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Introduction To Process Oils

1. Process oils are used as process aids to improve the processability of rubbers and lower production costs, and as extenders to increase the bulk of rubber. 2. Process aids work by lowering the viscosity and elasticity of rubber compounds through reducing intermolecular interactions between polymer chains. 3. The efficiency of process oils depends on their miscibility with rubber, with completely miscible oils being most effective at low dosages.

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162 views

Introduction To Process Oils

1. Process oils are used as process aids to improve the processability of rubbers and lower production costs, and as extenders to increase the bulk of rubber. 2. Process aids work by lowering the viscosity and elasticity of rubber compounds through reducing intermolecular interactions between polymer chains. 3. The efficiency of process oils depends on their miscibility with rubber, with completely miscible oils being most effective at low dosages.

Uploaded by

Daniel Daia
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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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.

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

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
4

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.

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

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
7

INTRODUCTION TO PROCESS OILS

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

Important Properties of 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

Important Properties of 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

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

15

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.
16

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)

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

Comparison of Different 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

Comparison of Different 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

Comparison of Different 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

Comparison of Different 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

Comparison of Different 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

Comparison of Different 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

Comparison of Different 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

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