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Krisda SUCHIVA
Research and Development Centre for Thai Rubber Industry,Mahidol University
INTRODUCTION TO PROCESS OILS
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INTRODUCTION TO PROCESS OILS
Process oils are used in the rubber industry to,
improve the processability of rubbers and rubbercompounds
process aids
increase the bulk of rubber in order to lower cost
oil-extended rubbers
Main application is process aid.
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INTRODUCTION TO PROCESS OILS
Process aids are increasingly important for the rubberindustry due to the following needs,
- improve efficiency and productivity
- lower energy consumption
In total,
- reduce production cost
- improve product quality
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INTRODUCTION TO PROCESS OILS
1. reduce viscosity
2. reduce elasticity
3. aid dispersion of fillers
4. reduce power consumption
Additional requirement
1. do not affect intended properties of finished products
2. act at low dosage level
3. non-toxic
Functions of process aids,
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INTRODUCTION TO PROCESS OILS
1. chemical peptizers
2. fatty acid soaps
3. fatty acid ester
4. petroleum oils
5. factice
6. resins
7. partially vulcanised rubber
8. liquid polymers
9. waxes
Materials used as process aids,
Process oil is just one of the process aids. 5
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INTRODUCTION TO PROCESS OILS
For reduction of viscosity and elasticity
2 Mechanisms,
1. Lowering molecular weight of polymer
How do process aids work ?
molecular entanglement reduced
easier flow of molecules
peptizer
Chemical processing aids 6
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INTRODUCTION TO PROCESS OILS
2. Lowering of intermolecular interactions
process aid
flow of molecules become easier
e.g. fatty acid soaps, fatty acid ester, oils, liquid polymers.
Most process aids work on this principle
No reduction in MW, hence the final properties not affected
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INTRODUCTION TO PROCESS OILS
Efficiency of physical process aids depend on degree of miscibilitywith polymer or solubility in polymers.
completely miscible
or
completely soluble
most efficient
most effective in reducingviscosity
only small amount is required.
partially miscible
or
partially soluble
less efficient
less effective in reducingviscosity
Higher amount is required.
immiscible
or
insoluble
least efficient
least effective in reducing
viscosity
large amount is required. 8
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PROCESS OILS
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derivatives naphthalene, debenzothiophene,carbazole, etc.
PROCESS OILS
PROCESS OILS are derived from petroleum (crude oil) after themore volatile petrol and heating oil fractions have been removed bydistillation.
PROCESS OILS are MIXTURES of paraffinic, naphthenic andaromatic compounds of wide distribution of molecular weight.
Origin and Composition of Process Oils
Paraffinic oils
Naphthenic oils
Aromatic oils
CH3CH2CH2CH2CH2 CH3CHCH2CHCH2CH3CH2
CH3 CH3paraffins isoparaffins
derivatives of cyclohexane or decalin
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PROCESS OILS
Type of Process Oils
Type%
paraffinic
%
naphthenic
%
aromaticVGC
Paraffinic oil 60-74 20-35 0-10 0.790-0.819
Naphthenic oil 35-45 30-45 10-30 0.850-0.899
Aromatic oi l 20-35 20-40 35-50 0.950-0.999
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PROCESS OILS
1. solubility or miscibility or compatibility with rubbers
Determine efficiency in reducing viscosity/flow characteristics
Depends on,
- % Aromaticity : the higher, the more efficient
- molecular weights (viscosity) : the smaller, the moreefficient
High solubility means more oil can be incorporated into the
rubber higher loading of oil possible.
Important Properties of Process Oils
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PROCESS OILS
Level of aromaticity measured by
1) VISCOSITY GRAVITY CONSTANT (VGC)
Important Properties of Process Oils
High VGC = high aromaticity
2) ANILINE POINT Aniline point = temperature at which equal volumes
oil and aniline are mutually soluble.
Low Aniline Point = high aromaticity
note : ● Aniline point can be influenced by MW of oil.● Can be difficult to determine with very dark and opaque oils.
specific gravity
= 1.0752-a10
G
VGC
log(V+38)a
Viscosity (saybolt)
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PROCESS OILS
Important Properties of Process Oils
Compatibility of process oils with various rubbers
Oil Type RubbersNR SBR BR NBR CR EPDM IIR
Paraffinic + + + - - + +
Naphthenic + + + 0 0 + 0
Aromatic + + + + + 0 -
+0-
compatiblepartially compatibleincompatible
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PROCESS OILS
2. Colour stability/Contact staining
Colour stability (increasing darkness) decreases with
increasing % aromaticity.
Important Properties of Process Oils
paraffinic oils > naphthenic oils > aromatic oils
3. Ageing resistance
Ageing resistance decrease with increasing % aromaticity.
paraffinic oils > naphthenic oils > aromatic oils
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PROCESS OILS
4. Loss of oil during high temperature service of rubberproduct containing oil.
Determined by FLASH POINT
5. Toxicity
Become increasingly important
Process oils contain Polycyclic Aromatic Hydrocarbons (PAHs)
or Polycyclic Aromatic (PCA) which are carcinogen and cancause mutation.
Regulations (European Directive 2005/69/EC) imposed ban ofprocess oils containing ≥ 10mg/kg (ppm) of PAH since2010.
Important Properties of Process Oils
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PROCESS OILS
Trend towards low PAH (
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PROCESS OILS
Polycyclic Aromatic Hydrocarbons
PAHS Chemical Formulas MW (g.mol-1) Chemical Structures
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PROCESS OILS
Polycyclic Aromatic Hydrocarbons
PAHS Chemical Formulas MW (g.mol-1) Chemical Structures
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PROCESS OILS
Comparison of Different Process Oils
Effects on properties of rubber compounds and vulcanisates
Process Oils Compared
Sample number Saybolt viscosity VGC
38°C 100°C
Aromatic123
43603500
-
2109681
0.9910.9540.981
Naphthenic
456
78910
25202206760
156-
110104
85.984.760
41.043.538.238.0
0.8830.8820.869
0.8780.8300.8860.871
Paraffinic
11121314
15
2642500-
110
-
15563.542.340.4
38.0
0.8000.8030.8050.807
0.832 20
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PROCESS OILS
Part by weight
NR
Zinc oxideStearic acidN-330 carbon blackN - Isopropyl-N ’ -phenyl-p -phenylenediamineOilN - Oxydiethylenebenzothiazole-2-sulphenamideSulphur
100
52.5
45
1.5
10 or 20
0.8
2.5
Time (min) Action
00.51.02.0
3.5
Add rubber.
Add small powders.
Add half black.
Half black plus oil.
Dump.
FORMULATION FOR OIL EVALUATION
MIX CYCLE : BR BANBURY
Comparison of Different Process Oils
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PROCESS OILS
Effects on Mooney Viscosity
Naphthenic oils tend to give lower
mooney viscosity
Paraffinic oils tend to give lower
mooney viscosity
20 phr
Comparison of Different Process Oils
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Aromatic Oi ls Naph thenic Oil s Paraffinic Oils
10
2020
40
30
50
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Mooney v iscosi ty, ML 1+4, 100 °C
Aromatic Oi ls Naphthenic Oil s Paraffinic Oils
10 phr
10
20
30
50
40
60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Mooney v iscosi ty, ML 1+4, 100 °C
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PROCESS OILS
Vulcanisation Characteristics (ODR 100°C)
Oil Type Sample 10 phr oil 20 phr oil
ts5
(min)
Tc(90)
(min)
MHR ML
(torque units)
ts5
(min)
Tc(90)
(min)
MHR ML
(torque units)
Aromatic123
4.123.424.16
14.3313.1313.47
33.035.632.9
7.357.458.25
4.513.584.25
16.0014.3214.28
24.327.230.3
8.467.089.00
Naphthenic
4567
8910
3.583.535.163.52
3.473.484.15
14.3113.4014.5114.43
14.2814.2113.56
32.535.530.233.5
32.135.532.7
7.397.369.257.41
8.167.377.58
4.394.285.004.17
4.254.174.31
15.1815.1116.0514.50
15.2416.0215.18
28.727.425.430.5
27.827.227.6
8.168.258.537.50
8.428.227.58
Paraffinic
1112131415
4.073.574.044.004.21
14.2014.2214.4513.4514.06
34.633.433.932.535.5
7.447.527.577.137.28
4.264.354.354.294.39
15.1314.3216.2814.5815.00
28.028.826.327.226.4
8.078.168.568.288.14
Little difference was observed for various oil types at 10 and 20 phr. 23
Comparison of Different Process Oils
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PROCESS OILS
Effect on Hardness
Some effects on hardness
Average Values of Hardness forthe Three Oil Types
Dosage ph r )
A N P
10 62 61.5 62
20 56.5 56 54.5
• Almost no effect on hardness at10 phr.
• At 20 phr. paraffinic oils showslightly greater softening effect.
Comparison of Different Process Oils
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Hardness, IRHD
Aromatic Naph thenic Paraffinic
20 phr
10
20
30
50
40
70
60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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PROCESS OILS
Effect on Tensile Strength
• Individual oils gave widely different values of T.S• Effect of different types of oils on unaged, 70°C aged or
100°C aged are slight. 25
Tensile strength, MPa
Aromatic Naphthenic Paraffinic
20 phr of oil
5
10
15
25
20
30
1
2 34 5
6 7
8
910
11 12 13 14 15
unaged
aged 3 days 100°C
aged 28 days 70°C
aged 7 days 100°C
Comparison of Different Process Oils
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PROCESS OILS
Effect on Compression Set
Paraffinic and naphthenic oils tend to give lower
compression set values than aromatic oil. 26
Compression set, %
Aromati c Naphthenic Paraffinic
20 phr of oil/25% initial compression
10
20
30
50
40
60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
1 day 100°C
7 days 70°C
Comparison of Different Process Oils
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PROCESS OILS
Effect on Dunlop Resilience
• Aromatic oil gave lower resilience• Higher viscosity oils gave lower resilience
Dunlop resilience, 23°C, %
Aromatic Naphthenic Paraffinic
20 phr of oil
20
30
40
60
50
80
70
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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Comparison of Different Process Oils
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PROCESS OILS
Performance of Low PAH/PCA Oils
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Rolling Resistance
DAE TDAE MES NAP RAE
110
108106
104
102
100
98
96
9492
90
Wet Grip
Rolling Resistance
TDAE
MES
NAP
RAE
+-
+
-
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PROCESS OILS
SUMMARY
1. Process oils are used to improve the processability of rubber
compounds or to increase the bulk of rubber in order to lower cost.
2. Although process oils are classified as paraffinic (CP) naphthenic
(CN) or aromatic (CA), they are mixtures of CP/CN/CA.
3. The efficiency of oil in reducing viscosity and elasticity depends on
its compatibility with rubber or its solubility in rubber.
- good compatibility/solubility efficient
- smaller quantity may be used.
4. Compatibility or efficiency depends on
- % aromaticity : the higher, the more efficient
- MW or viscosity : the smaller, the more efficient29
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Q & A
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