Webinar Compounding-103 Smithers-Rapra 2-27-2019

Compounding 103:
Cure Systems
Webinar
February 27, 2019
Click here to access a

recording of the webinar
www.smithersrapra.com
CONFIDENTIAL
Today’s Presenters
Christine Domer Maggie Olson

General Manager, Analytical and Marketing Specialist
Physical Testing Laboratories Smithers Rapra
Smithers Rapra
www.smithersrapra.com 2
CONFIDENTIAL
Rubber Compounding Webinars
Title Date
Compounding 101: Polymers December 12, 2018
Compounding 102: Fillers & Process Aids January 29, 2019
Compounding 103: Cure Systems February 27, 2019
Compounding 104: Anti-degradant systems March 2019
Compounding 105: Lab Testing April 2019
CONFIDENTIAL
Agenda
• Review: The recipe for an optimized compound
• The five basic systems of a rubber recipe:
– Polymer system
– Filler system
– Oils & plasticizers system
– Cure system
– Anti-degradant system
• Cure Systems
– Vulcanizing agents, accelerators, activators
• Anti-degradants – March Session
– Degradation mechanisms
– Antioxidants, antiozonants, waxes
• Summary – Compounders Toolbox
CONFIDENTIAL
Rubber compound development
• Rubber Compounding Ingredients

– Polymer system
– Filler system
– Oils & plasticizers system
– Cure system
– Anti-degradant system
– Specialty
• Processing
– Mixing, extrusion, calendaring, injection, curing process
• Product Performance & Testing
Toughness, tear strength, flex fatigue, abrasion, adhesion,
hysteresis and heat build-up, damping, shock absorption, end use
environment (resistance to O2, O3, UV, aging, solvents, oils, etc.)
CONFIDENTIAL
Rubber Formula Example: Sulfur
Vulcanizate
Material phr
Raw rubber 100
Filler 50-150
Plasticizer 5-100
Sulphur 0-5
Zinc oxide 5
Stearic acid 2
Accelerator 0.5-3
Antioxidant 104
Other additives 0-
CONFIDENTIAL
Cure Systems
CONFIDENTIAL
Cure System
• Vulcanization agents or crosslinkers
• Accelerator Activators
• Accelerators
Uncured Rubber Crosslinked Rubber
CONFIDENTIAL
Cure System Definitions
• Vulcanization agents are chemicals that will react with
active sites in the polymer to form connections or cross-links
between chains.
• Activators are materials added to an accelerated

vulcanization system to improve acceleration and to permit
the system to realize its full potential of cross-links.
• Accelerators are chemicals used in small amounts with a

vulcanizing agent to reduce the time of (accelerate) the
vulcanization process. In sulfur vulcanization today,
accelerators are used to control the onset, speed, and extent
of reaction between sulfur and elastomer.
Source: Edited by B. Rogers, Rubber

Compounding, Chemistry and Applications, CONFIDENTIAL
Copyright © 2004 by Taylor & Francis
Physical Effects of Vulcanization
CONFIDENTIAL
Choice of Cure System
CONFIDENTIAL
Vulcanization Agents
Chemicals that will react with active sites in the polymer to
form connections or cross-links between chains.
• Sulfur
• Peroxides
• Metal Oxides
• Resins
CONFIDENTIAL
Sulfur
S8 Rings SX Chains
Rubber Makers Sulfur Insoluble Sulfur
Soluble
CONFIDENTIAL
Sulfur Crosslinks
Bonding Energy kcal/mol

Polysulfide —Sx-- 34
Disulfide —S-S-- 54
Monosulfide —S-- 74
Source: Rubber Technology, 3rd Edition, www.smithersrapra.com 14

Morton, 1987 CONFIDENTIAL
Activators
Materials added to an accelerated vulcanization system to
improve acceleration and to permit the system to realize its
full potential of cross-links.
Inorganic Organic
• Zinc Oxide • Stearic Acid
• Magnesium Oxide • Lauric Acid
• Lead Oxide • Amines
• Guanidines
• Ureas, thioureas
• Amides
CONFIDENTIAL
Accelerators
Chemicals used in small amounts with a vulcanizing agent
to reduce the time of (accelerate) the vulcanization
process. In sulfur vulcanization today, accelerators are
used to control the onset, speed, and extent of reaction
between sulfur and elastomer.
Guanidines Slow
Thiazoles Semi-Fast
Sulfenamides Fast-delayed
Thiurams Very Fast
Dithiocarbamates Very Fast
CONFIDENTIAL
Accelerator Development
1919-1922: Guanidines, Thiazoles, Thiurams, Dithiocarbamates
1945: Sulfenamides
ZDCB
“Dithiocarbamate”
MBT Ultra-Fast
“Thiazole”
Semi-Ultra
DPG
“Guanidine” TMTD
Slow “Thiuram”
Ultra-Fast
CBS
“Sulfenamide”
Fast-delayed Action
CONFIDENTIAL
Accelerator Classes

Common accelerators for sulfur cures
Source: The Vanderbilt Rubber Handbook, 14th www.smithersrapra.com 19

Edition, 2010 CONFIDENTIAL
Accelerator summary
http://www.nocil.com/Downloadfile/DTechnical www.smithersrapra.com 20
Note-Vulcanization-Dec10.pdf CONFIDENTIAL
Three classes of sulfur cure systems
1. Conventional systems – high S/A ratio
2. Efficient (EV) systems – high A/S ratio
3. Semi-EV systems that are between 1 & 2
Bonding Energy kcal/mol

Polysulfide —Sx-- 34
Disulfide —S-S-- 54
Monosulfide —S-- 74
CONFIDENTIAL
Crosslink Structure and Properties
http://www.akrochem.com/pdf/technical_papers/ www.smithersrapra.com 22
curing_w_sulfur.pdf CONFIDENTIAL
Fatigue Compromise
EV

Sulfur Reaction
Schemes
CONFIDENTIAL
Reaction Scheme – Sulfur Cure System
Source: N. J. Morrison, M. Porter,

RUBBER CHEM. TECHNOL. 57, 63 (1984) CONFIDENTIAL
Reaction Scheme – Sulfur cured NR
Source: Reaction scheme – Mechanism of

crosslinking natural rubber with sulphur and CONFIDENTIAL
accelerators, Stelescu et al
Reaction Scheme – Sulfur cured EPDM
Source: The Vanderbilt Rubber www.smithersrapra.com 27

Handbook, 14th Edition, 2010 CONFIDENTIAL
Arrehnius Equation
k the rate coefficient

A a frequency constant (rxn order)
Ea the activation energy
R the universal gas constant
T the absolute temperature
CONFIDENTIAL
General Rule of Thumb
Sulfur Vulcanization Reaction:
• Reaction rate approximately doubles for every 10°C
increase in temperature
CONFIDENTIAL
Peroxides
CONFIDENTIAL
Peroxide Crosslink Mechanism
HEAT
RO-OR 2 RO 1. Radicals form
RO + -HC=CH-CH-CH2-
|
H
2. Hydrogen abstraction
ROH + -HC=CH-CH-CH2-
-HC=CH-CH-CH2- 3. Carbon-Carbon crosslink

formed between polymer chains.
-HC=CH-CH-CH2-
CONFIDENTIAL
Peroxide Cured Rubber Features
Carbon-Carbon bond Imparts (vs sulfur)
couples two polymer chains • lower compression set
• improved heat resistance
• C-C crosslink is rigid,
• lower tear strength
strong • lower abrasion resistance
• C-C crosslink is thermally • poor hot tear
stable
Bonding Energy kcal/
mol
Polysulfide -Sx- 34
-HC=CH-CH-CH2 Disulfide -S-S- 54
Monosulfide -S- 74
-HC=CH-CH-CH2 Carbon carbon –C--C- 80
CONFIDENTIAL
Peroxide RO-OR
• Rate of crosslinking is directly proportional to the rate of
decomposition of the peroxide.
• Cure time and cure temperature is related to the half life. Half
life is the time required for half of the peroxide to decompose
at the reaction temperature.
• Peroxide selection based on cure time and temperature

needed and physical properties for the application
Dialkyl > perketal > perester > diaryl peroxides
CONFIDENTIAL
Peroxide RO-OR Avoidances
• Avoid heat in storage.
• Avoid acidic ingredients such as non-treated clays and
silicas. Use water-washed clays or silane treated silicas
• Avoid aromatic and naphthenic oil; use paraffinic oil.
• Avoid ingredients that are strong H donors
• Avoid oxygen exposure during curing (autoclave or flash)
• Avoid peroxide curing butyl, halobutyls, polyisobutylene,
polypropylene, epichlorohydrin, and polyvinylchloride.
CONFIDENTIAL
Peroxide Cures with Coagents
• Coagents: multi-functional monomers which lend a hydrogen
to the peroxide radicals and they contain double bonds for
crosslinking.
• Usage: improve processability and modify physical properties
• Coagent can improve properties:
– Heat age resistance
– Increase modulus
– Increase tensile strength
– Increase tear strength
– Improve abrasion resistance
– Improve compression set
– Lower compound viscosity
– Improve adhesion
Source: P. Dluzneski (2001) Peroxide

Vulcanization of Elastomers. Rubber Chemistry www.smithersrapra.com 35
CONFIDENTIAL
and Technology: July 2001, Vol. 74
Peroxide Cure with Coagents
http://www.pentasil.eu/images/Fundamentals
%20of%20Curing%20Elastomers%20with% www.smithersrapra.com 36
CONFIDENTIAL
20Peroxides.pdf
Coagents
http://www.crayvalley.com/docs/technical-
paper/fundamentals-of-curing-elastomers-with- www.smithersrapra.com 37
CONFIDENTIAL
peroxides-and-coagents-part-2-(1).pdf
Metal Oxide cure of CR
Source: The Vanderbilt Rubber Handbook, 14th www.smithersrapra.com 38

Edition, 2010 CONFIDENTIAL
Resin Cure – Novolak
R’ form cross links:

Methylene bridges (-CH2-) or
dimethylene ether (-CH2-O-CH2)
https://patents.google.com/patent/EP1016691A1/en www.smithersrapra.com 39
Bayer inc., 1999 CONFIDENTIAL
Summary: Compounder’s Tool Box
• Elastomer properties
• Modifying raw materials (fillers, oils/plasticizers) affecting
cost, processing, and cured properties
• Cure systems
• Antidegradants
• Processing
• Test methods
CONFIDENTIAL
Smithers Lab Locations
Location Services Offered
Akron, Ohio Analytical Lab

Materials Testing
Whole Product Testing
Technical Consulting Services
Tire Analysis Reports
Information Services
Ravenna, Ohio Whole Tire & Wheel Testing
Lansing, Michigan Whole Product Testing

Package / Distribution Testing
Brimley, Michigan Winter Testing Facility
Tire Traction Testing
Shawbury, UK Analytical Lab
Materials Testing
Whole Product Testing
Technical Consulting Services
Leatherhead, UK Whole Product Testing
Package / Distribution Testing
Information Services
Suzhou, China Whole Tire & Wheel Testing
CONFIDENTIAL
Contact
Christine Domer Jeremy Elliott

General Manager, Akron Labs Technical Sales Representative
(330) 762-7441 (330) 762-7441
cdomer@smithers.com jelliott@smithers.com
CONFIDENTIAL

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Compounding 103:

Click here to access a

Christine Domer Maggie Olson

• Rubber Compounding Ingredients

Uncured Rubber Crosslinked Rubber

• Activators are materials added to an accelerated

• Accelerators are chemicals used in small amounts with a

Source: Edited by B. Rogers, Rubber

Bonding Energy kcal/mol

Source: Rubber Technology, 3rd Edition, www.smithersrapra.com 14

Source: Edited by B. Rogers, Rubber

Source: The Vanderbilt Rubber Handbook, 14th www.smithersrapra.com 19

Bonding Energy kcal/mol

Source: Edited by B. Rogers, Rubber

Source: N. J. Morrison, M. Porter,

Source: Reaction scheme – Mechanism of

Source: The Vanderbilt Rubber www.smithersrapra.com 27

k the rate coefficient

-HC=CH-CH-CH2- 3. Carbon-Carbon crosslink

• Peroxide selection based on cure time and temperature

Dialkyl > perketal > perester > diaryl peroxides

Source: P. Dluzneski (2001) Peroxide

Source: The Vanderbilt Rubber Handbook, 14th www.smithersrapra.com 38

R’ form cross links:

Akron, Ohio Analytical Lab

Lansing, Michigan Whole Product Testing

Christine Domer Jeremy Elliott

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