Introduction to Arlanxeo

NBR and Therban HNBR

NBR and HNBR short course

Herman Dikland

Kharagpur, September 4, 2017

Principles of Polymerization
Classification

Polymerization
chain

Kinetics
Step-growth Chain-growth
Polymerization Polymerization

Poly- Poly- Radical Cationic Anionic Coordi-

Mechanism conden- addition native
sation

3
Principles of polymerization and production processes
An overview

Emulsion Solution Dispersion/ Bulk Gas

Slurry Phase
Radical e-SBR, CR, NBR, EVM AEM,
polymerization e-BR, ACM, FKM EVM
Ziegler/Natta BR, EPDM EPDM EPDM
Anionic s-BR, s-SBR, IR Q
Polymerization
Cationic ECO, CO IIR Q
Polymerization
Polyaddition/ AU, EU EU AU, Q
condensation
Polymer CIIR, BIIP, CM, CM, CSM
modification CSM, HNBR

4
NBR in a nutshell:
The affordable Oil & Fuel Resistant
Rubber
Chemistry of emulsion polymerization

+ Emulsion polymerization
Water N
Initiator R* A water-soluble initiator is
+ introduced in the water phase
N
N N
Polymerization starts in the
N watery phase and first small
* n
* chains are entering the micelles
M
N Acrylonitrile-Butadiene Additional monomer diffuses into
Modifier Copolymer the micelles as polymer chains
Swollen Micelles = NBR grow

Latex Particle The water helps to control the

exothermic reaction of
Emulsifier Layer polymerization

Mooney controlled by chain

Start and propagation of the polymerization transfer agent

6
Structure of Nitrile Rubber NBR
NBR - a random copolymer of 1,3-butadiene and acrylonitrile

NBR polymer
3rd monomer possible
Random copolymer of
trans Butadiene (~78%)
N 1,3-butadiene and acrylonitrile
X
Butadiene can be incorporated
* in different ways
N (thermodynamically driven)

N Additional ter-monomers may

N be introduced in the polymer
cis Butadiene (~12%)
backbone
vinyl Butadiene (~10%)

Ratio of ACN to BD ranges

from 15 to 50%
Acrylonitrile

Microstructure of NBR

7
Industrial production of NBR
Polymerization and monomer recovery

Polymerization Monomer Recovery

Stopper

Stripping
column

Degassing
n Blow down (BD flash)
Reactor cascade tank
NBR latex
(monomer free)
Modifier, Catalyst, Emulsifier, Water, Monomers…

8
Industrial production of NBR
Latex storage and finishing

Latex Storage Finishing

Coagulant
water

NBR (wet)

Operating Coagulation +
tanks Washing
Dewatering

NBR latex
(degassed) Drying NBR
(dried)

9
NBR properties
Oil resistance governed by the content of ACN

260
FKM

Price
240
Temperature resistance (°C)

220
MVFQ MVQ
200

Price
180
90%VA ACM 40%VA
AEM EVM
160
HNBR
EPDM
140 CM IIR
CSM
CO/ECO
120 NBR

Price
SBR
100 CR BR
NR
80

60
0 20 40 60 80 100 120 140 160 180
Oil swelling IRM 903 (vol.%)

13
NBR properties
ARLANXEO Brands

3 strong Lanxess NBR brands

which represent highest quality

14
NBR properties
Key properties, markets and applications

Good mechanical properties Picture/Artwork size:

Key
Wherever oil resistance is required
Properties Height = 4.02 cm
Temperature of use up to 120°C Width = 7.09 cm

Picture/
Typical Artwork size:
cm
Applications HxW=
3.05 cm x 3.05 cm

Market volume : 540 kt (2016)

Picture/Artwork size:
Average market growth : 2%
Market
Powder market volume : 74 kt (2016) Height = 4.02 cm
Width = 7.09 cm
Powder market growth : 5%

15
NBR properties
Special product families for enhanced properties

Change of weight [%]

NBR – Rubber made of Acrylonitrile 300
250
and Butadiene NR
200
150 Test fluid
Unique Property SBR
100 IRM 903
CR
— Oil resistance 50
NBR
0
0 7 14 21
Additional Properties Immersion Time [days]
— Abrasion resistance (XNBR)
Oil resistance
— Ozone resistance (NBR/PVC) 6
5
Heat resistance
— Form stability (XL grades) 4
3 Fuel resistance
— Low temperature (low ACN) 2
1
0
— Mould fouling (clean grades) Resistance Low temperature
against abrasion properties
— Lowest oil/fuel swell (high ACN)
and wear NBR
— Low VOC (low emission grade) EPDM
Gas permeability Sealing force
SBR
retention

16
NBR properties
Mostly used for seals and hoses

belts
friction parts
sheets, flooring, 2%
4% others
blankets
7% seals
4% shoes
30%
5%
cables
6%

insulation
rollers 8% hoses
7% 27%

17
NBR properties
Grade code provides quick reference to the key polymer properties

Brand <ACN> <Mooney> <Country of origin>

Perbunan 2845 F: ACN content: 28 %
Perbunan® / Krynac®
Mooney: 45 MU
standard grades
origin: F (France) - C (China)
VP = trial product

Brand <Key property1> <Key property 2> X = carboxylated

Perbunan® / Krynac® Krynac X 740 7 = 7% carbox. acid
XL = pre-X-linked
special purpose grades Krynac XL 33.55
M = Mesamoll extended
Krynac M 3340 F

Special property :
XL = crosslinked ACN % content
Nothing = linear

Baymod ® N XL 33.61 1 = PVC

Baymod® N Mooney Viscosity
2 = Calcium Stearate
3 = CaCO3
5 = 50 4 = Silica
NBR 6 = 60
etc…

18
Choosing the best polymer regarding
application and process
Key properties of ARLANXEO NBR
ACN content impacts balance of oil resistance and low-temperature properties

Krynac
Perbunan Good oil resistance
Medium ACN
28-39%

Krynac Optimum oil resistance

Perbunan Fuel resistance
High ACN
39-50% Low-temperature properties compromised

Krynac
Good oil resistance
Perbunan
Low ACN Very good low-temperature flexibility (Tg -50°C)
18-28%

20
Key properties of ARLANXEO NBR
Glass temperature increases linearly with increasing ACN content
Glass transition temperature Tg [°C]

ACN content
0
Glass transition temperature
-10 (DSC) mainly depends on the
-20 ACN content

-30 Linear Gordon-Taylor relation:

-40
Tg = 1,45*[ACN] - 77,1
-50
Improved low-temperature
-60
performance at the expense of
-70 oil and fuel resistance for
standard NBR grades
-80
0 10 20 30 40 50
Bound ACN [%]

Low-temperature performance

21
Key properties of ARLANXEO NBR
Mooney impacts processing and vulcanizate properties

Krynac
Good processing behaviour
Perbunan
Medium Mooney Good mechanical and dynamical properties
45-80MU

Krynac
Best flowability / processing behaviour with high
Perbunan
Low Mooney reinforcement
25-45MU

Highly extendable / fillable

Krynac
Best mechanical and dynamical properties
Perbunan
High Mooney Blend partner for adjusting processing & properties
80-120MU
Krynac M 3340 already plasticizer extended

22
Key properties of ARLANXEO NBR
Choose the proper cure speed
Monsanto MDR 2000 E at 160°C
25 GL#30961
Normal cure speed
Normal cure speed for improved bonding 20
Krynac on textile or brass
normal

Torque dNm
cure speed
Normal cure speed for long flow paths in 15

moulding
Improved tackyness 10

5 Perbunan 3445 F

High cure speed Krynac 3345 F

0
High cure speed for shortest moulding 0 5 10 15 20 25 30
cycle times Time min
Perbunan
high Higher curing density
cure speed Higher modulus
Improved compression set values Equal ACN and equal Mooney is not
Higher abrasion resistance enough to select an NBR grade !

23
Specific properties of ARLANXEO NBR
Krynac X for best abrasion and wear resistance

Best abrasion resistance

Best wear resistance
Krynac X Best compression set
Carboxylated Best bonding to hydrophilic surfaces
Compatibilisation: Bonding to polyamide (2K)

24
Specific properties of ARLANXEO NBR
Krynac XL improves extrusion and calendaring

High dimensional stability

Improved collapse resistance (extrusion)
Krynac XL Smoother surfaces
Pre-crosslinked Low die swell (extrusion)
Low shrinkage (calendaring)

25
Specific properties of ARLANXEO NBR
Clean grades for injection moulding

Quick processing
Perbunan
Fast Short cycle times
cure speed
High modulus

Quick processing
Short cycle times
Perbunan CHM High modulus
Fast Low tendency to corrosion
cure speed
Clean High Modulus Low mould fouling
Low migration and extraction levels
Best for food contact applications

26
Specific properties of ARLANXEO NBR
Low emission grades for indoor requirements

Properties as already described

Current − Oil resistance
− Good chemical resistance
Krynac − Good dynamical properties
Perbunan − Abrasion resistance
− Low permeation

Low VOC Additionally to current properties

− Low emission (VOC)
Perbunan − Low fogging
Krynac − Best for indoor/closed environments

27
Specific properties of ARLANXEO NBR
Baymod N for rubber applications

Soluble in polar solvents

Mixed with fibers (e.g. glass fibers) in gaskets
Excellent oil and chemical resistance

Baymod N Sulfur
Non pre-crosslinked
Curing Needed
Peroxide

Easy-Peel Effect for cables’ internal layers

29
Specific properties of ARLANXEO NBR
Baymod N XL for thermoplastic modification

Excellent compatibility with PVC

PVC modification Good oil and fuel resistance
Less plasticizer migration
Baymod N XL High elasticity and dimensional stability
Precrosslinked
“Rubber touch” and smooth surface
Low shrinkage in calendaring

Friction Excellent compatibility with phenolic resins

Very good oil, fuel resistance, friction coefficient
Baymod N XL Noise reduction and better grip
Precrosslinked
No chemical curing needed

30
Summary of NBR key product properties
Good mechanical and dynamic properties and excellent resistance to oil

Excellent resistance to swelling in oils / lubricants / fuels / greases

⇒ Volume swell (ASTM oil #3) < 10% (110 °C, 14d, 34% ACN)
Good heat resistance
⇒ Service temperature < 110-120 °C (criterium 1000h)
Good low temperature flexibility
⇒ Glass transition temperature from -5 down to -50 °C (depending on ACN content)
High level of mechanical properties
⇒ Tensile strength up to 35 MPa; Hardness may range from 25 to 95 Shore A
Low permanent set
⇒ compression set < 10% (70h / 100 °C)
Good abrasion and wear resistance
Low gas permeability

33
Therban HNBR

1 Introduction - what is Therban?

2 Therban product portfolio and properties

3 Therban compounding

4 Applications

34
Properties of HNBR

Excellent
Good resistance
Very good
against
resistance to oil,
aggressive media
grease and fuel
(base)
Low gas
permeability

Very good low

temperature
flexibility
Excellent
resistance to HNBR
wear

Heat resistance
Excellent ozone up to 120°C
resistance Excellent physical 150°C
properties at Excellent physical
elevated properties
temperatures

35
What is Therban®?
From NBR to HNBR

NBR vs. HNBR

NBR: Poly(acrylonitrile-co-butadiene)
Therban® is made by hydro-
genation of NBR in a solution CH2 CH CH2 CH CH CH2 CH2 CH
a b c
process C CH

Basic properties of HNBR are N CH2

similar to NBR + Oil Resistance - Aging Behavior

H22
Key parameters
HNBR: hydrogenated NBR
ACN content
CH2 CH CH2 CH2 CH2 CH2 CH2 CH
Degree of hydrogenation / a b c
C CH2
Residual Double Bonds (RDB)
N CH3
Mooney viscosity
+ Oil Resistance + Aging Behavior

36
What is Therban®?
Synthesis

Therban® synthesis (direct polymerization not –yet- possible!)

NBR Synthesis
Removal of Thermal
Emulsion Latex- Mechanical Bale Packaging
residual drying
polymerization coagulation de-watering press and storage
monomers

HNBR Synthesis

Solvent
catalyst catalyst recovery

Bale Dissolving Steam

Metathesis Hydrogenation
grinding of NBR Stripping

Mechanical Thermal Bale Packaging and storage

de-watering drying press

37
Properties of Therban
Map of elastomers

Service temperatures and oil swell (acc. to ASTM D 2000) HNBR vs. other elastomers
HNBR and NBR are in the
260
class of polar rubber materials
FKM
240
NBR is limited to service
Temperature resistance [ºC]

220 temperatures below 120°C

MVFQ MVQ
200

180
Therban (HNBR) goes up to
90%VA ACM
AEM EVM
40%VA
approximately 150°C for long
160
HNBR term service temperatures, up
140 CM
CSM
IIR EPDM
to 180°C in peaks
CO/ECO
120
NBR
100 CR
SBR
BR
With certain formulations the
NR long-term service
80
temperature limit can be
60
0 20 40 60 80 100 120 140 160 180
extended to approximately
170°C
Oil swell IRM 903 [vol.%]

38
Properties of Therban
Excellent dynamic and low-temperature properties

Unique properties
Excellent dynamic properties
are a major advantage of
Low Temperature Flexibility

Therban
Therban has excellent low
HNBR NBR ACM temperature properties:
CR
AEM
Thanks to relaxation
phenomena, below Tg Therban
EVM behaves leathery, not glassy
Typical Therban compounds
show a brittleness temp.
FKM
below -50 °C. Brittleness
points below -70 °C are
accessible by use of adequate
plasticizers

Dynamic properties

39
Agenda

1 Introduction - what is Therban?

2 Therban product portfolio and properties

3 Therban compounding

4 Applications

40
Therban product portfolio

Typical data sheet values Nomenclature

Trade Name Derivation:
Placeholder for a default text with indention in Arial
Therban 3406
Therban 3406 Ther 16 pt. Thermal Resistant
ban Butadiene Acrylo- Nitrile
Line
34 spacing: Simple,
% 1 line
ACN (34, 39, 36, 43, 50)
ACN content 34
0 % RDB (0 = full, 2, 4, 6 = 5,5)
Paragraph
6
spacing: 12 pt. before paragraph
Mooney Viscosity (x 10) approx.
RDB <0,9
Font size for short text max. 18 pt.
Mooney viscosity 63 ACN content = acrylonitrile
Font size content
for more text min. 14 pt.
Amount of ACN incorporated into the HNBR rubber
− First indented line
− Second
RDB = residual double bonds indented line
Amount of double bonds left after hydrogenation, NBR could
− Paragraph
be described spacing
as having 100%should
RDB be 6 pt. before

Mooney viscosity
Correlated to molar mass of HNBR and an indication of
processability

41
Therban product portfolio
Broad range of standard and special grades

Therban AT and
Standard Grades Therban LT Therban XT
Therban ART
Key parameters: HNBR ter-polymer HNBR terpolymer with AT grades : low ML
carboxylic moiety
ACN content for Reduced Tg Improved flowability
media resistance Excellent adhesion to and filler loading
Improved low- metal surfaces
Mooney viscosity for temperature
processability properties Excellent abrasion
properties
Partially / fully
saturated grades
ART grades: Zn
diacrylate containing
masterbatch
Improved mechanical
and dynamical
properties

42
Therban product portfolio

Typical data sheet values 34 to 49 55 to 100 0.9 to 18

ACN content Mooney viscosity RDB
The standard Therban grades cover Placeholder for a default text with indention in Arial

Fully Hydrogenated
Therban 3406 63
a broad range of ACN-content, 16 pt. 34 <0,9
Mooney viscosity, and RDB Therban 3407 34 70 < 0,9
Therban 3607 Line spacing:
36 Simple, 1 line
66 < 0,9
The lowest ACN content for the Therban 3907 39 70 < 0,9
standard grades is 34%, the highest Therban 4307 Paragraph
43 spacing: 12 pt.63before paragraph
< 0,9
44% 100
Therban 4309
Font size43for short text max. 18 pt. < 0,9

Partially hydrogenated Therban 3446 34 61 4

§ Placeholder for a default text Font size for more text min. 14 pt.

Partially Hydrogenated
Therban 3467 34 68 5,5
Mooney viscosities range from 55 to Therban 3496 − First indented
34 line 55 18
100 MU Therban 3627 − Second36indented line 66 2
Therban 3629 36 87 2
The RDB content varies from <0,9% − Paragraph spacing should be 6 pt. before
Therban 3668* 36 87 6
to 18% Therban 4367 43 61 5,5
Therban 4369 43 97 5,5

*VP, trial product Therban 4498* 44 78 9

43
Therban properties
RDB strongly influences product properties

By controlled
Title - Arialhydrogenation
18 pt. bold of NBR
Therban grades with different
Peroxide crosslinking
amounts of RDB
Placeholder for a(residual double
default text
bond)
with contentsincan
indention be16
Arial produced
pt. Sulfur crosslinking

Line spacing: Simple,

RDB1can
linebe
Therban with high <1 % 5% 10 % RDB
crosslinkedspacing:
Paragraph using sulfur
12 pt. before
paragraph Picture/Artwork
Crosslinking density size:
High RDB increases crosslink
density,
Font sizealso in peroxide
for short cure 18
text max.
pt. Compression set
Compression set depends on Height = 12.29 cm
Font size forand
formulation more text min.
storage time 14
Modulus
pt. Width = 13.92 cm
Hardness
Highindented
First RDB reduces
line the ageing
stability of the material Temperature resistance
Second indented line
Paragraph spacing should be 6 Ozone resistance
pt. before
H2S resistance

44
Therban properties
Compression set influenced by RDB

T 3668 / T 3607 Title - Arial 18 pt. bold

100
90 6% RDB
80 <0,9% RDB

Compression Set [%]

70
60
50
40
30
20
10
0
168h 1008h 3024h
Compression set for high RDB grades often better
with same formulation compared to fully saturated
grades, but, ageing is worse.

45
Properties of Therban®
Low-temperature properties – CS

Tg and TR-10 Low-temperature compression set

0 100
Tg DSC TR -10
-5 90
Therban 3607
80
-10 Therban 3668
Temperature [°C]

Compression Set [%]

70
Therban LT 2007
-15 60
Therban LT 2057
-20 50
40
-25
30
-30
20
Therban 3607 10
-35
Therban 3668 0
-40
Therban LT 2007 -20°C/24h 175°C / 168h

46
Properties of Therban®
Ozone resistance

Influence of RDB content on ozone resistance Ozone resistance

Partially saturated HNBR

Ozone concentration: 50 pphm grades can be susceptible to
Temp: 40 ºC, ozone cracking!
Relative humidity 55%
Flow > 500 mm/s Occurrence and extent of crack
40% static elongation formation depends on
LT 2057 LT 2007 compound recipe and
5.5 % RDB fully hydrogenated measurement conditions
Use of fully saturated grades,
rating after 24 (hrs) 2/1/3/3 0/0/0/0
rating after 48 (hrs) antiozonants, waxes or TMQ
3/3/5/3 0/0/0/0
rating after 72 (hrs) can help
5/4/5/5 0/0/0/0
rating after 96 (hrs) 5/4/5/5 0/0/0/0
rating after 120 (hrs) 5/4 0/0/0/0
rating after 144 (hrs) 5/4 0/0/0/0
rating after 168 (hrs) 5/4 0/0/0/0

47
Properties of Therban®
Ozone Resistance

Influence of cure system on ozone resistance Ozone resistance

A sulfur cured compound with

Peroxide Cured Peroxide Cured Sulfur Cured
antiozonant Vulkanox® 4020
Therban® AT 3404 100
added, performed worse than a
Therban® AT 3443 100 100
peroxide cured one with
Vulkanox® 4020 1.0
Vulkanox® HS
Vulkanox® HS 1.2 1.2
Vulkanox® ZMB2 0.4 0.4 addition of wax and higher
Struktol® WB 222 0.5 0.5 0.5 dosage of antiozonant required
Ozone Test (20% Elongation, 200 pphm, 25°C, 60% rel. humidity, 46 h; > 500mm/s) => even if an antiozonant has
2h 0 0 0 been added, the final part has
4h 0 0 0 to be carefully tested, if ozone
6h 0 0 0 resistance is required
8h 0 0 0
24 h 0 0 4/2
46 h 0 0 5/2

48
Therban properties

ACN content
The nitrile group (ACN) strongly
34 % Placeholder39
for a%default text with
44indention
% ACN in Arial
influences the oil resistance
16 pt.
and low temperature flexibility
Oil resistance
Line spacing: Simple, 1 line
Higher ACN content means
Fuelspacing:
Paragraph resistance
12 pt. before paragraph
better oil resistance
Hardness
Font size for short text max. 18 pt.
Higher ACN content means
poorer low temperature Font size forDensity
more text min. 14 pt.
flexibility − Low
First temperature
indented line flexibility
− Second indented line
Elasticity
− Paragraph spacing should be 6 pt. before
Gas impermeability

49
Therban properties
Fluid Swell Follows ACN Content

Swell in oil and fluids

Swell depends on type of fluid Placeholder for a default text with indention in Arial
Typically, volume swell is 16 pt.
reduced with higher ACN Line spacing: Simple, 1 line
content
Paragraph spacing: 12 pt. before paragraph
Generally, HNBR with 39 %
ACN already has an excellent Font size for short text max. 18 pt.
oil resistance
Font size for more text min. 14 pt.
For oil exploration: H2S − First indented line
resistance is better with lower
− Second indented line
ACN content
− Paragraph spacing should be 6 pt. before

50
Therban properties
Low-temperature properties follows ACN content

Low-temperature properties
Low temperature flexibility Placeholder for a default text with indention in Arial
is strongly improved with 16 pt.
decreasing ACN content
Line spacing: Simple, 1 line
Materials with higher RDB
have less crystalline areas, Paragraph spacing: 12 pt. before paragraph
therefore lower TR-10
(especially for low ACN Font size for short text max. 18 pt.
grades) Font size for more text min. 14 pt.
Therban® LT grades for best − First indented line
low-temperature properties − Second indented line
and excellent low temperature
CS − Paragraph spacing should be 6 pt. before

51
Properties of Therban®
Oil and diesel fuel resistance

Plasticizer influence
Swell in oil and fuels can be
further reduced by use of
plasticizer (and filler)
Even by simple addition of 10
phr plasticizer (here: Rhenosin®
W 95) without correction of
hardness by increasing dosage
of fillers, an improvement can
be observed

52
Properties of Therban®
Relation between low-temperature properties and oil resistance

Tg vs. oil swell

The higher the ACN content,

the lower the oil swell
Unfortunately, Tg increases
simultaneously

53
Low-temperature properties
Linear dependency of Tg on ACN content for NBR

Gordon-Taylor equation Low-temperature properties of NBR

Tg mainly depends on the polymer composition due NBR has a linear correlation between ACN and Tg
to following the Gordon-Taylor equation
flexibility of chain segments Lower ACN content results in lower Tg
0
intermolecular interactions
crystallinity -10

Tg of random copolymers can be estimated from -20

Tg [°C]
the properties of the pure components by using the
-30
Gordon-Taylor equation
-40
∗ , + ∗ , +⋯
, = -50
+ +⋯ 0 10 20 30 40 50 60
ACN content [%]

= , , =
54
Therban® AT – A case study
O-ring formulation

Test Compound
phr phr phr phr phr phr
O-ring formulation
Therban® 3407 100 75 50 25
Three polymers with
Therban® 3406 100
different Mooney viscosity
Therban® AT 3404 100 25 50 75 70 MU; 60 MU and 39 MU
Vulkanox® ZMB-2 1.1 1.1 1.1 1.1 1.1 1.1
Additionally blends
®
Rhenofit DDA 70 0.4 0.4 0.4 0.4 0.4 0.4 between 70 MU and 39
N 550 50 50 50 50 50 50 MU tested
MgO 2 2 2 2 2 2 All other ingredients kept
ZnO active 2 2 2 2 2 2 constant
Plasticizer 5 5 5 5 5 5
TAIC 1.5 1.5 1.5 1.5 1.5 1.5
Perkadox® 14-40 7 7 7 7 7 7

62
Therban product portfolio
Therban XT for abrasion resistance and stiffness

Therban XT – hydrogenated, ACN content Mooney viscosity RDB

caboxylated, nitrile butadiene Therban XT KA 8889* 33 77 3,5
rubber

Developed to enhance abrasion

resistance, tensile strength and HXNBR
adhesion properties compared to
CH2 CH CH2 CH2 CH2 CH2 CH2 CH CH2 C
standard HNBR a b c d
C CH2 HO C

N CH3 O

+ Oil resistance + Aging behavior + Adhesion / Abrasion

*VP, trial product

66
Agenda

1 Introduction - what is Therban?

2 Therban product portfolio and properties

3 Therban compounding

4 Applications

69
How to chose the right Therban grade?
Grade selection

ACN-content
Low temperature

ACN
ACN

Oil resistance
properties

Sulfur cure RDB content

RDB
Peroxide cure
RDB

Excellent dynamic
Ozone resistance
properties

Mooney viscosity

MU
standard
MU

Injection moulding

70
Comparison of crosslinking types
Peroxide cure for high-temperature resistance and increased service life

Peroxide versus Sulfur Cure

Peroxide cured, carbon black filled HNBR was

Adhesion
taken as standard – this material has a good
balance of properties
Abrasion
service life
resistance Use of sulfur instead of peroxide cure slightly
improves adhesion and mechanical properties

Service life is influenced by heat ageing and tear

mechanical resistance
Ageing
properties
− Tear resistance is improved when using sulfur
processing instead of peroxide cure
PO cure − Heat resistance is significantly reduced, sulfur
S cure
cure should not be used above 135°C

71
Therban® basic compounding
Curing systems

Sulfur-Cure Peroxide Cure

Typical EV cure system for Therban®: Typical cure system:

˃ ZnO 4.0 phr ˃ TAIC 1.4 phr or
˃ stearic acid 1.0 phr ˃ TRIM/70 2.0 phr
˃ DCBS 2.0 phr ˃ Perkadox® 14-40 7.5 phr
˃ TMTD 1.5 phr
˃ S 0.4 phr

If a nitrosamine safe system is needed, one can Some rules of thumb:

use e.g. TBzTD instead of TMTD ˃ peroxide dosage has to be reduced for partially
saturated grades
Watch ozone resistance!
˃ peroxide dosage has to be increased for AT grades
˃ peroxide dosage has to be reduced for low filled
compounds

72
Coagents
Significant influence on properties

elongation compression set

299 3.000 T90
300 289
Scorch 2.620
249 2.500
250 2.161
2.000
200 178
1.500
150

100 1.000
542
50 500 325
23 26 24 267 282 219 273
21
0 0
TRIM HVA2 Ricon TAIC TRIM HVA2 Ricon TAIC
HVA2 most efficient co-agent, but scorchy
TRIM good combination of elongation and CS
TRIM low scorch safety
Ricon highest elongation
TAIC optimal combination

73
Filler comparison

Carbon black Silica + Silane RPA

Silica +
Silane
Carbon
500 Black

G' [KPA]
Van der Waals interaction Chemical bonds between filler
and polymer via silane 50
0,1 1 10 100 1000
Amplitude [%]

76
Therban® basic compounding
Carbon black

78
Compound phr Carbon Black
76
Therban 3907 100
N330
Carbon Black 50 74

Hardness [Shore A]
ZnO 5 N326
72
Stearic Acid 1 N550
MgO 3 70
N660
ZMB2 0,4 68
CDPA 2 N762
66
Ricon 153D 6 N774
Varox DBPH 50 10 64
N990 N 330 N 326 N 550 N 660 N 774 N 762 N 990

Variation of CB types, varying in both structure

Hardness increases with higher structure
and surface

77
Therban® basic compounding
Carbon black

Drop in tensile strength with lower activity of CB Lower surface area decreases compression set

78
Therban® basic compounding
Carbon black

Higher rebound with lower activity of CB Higher abrasion with lower activity

79
Filler comparison
Advantage of silica silane system

Silica-silane vs. carbon black

Adhesion is greatly improved by the use of silane

Adhesion
Abrasion resistance is slightly reduced
Abrasion
service life Silica and silane is influencing crosslinking of the
resistance
rubber, therefore processing is more challenging

Service life is improved, since life time in tear

mechanical analyzer is increased and heat build up reduced
Ageing
properties

processing
Carbon Black
Silica Silane

80
Therban® basic compounding
Plasticizers

Plasticizers for Therban® Test Recipe

Ester-type plasticizers are commonly used

Mineral oils are not suitable phr

Dosage normally between 0 and approximately 20 Therban® LT 1707 VP 100

phr N990 80
Watch volatility of the plasticizer! N550 20
Plasticizer 10
CDPA 1.5
Vulkanox® ZMB2/C5 0.4
Rhenofit® TRIM/S 1.6
Perkadox® 14-40 8.5

82
Therban® basic compounding
Plasticizers

Plasticizers
Uniplex® 546 TOTM
Broad variety of plasticizers has
Uniplex® 809 PEG Di-2-Ethylhexanoate been tested
TOTM as a kind of "standard"
Uniplex® 810 PEG Dilaurate for Therban® compounding
Uniplex® 810 TM-E C8-C10 trimellitate ester
Rhenosin® W-95 adipinic diester
Rhenosin® W-759 ether-ester compound
ADKCizer® RS-735 polyether-ester
TegMer 812 Polyether-ester

83
Agenda

1 Introduction - what is Therban?

2 Therban product portfolio and properties

3 Therban compounding

4 Applications

88
Therban applications

Automotive and industrial applications

Belts
Seals and gaskets
Dampers
Hoses
Boots and bellows
Rollers

Oil field applications

Stators for pumps and mud motors

Packers
Hoses
Seals
Blow out preventers

89
Therban application example:
Timing belt compound sulfur cured

Compound phr Values

Therban 3446 100 Hardness 65 Sh A
Carbon Black N772 60
M25 1,4 MPa
ZnO 5
Stearic Acid 1 M100 3,9 MPa
CDPA 1,1 Elongation at Break 410%
ZMB2 0,4
Tensile Strength 20 MPa
Sulphur 0,5
Vulkacit DZ 2
TMTD 1,5

SUM PHR 189

Use of two different carbon blacks to have good

High elongation, typical for sulfur cured materials
extrudability and high mechanical properties

90
Therban application example:
Timing belt compound long lifetime

Compound phr
Values
Hardness 75Sh A
Therban 3406 75 M25 1,7 MPa
Therban ART KA 8796 50 M100 7,9 MPa
Carbon Black N330 30 Elongation at Break 235%
Silica 10 Tensile Strength 25 MPa
CDPA 1,1 Goodrich HBU 40°C
ZMB2 0,4
MgO 3
Perkadox 14-40 8 Hot Air Ageing, 150°C, 7d
Change in Elongation -33%
TAIC 1,5
Change in Tensile Strenth 0%
Aramid fibers 0-5
Change in Hardness 7
SUM PHR 179

ZDA as in-situ filler for high tensile strength and

HBU lower than for carbon black formulations
good processability
Change in tensile strength negligible – excellent
silica/carbon black results in improved heat build
tooth stiffness after ageing
up

91
Therban application example:
Formulation for diesel hose

Highly filled compound

Good oil and media resistance

Compound
N990 for good extrudability Therban 4307 100
N-990 100
Flex fatigue resistance
TOTM 10
N990 allows higher filler level which reduces the ZnO 2
fuel swell CDPA 1
Vulkanox ZMB2 0,4
TOTM to improve low temperature properties and
MgO 2
retain properties after ageing
Peroxide (40 %) 7,5
Highly filled HNBR compounds are cheaper TAIC 2
compared to FKM based compound formulations

H ~70 ShA, TS 16,9 MPa, EB 325 %

93
Therban application example:
Heavy duty and soft rollers

Compound Compound
Therban 3629 100 Therban 3407 100
Ultrasil 7000 40 Carbon Black N990 30
ZnO 3 ZnO 2,0
Silquest RC1 3 MgO 2
Vulkanox ZMB2/C5 0,4 Vulkanox ZMB2/C5 0
Rhenofit DDA 1,1 Rhenofit DDA 1,1

TRIM 15 Ultramoll IV HV 15

ZDA 15 DOS 15
Perkadox 14-40 7
Perkadox 14-40 7
TAIC 1,5

High level of TRIM and ZDA for tight network Two plasticizers for low migration
Excellent abrasion resistance and high hardness Low amount of N990, soft black

95
High-performance Therban® helps to make future-oriented
applications a reality

Exceptional combination of oil and temperature

resistance
Resistance to abrasion, ozone, heat, diesel fuel,
chemicals and technical oils

Functions over a wide temperature range

Resistance to dynamical mechanical stress

Excellent retention of properties at elevated

temperatures

Long service life for system cost efficiency

96