Introduction To Process Oils

INTRODUCTION TO PROCESS OILS
Krisda SUCHIVA
Research and Development Centre for Thai Rubber Industry,
Mahidol University
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.
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
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
4
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.
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
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
7
Efficiency of physical process aids depend on degree of miscibility

with polymer or solubility in polymers.
most efficient
completely miscible
or
completely soluble
most effective in reducing

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

viscosity
Higher amount is required.
least efficient
immiscible
or
insoluble
least effective in reducing

viscosity
large amount is required.
PROCESS OILS
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
paraffins
Naphthenic oils
CH3CHCH2CHCH2CH3CH2
CH3
CH3
isoparaffins
derivatives of cyclohexane or decalin
Aromatic oils
derivatives naphthalene, debenzothiophene,
carbazole, etc.
10
PROCESS OILS
Type of Process Oils

%
paraffinic
%
naphthenic
%
aromatic
VGC
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
Type
11
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.
12
PROCESS OILS
Level of aromaticity measured by

1) VISCOSITY GRAVITY CONSTANT (VGC)
specific gravity
High VGC
1.0752-a
VGC
10
log(V+38)
Viscosity (saybolt)
high aromaticity
Aniline point
Low Aniline Point
temperature at which equal volumes

oil and aniline are mutually soluble.
high aromaticity
2) ANILINE POINT
note :
Aniline point can be influenced by MW of oil.

Can be difficult to determine with very dark and opaque oils.
13
PROCESS OILS

Compatibility of process oils with various rubbers
Oil Type
Rubbers
NR
SBR
BR
NBR
CR
EPDM
IIR
Paraffinic
Naphthenic
Aromatic
+ compatible
0 partially compatible
- incompatible
14
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
15
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.
16
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)
17
PROCESS OILS
Polycyclic Aromatic Hydrocarbons

PAHS
Chemical Formulas
MW (g.mol-1)
Chemical Structures
18
PROCESS OILS
Polycyclic Aromatic Hydrocarbons

PAHS
Chemical Formulas
MW (g.mol-1)
Chemical Structures
19
PROCESS OILS
Comparison of Different Process Oils

Effects on properties of rubber compounds and vulcanisates
Process Oils Compared
Sample number
Saybolt viscosity
38C
100C
VGC
Aromatic
1
2
3
4360
3500
-
210
96
81
0.991
0.954
0.981
Naphthenic
4
5
6
7
8
9
10
2520
2206
760
156
110
104
85.9
84.7
60
41.0
43.5
38.2
38.0
0.883
0.882
0.869
0.878
0.830
0.886
0.871
Paraffinic
11
12
13
14
15
2642
500
110
-
155
63.5
42.3
40.4
38.0
0.800
0.803
0.805
0.807
0.832
20
PROCESS OILS

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

Time (min)
0
0.5
1.0
2.0
3.5
Action
Add rubber.
Add small powders.
Add half black.
Half black plus oil.
Dump.
21
PROCESS OILS

Effects on Mooney Viscosity
Mooney viscosity, ML 1+4, 100 C
Mooney viscosity, ML 1+4, 100 C
50
60
50
40
40
30
30
20
20
10
10
1
Aromatic Oils
9 10
Naphthenic Oils
11 12 13 14 15
Paraffinic Oils
10 phr
Naphthenic oils tend to give lower

mooney viscosity
Aromatic Oils
9 10
Naphthenic Oils
11 12 13 14 15
Paraffinic Oils
20 phr
Paraffinic oils tend to give lower

mooney viscosity
22
PROCESS OILS

Vulcanisation Characteristics (ODR 100C)
Oil Type
Sample
10 phr oil
20 phr oil
ts5
(min)
Tc(90)
(min)
MHR
(torque
ML
units)
ts5
(min)
Tc(90)
(min)
MHR
(torque
ML
units)
Aromatic
1
2
3
4.12
3.42
4.16
14.33
13.13
13.47
33.0
35.6
32.9
7.35
7.45
8.25
4.51
3.58
4.25
16.00
14.32
14.28
24.3
27.2
30.3
8.46
7.08
9.00
Naphthenic
4
5
6
7
8
9
10
3.58
3.53
5.16
3.52
3.47
3.48
4.15
14.31
13.40
14.51
14.43
14.28
14.21
13.56
32.5
35.5
30.2
33.5
32.1
35.5
32.7
7.39
7.36
9.25
7.41
8.16
7.37
7.58
4.39
4.28
5.00
4.17
4.25
4.17
4.31
15.18
15.11
16.05
14.50
15.24
16.02
15.18
28.7
27.4
25.4
30.5
27.8
27.2
27.6
8.16
8.25
8.53
7.50
8.42
8.22
7.58
Paraffinic
11
12
13
14
15
4.07
3.57
4.04
4.00
4.21
14.20
14.22
14.45
13.45
14.06
34.6
33.4
33.9
32.5
35.5
7.44
7.52
7.57
7.13
7.28
4.26
4.35
4.35
4.29
4.39
15.13
14.32
16.28
14.58
15.00
28.0
28.8
26.3
27.2
26.4
8.07
8.16
8.56
8.28
8.14
Little difference was observed for various oil types at 10 and 20 phr.
23
PROCESS OILS

Effect on Hardness
Hardness, IRHD
70
60
Average Values of Hardness for

the Three Oil Types
50
Dosage
10
62
61.5
62
20
56.5
56
54.5
(phr)
40
30
20
10
1
Aromatic
9 10
11 12 13 14 15
Naphthenic
20 phr
Some effects on hardness
Paraffinic
Almost no effect on hardness at

10 phr.
At 20 phr. paraffinic oils show
slightly greater softening effect.
24
PROCESS OILS

Effect on Tensile Strength
Tensile strength, MPa
30
2
25
1
6
4
9
10
13
11 12
14 15
20
unaged
15
aged 28 days 70C
10
aged 3 days 100C
Aromatic
Naphthenic
Paraffinic
aged 7 days 100C
20 phr of oil
Individual oils gave widely different values of T.S

Effect of different types of oils on unaged, 70C aged or
100C aged are slight.
25
PROCESS OILS

Effect on Compression Set
Compression set, %
60
1 day 100C
50
40
30
7 days 70C
20
10
Aromatic
Naphthenic
9 10
11 12 13 14 15
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

Effect on Dunlop Resilience
Dunlop resilience, 23C, %
80
70
60
50
40
30
20
Aromatic
9 10
Naphthenic
11 12 13 14 15
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
108
TDAE
MES
106
NAP
104
RAE
102
100
98
96
94
92
90
DAE
TDAE
MES
NAP
RAE
+
Rolling Resistance
28
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
- smaller quantity may be used.
efficient
4. Compatibility or efficiency depends on

- % aromaticity : the higher, the more efficient
- MW or viscosity : the smaller, the more efficient
29
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
31

Introduction To Process Oils

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INTRODUCTION TO PROCESS OILS