin incorporated samples.................................................... 73
Figure 4.29 Graph of Puncture resistance of MMT. Calcium carbonate&
xv
Kaolin incorporated samples . 74
Figure 4.30 Graph of stiffness of MMT, Calcium carbonate & Kaolin
XVI
CHAPTER 01
INTRODUCTION
Gloves are fall in to two main categories as industrial and disposable gloves. Disposable
gloves are again categorized as medical examination and surgical gloves. Industrial and
examinatioii gloves are named as "Personal Protective Equipment or PPE" and its prime
concern is to protect wearer, whereas surgical gloves prime concern is to protect patient.
Personal protective equipment is divided in to three categories according to the degree

of risk against which they protect.
I). Category I: Gloves of simple design
Gloves are designed to protect from "minimal risk" or easily reversible effects. e.g.
Janitorial gloves. Manufacturers are permitted to test and certify glove internally.
2).Category II: Gloves of intermediate design
Gloves are designed to protect from "intermediate risk". e.g. general handling
gloves with good mechanical properties SLId] as Abrasion resistance. Cut resistance,
Puncture resistance and Tear resistance. Must be subjected to independent testing
and certification from Notified Body who issue the CE mark and without that
gloves caniiot be sold.
3).Category III: Gloves with complex design
Gloves are designed to protect against highest level, irreversible or mortal risk. e.g
Gloves provide Protection against chemical splashes and micro-organism. Must be
tested and certified by notified body. Periodic evaluation of quality assurance
system by iiidependent party is required. Notified body number who carries out the
evaluation must appear with the CE mark.
Gloves belongs to "Category II" are made out of mainly by the use of carboxylated
acrylonitrile butadiene latex (XNBR), natural rubber latex (NR), polyurethane latex (PU)
and styrene butadiene latex (SBR). However XNBR possess superior physical and
mechanical properties over other polymer latexes. Polychloroprene and polyvinyl
chloride are used to produce gloves against chemical risks.
Core competency is what a firiii does better than anyone else, its distinctive competence.
A firm's core competence can be service, higher quality faster delivery or lower cost.
One company may strive to be first to the market with innovative designs, whereas
another may look for siccess arriving later but with better quality or low cost.
Core competencies are not static. They should be nurtured, enhanced, and developed
over time. Close contact with customer is essential to ensuring that a competence does
not become obsolete. So that companies need to continually evaluate the characteristics
of their products that prompt the customer purchase: that is. order qualifiers and order
winners. Order qualifiers are the characteristics of a product that qualify it to be
considered for purchase by a customer. An order winner is the characteristics of a
product that wins orders in market place. Nowadays at competitive market place, price
of a product has become as order qualifier and features or quality has become as order
w inner.
Hycron" (Trade name) is one of an industrial fabric supported nitrile-dipped glove

belongs to "Category II" glove classification with excellent resistance to snags,
punctures, abrasions, cuts, greases and oils. Its extra-tough, heavy-duty nitrile coating
gives excellent dry grip and superior service when handling rough, abrasive materials.
Product was start widely used from the year 1990 and it has been in the market nearly
25 years. During first decade there was no significant competition from other glove
styles and glove manufacturers on "Hycron" industrial gloves. However with emerge of
"China factor" manufacturers were compelled to find ways to compete with Chinese
products on the grounds of cost and quality. Because of that "Hycron" has been
subjected to "continual improvement" for quite period of time and now those efforts
have been exhausted. Because of that glove needs "breakthrough" improvement or rapid
performance enhancement lollowed by refine process to be competitive in the market
place.
Overall goal of this research project is to introduce defects free, low cost industrial
fabric supported nitiile glove with enhanced mechanical properties by filler
incorporation. Specific objectives of the project are to reduce production cost of nitrile
compound and increase abrasion resistance: which is the most important mechanical
property and at least needs to perform up to 20000 cycles with the performance
enhancement. Improvements in cut resistance, tear resistance and puncture resistance of
2
the dipped glove are also expected.
Following fillers were selected to be blended with carboxylated acrylonitrile butadiene

latex compound.
I. Calcium carbonate dispersion {CaCO3}
Kaolin dispersion {Al2Si2O5(OH)4 }
MMT Clay {(Na, Ca)0.33(AL, M9)2(Si4010 )}
Fillers are to be incorporated individually and also as combinations with nitrite latex
compound. Dipped glove samples are to be tested for mechanical properties such as
abrasion resistance. cut Resistance, tear resistance, puncture resistance (EN388:2003
standard) and Clark stiffhess. Visual inspections are to be carried out prior to
mechanical testing for possible defects that caused by filler incorporation.
1.1 General Description of Industrial Nitrite Gloves.
A big tough glove thr a roLigh, tough life: three times more durable than heavy duty
leather. This glove is specialty made for heavy workers to protect their hands. Unique
nitrite formulation offers superior resistance to sharp and abrasive materials.
Carboxylated acrylonitrile butadiene (XNBR) rubber is stronger and more flexible than
PVC. Also excellent barrier to grease and oil, and does not degrade like leather or cotton.
Especially oil and grease resistivity of XNBR rubber allows using the glove in vast
range of applications. Gloves are made without silicones. Silicones are used as
anti-foams and anti-webbing agents. So usages of silicone based anti-foams are avoided
and that guarantee clean for metals and motor manufacturing environment. Component
materials comply with US Food & Drugs Administration (US FDA) regulations for food
contact. [20]
1.2 Ideal Applications.
Basically industrial nitrite glove can be used in heavy duty applications. High GSM
(grams per square meter) levels ensure higher safety for the hands when handling
materials such as construction materials, concrete and tiles. It is also recommended for
other applications such as rough timber, dry walling and ply wood, rough casting and
cold plastic mouldings, steel bars, sheet metals, cans and other metal products,
heavy-duty cables, street cleaning and refuse collection. Other than those, because of its
oil resistant properties. applications are elongated to auto mobiles industry as well.
1.3 EN Standard for Mechanical Protection.
This standard applies to all kinds of protective gloves in respect of physical properties
and mechanical aggressions caused by abrasion, blade cut, and puncture and tearing.
Protection against mechanical hazards is expressed by a pictograni followed by four
numbers (performance levels), each representing test performance against specific
hazard. [20]
Pictogram below shows how performance levels are indicated.
abcd
Abrasion resistance.
Based on the number of cycles required to abrade through the sample glove.
Blade cut resistance.
Based on the number of cycles required to cut through the sample at a constant speed.
Tear resistance.
Based on the amount of force required to tear a sample.
Puncture resistance.
Based on the amount of force required to pierce the sample with a standard- sized point.
Table 1.1 shows perfomance "reading" and corresponding perfomance "level" of each
properties. There are no perfomance levels between each reading. As an example. if a
test piece perfomed up to 250 abrasion cycle, that will consider as perfomane level 1,
not 1.5.
4
Table 1 .1 Mechanical properties
EN388 TEST TEST LEVEL LEVEL LEVEL LEVEL LEVEL

STDS EQUIPMENT I 2 3 4 5
Abrasion
resistance test Martindale 100 500 2000 8000 -
(cycles) abrasion tester
Cut resistance Blade cut

1.2 2.5 5 10 20
test (Index) resistance tester
Tear resistance Universal 10 25 50 75 -

test (N) extension tester
Puncture Universal
resistance test extension tester 20 60 100 150 -
(N)
Table 1.2 shows performance level of existing glove under standard weight and
thickness parameters. Defect rate is maintained under 0.5 % excluding machine break
downs, fabric and human errors. Total rejection rate has to be maintained under 1%.This
figures are monitored and controlled through 100% "on line inspection" method being
applied for all production lines.
Table 1.2 Performance levels of existing glove.
Abrasion resistance Cycles > 8000 Level 4
Cut resistance Index > 2.5 Level 2
Tear resistance N > 25 Level 2
Puncture resistance N > 20 Level I
Dimensional and weight parameters (Table 1.3) are checked randomly in production
5
line at ever)' two hours and recorded. If any variation is found especially on weight and
thickness, corrective measures are taken without any delay. It is rare to observe that
variations in finger lengths since it is an outcome of finger lengths of the mould. But
there can be variations between finger lengths of gloves made out of different types of
moulds like metal and fiber due to different thermal coefficient of expansion, which
results in shrinkage of cured films.
Table 1.3 Dimensional & weight parameters of existing gloves.
PARAMETER STANDARD TOLERENCE
Size 8 9 10
53,863 - 62.084 - 65.770

Glove weight (ram/pe)
60.950 70.589 -74.274
Palm width (mm) 108 118 130 ±5
Palm weight (gIm2) 695.04 ± 50.85
Thickness (Single Wall ) 1.30 ± 0.3
Length of palm (mm) 187 194 194 ±6
Length of cuff (mm) 72 72 72 ±3
Length of first flnger (mm) 63 68 72 ±3
Length of 2nd finger (mm) 61 69 68 ±3
Length of 3rd finger (mm) 75 78 78 +3
Length of4tli finger (mm) ) 64 71 75 +3
Length of little finger (mm) 47 56 57 ±3
Total Length (mm) Min240 Min250 Min260 10
6
1.4 REACH Compliance (Hazardous Cheniicals List)
REACH stand for Registration. Evaluation, Authorization and Restriction of Chemicals.
The main aim of REACII is to ensure high level of protection of human health and the
environment from the risks that can be posed by chemicals. Table 1.4 shows that
updated hazardous chemical list that has to be exempted from glove formulations. [20]
Table 1.4 Hazardous chemicals list with their availability details
SUBSTANCE PRESENT LIMIT
Thiuram(tetramethvlth i uram-d isu I ph ide,

NO Nil
thiourea or its derivatives)
Casein & other animal derivatives YES < 0.3%
Silicone NO Nil
Phthalate NO Nil
Talc NO Nil
Dimcthylformamide NO Nil
Formaldehyde NO Nil
Heavy metal: Cadmium (Cd), Mercury (Hg),

NO Nil
Chromium VI (Cr ). Lead (Pb)
Brom mates bi 1)henyl ethers NO Nil
Nonyl phenol and/or Nonyl phenol ethoxylate YES <0.1% or <1000 ppm
Nitrosarnines YES <0.01 ppm
Nitrosatable amities YES <0.1 ppm
Aromatic amities from azo-thes YES <30 ppm
7
CHAPTER 02
LITERARTURE REVIEW
2.1 XNBR Latex
Nitrite latex is increasingly used in the manufacture of many types of protective gloves,
includin thi wall. indstial heavyweight fock lined and fabric supported. It offers
advantages in terms of processability and the performance achieved by the gloves
produced compares very favorably to that given by other materials.
Nitrite latex is the product of the polymerization between butadiene, acrylonitrile and
methacrylic acid. The polymer particles are maintained in emulsion by surfactants.
The monomer composition, the polymer chain length and its cross linking can be
controlled during the polymerization. The choice of these parameters will depend on the
particular glove application required. Nitrite latex can therefore be designed to fit the
needs of a glove manufacturer [13, 14]. Figure 2.1 shows monomers consist in XNBR
latex.
CH2 /C
HI H3/C\
HC OH
CH2 CH2
CH2
Butaclene Acrylonitrile PJhaay1ic Add
Figure 2.1 Monomers of XNBR (Butadiene, Acrylonitrile and Methacrylic acid)
Each of the three monomers makes its own contribution to the overall properties of the
final material:
/ Acrylonitrile provides tensile strength and solvent resistance due to presence of CN

(cyanide) group.
' Methacrylic acid provides tensile strength and stability due to presence of
carboxylic acid group.
/ Butadiene provides the elasticity of the polymer, bec.ause of its liner structure.
Another benefit of using synthetic nitrile latex is that, unlike natural latex, it is not subject
to seasonal changes.
2,1.1 Stability of Carboxylated NBR Latex.
Nitrile lattices are protected against infection by a biocide system and, when properly
stored, have a shelf life of 6 months. This long storage stability gives extra flexibility to
the glove manufacturer.
Nitrile latex has a very good mechanical stability and can therefore be handled through
diaphragm pumps and most blenders without any risk of destabilization. In the finished
product, the polymer film produced by nitrile latex has a good resistance to ageing, and in
particular it demonstrates a high resistance to ozone and heat, unlike natural latex.
There are few leading XNBR manufacturers around the globe. Polymer Latex -Malaysia,
Synthomer -USA, Takeda -Japan, Nantex-Thaiwan and BST -Thailand are among the
main contenders and produce different grades of XNBR such as Synthomer 6322,
Synthomer 48C40, Perhunan VT-LA, Synthomer X 2000 and so on.
Synthomer 6322 is carboxylated butadiene acrylonitrile copolymer latex containing
non-staining antioxidant. Synthomer 6322 is designed for the manufacture of both thin
and thick gloves, prepared by coagulant dipping. it is easily adaptable to most
manufacturing conditions, providing high yield. With correct formulation, Synthorner
6322 gives high tensile strength. high abrasion resistance, tear resistance and consistent
performance on low weight gloves. It doesn't Contains protein, has good anti-static
properties and chemical resistance. Shelf life is 6 months from the manufacturing date.
Complies with FDA 21CFR 177.2600 and OSHA standards. Table 2.1shows that typical
properties of Sythomer 6322 XNBR latex properties.
Table 2.1 Synthomer 6322 XNBR latex properties
Property Limit
Total solids % 45 + 1.0 (ISO 124)
pH 8.0 - 8.5 (ISO 976)
9
Property Limit
Viscosity @23°C. BF LVT mPa.s 20-90 (ISO 1652)
Particle size nrn 160
Specific gravity (, 25 0 C 1.00
Surface tension mN/rn 32
Acrylonitrile content level % 30-32
2.2 Ammonia (25% Ammonium Hydroxide)
Ammonia was added prior to the addition of other additives to set required pH.
Ammonia works as an anionic stabilizer and p1-I adjuster. it was diluted with water
before being added to the compound vessel to avoid pH shock" and to ensure proper
and fast dilution with the latex.
Main Intention of addition of ammonia is to adjust pH of the compound up to its

optimum level which is around 8.7 to 9.0 as far as concern industrial nitrile glove
formLllations. At this range of p1-1. zinc oxide (ZnO) is dissolved well within the XNBR
latex emulsion and is the primary cross linking agent for XNBR latex. Therefore
ammonia dissolution ability has a direct impact on cross linking density and ultimately
its physical properties. Hence to get the optimum functionality of ZnO, pH of the
compound need to be adjusted.
XNBR latex contains small amount of methacrylic acid which is a weak acid. Increase
of pH in the compound is done via neutralizing of methacrylic acid by the addition of
ammonia. In this case ammonia is used because it is a weak base. It is not recommended
to use strong bases such as potassium hydroxide (KOH) or sodium hydroxide (NaOH)
with this particular XNBR Synthomer 6322 since it has low acid content. Strong bases
like KOH can be used for XNBR grades which contains high amount of rnethacrylic
acid where high level of zinc oxide loadability also possible due to high level of
earboxylic acid active sites.
It is a must to check and clarify pH of raw latex before compounding is taken place. If
10
latex pH has deviated from its normal level, ammonia content to be added should also
be changed accordingly. Addition of large quantity of ammonia will cause thickening
difficulties. So it is very important to add ammonia with proper attention and care with
proper agitation. Another main importance of ammonia is that it can act as a bactericide
to terminate microbial action up to some extent.
2.3 SABS (Sodium Alkyl Benzene Sulfonate)
This is an anionic surfactant which stabilizes and reduces surface tension of latex.
SABS is an odorless. hazy, nearly water white liquid at room temperature. Active
content of sulfonate is around 40%.Since this product has foaming and emulsifying
characteristics precautionary action must be taken to avoid foaming when mixing is
taken place. Ph. - 7.5
Optimum amount of SABS need to be used in formulation designing, otherwise it would

be led to severe penetration. Rubber technologists prefer to use 10-15% of diluted
solutions with the intension of proper compatibility with latex within a short period of
time under gentle mechanical agitation.
There are some alternative materials available in the industry to cater same purpose.
"SDBS", Foryl 197' and 'Poystep" are few trade names of them. Ammonium
caseinate is also a potential alternative to replace SABS.
2.4 Zinc Oxide (ZnO)
Zinc oxide is the primary vulcanizing agent for XNBR latex. High purity
pharmaceutical grade was selected being produced through the French process (indirect
process) where metallic Zn is vaporized at 1000 C and finally it is allowed to react with
oxygen to form ZnO. Since Zn is a heavy metal ion that is harmful for aquatic
environment. Extensive studies have been done in order to replace it by magnesium
oxide; however less cross linking formation ability has been limited the industrial
applications. Zinc carbonate can also be applicable at some instances where high clarity
or transparency is needed. Composition of pharmaceutical grade of zinc oxide is given
be low.
Table 2.2 Contents of zinc oxide
Substance Content
Zinc oxide 99.9%
Lead 0.005%
Cadmium 0.001%
Color White
Specific gravity 5.6 approx.
Bulk density 0.6-0.7 g/crn3
Minus 325 mesh 99.9%
Mean particle diameter 0.2 micron
The single most important ingredient in the compound is the zinc oxide. In nitrile curing,
the tensile strength and many of the mechanical properties are achieved by ionic bonds
between the zinc and the acid groups on the nitrile chain. By varying zinc oxide level,
desired properties of the finished glove can be determined. Once again, the zinc oxide
dispersion should be added slowly to the compound with sufficient agitation. [13, 14. 15]
2.5 Sulphur
Sulphur is also important as it has been shown to give the glove improved water
resistance, durability and chemical resistance. As with the other ingredients the sulphur
dispersion should be added slowly to the compound with sufficient agitation, otherwise
there is a tendency to settle it down to the bottom. As far as concern XNBR, sulphur
shows less importance unlike natural latex due to lower level of unsaturation present in
the structure. Also it is possible to cure some of XNBR grades eliminating sulphur and
accelerators from the formulation completely. [13. 14. 15]
In rubber industry there are two main grades are available, categorized according to their
purity. 99% and 95% High purity Indonesian grade was selected for the experiment.
Shelf life of the product is two years from the date of manufacture.
12
Purity 99.5%
Moisture 0.15%
Ash 0.15%
Acidity 0.05%
Carbon 0.05%
2.6 Organic Accelerator ZDBC
The ultra-fast lion staining accelerator. usuaLly ZDBC is required to assist with the
sulphur vulcanization, which Linhike the zinc, bonds covalently with the nitrile chain.
Without the presence of the accelerator this vulcanization would require much higher
temperatures and longer dwells in the oven. It is usual to have sulphur to accelerator
ratio of 1:1.
Zinc Content 14-16%
TSC (powder) 99•5 %
Melting point 105-108 °C
ZDEC and ZDEC/ZMBT combinations are potential alternatives for ZDBC. But
restrictions have been imposed by Europe to limit the use of ZDEC due to its hazard
constituents, which is having almost same impact on NBR properties as
ZDBC. [13,14,l5j
2.7 Viscosity Modifier- Culminal MHPC 50
In applications such as unsupported industrial and fabric supported gloves, it is necessary

to use thickeners to achieve the required viscosity. The actual viscosity is dependent on
the film thickness needed for the final application. When selecting a thickener it is
important that the following are known:
The efficiency
The viscosity stability over time
The effect on the nitrile latex emulsion
13
For fabric supported industrial gloves there are three thickeners. That are widely used
sodium polyacrylate, methyl cellulose and ammonical casein. Special attention must be
made to shelf life of prepared solution of methyl cellulose and ammonical casein since
those are more vulnerable to bacteria attacks. Bactericide is recommended to add while it
is being prepared. The use of ammonical casein has declined due restriction imposed by
European Union on animal derivatives.
Culminal MHPC 50 (Trade name of Methyl hydroxy piopyl cellulose) was selected
because of its viscosity stability and compatibility over others.
2.8 Hydro Wax 215
Hydro wax 215 can be an effective addition to the anti-degrading component of latex
rubber, especially in combination with non-staining antioxidants. Hydro wax 215 is an
emulsion of blended waxes, paraffin and microcrystalline, which may be used in Nitrile
latex as an anti-ozonant. The wax "blooms' during the cure process from the emulsion
to the rubber surface, providing a protection against ozone attack.
Wax Emulsions also improve anti-tack properties of finished latex articles. Excessive
addition of Hydro wax might soften NBR film. Hydro wax 215 is designed to be added
directly to latex compounds. Usage levels are generally 1.0 - 5.0 parts based on the dry
weight of the latex. There are no volatile organic compounds in Hydro wax 215.
2.9 Pigment Blue- Flexi verse BCD 9907
Flexi verse BCD 9907 (Trade name) is a synthetic organic pigment and is complied with
OSHA hazard communication standard 29 CFR 19 10.100. Traces of heavy metal ions
such as antimony, arsenic, cadmium, lead and chromium content are lesser than to 25 ppm.
It is free from azo dyes (R-NN-R) as per European regulations established on 2003.
TSC is around 43% and pH is around 7.5. High heat ageing properties are exist and can
withstand for 200 °C.This a customize color (develops for specific buyers) and is well
dispersible in XNBR emulsion.
2.10 Calcium Carbonate Filler
Mainly there are two types of calcium carbonate as ground calcium carbonate (GCC)
and precipitated calcium carbonate (PCC).Two different processes are used to
manufacture GCC.
14
Dry process - \Vhete series of crushing and milling stages are taken place and size of
the standard output product is around 5 micron.
Wet process- initial stages of processing is similar to dry process. Then it is subjected to
removing of silica and carbonaceous matter. Purified CaCO3 is then filtered and dried,
followed by series of milling operations to adjust required particle size somewhere
around 3 micron. [04]
Precipitated CaCO3 is produced through calcination (heating) process and under which
calcium carbonate contained material is heated up to 900 °C and decomposes to give
Finally it is
CaO and CO2 Produced time is then reacted with H2 0 and results Ca (OH) 2
carbonated to produce PCC. Particle size is less than 0.7 micron. Dispersed calcium
carbonate in water, was used for entire experiment. This was to improve its
compatibility with polymer matrix. Smaller particle size will also increase number of
contact surfaces with NBR latex particle and it may leads to possible reinforcement or
higher loading capacities without losing XNBR compound softness.
Since calcium carbonate is in dispersed form with water that improves compatibility not
only with latex but also with other materials such as sulphur, waxes and accelerators
while it is being mixed with nitrile compound. Reduced particle size will also minimize
the settling tendencies during storage andcompound
copond maturation period.
Another significant aspect that decides calcium carbonate is useful filler for XNBR is
that, it does not interrupt NBR chemical structure and anionic stabilization even at
higher loadings. Hydrophilic nano scale calcium carbonate improves most of desired
properties oINBR vulcanized film such as tensile strength and tear properties [03, 04]
"IMERYS" is the global leader in manufacturing of calcium carbonate in slurry form

under the trade names of "Carbital", "lmercarb". and "filrnlink". Carbital 300 grade is
widely used in nitrile disposable glove application around the globe.
"Lanka minerals and chemicals Pvt ltd" (LMC) produces 'Disper C703' and Disper
C705' calcium carbonate dispersions for Sri Lankan latex industry in wet processing
with the use of high bright & pure Calcite. which are also free from transition metal ions
that can cause defects especially in white colored products. Table 2.3 shows properties
of two different grades of calc i urn carbonate.
15
Table 2.3 Comparison of properties of calcium carbonate grades
PARAMETER C703 C705
pH Value 9+1-1.0 9+/-l.0
Density 1.8-1.85 1.86-1.92
Part. Size less than 2 micron 90%+I-3% 90%+/-3%
Residue on 45 mic. Sieve 0.002% 0,002%
TSC 71+/-1% 72-75%
Viscosity. cps 100-200 300-500
Calcium carbonate 98.5% 98.5%
Magnesium carbonate 1 .5% 1 .5%
(MgCO3)
C703 was identified as the most appropriate grade of calcium carbonate filler and it was
used throughout the research work by taking consideration of its low density and
viscosity that leads to far better compatibility over other grade.
2.11 Clay Minerals
Clay minerals are hydrous alurninosilicates. Clay minerals are used to add with natural
and synthetic latexes to enhance their properties and to get cost benefit. Their smaller
particle size, higher aspect ratio and proper adhesion with polymer chain make them
correct choice to be blended with polymers. There are four types as explained below.
Kaolinite group: This group includes kaolinite, dickite, nacrite and halloysite. They are
formed by the decomposition of orthoclase feldspar. Kaolin is the main constituent of
china clay. Kaolinite clays are 1:1 phylosilicates.
Illite group: Hydrous silica, phengite, calodonite, micas, brammalite and gluconite are
the main constituents of the group. These materials result in decomposition of micas and
feldspars and largely find in marine clays and shales.
16
Smectite group: Members of this group are montmorillonite, bentonite, nontronite,
liectorite, saphonite and saiicconite. Particular clays are formed by weathering or
hydrothermal altercation of volcanic ash or rnatc rich in Ca and Mg. Smectite clays are
2:1 phylosilicates and those are expansible when it's come to contact with water.
Veniiculite group: These are trioctahedral minerals with interlayer Magnesium and 2
layers of H2 0. They are expandable by heating and exfoliation is taken place when
sufficient heat is applied and those clays are formed by altercation of biotite and chlorite.
[18]
2.11.1 Kaolin Filler
Kaolin consists of alternating sheet of tetrahedral silica units and octahedral alumina
units. Combination of such sheets forms physical entities called 'layers". Those layers
are stacked together with strong hydrogen bonds. Kaolin clay does not absorb water and
does not expand when irs come to contact with water. Also it becomes white when it is
fired. These properties have made it preferred material for latex and ceramic industry.
[01, 17]
There are two types of clay depend upon their particle size. Clay which is having finer
particle size in between 250 - 500 rim is called as "Hard clay" and comparatively larger
particle size between 1000-2000 nm is called as "Soft clay". Hard clay shows better
reinforcing properties and whereas soft clay possess higher load ability. Table 2.4 shows
properties of three different grades of kaolin.
Table 2.4 Property comparison of kaolin grades
HIMAFINE SUPERLUTRE BCKIP

PARAMETER
Brightness 93+1-0.5 90.0 87.0
Yellowness 2+/-0.5 4+1-I .0 4+1-1.0
2< micron w/w% min 90 100 80
+500w/w%Max 0.15 0.01 0.01
Moisture wlw% Max 0.5 1.5 1.5
Bulk Density 0.4-0.50 0.2-0.24 0.2-0.24
Si02 %/Al203% 52/46 45/38 45/38
17
Kaolin clay is a platy aluminosilicates. Himatine, superlustre and BCK/P are ultrafine
grade calcined clay kaolin derived from specially selected kaolin and manufactured by a
multistage refining and calcining process. Superlutre was used in this trial series and
deciding factor was particle size and bulk density. All particles in superlutre are less
than two microns. This is very important when high amounts of fillers are loaded, as it
leads to formation of defects free. glossy film due to smaller particles. As usual slurry
form is preferred with XNBR latex. Total solid content of the used slurry was 50%.
2.12 Montmorillonite
Bentonite is a clay mineral of the smectite group and is composed mainly

ofmontmorillonite (MMT). The smectites are a group of minerals in 2:1 type
comprising montmorillonite. hectorite and saponite that swell as they absorb water or
organic molecules within the structural layers. They also have considerable cationic
exchange properties. Due to high hydrophilicity of the clay water molecules are usually
present between layers. Layers are heLd together by Vaii der waals" forces.
Hydrophobic Modification- Cations residing between layers are exchangeable by the

use of quaternary ammonium ions. This process converts hydrophilic nature of the
surface to hydrophobic one enabling higher compatibility of nano clay into polymer
matrix. [11]
intercalation - This is a physical process by which polymer molecules are inserted in to

the clay gallery.
Exfoliation - It is a delamiiiating process by which gallery is expanded from Inni scale

to 20 nm or more results in Nano clay dispersion with in the polymer matrix. (Fig 2.3)
Montmorillonite is structured with silica (SiO4) tetrahedron and alumina (A106)

octahedron sheets as shown below. (Fig 2.2)
L, HOn ç, dOin
SI
€,=0
(=OH
(=Al
ç=M (Na',Co',Mg.)
n= I, 2, ...,
(. d.0)n , lHOn
Figure 2.2 Structure of rnontmorillonite
I I
I ' Nano meter scale

I- I
__ Gall cry
Layered structure with gallery Intercalation with polymer
Exfoliation through galLery expansion
Figure 2.3 Exfoliation and intercalation
Montmorillonite ( Dellite 43 B) received from 'Laaviosa Chemica Mineraria - Italy

was used in this experiment in dry powder form and this was to avoid any kind of
19
possible structural changes that might cause whilst pearl milling or Ball milling. Its
"swelling behavior" when it comes to contact with water make restrictions on further
processing as well
ViscoGel S4, ViscoGel S7 and Dellite 43B are three different MMT clays made out of
bentonite by reacting with ammonium salts.
ViscoGel S4
Chemical name: DihydrogenatedtallowdirnethylammoniUm salt with bentonite
Specific gravity: 0.45-0.5 5 g/ml
ViscoGel S7
Chemical name: BenzylhydrogenatedtallowdimethYlammofliUm salts with bentonite.
Specific gravity: 0,45 -0.55 g/ml
I Dellite 43B
Chemical name: Dimethylbenzylhydrogenated tallow ammonium salt with bentonite
From those three samples 'Dellite 43 B" was selected for the experiment as it has been
well purified to remove all heavier particles through screening, sedimentation and
centrifugation processes remaining only montmori I lonite platelets. Properties of "Dellite
43 B" are given below.
Table 2.5 Properties of Dellite 43B
Property unit Reading
Colour Off white
Moisture [%J 3 (max)
SG [g/cnY] 1.6
Bulk density [g/cm3 ] 0.40
Particle Size micron 7-9

(dry)
20
Extensive studies have been done on fillers and its incorporation to natural latex but it
was limited as far as concern synthetic latexes such as XNBR and SBR. Z.N. Am,
A.R,Azura have compared physical properties of NBR latex filled with CaCO3. mica,
silica and C-Black but never discussed about defects that can be caused by the fillers on
NBR film , which is having comparatively smaller size of particles than natural latex.
The impact that can be implied by filler combinations have not been discussed
extensively, especially when it comes to nano and conventional fillers together. Also
reinforcing fillers like C-Black and Silica cannot be used at all the time with latex
articles. C- Black cannot be used with colored and white products. Silica, since it
possesses abrasive nature restrictions have been made to curtail its usage with personal
protective equipment (PPE) such as Gloves and Aprons.
When natural or synthetic latex films are being supported by a fabric, it shows different
film properties to that of pure latex films. In other words disposable and supported
glove films show different mechanical properties. Tensile strength, elongation at break
and breaking strength are important properties as far as concern disposables whereas
abrasion, cut, tear, puncture resistance and adhesion between rubbers with fabric are
important aspects for industrial supported gloves. That means ingredients in a
formulation including fillers have different impacts on these two different films.
Calcium carbonate is largely used in disposable glove industry as cost reduction filler;
however it does not mean that it does not possess reinforcing influence on thick films if
smaller particle size is chosen. These influences are need to be monitored and discus
under selected fillers.
Impacts, those can be created by MMT on other fillers and films when all of them in a
same medium, need to be monitored. Especially on mechanical properties in defect free
environment and kind of defects which could be surfaced during the compounding
process and maturation period. That is something has not been discussed extensively
and deeply through research journals.
21
CHAPTER 03
MATERIALS AND METHODS
3.1 Glove Formulations
Existing glove formulation, which is used to produce XNBR industrial nitrile glove is
given below. Constituents and dosages are mentioned along with their functionality.
Zinc oxide, sulphur and ZDBC are in dispersion form in water. XNBR and hydro wax
are emulsions. More importantly there is no any filler in existing formulation.
Table 3,1 Existing standard glove formulation
Ingredients phr Function Chemical Name
45% NBR latex Carboxylated acrylonitrile

(Synthonier 6322) 100 Base material
hutadiene latex
25% Ammonia p1-I adjuster. Ammonia

0.2
Stabilizer
40% SABS 0.23 Anionic surfactant Linear alkyl benzene sulphonate
Vulcanizing agent.
Zinc oxide
60% Zinc oxide 2.2 Activator
60% Sulphur 0.7 Vulcanizing agent Sulfur
0.65 Accelerator Zinc dihutyl dithiocarbarnate

50% ZDBC
Solid saturated
Anti-lack hydrocarbons.(MC and paraffin
45% 1-lydro wax 0.9 agent/Anti-ozonant waxes)
43% Pigment
Blue blend
Blue 1.5 Colorant
Methyl hydroxyl propyl cellulose

10% Culminal 0.06 Viscosity modifier
22
Experimented lormLrlation with the incorporation of tillers for the research project is
given below with constituents and dosages (Table 3.2). Calcium carbonate and kaolin
were converted in to dispersion to increase surface area for better compatibility and
interaction. Calcium carbonate dispersion contains 70 dry parts of CaCO3 with 30 parts
of water. Likewise kaolin to water ratio is 50:50. Filler dosages were changed for each
experiment keeping others constant.
Table 3.2 Formulation used for experiments
phr
Ingredients
45%NBR Latex 100

(Synthomer 6322)
25% Ammonia 0.2
40% SABS 0.23
60% Zinc oxide 2.2
60% Sulphur 0.7
50% ZDBC 0.65
45% Hydro wax 0.9
43% Pigment blue 1 .5
1 0% Methylcellulose 0.06
70% Calcium carbonate filler 5 to 25
50% Kaolin filler 5 to 25
Montmorillonite filler 0 to 2
3.2 Filler Matrix
Table 3.3 shows that possible filler dosages to be tested with nitrile glove formulation.
As the primary step, standard formulation is to be incorporated with fillers individually,
and then with combinations by considering outcome of first step. Combining of all three
tillers will be based on outcomes of primary and secondary steps. Calcium carbonate
and kaolin are to be changed by 5 parts at a time while MMT by 0.25 parts at initial and
then 0.5 parts by considering it cost, functionality and compatibility issues.
23
Table 3.3 Filler and filler combinations to be tested
First step-Individual filler dosages
Filler Added amount (phr)
CaCO3 5 10 15 20 25 -
kaolin 5 10 15 20 25 -
MMT 0.25 0.5 1.0 1.5 2.0 -
Second step - Conibined filler dosages - Two fillers
Combinations Added amount (phr)

CaCO3 & Kaolin 5 5 5 5 5
kaolin (I) CaC01 5 10 15 20 25
CaCO3 & Kaolin 10 JO 10 10 10
kaolin (II) CaCO3 5 10 15 20 25
CaCO3 & Kaolin 15 15 15 15 15
kaolin (III) CaCO3 5 10 15 20 25
CaCO3 & Kaolin 20 20 20 20 20
kaolin (IV) CaCO 5 10 IS 20 25
CaCO3 & Kaolin 25 25 25 25 25
kaolin (V) CaCO3 5 10 15 20 25
CaCO3 & CaCO3 5 10 15 20 25
MMT (I) MMT 0.5 0.5 0.5 0.5 0.5
CaCO3 & CaCO3 5 10 15 20 25
MMT(ll) MMT I I I I
CaCO3 & CaCO3 5 10 15 20 25
MMT (III) MMT 1.5 -
1 .5 1.5 1.5 1.5
CaCO3 & CaCO3 5 10 IS 20 25
MMT(IV) MMT 2 2 2 2 2
kaolin& Kaolin 5 10 15 20 25
MMT (I) MMT 0.5 0.5 0.5 0.5 0.5
MMT(1l) MMT I I I I
24
MMT (III) MMT ' 1.5 1.5 1.5 1.5 1.5
MMT(IV) MMT 2 2 2 2 2
Third step - Combined filler dosages -Three Fillers

Combination Added amount (Phr)
CaCO3 CaCO3 5 10 15 20 25
kaolin & kaolin 5 5 5 5 5

MMT (1) MMT 0.5 0.5 0.5 0.5 0.5
CaCO3 , CaCO3 5 10 IS 20 25
MMT(1I) MMT 1 1 1 1 1
CaCO3 , CaCO3 5 10 15 20 25
MMT(11l) MMT 1.5 1.5 1.5 1.5 1.5
CaCO3 , CaCO3 5 10 15 20 25
kaolin& kaolin 10 10 10 10 10
MMT (IV) MMT 0.5 0.5 0.5 0,5 0.5
CaCO3 , CaCO3 5 10 15 20 25
MMT(V) MMT I 1 1 1 1
CaCO3 , CaCO3 5 10 15 20 25
MMT (VI) MMT 1.5 1.5 1.5 1.5 1.5
3.3 Preparation of Blank Compound
Chemicals were added as per the sequence shown below. None of three fillers are
included in the blank glove lormulation.
12 kg of XNI3R latex was weighed to a elean container and added 43.2g of 25%
Ammonia as pH adjuster. Latex was allowed to mix for 10 mm. Then anionic surfactant
SABS was added. Mixture was allowed to withstand for approximately 15 minutes with
gentle agitation. Whilst slow agitation was taking place small amount of Freesil (Silicon
25
free Anti foam) was sprayed on to the compound to avoid formation of bubbles.
Then 60% Zinc oxide, 60% Sulphur and 50% ZDBC (accelerator) dispersions were
measured in to a one container and mixed well. Mixture was then added to the latex
while compound was being agitated It was mixed for 20 minutes. Slow agitation was
result in less bubble formation. Since it was the blank compound with no fillers, fillers
were not added in this stage. Then 43% l88g of blue pigment was added. Kept the
compound for 15 minutes to mix it well and then 45 grams of 45% Hydro wax was
added. Whole compound was then allowed to mix about an hour. Then it was filtered
and kept for 24 hours for maturation. Though there is no real term of maturation for
XNBR latex compounds it is highly recommended to keep it for 24 or 48 hours for
homogenization and dc-aeration.
Added amount of chemicals to make blank compound are given below with sequence.
Table 3.4 Blank compound formulation
Sequence Ingredients phr Amount Added (kg)
45% NBR latex 100 12.000
2 25% Ammonia 0.2 0.0432
3 40% SABS 0.23 0.03105
4 60% Zinc oxide 2.2 0.198
5 60% Sulphur 0.7 0.063
6 50% ZDBC 0.65 0.0702
7 43% Pigment Blue 1.5 0.188
8 45% Hydrowax 0.9 0.108
9 10% Methvlcellulose 0.06 0.0324
After the period of maturation. lSC and p1-1 were checked and recorded. pH and TSC
maintained at 8.7-9.0 & 45+1-1 respectively. Then viscosity of the prepared compound
was increased and this step was taken to avoid compound penetration during dipping
and to get sufficient thick XNBR llm deposit on the shell. Methyl cellulose derivatives
were used as the thickening agent which is called Culminal M1-IPC 50. It was slowly
26
added until viscosity of the compound reach 6000 cps. To measure the viscosity
Brookfield viscorneter was used (Model RVT). Speed of the viscometer was set to 5
rpm and spindle # 2 was used.
3.4 Preparation of dipped gloves
Twenty Four number of Hycron" fiber lormers were obtained and dressed with fleece
cotton liners. Then they were manually dipped in the compound and kept for draining
for 3 minutes. Then they were dipped in calcium nitrate {Ca(NO3)2} coagulant and hot
water dip (45-50 °C) was followed for leaching. All dipped gloves were kept for an hour
under an industrial fan for air drying. Then gloves were dried and cured in an oven for
20 minutes at 70 degrease of centigrade, then at 90 degrees for 20 minutes. Third curing
condition was at 110 degrees for 20 minutes and finally at 140 degrees for 20 minutes.
Once the time was elapsed Gloves were taken out froni the oven and stripped off from
the former. Thn pair of gloves was used for testing and rests were kept for future
reference. After 24 hours of conditioning period (Humidity 64+/- 5% and temperature
22+/-2 C) abrasion resistance, tear resistance, puncture resistance, stiffness, and cut
resistance were tested.
When dipping was taking place special precaution was made to avoid bubble formation.
Otherwise subsequent dip might get touch with foamed bubbles resulting pin holes or
blow holes on the glove and those would not useful for testing.
Compounds were slowly mixed after each dip to have fresh surface for next dip and that
improved uniformity of the thickness on the glove and among the glove as well.
Though XNBR latex does not has protein, hot water leaching was carried oLLt to wash
off excess surfactant and unreacted Ca (NO)2 If those things are present, it gives bad
ordour and stickiness to the glove later stage in the process. Since wet gel strength of
the XNBR latex is comparatively lower than the natural latex, washing tank temperature
was maintained around 45-50 C. Excessively high temperatures accelerates crack
formation on XNBR. Time. Temperature, Turbulence and Avoid Turbidity (4T) are
important factors in leaching.
3.4.1 Main Steps Involved in Blank Compound Dipping Operation.
Main steps that are involved in compound and finished glove production illustrated
below.
27
DRESSING LATEX
p
FORMER HEATING ADDITION OF
STABILIZERS
COMPOUND SPRAYING OF
DIPPING ANTIFOAMS
p ft
DRAINING I ADDITION OF
CURATIVE AGENTS
F"
p
COAGULANT ADDITION OF WAX
DIPPING AND PIGMENT
p p
COAG U LANT ADDITION OF
DRAINING THICKENER
L
WATER LEACHING ill
~= <~:= 4~:= COMPOUND
p
AIR DRYING
p
OVEN DRYING &
CUREING
p
STRIPPING
Figure 3.1 overall process illustration
28
Figure 3.2 Fiberglass Formers
Figure 3.3 Dressing a former
29
j
Figure 3.4 Dressed formers
-
V
Figure 3.5 Manual glove dipping step 01
30
Figure 3.6 Manual dipping step 02
Figure 3.7 Keeping for drain off
31
2<
N
Figure 3.8 Calcium Nitrate Coagulant Dipping
jj
Figure 3.9 Curing In Oven
32
Figure 3.10 Stripping
3.5 Preparation of Calcium Carbonate Incorporated Compounds
Compounds were prepared by following basic steps that involved in blank compound
preparation. Finally calcium carbonate incorporation was done in the range of 5phr to
25phr. Agitation was continued for another 1 hour after addition of the filler. Mixture
was then allowed to withstand for 24 hours of maturation period prior to filtering and
dipping. Calcium carbonate dispersion contains 70 parts of filler and 30 parts of water.
Table 3.5 Amount of 70% CaCO3 added
phr (parts per hundred Amount of 70% CaCO3

rubber added (g)
5 386
10 771
15 1157
20 1542
25 1928
33
12 pairs of gloves were made and content of filler of each compound was marked on the
cuff of the glove to avoid possible mix-up. Then they were tested for mechanical
properties, stiffness, thickness and GSM (grams per square meter) after conditioning.
3.6 Preparation of Kaolin Incorporated Compounds
Dipping procedure was same as above and obtained 12 pairs of gloves. Incorporated
filler content was marked on the cuff. Then they were tested for physical properties and
other tests as mentioned above after stipulated time of conditioning. Pre-prepared kaolin
dispersion contains 50 parts of filler and 50 parts of water.
Table 3.6 Amount of 50% kaolin added
Phr (Parts per hundred Amount of 50% kaolin

Rubber added (g)
5 540
10 1080
15 1620
20 2160
25 2700
3.7 Preparation of MMT Incorporated Compounds.
Here the only difference from the blank compound was that the incorporation of MMT.
It was in powder form unlike calcium carbonate dispersion and Kaolin dispersion; so
that deep agitation was required in order to enhance frequent contacts of MMT particles
with the XNBR polymer matrix. Table 3.7 shows loaded amount of MMT with each
compound. Filler was added under vigorous agitation as mentioned above (20 min at 100
rpm) and followed slow speed mixing (40 min at 10 rpm) at latter part of the operation
for the benefit of de-aeration and homogenization. Little amount of anti-foam was
sprayed to avoid bubble generation and to break bubbles which were already formed.
34
Table 3.7 Amount of MMT added
phr (Parts per hundred Amount of MMT added (g)

Rubber)
0.25 13.5
0.5 27.0
1.0 54.0
1.5 81.0
2.0 108.0
2.5 135.0
Experiments on Filler Combinations:
After incorporation of calcium carbonate (CaCO3), kaolin & montmorillonite (MMT)

separately, filler combinations were in place. Performances of each filler with nitrile
latex were taken into consideration when combinations were designed. That was to
eliminate combinations which would be given inferior mechanical properties at dipping
and testing.
3.8 Preparation of Kaolin & Calcium Carbonate Incorporated Compounds
Base compound preparation procedure was same as blank compound preparation. At the
final stage of the mixing, filler combinations were added and matured for 24 hours prior
to filtering and subsequent dipping. Time intervals between each addition was kept as
same as blank compound. Some combinations were omitted. Only optimum amount of
Kaolin was used. From previous trials it was identified that 5phr and lOphr of kaolin
samples were good with their physical properties and free from surface defects as well.
However full range of calcium carbonate was considered for the experiment since it
doesn't show much negative impact on mechanical properties in comparison to kaolin.
Five numbers of combinations were experimented as shown below (Table 3.8). Their
physical properties were measured and tested after keeping dipped gloves for 24 hours
35
of conditioning period.
Table 3.8 Kaolin & Calcium carbonate combinations
Compound 50% kaolin 70% CaCO3
phr Amount (g) phr Amount (g)
1 5 540 5 386
2 5 540 10 771
3 5 540 15 1157
4 5 540 20 1542
5 10 1080 5 386
3.9 Preparation of Kaolin & MMT Incorporated Compounds
This trial was also same as previous trials. The main difference was 0.5phr of MMT and
Kaolin (Sphr to 20phr) were added as filler combinations. Series of Kaolin amounts
were experimented with MMT, without pre-selection of optimum values that had been
observed during individual filler testing. But in the case of MMT, optimum value
(0.5phr) was used by considering its cost and finished glove mechanical properties.
As mentioned below six compounds were prepared with six combinations (Table 3.9).
After preparation of blank compound, kaolin was added and then it was followed by
MMT under vigorous mixing. Antifoarning agent was applied as usual to arrest bubble
formation and then it was filtered and kept for 24 hours of maturation period. Curing
time was extended for 20 parts and 25 parts of Kaolin from 20 minutes to 30 minutes at
90 °C and 110 °C temperatures.
36
Table 3,9 Kaolin & MMT combinations
Compound 50% kaolin MMT

1 5 540 0.5 27
2 10 1080 0.5 27
3 15 1620 0.5 27
4 20 2160 0.5 27
5 25 2700 0.5 27
6 5 540 1.0 54
3.10 Preparation of Calcium Carbonate & MMT Incorporated compounds
Basic steps were same as previous trials. The only difference was 0.5 parts of MMT and
calcium carbonate (Sphr to 25phr) were added as filler combinations. Firstly Calcium
Carbonate was filled and then it was followed by MMT under deep agitation. Gloves
were dipped, cured and finished under the same conditions as it was proceed for control
sample. Mechanical properties were tested after conditioning of gloves as usual.
Table 3.10 Calcium carbonate & MMT combinations
Compound 70% CaCO3 MMT

1 5 386 0.5 27
2 10 771 0.5 27
3 15 1157 0.5 27
4 20 1542 0.5 27
5 25 1928 0.5 27
3.11 Preparation of Calcium Carbonate, Kaolin & MMT Incorporated

Compounds.
This trial was carried out with three types of fillers together. Calcium carbonate &
kaolin were added respectively and MMT was filled afterwards under turbulent
37
agitation. Both Calcium carbonate and kaolin were in slurry form whilst
montmorillonite was in dusty powder form.
Five combinations (Table 3.11) were prepared with all three fillers changing CaCO3
content from 5phr to 25phr while keeping other two fillers at constants levels. Optimum
values of MMT and kaolin were used which were identified by their preliminary trials.
This was done to see whether there is a synergistic effect when combine these three
together.
Table 3.11 Calcium carbonate, Kaolin & MMT combinations
Compound 70% CaCO3 50% Kaolin MMT
phr Amount (g) phr Amount (g) phr Amount (g)

5 386 5 540 0.5 27
2 10 771 5 540 0.5 27
3 15 1157 5 540 0.5 27
4 20 1542 5 540 0.5 27
5 25 1928 5 540 0.5 27
3.12 Calculations
Procedure that was followed to calculate amount of filler should be added to the
compound is given below. How Sphr of filler converts in to weight parameters is taken
as an example.
Rubber content in 12kg of 45% NBR latex = 12 x 45/100
= 5.4 Kg
Calcium carbonate required = 5.4 x 5/100 xl000
270g
70% Calcium carbonate to be added =270 x 100/70
=386g
= 5.4 Kg
38
Kaolin required =5.4 x 5/100 x 1000
270g
50% Kaolin to be added = 270 x 100/50
= 540 g
= 5.4 Kg
MMT to be added 5.4 x 0.5/100 x 1000
27g
3.13 Testing
Basically 5 main tests were carried out for each and every trial and results were
recorded. They are,
Abrasion resistance
Puncture resistance
Tear resistance
Cut resistance
Stiffness
Thickness and GSM of every test piece were measured irrespective of test to be
performed and it was always kept between 1.3 +/- 0.1mm and 695 +/- 25 g/m2
respectively to minimize impact on the mechanical properties to be tested, under EN
standard, Four test pieces were tested each and every time for abrasion, puncture, tear
and cut resistance.
Gloves were inspected for possible defects such as pinholes, cracks, blisters, foreign
particles, coagulum, web holes, over cure, heavy fingertips and penetration (Appendix ii)
prior to mechanical tests and were recorded.
General permissible level of rejection rate is 0.5%. Anything beyond 1% is considered
39
as production process is out of control" and attention must be paid. In that scenario all
12 pairs made out of each compound must be in acceptable range other than machine,
man and fabric related issues. Out of three categories, critical, major and minor; critical
defects are considered as something that is harmful to wearer and minor defects are
basically considered as cosmetic issues.
3.13.1 Martindale Abrasion Resistance Tester
Model M235 abrasion and pilling tester shown below is used to determine the abrasion
and pilling resistance of all kinds of textile structures. Samples are rubbed against
abradants at low pressure and the amount of pilling or abrasion is compared against
standard parameters.
Figure 3.11 Martindale abrasion resistance tester
Amount of abrasion was inspected at every interval such as after 100, 500, 2000 and
8000 cycles respectively. From there on words it was inspected at every 500 cycles up
to 20000.
Figure 3.12 Abraded test pieces
40
3.13.2 Universal Extension Tester (For Puncture & Tear resistance)
Universal extension tester is used to check tear and puncture properties of finished
gloves.
Figure 3.13 Universal Extension tester
Table 3.12 is shown operational parameters of the tester has been set to check industrial
gloves. However clamping jaws must be changed for puncture and tear test as
introduced.
Table 3.12 Features of universal extension tester
del H5KS
Test speed 0.001-1 000mm/mm (0.001-40 in/mm)
Jog speed 0.001 - 1000mm/mm
Return speed 0.001 - 1500mm/mm
Test area: vertical 750 mm
Test area: Horizontal unlimited
Test area: Depth 100 mm
41
Figure 3.14 Tear resistance test is performed
7M
-IL :.,___
Figure 3.15 Puncture resistance test is performed
3.13.3 Circular Blade Cut Resistance Tester
Prior to test is to be performed it is advisable to check blade's sharpness at all the time.
Control fabric provided must be checked alternatively with the coated fabric to be tested
to have more reliable readings.
When preparing test pieces for cut resistance test, out of a pair one piece was cut
diagonally to palm and other one was opposite to that. Likewise two pairs were tested
and average per pair was shown. ( X )
42
Figure 3.16 Blade cut resistance tester
L—,
im
Figure 3.17 Cut resistance test is performed.
3.13.4 Clark Stiffness Tester.
Clark stiffness is not a test coming under EN 388 standard and is done to have an idea
of flexibility of coated product.
zwr-
Figure 3.18 Clark stiffness tester
43
CHAPTER 04
RESULTS AND DISSCUSSION
4.1 Calcium Carbonate Filler Incorporated Test Results
Table 4.1 is shown mechanical properties test results obtained for different level of filler
loading. It was changed by 5 parts for each trial and an extra experiment was done for
18 parts of filler to have more precise reading between 15 and 20 parts.
Table 4.1 Calcium carbonate incorporated sample test results.
Blank
Property (control) Sphr lophr 15phr 20phr 25phr 18phr
12000 12000 15000 20000 20000 8000 20000
Abrasion 12500 13000 18500 20000 16000 12000 20000
resistance 11500 12500 13000 20000 15000 11000 20000
(Cycles) 13000 14000 17000 20000 15000 11000 20000
Average 12250 12875 15875 20000 16500 10500 20000
Cut resistance 2.61 2.70 2.87 2.85 2.67 2.63 2.73
(Index) 2.58 2.50 2.73 2.57 2.60 2.71 2.67
Average 2.60 2.60 2.80 2.71 2.64 2.67 2.70
27.05 26.96 29.5 26.60 28.16 29.52 26.04
25.98 21.08 34.48 28.72 25.24 28.40 26.76
Tear resistance 26.55 29.44 25.04 26.32 30.60 28.72 34.72
(N) 26.34 28.32 22.4 32.04 28.48 25.76 29.89
Average 26.48 26.45 27.86 28.42 28.12 28.10 29.35
25.65 60.30 44.50 45.5 54.45 44.30 47,50

Puncture 46.45 54.20 43.85 50.20 41.20 49.80
37.65
28.62 41.80 46.70 61.20 51.70 40.25 54.10

resistance (N)
31.62 46.70 63.50 45.40 49.20 47.20 52.10
Average 30.88 48.81 52.23 45.64 51.39 43.24 50.88
Avg. stiffness 7.05 7.12 7.13 7.32 7.43 7.54 7.48
-(cm)
Note: Thickness and the GSM of the gloves were maintained between 1.3+1- 0.1mm and
695±/-25 g/m2 respectively.
44
4.1.lAbrasion Resistance of Calcium Carbonate Filled Samples.
Figure 4.1 shows abrasion resistance performance of calcium carbonate incorporated

samples. Brown line clearly denotes the minimum standard level of abrasion resistance
(8000 cycles) need to be full filled by an industrial glove. Naturally, in practice
manufactures are eager to get abrasion cycles more than the minimum to meet exceed
customer expectations". In general an industrial glove without any filler loading shows
abrasion level around 12000 cycles. Black line indicates the abrasion level for blank
(Control) formulation and it is 12250 cycles.
Average Abrasion resistance vs CaCO3 content
ci
V
- 25000
20000
C
15000
cc
0
5 10 15 20 25
CaCO3 Content (phr)
——Avgaiones11nce - standard -- Control
Figure 4.1 Abrasion resistance of calcium carbonate filled samples
According to the results illustrated above, it is obvious that Sphr, lOphr, and 15phr,
20phr calcium carbonate samples have shown very much higher abrasion cycles than
8000 and even above 12250 cycles. Among them 15 and 20phr CaCO3 incorporated
samples have possessed higher abrasion resistance in comparison to other loadings. But
25phr CaCO3 sample has shown somewhat lower abrasion resistance.
In addition, as per the observations made on 20phr and 25phr calcium carbonate filled
samples were found with tiny cracks on the surface of the glove film and it was led to
low abrasion resistance. Small coagulated particles were also observed in the compound.
When abrasion resistance and amount of filler loaded is considered, it can be noted that
I 5phr & 20phr calcium carbonate samples have shown best abrasion resistance out of
the lot. To get more precise reading, series of samples from l5phr to 20phr were
prepared and l8phr CaCO3 sample topped up with the indication of optimum interaction
between filler and polymer matrix. It is denoted by a triangle in the graph.
4.1.2 Blade Cut Resistance of Calcium Carbonate Filled Samples
Figure 4.2 shows that how blade cut resistance properties were behave with filler
loadings. Brown line denotes minimum standard requirement of blade cut resistance of
an industrial glove and black line indicates existing performance or performance of the
control sample. So it was obvious that all loading amounts of CaCO3 have a positive
impact on blade cut resistance, though it was declining aller 10 parts. Polymer to filler
interaction and bonding between polymer matrix and cotton fibers has reinforced the
entire structure to give improved cut properties. Cut resistance of 18 parts of filler
loading also indicated by a triangle in the graph.
When produce a glove with very high cut properties, it is required to look for yarn or
thread that possesses high tensile and cut properties. Dyneema, glass fibre and metallic
threads are few examples.
Average Cut resistance vs CaCO3 Content
-' 2.85
l8phr, 2.60
° 2 70
2:65
2.60
2.55
7
2.50 --------- -
2.45
2.40
2.35
5 10 15 20 25
CaCO3 Content (phr) -—Cut Avg. - Stondara Control
Figure 4.2 Graph of blade cut resistance of calcium carbonate filled samples
4.1.3 Tear Resistance of Calcium Carbonate Filled samples
Tear resistance was in inclined trend with the addition of filler up to 1 8phr and then it
was decreased at higher loadings. As explained above interaction between polymer and
filler, in addition to reinforcement which was created by cotton fibre has resulted in
improved tear resistance properties as shown in figure 4.3.
46
Avg. Tear resistance vs CaCO3 content
30.00 18phf 29.35
29.00
26.00
25.00 --- --
24.00
23.00
22.00
5 10 15
CaCO3 Content (phr)

20
——Avg. Tear Resi5tance - 25
Standard - Control
Figure 4.3 Graph of tear resistance of calcium carbonate filled samples
4.1.4 Puncture Resistance of Calcium Carbonate Filled Samples
As Graph displays below, filled compounds have a positive impact towards puncture
resistance due to interaction between filler and polymer compare to control sample.
Property has reached its maximum at 20phr and no significant change was observed
with further addition. However it was also observed that there was no significant change
on puncture from 5phr to 20phr other than impact made on cost with increased amount
of filler.
Average Puncture resistance vs CaCO3 content
55.00
45.00
!U, 40.00
35.00
30.00 ------
25.00
e. 20.00 ----
15.00
10.00
5 10 15 20 25
CaCO3 content (phr) + &vg pmcture - stsxaara - - Control
Figure 4.4 Graph of puncture resistance of calcium carbonate filled samples
4.1.5 Stiffness of Calcium Carbonate Filled Samples
A brown line denotes lower limit and upper control limit of stifuiess needs to be
47
possessed by an industrial glove. So that stiffness readings of the gloves which are made
out of filled XNBR must be laid between 7.00 and 9.00 cm. However it is preferred to
have between 7.5 -8.0 cm as it gives comfort to wearer with sufficient rigidity and
dexterity.
Clark Stiffness vs CaCO3 content
9.50
9.00 - --- ---- -- ---- uct.
8.50
8.00
7.50
7.00 - -
r
LL
6.50 I
5 10 15 20 25
CO3 Content (p) -4-Stiffxess -- Coitro1
Figure 4.5 Graph of Stiffness of Calcium carbonate filled Samples
According to the results shown above, stiffness was good for all calcium carbonate
samples including 25phr loading level. Therefore it can be concluded that there was no
significant negative impact on stiffness by calcium carbonate, other than slight positive
outcome at higher levels. Since Clark stiffness test is a manual operation, operators must
be trained to handle it correctly otherwise reading would be different and less reliable.
4.2 Kaolin Filler Incorporated Sample Test Results
Test results of Kaolin and XNBR blended samples are given below in table 4.2.
Table 4.2 Kaolin Filler Incorporated sample test results.
Property Blank(Control) Sphr lophr 15phr 20phr
12000 15500 16000 16000 14000
Abrasion resistance 12500 16000 17000 15000 13000
11500 17500 20000 13000 13500
(Cycles) 13000 17000 19000 14000 11000
Average 12250 16500 18000 14500 12875
Cut resistance 2.61 2.52 2.67 2.31 2.34
(Index) 2.58 2.60 2.73 2.77 2.56
Average 2.595 2.56 2.70 2.54 2.45
27.05 37.90 37.84 39.6 30.16
25.98 37.00 37.48 36.44 33.48

Tear resistance
26.55 44.10 39.60 34.67 35.70
(N) 26.34 33.60 38.40 28.12 31.44
Average 26.48 38.15 38.33 34.71 32.70
25.65 25.84 60.60 38.30 28.60
37.65 29.92 60.80 29.60 24.10

Puncture resistance
28.62 29.80 51.10 40.30 26.30
(N)
31.62 33.62 50.80 39.30 27.40
Average 30.88 29.80 55.82 36.88 26.60
Avg stiffness
7.05 7.10 7.12 7.32 7.52
(cm)
Note: Thickness and the GSM of the gloves were maintained between 1.3+!- 0.1mm and
695+1-25 g/m2 respectively.
4.2.1 Abrasion Resistance of Kaolin Incorporated Samples
Figure 4.6 show that abrasion results of kaolin incorporated samples. According to the
results illustrated below it is obvious that abrasion resistance was in increasing trend in
first two combinations and then it was decreasing. lOphr of kaolin incorporated sample
49
has shown the best result.
Avg Abrasion resistance vs kaolin content
24000
18000
:::: T .
6000
kaolin content
(phr) --40--Avg abrasion resistance - Standard
- Control
Figure 4.6 Graph of abrasion resistance of kaolin incorporated samples
Only I Ophr kaolin loaded sample has reached up to the 18000 abrasion cycles. However
all loading levels from 5phr to 20phr have made a positive out comes due to interaction
between filler and polymer matrix.
The most significant and considerable observation with kaolin samples was that, in
parallel to the increase of kaolin content, cracks were increased dramatically. This
phenomenon was the major reason for abrasion resistance to drop. Industrial glove
should not contain even single crack on it and if present that would be categorized as a
reject or defective glove. Because cracks might propagate easily while handling material
with sharp edges and exposes wearer in to risk. So formation of cracks should be
avoided. According to the results and observations, samples which contained 20phr and
25phr kaolin contents were shown very high amount of cracks throughout the film.
Therefore it was difficult to make a glove incorporating 25 parts of kaolin and that led
to omitting it from sample making process and mechanical testing.
Curing time was another prime concern. In normal curing conditions 20phr and 25phr
kaolin sample couldn't be cured. Therefore curing time was extended to provide enough
time and temperature to evaporate moisture which was trapped inside the nitrile film.
Gloves were kept 30 minutes in oven at 90 degrees of centigrade instead of keeping it
20 minutes as planned. Third stage curing time was also increased from 20 minutes to
30 minutes at Ii 0 °C degrees. Since 20phr and 25phr requires more time to cure, it is
50
not suitable for cheapen the product. Because when curing time is increased, energy
being supplied for curing will also increases with time extension.
4.2.2 Cut Resistance of Kaolin Incorporated Samples
Referred to fig.4.7 brown line indicates standard level of cut resistance and blue line
indicates achieved levels against relevant kaolin loadings. Cut resistance was taken as
an average value to get best and non-biased reading. Four values were taken to get
average cut resistance value. (Average of two opposite direction in 90 degree angle)
According to the results lophr sample showed best cut resistance from all. From lOphr
to 20phr of it was decreasing. 20phr of filler incorporated sample has shown very poor
cut resistance and it was below to the standard as well. Drop in cut resistance at higher
dosages due to less bonding affinity between filler and XNBR latex and also formation
of cracks.
Average Cut resistance vs Kaolin Content
L. 75
2. 7
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
5 10 15 20
—$—Cut Avg. - Standard - Control
Kaolin Content (ptw)
Figure 4.7 Graph of cut resistance of kaolin incorporated samples
4.2.3 Tear Resistance of Kaolin Incorporated Samples
According to the graph drawn below (Fig 4.8) based on results of the experiment it is
clearly shown that achieved level of tear resistance of kaolin incorporated samples is
laid beyond the standard minimum level of tear resistance as per EN 388. Also it shows
that kaolin does not create a negative impact on standard minimum level of tear
resistance.
51
Average Tear resistance vs Kaolin Content
40
38
36
34
32
30
28
22
20
5 10 15 20
Kaolin Content (phr) --*—Tear Avg - St andard - - Cont rol
Figure 4.8 Graph of tear resistance of kaolin incorporated samples
However it was noted that, with the increment of kaolin filler has caused gradual
decrement of tear resistance of the glove. As abrasion and cut resistance, tear resistance
also showed good properties with 5phr and lOphr filler loading and which were beyond
the properties of control sample indicated by black line.
Tear properties are also depend on the fabric used. Tear resistance is a combined
outcome of polymer and the fabric and their bonding strength. If we use fabric with high
cut strength like keviar, dyneerna or glass fibre with nylon might result in imparts
properties. However in generally these fibers are far more expensive than cotton.
Polyesters are cheap but don't possess good mechanical properties when it comes to
contact with a polymer matrix.
4.2.4 Puncture Resistance of Kaolin Incorporated Samples
Standard minimum level of puncture resistance is denoted by red line and achieved
puncture resistance for different amount of filler loading is denoted by blue line.
According to the graph drawn based on experimental data, achieved levels of average
puncture resistance is always higher than the required level of EN 388 standard, level 2.
52
Average Puncture resistance vs Kaolin content
60
50
1:
0. 20 -
to
10
0
5 10 15 20
Kaolin content (pIn) —4-- Avg puncture - Stndai-d -- Control
Figure 4.9 Graph of puncture resistance of kaolin incorporated samples
There was a significant improvement of puncture resistance against kaolin filler content
up to 10 phr. There after downwards trend was observed from lOphr to 20phr. However
all samples possessed improved puncture resistance than the standard level and it
crossed the property belongs to control sample somewhere around 18 phr. As described
earlier crack formation have made an impact on puncture properties as well.
In general, conventional protective gloves provide puncture level I or 2. Polyurethane is

used as dipping or coating media with reinforced dyneema structured shells where high
puncture resistance is needed. Bullet proof clothing, butchers over coats and gloves are
few examples. Also finely grinded metal dust is used in high - tech glove applications to
have prominent puncture properties.
4.2.5 Stiffness of kaolin Incorporated Samples
Specified lower and upper stiffness levels that are to be maintained are denoted by
brown lines as shown in fig 4.10. According to the outcomes observed, it was obvious
that achieved level of stiffness almost there for all samples tested and it was increasing
parallel to added kaolin content.
53
Stiffness vs Kaoline content
10
- --tEL
6
5 10 15 20
Kao1ii (nix) --Stiffness --- Control
Figure 4.10 Graph of stiffness of kaolin incorporated samples
Table 4.3 is shown maximum properties which were able to achieve by incorporating
CaCO3 and Kaolin into the nitrile polymer matrix. CaCO3 blended samples have shown
highest abrasion properties than Kaolin, which is the most important property as far as
concern industrial nitrile gloves. (Also refer table 4.1 and 4.2)
Another concern with kaolin is that it needs more time to cure than calcium carbonate
when 20phr or 25phr amounts are added. Because of that third stage of curing time
(temp 110°C) was increased from 20 minutes to the 30 minutes. It was same with curing
stage 02 as well (temp 90 °C). For a commercial production, curing or vulcanizing
energy is provided by L.P. Gas, thermic fluid or by steam. Those are expensive energy
sources. Therefore by incorporation of high amount of kaolin doesn't help towards the
achievement of goal of this project since it consumes more energy.
As additional step 18 parts of Calcium carbonate loaded trial was done. It was marked
separately on graphs by a triangle (fig 4.1, 4.2, 4.3, 4.4). It was to find out behavior of
filler in between 15 and 20 parts. By considering all these factors including poor curing
properties and surface defects such as cracks it can be decided that calcium carbonate is
more preferable to blend with nitrile than kaolin as a filler.
54
Table 4.3 Comparison of properties of CaCO3 and kaolin glove samples
Property CaCO3 Kaolin
Max .reading Max. reading Max. reading

(l8phr) (lophr) (Sphr)
Abrasion 20000 18000 16500
(cycles)
Cut (index) 2.7 2.7 2.56
Tear(N) 29.35 3 8. 33) 38.15
Puncture (N) 50.88 55.825 29.795
Stiffness (cm) 7.48 7.52 7.1
4.3 MMT Filler Incorporated Sample Test Results
Achieved mechanical properties of MMT blended samples are given in table number 4.4.
Incoporation was done in small proportion considering its cost impact and poor
compatibility compare to other two selected fillers.
Table 4.4 MMT filler incorporated sample test results
Blank
Property
(Control) 0.25phr 0.5phr l.Ophr 1.5phr Zphr
12000 17000 20000 13000 14000 10000
12500 16000 20000 17000 13000 16000

Abrasion resistance
11500 18000 20000 17000 18000 13000
(Cycles)
13000 16000 20000 17000 15000 10000
Average 12250 16750 20000 16000 15000 12250
Cut resistance 2.61 2.95 2.53 2.81 2.65 2.34
(Index) 2.58 2.83 2.63 2.57 2.23 2.55
Average 2.60 2.89 2.58 2.69 2.44 2.445
27.05 57.90 52.84 39.60 21.16 18.32
Tear 25.98 47.10 47.48 36.44 28.48 16.32

resistance ( N ) 26.55 44,81 59.12 43.67 27.70 15.31
26.34 47.60 51.32 42.12 31.44 19.11
Average 26.48 49.35 52.69 40.46 27.20 17.26
55
25.65 55.84 52.60 45.80 32.10 21.52
37.65 49.92 51.80 40.92 33.27 15.84

Puncture resistance
28.62 59.80 51.05 54.18 28.03 18.25
(N) 25.80 19.89
31.62 43.62 5085 50.40
Average 30.88 52.30 51.58 47.82 29.80 18.88
Avg .stiffness (cm) 7.05 7.10 7.20 6.99 7.00 6.88
Note: Thickness and the GSM of the gloves were maintained between 1.3±!- 0.1mm and
4.3.1 Abrasion Resistance of MMT Incorporated Samples
According to the graph shown below, 0.5phr of MMT loaded sample has given highest
abrasion resistance and whereas 0.25phr has given comparatively higher value than the
rest. With the increase of MMT filler, abrasion properties have come down significantly.
Kind of 'gelation" was observed when preparing 1.0. 1.5 and 2phr MMT incorporated
samples. That was due to absorption of water by MMT particles which was in
surrounding of nitrile latex particles and ultimately it had led to destabilization of entire
compound. Because of that gloves made out of from particular compound were shown
micro cracks on their surfaces. Cracks lead to decrease in abrasion resistance.
Avg. Abrasion resistance vs MMT content

25000
I 1!
to
.15000
.....
10000
5000
. .. . . .....
015 0.5 0.75 1 1.25 1.5 1.75 2
MMT Content (phr)

+Avg.Abrasion resistance - Standard - - Control
Figure 4.11 Graph of abrasion resistance of MMT incorporated samples
4.3.2 Cut Resistance of MMT Filler Incorporated Samples.
Samples starting from 0.25 phr MMT to I .Ophr MMT showed cut resistance above the
56
standard and control sample performance levels. There after decreasing trend was
observed as shown in Fig 4.12. Inferior properties were shown at 1.5 and 2.0 parts of
MMT. Cracks fonTiation and settling of material were observed in those two levels and
that have been led for poor cut resistant properties.
Avg. Cut resistance vs M MT content
2.6
2.4
2.2
F-
0.25 05 0.75 1 125 1.5 1.75 2
MMT conteni (ph,) 0 Avg. cut resistance - Standard - - Control
Figure 4.12 Graph of cut resistance of MMT filler incorporated samples
4.3.3 Tear Resistance of MMT Incorporated Samples
Only 2phr of MMT incorporated sample showed inferior properties of tear resistance
against standard and control sample value. Up to 1.5 parts it was acceptable; however
from 0.5phr there was an almost straight line which showed declining trend in tear
values against amount of filler loading. (Figure 4.13)
Avg. Tear resisitance vs M MT content]

60
50
0.25 0.5 0.75 1 1.25 1.5 L75 2
MMT content (phr) 0 Avg. Tear resistance - Standard -- Control
Figure 4.13 Graph of tear resistance of MMT incorporated samples
57
Formations of micro cracks have created negative impact in losing the tear resistance of
the glove. Because when there is lot of cracks on the surface it is easy to tear through
the cracks being formed. A crack means that there is no proper interaction between filler
and polymer.
4.3.4 Puncture Resistance of MMT Incorporated Samples
According the graph shown below (fig 4.14) first three samples of the series was good
in puncture resistance. However still there was a drop of particular property with the
increase of MMT filler loadings. It seems to be formation of cracks due to
destabilization of latex and that has imposed negative impact on puncture resistance.
Thickness of a sample also has a huge impact on puncture resistance therefore when
choosing samples to test puncture resistance even thicknesses are need to be selected.
Puncture resistance vs MMT content
60
50
40
Ja
IL
20
10
0.25 0S 0.75 1 1.25 1-5 1.75 2
MMT content (phr)

Avg. Puncture resistance - Stndaard -- Control
Figure 4.14 Graph of puncture resistance of MMT incorporated samples
4.3.5 Stiffness of MMT Incorporated Samples
As shown below in fig 4.15, beyond 0.5phr filled level, stiffness of the glove was
inversely proportional to the filled MMT amount. Though the standard is 8+1-1 it is
advised to maintain lower margin of the specifications (i.e. in between 7and 8) because
it enhance flexibility and comfort usually demanded by the user. First four loading did
not show negative impact or considerable deviation from existing property.
58
Stiffness vs MMT content
9.5
- --------------------UCL
85
E
U
=
7.5
6.5
025 0.5 0.75 1 1.25 1.5 1.75 2
MMT content (phr) +stiffness Control
Figure 4.15 Graph of stiffness of MMT incorporated samples
4.4 Kaolin & Calcium Carbonate Filler Combinations Incorporated Samples Test
Results
After nitrile latex was blended with kaolin, calcium carbonate and MMT separately,
combination of those fillers ware tested to see possible positive outcomes. When
deciding combinations, optimum loading amounts and performances of fillers, which
were shown whilst those blending with nitrile separately, were taken in to consideration.
Especially fillers that were given inferior properties in both physical and cosmetic point
of view (surface defects) at higher loading, were subjected to such consideration. Kaolin
and MMT were given poor performances at higher ratios.
Kaolin and calcium carbonate collectively added sample test results are given below in
table 4.5. Five and ten parts of kaolin were selected to combine with CaCO3 and finally
with polymer matrix.
59
Table 4.5 Kaolin & calcium carbonate filler incorporated sample test results
Sphr CaCO3 + lophr CaCO3+ 15phr CaCO3+ 20phr CaCO3+ 5phr CaCO3 +
Property
Sphr kaolin 5phr Kaolin 5phr Kaolin 5phr kaolin lOphr Kaolin
13500 20000 20000 16000 9000

Abrasion
16500 20000 20000 18000 7000
resistance
15000 20000 18000 17000 7500
Cycles)
15000 19500 17500 16000 7500
Average 15000 19875 18000 16750 7750
Cut resist 2.97 2.97 2.99 2.01 1.94
(Index) 2.20 2.31 2.43 2.46 1.96
Average 2.58 2.64 2.71 2.24 1.95
28.90 25.14 31.60 22.16 19.85

Tear
26.00 27.48 27.44 22.48 19.50
resistance
30.15 37.65 27.67 22.70 18.75
(N)
30,55 32.35 32.12 26.44 18.00
Average 28.90 30.65 29.71 23.44 19.02
29.84 54.68 55.80 54.35 20.50

Puncture
27.92 60.72 60.83 57.55 18.85
resistance
29.83 69.15 59.20 59.14 19.00
(N)
33.62 60.75 58.47 52.76 20.00
Average 30.30 61.32 58.58 55.95 19.58
Av. Stiff (cm) 6.98 7.01 7.15 7.25 6.98
Note: Thickness and the GSM of the gloves were maintained between 1 .3+1- 0. 1mm and
695+/-25 g/m2 respectively.
4.4.1 Abrasion Resistance of Kaolin & CaCO3 Filler Combinations Incorporated

Samples
Incorporated total filler content was used to plot the graph shown in fig 4.16. Abrasion
îid
resistant has come to peak with 2 combination and performed up to 20000 cycles,
which contained 5 parts of Kaolin and 10 parts of CaCO3 indicating better interaction
between filler to filler and filler to polymer.
Average Abrasion resistance vs filler content
25000
20000
15000
10000
----------------------------
5000
.0
0
10 15 filiercontent(phr) 20 25
—*vg. brior. - - - Ctro1
Figure 4.16 Graph of abrasion resistance of kaolin & CaCO3 fillers incorporated
samples
As mentioned in table 4.5, 10 parts of Kaolin incorporation was also done along with
CaCO3 . But it showed poor abrasion properties with huge amount of surface defects
such as cracks, surface irregularities and coagulum due to poor interaction of filler to
filler at higher loadings. Because of that further trial on 10 parts of kaolin with the
combination of calcium carbonate was omitted.
4.4.2 Cut Resistance of Kaolin & Calcium Carbonate Filler Combinations

Incorporated Samples.
According to the results illustrated below (fig 4.17) 1 Sphr and 20phr filled sample has
shown better cut resistance properties over others. There after it showed period of
declining as a result of poor interaction between fillers and polymer. When considering
filler content incorporated and cut resistance property being improved, 15 parts of
CaCO3 and 5 parts of kaolin filled sample can be taken as the better combination since it
makes higher impact on cost reduction.
61
rage Cut resistance vs filler Content
10 15 20 25
Filler Content (phr) —+—Averae Cit F.esisiance - - Cotro1 - Star2ar
Figure 4.17 Graph of cut resistance of kaolin & calcium carbonate filler combinations
incorporated samples
4.4.3 Tear Resistance of Kaolin & Calcium Carbonate Filler Combinations

Incorporated Samples
At first three combinations tear resistance was well over the control sample value and
then there was a decreasing trend with increasing amount of filler content. Last
combination which contains 25phr of total filler content showed lowest value and
poorest cosmetic properties. As for other mechanical properties it was affected by poor
filler to filler and filler to polymer interaction. Tear resistance was reached to its peak
7nd combination.
with
Average Tear resistance vs filler Content J

32
30
28
26
22
20
filler Content (phr) —.—vs. Tear resistance - Standard Ccatzo1.
Figure 4.18 Graph of Tear resistance of kaolin & calcium carbonate filler combinations
62
4.4.4 Puncture Resistance of Kaolin & Calcium Carbonate Filler Combinations
Incorporated Samples
According to the graph drawn below based on experimental data puncture resistance
was in increasing trend initially and then there was a slight decreasing trend with the
increasing amount of calcium carbonate, where amount of kaolin filler at a constant.
However there was no significant improvement on puncture after 15 parts and it was
almost a constant and that indicates optimum interaction of particles already has been
reached with 2' combination.
Average Puncture resistance vs filler content
70
50
40
30
49
20
10
tOter content (plir)
Staadard -- Control
Figure 4.19 Graph of puncture resistance of kaolin & CaCO3 filler combinations
4.4.5 Stiffness of Kaolin & Calcium Carbonate Filler Combinations Incorporated

Samples
It is obvious that there was no significant difference among data points in the graph
shown in fig 4.20 and almost same in stiffness. Additions of filler combinations did not
make any considerable effect on glove flexibility and highest stiffness has shown by
25phr filler incorporated sample.
Stiffness vs filler content
- - - —tXL
8.
8.
77
—.
7.1 _._._._._._._._.__.__----- 1 -.-- -- ----.—LCL
6.5
10 15 20 25
jc. -- Corol
filler Content (phx)
Figure 4.20 Graph of stiffness of kaolin & calcium carbonate filler combinations
By considering all those factors such as stiffness, tear, puncture , abrasion and cut
resistance properties, it was clear that 1 5phr of filler incorporated sample has given best
results in terms of mechanical properties, cosmetic aspects and filler content. That
combination contained lophr of CaCO3 and 5phr of kaolin.
4.5 MMT with CaCO3 and Kaolin Combinations Incorporated Sample Test
Results.
Intension of this trial series is to check whether MMT makes any positive impact on
amount of filler loading when it comes to contact with CaCO3, Kaolin and polymer
matrix at once. In other wards to see whether there is a synergistic effect when it
combining with other two fillers.
MMT incorporated amount was 0.5 parts. That amount was selected based on
preliminary studies which were discussed under chapter 4.3.
4.5.1 MMT & Calcium Carbonate Filler Combinations Incorporated Samples Test
Result.
Table 4.6 shows experimented filler combinations. Apart from 0.5 parts of MMT,
additional trial was done with 1 part of MMT and 5 parts of CaCO3 to see deviations.
64
Table 4.6 MMT & calcium carbonate filler combinations incorporated samples test
result
5phr lOphr 15phr 20phr 25phr

CaCO3 CaCO3 CaCO3 CaCO3 CaCO3
property CaCO3 +
+0.5phr +0.5phr +O.Sphr +O.Sphr +0.5phr
lphr MMT
MMT MMT MMT MMT MMT
Abrasion 16000 16000 20000 20000 17000 8500
resistance 15500 17500 20000 20000 20000 6500
16000 16500 20000 20000 18000 9000

Cycles
15000 19000 19000 20000 19000 7500
Average 15625 17250 19750 20000 18500 7875
Cut resist. 2.60 2.65 2.58 2.61 2.58 2.15
2.52 2.66 2.65 2.64 2.30 2.21

(Index
Average 2.56 2.66 2.62 2.63 2.44 2.18
Tear 24.96 24.90 26.60 28.16 22.60 23.70
resistance 27.08 28.48 28.72 26.24 28.40 25.70
23.44 25.04 26.32 26.60 25.72 25.42

(N)
27.32 25,76 26.04 26.48 25.76 24.65
Average 25.70 26.05 26.92 26.87 25.62 25.62
47.30 44.50 49.12 38.00 43.40 39.65

Puncture
46.45 40.20 43.85 35.80 33.95 35.65
resistance (N)
41.80 46.70 48.20 42.03 32.00 37.91
30.70 37.50 41.40 28.50 28.04 39.81
Average 41.56 42.23 45.64 36.08 34.35 35.25
Av.stiff (cm) 7.38 7.25 7.43 7.11 6.89 6.45
4.5.2 MMT & Kaolin Filler Combinations Incorporated Samples Test Results
Table 4.7 shows experimented filler combinations. Apart from 0.5 parts of MMT,
additional trial was done with I part of MMT and 5 parts of CaCO3 collectively to see
deviations.
65
Table 4.7 MMT & Kaolin filler combinations incorporated samples test results
5phr lOphr 15phr 20phr 25phr 5phr

kaolin+ kaolin + kaolin+ kaolin+ kaolin+ kaolin+
Property
0.5 MMT 0.5 MMT 0.5 MMT 0.5 MMT 0.5 MMT 1.0 MMT
Abrasion 15500 16000 18000 12000 7000 7500
resistance 16500 17500 17000 16000 7000 6500
14500 18000 19000 13000 9000 6500

Cycles
15500 18500 17000 8000 6000 7000
Average 15500 17500 17750 12250 7250 6875
Cut Resist. 2.52 2.50 2.55 2.40 2,25 2.25
2.57 2.52 2.60 2.42 2.35 2.35

(Index)
Average 2.55 2.51 2.58 2.41 2.30 2.30
Tear 27.60 22.90 26.60 26.16 22.30 20.65
resistance 24.08 28.48 25.72 26.24 25.78 21.21
25.44 25.04 26.32 25.60 26.31 23.47

(N)
24.32 25.76 26.04 20.48 22.87 19.97
Average 25.36 25.55 26.17 24.62 24.32 21.33
42.30 33.50 39.12 33.00 32.15 31.84

Puncture
36.32 33.80 33.65 37.80 34.25 32.95
resistance
41.80 41.75 39.95 38.03 32.00 29.82
(N)
33.25 37.50 35.65 28.50 27.00 25.61
Average 38.42 36.64 37.09 34.33 31.35 30.05
Av.Stiff (cm) 7.24 7.35 7.15 6.98 6.95 7.01
4.5.3 Abrasion Resistance of MMT in Combination with Calcium Carbonate and
Kaolin.
As illustrated in fig 4.21, Calcium carbonate and MMT collectively incorporated

sample has shown extremely good abrasion resistance. Most importantly all samples
were above the EN standard and control sample values. This is a very significant result.
Because when CaCO3 alone was used as filler, maximum filler loading which could
retain abrasion resistance at highest level was 15-18phr (fig 4.1). But here it has risen to
20.5 phr. That means addition of 0.5phr of MMT has a significant effect on properties
and volume of filler loading, when MMT is combined with CaCO3
When considering kaolin and MMT combination, it too has an improvement up to 15.5
parts of total filler content and it was the best in abrasion resistance. But with the
increase of Kaolin content Abrasion resistance has dramatically dropped. At high
concentrations of kaolin cracks were appeared and that has led to the drop in abrasion
resistance.
Average Abrasion resistance vs filler content
25000
20000
:: EIIIIIIIIIEIII ET
kiohzi+MMr
5000
.0 - - Co.tri
0
5.5 10,5 15.5 20.5 25.5
filler content (phr)
Figure 4.21 Graph of abrasion resistance of MMT in combination with CaCO3 and
kaolin
4.5.4 Cut Resistance of MMT in Combination with Calcium Carbonate and

Kaolin.
According to the graph drawn below based on the results obtained, CaCO3 with MMT
combination has shown good Cut resistance than kaolin with MMT combination. MMT
and CaCO3 filler incorporated samples were shown good cut properties at 20.5phr with
maximum impact on cost and for MMT and kaolin incorporated sample it was 15.5 phr.
Extra amount of filler loading was leading to inferior properties in both combinations,
which is clearly shown in the graph. Both kaolin and CaCO3 incorporated samples
showed micro cracks and surface irregularities due to poor interaction between polymer
and filler particles at high concentrations and that was the major reason for the steep
67
drop of cut resistance. (See 25phr with O.Sphr MMT)
Average Cut resistance vs filler Content
'3.00
C
13 —*A—ra Ctt res
15t&C CO3
MT
Standard
2.50 ~2E
irtance kaolin
IW
- - Coitro1
2. 00
5.5 10.5 15.5 20.5 25.5
FiRer Content phr)
Figure 4.22 Graph of cut resistance of MMT in combination with CaCO3 and kaolin
4.5.5 Tear Resistance of MMT in Combination with Calcium Carbonate and

Kaolin.
When MMT/CaCO3 combination is considered, tear resistant was proportional to

amount of filler added up to 15.5 parts and then it retained up to 20.5 parts with
minimum deviation. For kaolin there was a sharp drop of intended property from 15.5
parts.
Average Tear resistance vs filler content
27.50
27.00 ________________ --*-Tear Ees ieta
of Ca CO3 -
26.50 -
Star4ar
26.00
25.50 ——Tear ieo it aice
U Xaolir.
25.00 -
24.50 - - Cootrol
24.00
5.5 10.5 15.5 20.5 25.5
filler Content phr)
Figure 4.23 Tear resistance of MMT in combination with calcium carbonate and kaolin.
68
4.5.6 Puncture Resistance of MMT in Combinations with Calcium Carbonate and
Kaolin.
Both CaCO3/MMT and kaolin/MMT combinations showed good puncture resistance

readings which were beyond the minimum standard as well as control sample values.
Therefore Puncture resistance was not severely affected with the addition of MMT to
calcium carbonate or kaolin. Therefore addition of MMT as combinations has not affect
puncture resistance negatively.
However there was a downwards trend with the increase of filler due to poor interaction
between filler to filler and filler to polymer.
Average Puncture resistance vs filler content
50. 00
! ::::
20.00
3 + M.MT
Standard
puncture reSS
triceofotri
+MMT
— -. Contri
10.00
5.5 10.5 15.5 20.5 25.5
filler content (phi)
Figure 4.24 Graph of puncture resistance of MMT in combination with calcium

carbonate and kaolin
4.5.7 Stiffness of MMT in Combination with Calcium Carbonate and Kaolin.
Stiffness of both calcium carbonate with MMT and kaolin with MMT filled samples
started deviate from 25.5 parts from its existing values (Control sample). After that
gloves have become too soft and too flexible losing its three dimensional structure
resulting poor boding between polymer and filler particles.
Stiffness vs Filer oontent
9. 50
- —L
8.50 —*.Stfne-CaO3+MMT
—LCL
—UCI
—I--Stiffness -aon • MMT

- - -. -. - -- 1LCL - - Contr
6.50
5.5 10.5 15.5 20.5 25.5
filler Conttt (phr)
Figure 4.25 Graph of stiffness of MMT in combination with calcium carbonate and
kaolin
According to the results of this series of trials, it could he noted that MMT has shown
significant impact on both kaolin and CaCO3 fillers. The maximum amount of CaCO3
that can be accommodated while retaining excellent physical properties was gone up to
20 parts from 18 parts as far as concern abrasion resistant (fig 4.1). In the case of kaolin
with MMT, maximum filler loading has improved up to 15phr from lOphr (fig 4.6).
Therefore MMT has synergistically acted with kaolin and CaCO3 to improve filler
loading ability while retaining excellent mechanical properties.
In 25phr of CaCO3 incorporated sample, pinholes and coagulum were appeared in some
gloves. This is due to increasing amount of Ca2 ions per latex particle leading to
destabilization of latex in the presence of MMT.
I .Ophr of MMT was blended with both Calcium carbonate and Kaolin separately. But
results were not satisfactory as it showed inferior mechanical properties and surface
defects. It was also experienced that processing difficulties engaged with MMT due to
high degree of 'gelling" tendency as a result of latex destabilization. Therefore further
trials using 1 .Ophr of MMT or higher were omitted.
4.6 MMT, Calcium Carbonate and Kaolin Incorporated Sample Test Results
In previous trials it was identified that 15 parts of CaCO3 and 5 parts of Kaolin (table
4.4), 20 parts of CaCO3 and 0.5 parts of MMT (table 4.5). 15 parts of Kaolin and 0.5
parts of MMT (table 4.6) collectively have performed well in abrasion resistant ,which
70
is the most important property as far as concern an industrial glove. But 10 parts of
kaolin has not given advanced properties when it comes collectively with CaCO3 (table
4.4). Because of that it was interested trial out an experiment three types of filler
collectively to see how it behaves. Initially two conventional fillers were added and later
MMT was followed under deep turbulence mixing. Table 4.8 is shown that prepared
filler combinations and their outcomes.
Table 4.8 MMT, Calcium carbonate and kaolin Incorporated sample test results
5phrCaCO3 + 10phrCaCO3+ 15phrCaCO3+ 20phr
5phr 5phr 5phr CaCO3+5phr

Property
Kaolin+0.5MMT Kaolin+0.5MMT Kaolin+0.5MMT kaolin+0.5MMT
Abrasion 18000 17500 20000 17000
resistance 17500 19500 20000 18000
16500 18000 20000 16500

Cycles
17000 20000 20000 18000
Average 17250 18750 20000 17375
Cut resist. 2.60 2.87 2.85 2.17
2.80 2.73 2.57 2.60

(Index)
Average 2.70 2.80 2.71 2.39
26.96 39.90 26.60 26.16

Tear
22.08 33.26 28.72 25.24
resistance
29.36 25.04 26.32 25.60
N)
28.32 22.10 32.04 24.48
Average 26.68 30.08 28.42 25.37
30.30 44.50 32.12 36.90
Puncture 36.45 44.20 43.85 35.80

resistance (N) 36.70 61.20 38.30
41.80
36.70 43.50 45.40 41.50
Average 36.31 42.23 45.64 38.13
Av.stiff. (cm) 7.12 7.53 7.71 7.51
Note: Thickness and the (3SM of the gloves were maintained between 1.3±1- U. 1mm and
71
4.6.1 Abrasion Resistance of MMT, Calcium Carbonate & Kaolin Combinations
Incorporated Samples.
According to the graph illustrated below, first three filler combinations incorporated
samples have shown increment in abrasion resistance in parallel to filler loadings.l5phr
CaCO3 , 5phr kaolin and 0.5phr MMT incorporated sample showed highest filler loading
capability with superior level of abrasion resistance resulted by maximum interaction.
Abrasion resistance is the most important physical property under EN 388 standard,
wearer safety and shelf life.
Average Abrasion resistance vs Total filler content
21000
19000
17000 A —
15000
U
13000
11000
.0
9000
7000
5000
-
10.5 15.5 20.5 25.5

-
——M'g. Abrasion -- Control
Stondard
Figure 4.26 Graph of abrasion resistance of MMT, calcium carbonate & kaolin
combinations incorporated samples.
4.6.2 Cut Resistance of MMT, Calcium Carbonate & Kaolin Incorporated Samples
According to the results only 25.5phr filler incorporated sample showed poor cut
resistance properties which is lesser than to the control sample or in other wards existing
level (without filler addition). However 20.5 parts of filler added sample was a good
combination when cut resistance and amount of filler loaded was considered.
When filler loading was increased, formation of cracks also increased resulting drop in
cut resistance due to incompatibility. If there are considerable amount of cracks that will
fail in general requirements coming under EN 420.
7
Average Cut resistance vs Total filler Content
3. 00
275
2.50
2.25
10.5 15.5 20.5 25.5
Filler Cantent (phr)
—.—Average Cut resi starjte

Cctro1
— Star4ard
Figure 4.27 Graph of cut resistance of MMT, calcium carbonate & kaolin incorporated
samples
4.6.3 Tear Resistance of MMT, Calcium Carbonate & Kaolin Incorporated

Samples
As shown in fig 4.28, tear resistance was not badly affected with filler incorporation.
However according to the graph trend was in downwards with the increasing amount of
filler. 25.5 parts of filler filled sample was shown micro cracks, however most
interestingly it showed higher tear resistance than unfilled level. Therefore it is obvious
that creation of interaction density is high when those three fillers are used as a
combination.
Average Tear resistance vs Total filler Content
32
28
26
. 24
22
10.5 15.5 20.5 25.5
-Stenderd
filler Content (phr)
-- ConIr
ege Tr roit.ne
Figure 4.28 Graph of tear resistance of MMT, calcium carbonate& kaolin incorporated
samples
73
4.6.4 Puncture Resistance of MMT, Calcium Carbonate & Kaolin Incorporated
samples
Referring to the graph drawn below, there were no negative deviations in puncture
resistance due to three filler combination. It showed increment up to 20.5phr of filler
loading and then a decrement was observed. Incorporation of three filler combination
has significantly improved the puncture resistance.
As per the results obtained, it seemed that combination of these three fillers have
generated something like 'Shield" against sharp objects like nails. So that this kind of
combinations useful in manufacturing bullet proof jackets and gloves which are used in
glass producing industry supported by technically modified shells or fabrics.
Average Puncture resistance vs Total filler contentj
50.00
40.00
30.00
1
C
20.00 ---
10.00
10.5 15.5 20.5 25.5
Avg. puncture resistance
- Standa
-- Cootrc
Figure 4.29 Graph of puncture resistance of MMT, calcium carbonate& kaolin

L4.6.5 Stiffness of MMT, Calcium Carbonate & Kaolin Incorporated Samples
Stiffness of all samples was in the required range. Stiffness was in increasing trend with
the amount of incorporated filler content. Therefore combination of these three fillers
did not affect stiffness of the glove badly.
74
Stiffness vsTotal filler content
9. 50 — — — — — — — — — — — — — — — UCL
8.50
E
j 7.50
LCL
6.50
10.5 15.5 20.5 25.5
filler Content (j*ir)
—*—Sbffness LCL - UCL - - Contml
Figure 4.30 Graph of stiffness of MMT, calcium carbonate & kaolin incorporated
samples
According to the results 20.5 parts of filler incorporated sample was the best from all. It
contained Sphr of kaolin, I Sphr of calcium carbonate and 0.5phr of MMT. When it was
stretching beyond 20.5 parts of filled level, properties were going down drastically and
also micro cracks could observed. When kaolin and calcium carbonate collectively
incorporated samples were compared with the samples that got out from three filler
combination, it was noticed that due to the effect of MMT. filler loading capability and
physical properties had significantly improved.
4.7 Tested Filler Combinations.
In table 4.8 highlighted shells are shown tested filler combinations during the research
project. Some of the combinations were omitted by considering observation made on
previous tests results including mechanical properties, cosmetic aspects, defects and
processing difficulties.
Table 4.9 Tested filler combinations.
Individual fillers
Filler Added amount (phr)
CaCO3 5 10 15 20 25 -
kaolin 5 10 15 20 25 -
MMT 0.25 0.5 1.0 1.5 2.0 -
75
Combinations with two tillers
Combinations Added amount (Phr)
CaCO3 & kaolin Kaolin 5 5 5 5 5
CaCO3 5 10 15 20 25
CaCO3 5 10 15 20 25
(Ill) CaCO3 5 10 15 20 25
CaCO3 5 10 15 20 25
CaCO3 5 10 15 20 25
CaCO3 & MMT CaCO3 5 10 15 20 25
MMT 0.5 0.5 0.5 0.5 0.5
CaCO3 &MMT CaCO3 5 10 15 20 25
MMT 1 1 1 1 1
CaCO3 &MMT CaCO3 5 10 15 20 25
(Ill) MMT 1.5 1.5 1.5 1.5 1.5
CaCO3 &MMT CaCO3 5 10 15 20 25
(IV) MMT 2 2 2 2 2
kaolin & MMT Kaolin 5 10 15 20 25
MMT 0.5 0.5 0.5 0.5 0.5
kaolin& MMT Kaolin 5 10 15 20 25
MMT 1 1 1 1 1
kaolin & MMT Kaolin 5 10 15 20 25
(Ill) MMT 1.5 1.5 1.5 1.5 1.5
kaolin& MMT Kaolin 5 10 15 20 25
(IV) MMT 2 2 2 2 2
Combinations with three fillers
Combination Added amount (Phr)
CaCO3 CaCO3 5 10 15 20 25
kaolin & MMT kaolin 5 5 5 5 5
76
MMT 0.5 0.5 0.5 0.5 0.5
CaCO3 CaCO3 5 10 15 20 25
MMT 1 1 1 1 1
CaCO3 CaCO3 5 10 15 20 25
(Ill) MMT 1.5 1.5 1.5 1.5 1.5
CaCO3 CaCO3 5 10 15 20 25
MMT 0.5 0.5 0.5 0.5 0.5
CaCO3 CaCO3 5 10 15 20 25
MMT 1 1 1 1 1
CaCO3 , CaCO3 5 10 15 20 25
MMT 1.5 1.5 1.5 1.5 1.5
In this research project three different fillers and four combinations were experimented
by varying the filler content and the composition. They are,
Calcium carbonate as a filler
Kaolin as a filler
MMT as a filler
Calcium carbonate & kaolin combination as a filler
Calcium carbonate & MMT combinations as a filler
Kaolin & MMT combination as a filler
Calcium carbonate, kaolin & MMT combination as a filler
1) Use of Calcium carbonate as a filler
Calcium carbonate was a useful and convenience filler to incorporate with NBR latex.
Results of first trial series have shown that I 8phr of Calcium carbonate can be
77
incorporated with industrial glove compound without losing intended properties. When
filler loading was increased over around 18 parts physical properties were dropped. In
this experiment we used wet ground calcium carbonate and which is having particle size
more or less around 2 micron. If polymer matrix is blended with precipitated calcium
carbonate, physical properties might go up due to smaller particle size though glove
may become so expensive.
Use of kaolin as a filler.
Kaolin wasn't good as calcium carbonate for XNBR compounds to be used as cost
reduction or reinforcing filler though it improved surface finish. When kaolin content
was high, around 20 to 25phr, small cracks were appeared and curing was become
difficult. When physical properties were considered, 5phr kaolin sample had retained all
physical properties. Therefore 5phr was the best amount to be incorporated with nitrile
compounds as far as concern physical properties, surface finish & visual defects such as
cracks and coagulurn. However Kaolin might be a good filler to reduce cost of NR latex
due to its bigger particle size and high TSC, preferably for products made out of
rotational molding.
Use of MMT as a filler.
MMT is expensive filler. With the small amounts of MMT incorporation, physical
properties were improved. Because of high water absorption property of MMT, it led to
formation of cracks whilst latex destabilization was taken place at 1.0 part and above
filler loadings. Optimum amount of MMT could be added was 0.5phr as far concern its
cost and processing difficulties compare to others. When MMT was added vigorous
mixing had to be followed for better incorporation of filler to the polymer matrix where
as other two fillers did not need such a deep agitation.
Use of calcium carbonate & kaolin combination as filler.
Ten parts of calcium carbonate and 5 parts of kaolin filled experiment showed better
properties than other combinations. Until total filling factor was reached 20 parts all
other combinations were useful as it showed higher mechanical properties than existing
glove though there was a declining trend from 15 to 20 parts. When compound was
loaded with more than 20 parts tear and cut properties became inferior. Some surface
defects such as flow marks were begun to appear after 15 parts of CaCO3 loading level
78
along with Kaolin. As per out comes it was obvious that these two fillers have dealt with
nitrile polymer matrix individually, and there was no collective outcome.
Use of calcium carbonate & MMT combination as a filler.
Physical properties were improved significantly. Even 20phr of calcium carbonate and
0.5phr of MMT incorporated samples showed good mechanical properties. This would
be a very good combination to be commercialized.
Use of kaolin & MMT combination as a filler
There was a significant improvement in kaolin loading levels when it was coupled with
MMT. Amount of filler content was able to increase up to 15 phr. Otherwise it was
difficult to load even 10 parts of kaolin for the XNBR compound alone. So in practical
sense this improvement is vital. Since result was encouraging trials were extended to the
three filler combination as well.
Use of calcium carbonate, kaolin & MMT combination as a filler
This experiment was carried out see whether there any synergistic effect when using all
these three fillers collectively with XNBR latex. As expected a significant improvement
was observed in visual quality point of view addition to compromise physical properties.
According to the results 5 parts of kaolin, 15 parts of CaCO3 and 0.5phr MMT was the
best combination and it retained all required mechanical properties.
Out of all combination three combinations were selected considering all positive factors
including superior mechanical properties, cosmetic aspects, higher loadability of fillers,
processing easiness and less vulnerability for the defects. Table 4.10 shows selected
combinations and table 4.11 shows mechanical properties of those combinations.
Table 4.10 Selected fillers and combinations
Selected Filler Combinations (Phr)
Filler Material 1st 2nd 3rd
Calcium Carbonate 18 20 15
Kaolin 5
MMT 0.5 0.5
79
Table 4.11 EN 388:2003, Mechanical Properties comparison.
Property units Control 1 2 3

Abrasion Cycles 12250 20000 20000 20000
Cut Resist, Index 2.595 2.7 2.63 2.71
Tear Resist. N 26.48 29.35 26.87 28.42
Punct. Rest. N 30.885 50.88 36.08 45.64
Cost calculation was done for selected combinations. Since base compound was same
for all combination except fillers, other compounding ingredients prices were not
considered for cost calculation. Fillers and latex prices are given in table 4.12.
Table 4.12 Raw Material prices
Material Price (USD/Kg)
Kaolin 2.4
CaCO3 0.85
MMT 10.275
NBR Latex (Wet) 1.3
NBR Latex (dry) 2.9
Average glove weight was calculated for a piece of glove and ultimately coated
compound weight calculated by reducing cotton shell weight. Finally it was converted
in to wet compound weight by considering compound TSC, which is 45%.
Table 4.13 Raw Material Consumptions (Consumption! glove)
Material Weight (kg)
Avg. finished glove 0.070022
Cotton liner 0.0317
NBR coating (Dry) 0.038322
NBR coating (wet) 0.08516
Cost calculations were done according to composition of cured nitrile film. Sub
columns indicate composition in percentage, consumption and calculated cost for each
80
component. (Refer table 4.14)
Table 4.14 Cost comparison of selected combinations (cost/glove)
NBR/MMT/CaCO3/
NBR NBR/CaCO3 NBR/MMT/CaCO3
Material Kaolin
Phr Cons. Cost Phr Cons. cost Phr Cons. cost Phr Cons. Cost
NBR Latex 100 0.0383 0.1111 82 0.0314 0.0911 79.5 0.0305 0,0884 79.5 0.0305 0.0884
Calcium
18 0.0069 0.0059 20 0.0077 0.0065 15 0.0057 0.0049
Carbonate
Kaolin ' " 5 0.0019 0.0046
MMT " " " " 0.5 0.0002 0.0020 0.5 0.0002 0.0020
Eotal Cost - 0.1111 - 0.0970 - 0.0968 0.0998
81
CHAPTER 05
CONCLUSION AND FURTHER WORK
Calcium Carbonate, Kaolin and Montmorillonite fillers can be used to enhance
Mechanical properties of a XNBR film whilst reducing manufacturing cost in a defect
free environment. Montmorillonite alone is acted as reinforcing filler; however it makes
glove expensive and will be a drawback in marketing point of view. Mechanical
properties are discussed under EN 388:2003 are Abrasion resistance, Cut resistance,
Tear resistance and Puncture resistance.
When considering cost factor, 0.5phr MMT and 20phr CaCO3 combination was
marginally cost effective than the "three filler combination" which represents all three
fillers and gloves which were reinforced by calcium carbonate alone as single filler. It
secures 12.9% cost saving over existing glove whilst other two secures 10% and 12.7%
respectively. Calcium carbonate is cheaper than kaolin. It depicts in cost comparison
between 2u1c and 3 combinations.
However in cosmetic point of view 0.5phr MMT, 5phr Kaolin and lsphr CaCO3
combination is the best. Because evenly distribute small particles of kaolin gives an
excellent surface finish to the glove when it is used in small proportions. Pinholes and
coagulurn are totally absent with this combination. However those defects appear in
nd
small proportions on the gloves which are produced out of 2 combinations where
Montmorillonite and Calcium carbonate are incorporated. Therefore by considering all
those of factors finally, it can be concluded that three filler combination is the best one
to be commercialized which secures 10% cost reduction as well.
Since CaCO3 readily available and easier to get down, it is good to go with that though
cosmetic properties are bit below to third combination. This has been already
implemented in one of our production lines, its monthly output is about 425,000 pairs
and after filler incorporation we have been able to save 11,900 USD per month. Pilot
runs have already been started with third combination and would commercialize for
specific customers where gloss finish is a decisive factor.
Since HYCRON is a Blue coloured product, transition metal ions which could be
present in calcium carbonate does not play significant inferior role on glove appearance
and surface finish. However if we suppose to use fillers for white colored products such
82
as disposable examination gloves, desperately we need to have fillers free from
transition metal ions to avoid formation of colour patches on cured product and heavy
metal ions such as Cadmium, Mercury, Chromium and Led which are considered to be
carcinogenic. This project is in pipe line and currently properties like Tensile strength,
Breaking strength and elongation are being monitored in true environment.
Preliminary studies have also been started to replace Titanium dioxide from Most of
Synthetic latex glove formulation by the use of high purity Calcium carbonate and
calcium Magnesium carbonate (Dolomite or Dolostone) to be used as a filler for Natural
latex, in the aim of cost reduction which is considered to be the main parameter to be
competitive in the glove market apart from quality and JIT resource planning.
Another aspect that has to be monitored and improved on industrial glove is its chemical
permeation properties comes under EN 374 (International standard on Chemical
permeation and penetration) with filler incorporation and functional properties such as
fire retardant with MMT. These trials are underway and which would focus a separate
niche market segment where higher margin of profit is possible.
83
REFERENCES
Preetha Nair K, Dr Rani Joseph,(20 12), 'Nano kaolin clay as reinforcing

filler in Nitrile rubber', International Journal of ScientUic & Engineering
Research, vol. 03
M.N.Ichazo, M.Hernandez, C.Albano, J.Gonzalez, W.De.Sousa, (2008),
'Treatment of the filler on rheometric and tensile properties of
NBR/BENTONITE vu lean izates', NBR/BENTONJTE Composites.
Z.N. Am, A.R. Azura, (2010), Effect of d4fy'èrent types of filler and filler
loadings on the properties of Carboxylated Acrylonitrile- Butadiene rubber latex
films.
Qingguo Wang,Qingmei Song, Jinliang Qiao, Xiaohong Zhang, Liqun Zhang,

Zhihai Song, (2003), Good dispersion of hydrophilic nanoscale Calcium
Carbonate particles in Nun/c batadiene rubber matrix.
Haydn H. Murray, (1961), Industrial applications of Kaolin.

Xiaodong a,b,c,Chuanhui Xu a,c,Yanpeng Wang a,Yu Liu b,Yuhong Liu,(20 13),
New Nanocomposite materials reinforced with cellulose nanociystals in Nitrile
rubber.
R.Rajsekar a,Kaushik Pal a,Gert Heinrich b,Amit Das b,C.k Das, (2009),
Development of Nitrile butadiene rubber-Nanoclay composites with epoxidized
natural rubber as compatbilizer
Leilei Wang,nanying Ning,Liquan Zhang,Yanglai Lu, Ming Tian,Tung Chan,

(2013), Filler dispersion evolution oJNBR/Graphite nano composite during
processing.
John Bieleman, (2008), Additives for coatings.
Ashish Kumar Sen, (2007), Coated textiles-Principles ofApplications.
J.M. Hartwell, (1965), The diverse use of Montmorillonite.
Maurizio Galimberti, (2011), Rubber clay nanocomposite.
D.0 .Blackley, (1997), Polymer Latices-Science and Technology -Application
84
of latices, 4th edn, vol. 3.
D.C.Blackley, Polymer Latices-Science and Technology-Fundamental

Principles, 2nd edn, vol. 3.
D.C.Blackley, Polymer Latices-Science and Technology-Types of Latices, 2nd

edn, vol. 3
Adnan Mujkanovic, Ljubica Vasiljevic, Gordana Ostojic, (2009), Non-Black

fillers for elastomers.
17, L.A.Dobrzanski,M. Gorn iak,L.Reimann,M.StaSZUk, (2012), Characterization

ofAluniino silicates nano particles as a reinforcement in composite material
bond on polymer matrix.
L.R. Evans, (2001), 'Introduction to Mineral fillers for Rubber', Rubber world.
Quinfu Liu,Yude Zhang,Hong hang Xu, 2008,'Properties of Vulcanized Rubber

Nanocomposites Filled with Nano Kaolin and Precipitated Silica', Applied clay
Science, vol.42, pp. 232-237.
(2010), Ansell health care technical bulletin.
85
APPENDIX I
Abbreviation Meaning
cps Centi poise
HYCRON Name of an industrial glove
MMT Montmorillonite
PPE Personal protective equipment
phr Parts per hundred rubber
rpm Revolutions per minute
TSC Total solid content
XNBR or NBR Carboxylated Acrylo Nitrite butadiene rubber
ZDBC Zinc dibutyl dithiocarbamate
ZMBT Zinc Mercaptobenzothiazole
86
APPENDIX II
Defect Recording Sheet
Glove Style: Size: Shift;
-
-- -- -- --_
• _ _ _ _ _ _ _ _ _ --_--
_____________ --
LS)JII(ITt
- -- -- --
--
--
--
aI. --
Split
-- -- --
-- -- --
EEO
--
ILIFAWn- --
IItTIci
Ths
- -- --
-- --
--
--
ajr.
L1j.1ufl.I1JI 1I
--
-- --
-- --
--
•-
runs
-
---
-- --
--
Forie iiiiiiticle
!_
IA,li1I1[0)YI
IiT?1[.1l
IJIE1i
-1
--
-I-
--
--
--
--
--
--
--- -- --_
IiflI7Ii --
-- --
IliTiJlE!1[.A'L -- -- --
-
-- -- --
-- -- -
87
Wrinkle
-Other
Badload
Cuff Crack -
L
Dirtymark
P
O Foriegn particles
- -P
L
C
Put air
R
Soft air
L
web
R
L
Total Defect
R
Total Production
L
P
-
L
Total Acceptable
R
Defect %
CheCked By : Approved By FO/DP/02
88

Study On The Effect of Filler Combination To The Cost and Quality of An Industrial Nitrile Glove

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Study On The Effect of Filler Combination To The Cost and Quality of An Industrial Nitrile Glove

Caricato da

Copyright:

Formati disponibili

STUDY ON THE EFFECT OF FILLER COMBINATIONS TO THE

COST AND QUALITY OF AN INDUSTRIAL NITRILE GLOVE

The Faculty of Graduate Studies

University of Sri Jayewa rdenepura

of the Requirements for the Degree

Master of Science in Polymer Science & Technology

Rajitha Gunarathne, Date

University of Sri Jayewardenepura,

University of Sri Jayewardenepura,

I must extend to my Research supervisors, Prof. Sudantha Liyanage, Dean, Department

Senior Lecturer. Department of Chemistry. University of Sri Jayewardenepura, Sri

Furthermore I would like to extend my sincere gratitude to Dr. K.M.T.D Gunasekara,

Carboxylated acrylonitrile butadiene (XNBR) is vastly used synthetic latex for

DECLARATION........................................................... . ........ . .................. I

ACKNOWLEDGRMENT................................. ... ......................... II

ABSTRACT. ............................................................................. III

TABLEOF CONTENTS ...................................... .... ....................... V

LISTOF FIGURES ....................................... ......................... XIII

1.1 General Description of the Nitrile Glove ..............................3

1.3 EN Standard for Mechanical Protection ................................4

1.4 REACH Compliance (Hazardous Chemicals List).........................7

CHAPTER 02- LITERARTURE REVIEW. ......................................... 8

2.1 XNBR Latex................................................................8

2.1.1 Stability of Carboxylated NBR Latex ...................................9

2.2 Ammonia (25% Ammonium Hydroxide) .... .................................... 10

2.3 SABS (Sodium Alkyl Benzene Sulfonate)......................................11

2,4 Zinc Oxide....................................................................................... 11

2.6 Organic Accelerator ZDBC............................................................. 13

2.7 Viscosity Modifier- Culminal MHPC 50..................................... 13

2.8 Hydrowax 215............................................................................... 14

2.9 Pigment Blue- Flexiverse BCD 9907........................................... 14

2.10 Calcium Carbonate Fille. ............................................................... 14

2.11 Clay Minerals................................................................................ 16

2.11.1 Kaolin Filler......................................................................... 17

CHAPTER 03- MATERIALS AND METHODS...............................22

3.1 Glove Formulations......................................................................22

3.2 Filler Matrix.....................................................................................23

3.3 Preparation of Blank Compound (added amounts)..........................25

3.4 Preparation of Dipped Gloves..........................................................27

3.4.1 Main Steps Involved in Blank Compound Dipping

3.5 Preparation of Calcium Carbonate Incorporated Compounds..........33

3.6 Preparation of Kaolin Filled Compounds .......................................... 34

3.7 Preparation of MMT Incorporated Compounds ................................ 34

3.8 Preparation of Kaolin &Calcium Carbonate Combination

3. 10 Preparation of Calcium Carbonate& MMT Incorporated Gloves... 37

3.11 Preparation of Calcium Carbonate, Kaolin & MMT Incorporated

3.13.1 Martindale Abrasion Resistance Tester........................... 40

3.13.2 Universal Extension Tester (Puncture & Tear resistance),, 41

3.13.3 Circular Blade Cut resistance Tester.................................... 42

3.13.4 Clark Stiffness Teste. ........................................................... 43

CHAPTER 04- RESULTS & DISSCUSION......................................... 44

4.1 Calcium Carbonate Filler Incorporated Test Results.................. 44

4.1.1 Abrasion Resistance of Calcium Carbonate Incorporated

4. 1 .2 Blade Cut resistance of Calcium Carbonate Incorporated

4.1.3 Tear Resistance of Calcium Carbonate Incorporated

4.1.4 Puncture Resistance of Calcium Carbonate Samples.......... 47

4.1.5 Stiffness of Calcium Carbonate Samples........................ 47

4.2 Kaolin Filler Incorporated Test Results................................. 49

4.2.1 Abrasion Resistance of Kaolin Incorporated Samples......... 50

4.2.2 Cut Resistance of Kaolin Incorporated Samples............... 51

4.2.4 Puncture Resistance of Kaolin Incorporated Samples........ 52

4.2.5 Stiffness of Kaolin Incorporated Samples....................... 53

4.3 MMT Filler Incorporated Sample Test Results............................... 55