INTRODUCTION TO PROCESS OILS

Krisda SUCHIVA
Research and Development Centre for Thai Rubber Industry,
Mahidol University
INTRODUCTION TO PROCESS OILS

Process oils are used in the rubber industry to,

 improve the processability of rubbers and rubber

compounds
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 rubber

industry 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

Functions of process aids,

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
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INTRODUCTION TO PROCESS OILS

Materials used as process aids,

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
Process oil is just one of the process aids. 5
INTRODUCTION TO PROCESS OILS

How do process aids work ?

For reduction of viscosity and elasticity
2 Mechanisms,

1. Lowering molecular weight of polymer

peptizer

 molecular entanglement reduced

 easier flow of molecules

Chemical processing aids 6

INTRODUCTION TO PROCESS OILS

2. Lowering of intermolecular interactions

process aid

 flow of molecules become easier

Most process aids work on this principle

e.g. fatty acid soaps, fatty acid ester, oils, liquid polymers.

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 miscibility

with polymer or solubility in polymers. most efficient

completely miscible most effective in reducing

or viscosity
completely soluble
only small amount is required.

less efficient
partially miscible
or less effective in reducing
viscosity
partially soluble
Higher amount is required.

least efficient
immiscible
or least effective in reducing
viscosity
insoluble
large amount is required. 8
PROCESS OILS

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PROCESS OILS

Origin and Composition of Process Oils

 PROCESS OILS are derived from petroleum (crude oil) after the
more volatile petrol and heating oil fractions have been removed by
distillation.

 PROCESS OILS are MIXTURES of paraffinic, naphthenic and

aromatic compounds of wide distribution of molecular weight.
Paraffinic oils
CH3CH2CH2CH2CH2 CH3CHCH2CHCH2CH3CH2
paraffins isoparaffins
CH3 CH3
Naphthenic oils
derivatives of cyclohexane or decalin

Aromatic oils
derivatives naphthalene, debenzothiophene,
carbazole, etc. 10
PROCESS OILS

Type of Process Oils

% % %
Type VGC
paraffinic naphthenic aromatic
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 oil 20-35 20-40 35-50 0.950-0.999

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PROCESS OILS

Important Properties of 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 more
efficient
 High solubility means more oil can be incorporated into the
rubber higher loading of oil possible.

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PROCESS OILS

Important Properties of Process Oils

 Level of aromaticity measured by
1) VISCOSITY GRAVITY CONSTANT (VGC)

G = 1.0752-a log(V+38)
a
10
specific gravity Viscosity (saybolt)
VGC

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. 13
PROCESS OILS

Important Properties of Process Oils

Compatibility of process oils with various rubbers

Rubbers
Oil Type
NR SBR BR NBR CR EPDM IIR
Paraffinic + + + - - + +
Naphthenic + + + 0 0 + 0
Aromatic + + + + + 0 -

+ compatible
0 partially compatible
- incompatible

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PROCESS OILS

Important Properties of Process Oils

2. Colour stability/Contact staining
Colour stability (increasing darkness) decreases with
increasing % aromaticity.

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

Important Properties of Process Oils

4. Loss of oil during high temperature service of rubber
product 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 can
cause mutation.
 Regulations (European Directive 2005/69/EC) imposed ban of
process oils containing ≥ 10mg/kg (ppm) of PAH since
2010.
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PROCESS OILS

Important Properties of Process Oils

 Trend towards low PAH (<10 ppm) process oils

- Treated Distillate Aromatic Extract (TDAE)
- Mild Extract Solvated (MES)
- Naphthenic oil (NAP)
- Residual Aromatic Extract (RAE)
- Vegetable oils (rubber seed oil, bean oil, castor oil,
coconut oil)

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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
1 4360 210 0.991
Aromatic 2 3500 96 0.954
3 - 81 0.981
4 2520 85.9 0.883
5 2206 84.7 0.882
6 760 60 0.869
Naphthenic 7 156 41.0 0.878
8 - 43.5 0.830
9 110 38.2 0.886
10 104 38.0 0.871
11 2642 155 0.800
12 500 63.5 0.803
Paraffinic 13 - 42.3 0.805
14 110 40.4 0.807
15 - 38.0 0.832
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PROCESS OILS

Comparison of Different Process Oils

FORMULATION FOR OIL EVALUATION
Part by weight
NR 100
Zinc oxide 5
Stearic acid 2.5
N-330 carbon black 45
N - Isopropyl-N’ - phenyl-p- phenylenediamine 1.5
Oil 10 or 20
N - Oxydiethylenebenzothiazole-2-sulphenamide 0.8
Sulphur 2.5

MIX CYCLE : BR BANBURY

Time (min) Action

0 Add rubber.
0.5 Add small powders.
1.0 Add half black.
2.0 Half black plus oil.
3.5 Dump. 21
PROCESS OILS

Comparison of Different Process Oils

Effects on Mooney Viscosity
Mooney viscosity, ML 1+4, 100 °C Mooney viscosity, ML 1+4, 100 °C

60 50

50
40

40
30
30
20
20

10
10

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Aromatic Oils Naphthenic Oils Paraffinic Oils Aromatic Oils Naphthenic Oils Paraffinic Oils
10 phr 20 phr

Naphthenic oils tend to give lower Paraffinic oils tend to give lower
mooney viscosity mooney viscosity 22
PROCESS OILS

Comparison of Different Process Oils

Vulcanisation Characteristics (ODR 100°C)
Oil Type Sample 10 phr oil 20 phr oil
ts5 Tc(90) MHR ML ts5 Tc(90) MHR ML
(min) (min) (torque units) (min) (min) (torque units)
1 4.12 14.33 33.0 7.35 4.51 16.00 24.3 8.46
Aromatic 2 3.42 13.13 35.6 7.45 3.58 14.32 27.2 7.08
3 4.16 13.47 32.9 8.25 4.25 14.28 30.3 9.00
4 3.58 14.31 32.5 7.39 4.39 15.18 28.7 8.16
5 3.53 13.40 35.5 7.36 4.28 15.11 27.4 8.25
6 5.16 14.51 30.2 9.25 5.00 16.05 25.4 8.53
Naphthenic 7 3.52 14.43 33.5 7.41 4.17 14.50 30.5 7.50
8 3.47 14.28 32.1 8.16 4.25 15.24 27.8 8.42
9 3.48 14.21 35.5 7.37 4.17 16.02 27.2 8.22
10 4.15 13.56 32.7 7.58 4.31 15.18 27.6 7.58
11 4.07 14.20 34.6 7.44 4.26 15.13 28.0 8.07
12 3.57 14.22 33.4 7.52 4.35 14.32 28.8 8.16
Paraffinic 13 4.04 14.45 33.9 7.57 4.35 16.28 26.3 8.56
14 4.00 13.45 32.5 7.13 4.29 14.58 27.2 8.28
15 4.21 14.06 35.5 7.28 4.39 15.00 26.4 8.14

Little difference was observed for various oil types at 10 and 20 phr. 23
PROCESS OILS

Comparison of Different Process Oils

Effect on Hardness
Hardness, IRHD
70

60
Average Values of Hardness for
50
the Three Oil Types
Dosage A N P
40 (phr)
30 10 62 61.5 62

20
20 56.5 56 54.5

10
• Almost no effect on hardness at
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 10 phr.
Aromatic Naphthenic Paraffinic • At 20 phr. paraffinic oils show
20 phr slightly greater softening effect.
Some effects on hardness 24
PROCESS OILS

Comparison of Different Process Oils

Effect on Tensile Strength
Tensile strength, MPa
30
8
25 2 6 7 9 13
3 11 12 14 15
10
1 4 5
20 unaged

15
aged 28 days 70°C
10

aged 3 days 100°C

5

aged 7 days 100°C

Aromatic Naphthenic Paraffinic
20 phr of oil
• 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
PROCESS OILS

Comparison of Different Process Oils

Effect on Compression Set
Compression set, %
60

50
1 day 100°C

40

30
7 days 70°C
20

10
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Aromatic Naphthenic Paraffinic
20 phr of oil/25% initial compression

Paraffinic and naphthenic oils tend to give lower

compression set values than aromatic oil. 26
PROCESS OILS

Comparison of Different Process Oils

Effect on Dunlop Resilience
Dunlop resilience, 23°C, %
80

70

60

50

40

30

20 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Aromatic Naphthenic Paraffinic
20 phr of oil
• Aromatic oil gave lower resilience
• Higher viscosity oils gave lower resilience 27
PROCESS OILS

Performance of Low PAH/PCA Oils

Rolling Resistance Wet Grip

110
TDAE
108 +
MES
106
NAP
104 RAE
102
100
98
96
94 -
92
90
- +
DAE TDAE MES NAP RAE Rolling Resistance

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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 efficient
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PROCESS OILS

SUMMARY
5. Study on NR compounds showed that the vulcanisation properties
and vulcanisate properties, unaged and aged, are not greatly
affected by type of process oil.
6. Toxicity of process oils is of major concern at present.
- Polycyclic Aromatic Hydrocarbon (PAH) is carcinogen and
may cause mutation.
7. European Directive 2005/69/EC imposed ban on process oils
containing ≥10 ppm of PAH since 2010.
8. The developing trend in process oil is towards low PAH oils.
- TDAE
- MES
- NAP
- RAE
- Vegetable oils 30
Q&A

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