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the tire and rubber industry

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2925 Briarpark Dr., Suite 1130, Houston, TX 77042
Tel +1 713 955-9230 - Fax +1 713 955-9226
sales.america@hur.com www.hur.com
 FEBRUARY 2018
years

129
The technical service magazine for the rubber industry Volume 257, No. 5

Mechanical reinforcement of rubber

by sp2 carbon allotropes such as carbon black

Titanates and zirconates

may be better adhesion promoters than silanes

Optimization of the silica/polymer interface

in the case of very high surface silica

Technical Service:
Six rules for rubber release agents

Advancing carbon black technologies

to improve tire performance
www.rubberworld.com

ACS Events, page 44

@rubberworld
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Contents Vol. 257, No. 5 February 2018

FEATURES
FEBRUARY
2018

14 Technical Service: Six

years

129
The technical

rules for release agents

service mag
azine for the
rubber indu
stry Volume 257
, No. 5

by Bob Edelmayer, McLube Release Coatings.

Six rules of thumb for selecting and applying Mechanical
reinforceme
by sp2 carbo nt of rubber
release agents will help molders navigate the n allotropes
such as carbon black
Titanates an
release industry and break bad habits. may be bette d zirconates
r adhes ion promoter
s than silanes
Optimizatio

24 Reinforcement of rubber
n of the
of very high silica/polymer int
in the case
surface silica erface
Technical Se

by sp2 carbon allotropes

Six rules for rv ice :
rubber releas
e agents
Advancing ca
rbon black te
by Maurizio Galimberti, Giuseppe Infortuna, to improve
tire perform
ance
chnologies

Vincenzina Barbera, Silvia Guerra and Andrea

.comorld
Bernardi, Politecnico di Milano; and Silvia Agnelli

www.rubberw
and Stefano Pandini, Universita degli Studi di ACS Events
, page 44
Brescia, Italy. An investigation examines the @rubberworl
d
parameters governing the reinforcement
effects on rubber promoted by carbon black Cover photo:
h Courtesy off Orion
and carbon nanotubes. Engineered Carbons

31 Titanates and zirconates

35 Optimization of the
may be better adhesion silica/polymer
promoters than silanes
by Salvatore J. Monte, Kenrich Petrochemicals. interface in the case
The reason why titanates and zirconates may
be better adhesion promoters than silanes for
of very high surface
silica and carbon reinforced polymeric area silica
composition lies in the intrinsic multi- by Laurent Guy and Thomas Chaussée,
functional chemistry of neo-alkoxy titanium Solvay. An experimental method aimed
and zirconium organo-metallics compared to at evaluating reactivity of the silica
trisalkoxy silanes at the nano-interface. surface has been developed.

DEPARTMENTS Digital Edition Content

4 Editorial See the February digital edition of
Rubber World for additional content
7 Business Briefs not found in the print edition
10 Market Focus
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12 Oil, Gas & Energy  ‡([SDQGHGEXVLQHVVQHZV
18 Perspective  ‡([SDQGHGHTXLSPHQWLQIRUPDWLRQ
42 Meetings  ‡([SDQGHGLQVWUXPHQWDWLRQLQIRUPDWLRQ
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48 Suppliers Showcase
53 People in the News Visit: www.rubberworld.com

FOLLOW US ON TWITTER @rubberworld 3

From the Editor Jill Rohrer

Recovered carbon black input sought Rubber industry report released

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DYDLODEOHRQWKDWLWHPE\DFFHVVLQJWKHGLJLWDOHGLWLRQRIRubber WorldDWZZZUXEEHUZRUOGFRP

EDITORIAL STAFF BUSINESS STAFF

RUBBER WORLD, (ISSN-0035-9572),
February, 2018, Vol. 257, No. 5, Copy-
Jill Rohrer editor Chip Lippincott publisher right: Lippincott & Peto, Inc. 2018; all
rights reserved. J.H. Lippincott, Chair-
Patrick J. DiMauro technical editor Dennis Kennelly senior vice president, man. Published monthly at 1741 Akron-
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by Lippincott & Peto, Inc. Editorial and
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TIRE
 Rubber and polymer
companies know Burgess

B URGESS provides a complete

line of functional anhydrous and
hydrous aluminum silicates specifically
designed to contribute key properties
to our customers’ final products.
Burgess products have been widely
accepted in the paint, wire and cable,
plastic, rubber, and related industries.
Burgess Pigment’s new Polymer
Applications Laboratory in
Sandersville, Georgia, represents a
major commitment to its customers
and prospects. The lab will be able to
compound and test rubber and plas-
tic formulations to help customers
decide which clay is best for a
particular application.

+001-478-552-2544 s 800-841-8999 s www.burgesspigment.com

PO Box 349, Sandersville, GA 31082, USA

Hydrous Kaolin clays l Calcined Kaolin clays l Silane-treated Kaolin clay

ISO 9001
 Business Briefs VESTENAMER ®

LyondellBasell to ADDITIVE FOR THE RUBBER INDUSTRY

WITH UNIQUE PROPERTIES
acquire A. Schulman
LyondellBasell (www.lyondellbasell.com), Rotterdam, The
Netherlands, said to be one of the largest plastics, chemicals
and refining companies in the world, and A. Schulman, a

A
EXPANSIONS
,
global supplier of high-
CQUISITIONS performance plastic com-
pounds, composites and
powders, have entered
into a definitive agree-
ment under which LyondellBasell will acquire A. Schulman
HB
CHEMICAL
for a total consideration of $2.25 billion. The acquisition is
said to build upon LyondellBasell's existing platform in this Evonik’s VESTENAMER® has been used
space to create a premier Advanced Polymer Solutions busi- as an additive in the rubber industry for
ness with broad geographic reach, leading technologies and a years. By virtue of its properties, the
diverse product portfolio. versatile polyoctenamer can solve a variety
Kraiburg TPE (www.kraiburg-tpe.com), Waldkraiburg, of problems in the compounding and
Germany, announced the start-up of an extrusion line for the processing of rubber. It can also improve
production of thermoplastic elastomers at its headquarters in the dynamic properties of the vulcanized
Waldkraiburg. The line expands the company's total capacity material and as well be used to recycle
to 56,000 metric tons worldwide. waste rubber.
Cooper Tire & Rubber (www.coopertire.com), Findlay,
OH, announced it will expand its product distribution network
in the United States with the opening of a one million square
foot warehouse in Byhalia, MS. It is anticipated that the proj-
ect will create approximately 100 jobs in the region, and the
site will be the largest distribution center for Cooper in the
country. Cooper also announced it will open a North America
VESTENAMER® provides unique
distribution center dedicated to its truck and bus radial tire
processing advantages to all types of
business. The 400,000 square foot facility is located in San rubber processors.
Bernardino, CA.
Maxcess (www.maxcessintl.com), Oklahoma City, OK, a VESTENAMER® a truly cross-linkable
provider of products and services for web handling applica- processing aid reduces viscosity and
tions, celebrated its 10-year anniversary in China by unveiling increases homogeneity with no effect on
an additional 25,000 square foot facility in Zhuhai. dynamic properties.
TBC Brands (www.tbcbrands.com), Palm Beach Gardens,
FL, a distributor of private brand tires in North America, has VESTENAMER® when used as a blend
added four flagship highway light truck lines with Multi-Mile, component enhances overall consistency,
Eldorado, Delta and Vanderbilt brands. speeds mixing, processing, and reduces
BASF (www.basf.com), Ludwigshafen, Germany, will energy costs.
start construction of a methylene diphenyl diisocyanate (MDI)
synthesis unit at the company's Verbund site in Geismar, LA, HB Chemical is the main distributor of
early in the second quarter. The plant is said to be an important Evonik’s VESTENAMER® in North America.
step to double BASF's annual MDI capacity in Geismar from
300,000 metric tons to close to 600,000 metric tons in the
medium term.
BASF has completed the announced divestiture of the
HB
CHEMICAL
production site for styrene-butadiene paper dispersions in
1665 Enterprise Pkwy, Twinsburg, OH 44087
Pischelsdorf, Austria, to Synthomer Austria GmbH, a Ph: (800) 991-2436 F: (330) 920-0971
subsidiary of the British speciality chemicals manufacturer www.hbchemical.com
Synthomer plc.

FOLLOW US ON TWITTER @rubberworld 7

 Business Briefs
Safic-Alcan partners
with Orion Carbons
Safic-Alcan (www.safic-alcan.com), Paris-La Defense, France,
has entered into an extended distribution agreement with Orion
Engineered Carbons in Iberia and central eastern Europe.
The extended distribution
C ONTRACTS , agreement for specialty and
rubber carbon blacks includes
LICENSES Portugal, Spain, Poland,
Czech Republic, Slovakia,
Hungary, Romania, Moldavia, Slovenia, Croatia, Bosnia Herze-
govina, Serbia, Montenegro, Macedonia and Bulgaria.
Cooper Tire & Rubber (www.coopertire.com), Findlay,
OH, has entered into a multi-year manufacturing offtake agree-
ment with Sailun Vietnam Ltd. for the production of truck and
bus radial tires for global markets. The offtake agreement gives
Cooper a third global source of TBR tire production to meet
growing customer needs. Tires will be manufactured under the
Roadmaster, Dean and Starfire brands.
The Association for Rubber Products Manufacturers
(www.arpminc.org), Indianapolis, IN, announced that Great
Lakes Rubber, R.E. Darling, Seal Science and Vicone
Rubber have recently joined the association.
TBC Brands (www.tbcbrands.com), Palm Beach Gardens,
FL, a distributor of private brand tires in North America, con-
tinues the rapid expansion of the Sailun program with the
introduction of the S668, a regional all position tire for use in the
most severe trailer applications. The line is offered exclusively
in the U.S. by TBC Brands.
Falken Tires (www.falkentire.com), Rancho Cucamonga,
CA, has been selected by FCA US LLC to provide its Falken
Wildpeak A/T3WA as a tire of choice for the all-new Ram 1500
pickup truck, built in Sterling Heights, MI.
Yokohama Tire (www.yokohamatire.com), Santa Ana, CA,
announced that its Geolander M/T G003 is the specification tire
of the 2018 TrophyLite R4 Series.
Yokohama Tire has signed a multi-year partnership agree-
ment with Southern Soccer Academy.
DRT (www.drt.fr), Saint-Ouen, France, a global producer of
ingredients derived from plant-based chemistry, and Mangalam
Organics Ltd., a manufacturer of resins, have entered into a
supply and distribution alliance for terpene phenolic resins.

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8 RUBBERWORLD.COM ‡ FEBRUARY 2018

 Business Briefs
ARPM releases exhaust
gas condensate guide
The Association for Rubber Products Manufacturers (www.
arpminc.org), Indianapolis, IN, released its newly created
SP-912 Description of Standard Reference Recipe for Exhaust

C ORPORATE ,
Gas Condensate.
This publication was
drafted and approved
SBR
FINANCIAL NEWS by the member rep-
resentatives of the
ARPM's Sealing Products Dynamic Technical Committee.
“As the automotive industry continues to evolve and rely upon
new technologies, materials and fluids, ARPM and its member
9HIGH QUALITY
organizations have jointly developed new standards for exhaust
gas condensate that can be universally referenced in research
and development activities,” said F. Joseph Walker, chair of the
ARPM Sealing Committee.
Bridgestone Tires (www.bridgestone.com), Tokyo, Japan,
9IN STOCK
released a Global Sustainable Procurement Policy that com-
mits to protecting rainforests that are critical habitat for wild-
life, as well as addressing labor and human rights abuses. This
announcement makes Bridgestone the third major tire company,
along with Michelin and Pirelli, to commit to a “no deforesta-
9GREAT SERVICE
tion, no exploitation” policy.
Orion Engineered Carbons (www.orioncarbons.com),
Luxembourg, began implementing price increases on all spe-
cialty carbon blacks worldwide. The increases vary depending
High Duty &
on the grade, the sales region and the end market.
Apollo Tyres (www.apollotyres.com), Gurgaon, India, was
identified as one of India's Best Workplaces in Manufacturing
Dumping Fees
2018 by the Great Places to Work Institute. The company
was ranked among the top 10 workplaces in the manufacturing
segment in India. Call us today and see how
BASF (www.basf.com), Florham Park, NJ, has declared
force majeure in North America on 1,4-butanediol (BDO) and HB Chemical can save you money.
its derivatives following two separate events last month that
impacted production at its Geismar, LA, manufacturing facility,
including a natural gas fire and record low temperatures.

HB
Quality registrations
Analytic Systems (www.analyticsystems.com), Delta, British
Columbia, Canada, has updated to the International Standards
Organization, ISO 9001:2015 quality standard.
Rahco Rubber (www.rahco-rubber.com), Des Plaines, IL, has
received ISO 9001:2015 certification.
CHEMICAL
1665 Enterprise Pkwy, Twinsburg, OH 44087
For all the latest Ph: (800) 991-2436 F: (330) 920-0971
business briefs www.hbchemical.com
click here:

FOLLOW US ON TWITTER @rubberworld 9

 Market Focus
Nitrile butadiene market to top $2.5 billion
The global nitrile butadiene rubber
(NBR) market is expected to reach $2.59
billion by 2025, growing at a compound
annual growth rate (CAGR) of 3.3%, ac-
cording to a ResearchandMarkets study.
$VLD 3DFL¿F LV H[SHFWHG WR SURYLGH WKH
impetus for the industry growth of NBR
by the end of 2025. China, India and
Southeast Asian countries are likely to
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sumed in high end applications requiring
the product to be highly sustainable to
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tions. This makes the product suitable for
use in a wide array of industries.
NBR demand in China and India is ex-
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transportation, metallurgy and mining,
oil and gas, equipment and machinery,
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chanical goods such as cables, belts, gas-
kets and seals.
A rise in consumer disposable income
and purchasing power in ASEAN coun-
tries, including Indonesia and Thailand,
has led to a rapid growth of the automo-
WLYHLQGXVWU\DVZHOODVDVWURQJLQFUHDVH
LQ DIWHUPDUNHW DFWLYLWLHV 0RUHRYHU DQ
increase in the healthcare expenditure in
global market in 2016. CIS countries,
is expected to boost the consumption of
QLWULOHJORYHVE\DFFRUGLQJWRWKH
study.
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rings segment is expected to rise at a
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timated to increase at the fastest growth
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in the healthcare and hygiene sector.
Wide production expanse in China
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sumption in mechanical engineering ap-
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ing materials, impact machinery, pumps,
hydraulic equipment and compressors.
Europe accounted for the second-
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mainly Russia, are likely to witness fast
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cant use of hoses, seals and o-rings in the
oil and gas sector.
Butyl to grow at 4.7% rate
A research report by Persistence Market
Research shows the global butyl rub-
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growing at a compound annual growth
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Increasing demand for butyl rubber is
Global natural rubber market to grow over 4% due to its growing applications, includ-
7KHJOREDOQDWXUDOUXEEHUPDUNHWLVSURMHFWHGWRJURZDWD&$*5RIGXULQJ ing a rapid increase in demand from the
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facing NR include increasing preference for synthetic rubber and the increasing of the market is an increase in the rate of
SRSXODULW\RIJXD\XOHGHULYHGQDWXUDOUXEEHU tire replacements taking place in the au-
Commenting on the report, an analyst from the research team said: “The latest tomobile industry.
trend gaining momentum in the market is the increasing popularity of guayule- The global butyl rubber market is
GHULYHGQDWXUDOUXEEHU$OPRVWDOOWKHZRUOG¶VQDWXUDOUXEEHULVGHULYHGIURPHevea expected to witness maximum demand
brasiliensis. Relying only on one plant for natural rubber is critical for all the major from tires and tubes, which is projected
players. This encouraged them toward an alternate source of natural rubber. Cur- WRUHDFKDPDUNHWYDOXHRIRYHUELO-
rently, they are attracted toward the potential of a perennial shrub called guayule, lion by the end of 2025. Halobutyl rub-
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plant is similar to that of para rubber trees.” 5.0% during the forecast period. Among
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contributing to the regaining market prosperity. It is expected to gain from the growth of the halobutyl rubber market.
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10 RUBBERWORLD.COM ‡ FEBRUARY 2018

 Oil, Gas & Energy
Seal technology, friction, weight and fuel usage
7KH DXWRPRWLYH LQGXVWU\¶V pursuit of state-of-the-art compo-
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tomated transmissions. A special seal design produces a hydro-
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 Oil, Gas & Energy
Deep-well cable coatings withstand extremes
Fluon ETFE compounds from AGC Chemicals Americas are
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tion for cables used in demanding downhole conditions in oil
and gas exploration and recovery.
Fluon ETFE compounds are said to be ideal for use in wire
and cable insulation for motors and windings, generators, trans-
formers, logging and communications instrumentation, and
electrical submersible pumps. In addition, Fluon ETFE com-
pounds insulate and protect cables for reliable data transmission
and power, resulting in optimized performance of monitoring
systems in deepwater oil and gas exploration and recovery.
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ethylene and ethylene. Fluon ETFE compounds contain con-
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extreme temperatures, pressures, harsh chemicals and volatile
weather conditions found in insertion and extraction operations.
Cable components made with Fluon ETFE compounds can
withstand depths of 25,000 feet and 15,000 psi; resist abrasion
and bending fatigue; have an ultra-smooth outer surface; and
endure torsion, tension and extreme temperature cycling, ac-
cording to the company.
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to perform better in continuous insertion/extraction operations.
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electrical charges that accumulate within the cable construction
during operation, it reduces spark-outs and heat build-up, keep-
ing the cable operable.
Spooling and other motions of the cable can cause stress
cracking and breakage. By using reinforced ETFE compounds
for the inner and outer layers of the jacket, cables are more pro-
tected due to the inherent mechanical strength of the resin that
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ufacturing, because these compounds exhibit excellent adhe-
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company.




 

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FOLLOW US ON TWITTER @rubberworld 13

 Technical Service
Thirty-one years of lessons learned: Six
rules of thumb for rubber release agents
Tenacious rubber compounds are a constant challenge for rubber
molders manufacturing the parts on which our modern society re-
lies. Not least among the challenges rubber molders face is what
release agent to use on their tooling and how to apply it. Many rub-
ber molders do not do their due diligence when selecting a release
agent, and even more fall short of applying it properly, resulting in
poorer quality parts, shorter tooling life-spans and costly downtime,
among other problems. During my 31-year career as a technical
representative for McLube, a global manufacturer of quality release
agents and process aids, I have seen rubber molders make the same
release mistakes over and over again. In this article, I describe six
rules of thumb for selecting and applying release agents to help
molders navigate the release industry with ease and break bad hab-
its. The six rules of thumb for rubber release agents are:
1. A little works, a lot usually does not!
2. Stop guessing, call someone.
3. Better yet, call everyone.
4. Take charge of your release agents.
5. Avoid “corporate coatings.”
6. Semi-permanent is not always the answer.
A little works, a lot usually does not!
The most common bad habit of rubber molders is over-application
of the release agent. Over-application almost always leads to failed
release, part rejection and hours wasted cleaning fouled tooling. I
have been on countless production floors to run trials with my
customers and witnessed press operators applying an over-abun-
dance of release agent. Inexperienced operators are prone to
drowning the mold with release agent, thinking the parts will just
start flying out of the mold. After a failed or insufficient release has
occurred, operators will often fall into the trap of applying more
and more release, when over-application was the original cause of
the problem. Over-application is a bad habit that is especially com-
mon in operations using semi-permanent coatings that do not re-
quire frequent reapplication. Ladies and gentlemen, to be blunt:
Just use as directed!
Release trial tip: If a coating fails to release during a trial, do not
discount it automatically. Consult one of the release manufacturers’
technical representatives. Very often, the application method sim-
ply needs adjustment to achieve superior results. Do not forget to
inquire about mold conditioning factors and how much reapplica-
tion will be necessary after the first couple pulls.
Stop guessing, call someone
When a new part or compound is being considered for production,
initial tests are run to iron out any problems associated with the job.
Molders often use a release coating for the new compound that is
already used in-house because it works on a similar rubber mate-
14 RUBBERWORLD.COM ‡ FEBRUARY 2018
by Bob Edelmayer,
McLube Release Coatings
rial. There is nothing wrong with trying: It works some of the time,
but things do not always go as planned.
It is always a good idea to call release manufacturers for assis-
tance before using a coating in a process for which it was not
originally intended. You will save time, raw material and money if
you seek help beforehand, rather than trying to put out the fires
after the fact. Release manufacturers have a wealth of knowledge.
We know what works where, and how to apply it. Take advantage
of our desire to sell you something to get the most out of your
process. In a perfect world, molders could use the same release
agent for every compound on every press; unfortunately, special-
ized release agents catered to your various compounds are usually
the only way to achieve superior results across the board.
Better yet, call everyone
Whether you are releasing a new compound or replacing what you
currently use, please ask around! You will never get the best with-
out doing your due diligence. Get a second, third and fourth opin-
ion from different release manufacturers, and allow them to send
you additional samples based on trial results. Those of us who sell
release agents do not want you to know that it is often unclear why
one coating works and another does not. One coating may be ef-
fective with FKM at one facility, and fail under the same condi-
tions at another. Trial and error are a fundamental instrument of the
molding industry. Trust the process and never settle for “close
enough.” The perfect coating is out there. The more you try, the
closer you will get. Even if you want to stick with a particular
brand, try some others and look for patterns among their recom-
mendations. Are they all suggesting semi-permanent options?
Sacrificial? Get a second opinion to ensure you are being taken
care of properly. Ask the release salesmen how their coatings work
under similar conditions elsewhere to gauge your process’s effec-
tiveness. Samples are free, so take advantage! Call everyone.
Search tip: Share as much information as possible with the re-
lease manufacturer to get the best coating for your operation.
Temperature, humidity, cycle time, compounds, process details,
available equipment and plant requirements are just a few vital
pieces of information your release specialist should know before
recommending a release coating for your rubber. If you are worried
about proprietary information being misused, then sign a non-dis-
closure agreement.
Take charge of your release agents
It is important to keep all release coatings in the hands of a capable
production foreman, shift supervisor or process engineer. Over the
years, I have witnessed all kinds of misuse from well-meaning
plant employees who come up with their own concoction of what
they think is the ultimate release coating. They are usually doing
 WORKING WITH
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ISO 9001:2008

Polymer Valley Chemicals offers a

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CARBON BLACK CONCENTRATES
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 Technical Service
more harm than good. Do not apply guesswork to your dilutions.
Maintain consistency of the ratio by employing exacting dilution
methods for reliable results. Train employees to use the release
coatings carefully and correctly, and be ever-mindful of rule num-
ber one: A little works, a lot usually does not!
Dilution tip: Use deionized or distilled water whenever possi-
ble to avoid contaminating or compromising the release blend.
Avoid “corporate coatings”
There are release manufacturers out there without the technology
or even the desire to supply you with the ideal coating. Many of
the corporate giants in this industry boast of innovative release
technology, but only offer mass-produced, generalized “corporate
coatings” that are not ideally suited to the chemical diversity of the
rubber industry. Be wary of the giant after that big fish; they will
spend little time working with smaller operations to find the best
solution. There are quite a few release agent manufacturers. Do
some shopping to find that one or those few who will work with
you to find the best solution.
Semi-permanent is not always the answer
Semi-permanent coatings are very popular among rubber molders,
but many should probably be using something else. Everyone
wants multiple cycles before reapplication is necessary. Semi-
permanent coatings speed up manufacturing, transfer little, and
16 RUBBERWORLD.COM ‡ FEBRUARY 2018
usually do not cause knit lines or flow problems. Unfortunately for
some molders, certain rubber compounds are infamously difficult
to release because of microscopic abrasions that degrade release
coatings in minutes, or even seconds. Frequent reapplication of
semi-permanent coatings becomes necessary to combat the abra-
sive compounds, which lead to persistent fouling of the mold sur-
face and hours spent cleaning. If you are applying a semi-perma-
nent type release agent more than four times in an hour, then it is
high time you test a dilute sacrificial coating. Sacrificial coatings
are applied before every cycle, generally do not build up over time,
and may be your solution to abrasive compounds.
These six rules of thumb will help molders navigate the release
market and avoid the bad habits I have witnessed over the last three
decades as a McLube technical representative for rubber molders.
Perhaps the most common bad habit is overapplication. I cannot
stress enough how important it is for rubber molders to use their
chosen coating as directed, and seek the experienced advice of a
release specialist before they risk wasting time, money and mate-
rial. Please keep an open mind. Shop the vast release agent market
and find a technical representative that has the desire and ability to
work with you to provide the perfect coating for your operation.
Never settle for those “corporate coatings” or attempt to guess dilu-
tion ratios. Take advantage of free samples, trust the process and
find the best release agent for your rubber.
 CUSTOMIZED
TREATED SILICA ISO 9001:2008

Polymer Valley Chemicals PV-Sil ®

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• Customize Substrate, Silane Chemistry,
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• Create a unique product specific to the
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 Perspective
Advancing carbon black technologies
to improve tire performance
Orion Engineered Carbons is one of the world’s leading sup-
pliers of carbon black. Two years ago, Rubber World (Febru-
ary 2016) interviewed Jose Briones, Ph.D., marketing man-
ager, rubber, and Lin Bradley, technical market manager, about
industry trends and new developments in rubber carbon black
at the company. For this issue, we checked in again with Brio-
nes and Bradley specifically about rubber carbon blacks and
the tire market, discussing challenges, solutions and technol-
ogy advancement.
First, let us set the stage: When we conducted the interview
two years ago, you said that replacement tires account for
more than two thirds of the demand for rubber carbon blacks,
with original equipment tires and mechanical rubber goods
accounting for the rest. Tire production, in general then, is a
very large market segment. How does it look for 2018?
Briones: All indications are that 2018 will be a robust year for
tire manufacturing. Market researchers forecast expansion of
the auto industry, which will drive demand for automotive
tires. For example, Transparency Market Research (TMR)
estimates the global automotive tire market will grow at a
compounded annual growth rate (CAGR) of 6.8% through
2021, due to increased passenger car production.
Meanwhile, Smithers Rapra predicts global tire volume
will hit 2.7 billion tires by 2022, with growth continuing at a
3.4% CAGR. Focusing on the U.S., Notch Consulting esti-
mates that tire manufacturers will spend $5.2 billion here on
building new tire production capacity. Toyo Tire, Hankook,
Giti Tire Group, Triangle Group and others are all expanding
capacity at existing production facilities or bringing new
plants online through 2021.
How are carbon black suppliers responding?
Briones: We see global rubber carbon black capacity continu-
ing its typical growth rate of 2% to 4% annually. We do not see
new capacity coming online in the U.S., but we do see capac-
ity expansions in China, India and Belarus. It is likely that the
recently announced settlement with the EPA by the last three
major carbon black producers in North America will be the
catalyst for future capacity additions.
Lin Bradley is technical market manager, rubber,
Americas, for Orion Engineered Carbons. Re-
sponsible for technical interactions with rubber
carbon black tire customers, Bradley oversees
market research, coordination of technical ap-
provals of ASTM and non-ASTM carbon blacks,
and new product and solution introductions.
18 RUBBERWORLD.COM ‡ FEBRUARY 2018
by Lin Bradley and Jose Briones,
Orion Engineered Carbons
What challenges have tire manufacturers faced recently re-
garding tire performance, and how has Orion worked to solve
them and improve tire properties?
Bradley: At Orion, we continually ask ourselves and our cus-
tomers what challenges need to be addressed now and in the
future. As a result, we developed a range of non-ASTM carbon
black grades, which we call “technical rubber grades,” de-
signed to expand the parameters of the tire performance tri-
angle. They improve rolling resistance, tread wear and/or
traction, while minimizing the trade-offs that were believed
necessary to improve one property or another.
For example, our narrow aggregate size distribution
(nASD) tread grades improve abrasion resistance relative to
standard ASTM grades without the expected increase in roll-
ing resistance. We also offer products which allow the com-
pounder to improve the energy dissipation characteristics of
tread compounds while maintaining excellent wear properties.
What is Orion doing to bring new solutions to U.S. tire manu-
facturers?
Bradley: To achieve the goal of reducing carcass rolling
losses, we developed two grades with very low surface areas.
Ecorax S 204 and Ecorax S 206 have the lowest surface areas
of any commercially available furnace grades of carbon black,
in the range of an N800 series.
We developed Ecorax S 204, a high structure carbon black,
for blending with standard ASTM grades in tire sidewalls. For
example, blended with N330, Ecorax S 204 compounds have
shown significant reductions in hysteresis loss, while main-
taining the stiffness, tensile and tear properties required for a
functional sidewall.
Ecorax S 206, when used to replace ASTM grades in tire
inner liners, reduces permeability and potentially allows com-
pounders to reduce inner liner thickness. This significantly
reduces material costs, as well as tire weight.
While we started the Ecorax product line to reduce rolling
losses in tread compounds, we recently developed additional
Ecorax grades for tire carcass compounds. The new Ecorax
carcass grades, for example Ecorax S204, S206 or S470, in-
crease the options available to compounders to address heat
Jose Briones, Ph.D., is marketing manager for
Orion Engineered Carbons in the rubber carbon
black segment. His responsibilities include achiev-
ing strategic sales goals and development of busi-
ness strategy, pricing policies and business cases
for new product development. He has helped de-
velop more than 40 new products for Orion.
 Perspective
buildup originating in the inner liner or sidewalls. Using one
or more Ecorax grades may also enable a tire designer to re-
duce inner liner or sidewall thickness to achieve a lighter-
weight tire. Used in combination with the Ecorax tread grades,
the Ecorax carcass grades can substantially reduce tire weight.
Tell us about Orion’s latest advances in rubber carbon black
technology for tires.
Bradley: Orion recently introduced to North America two new
grades that address the need to balance rolling resistance and
abrasion resistance (wear) in truck and passenger tires. Both
grades, HP 130 and HP 1107, exhibit adjusted ASD, which
enhances tire performance. They are both part of our high-
performance (HP) family.
HP 130 carbon black targets applications similar to those of
N234. Unlike N234, HP 130 has a broader ASD and slightly
higher structure than N234 to compensate for the effect of the
broader ASD. These differences lead to tread compounds with
lower rolling resistance, but with equal or better abrasion re-
sistance, depending on the polymer system used.
HP 1107 is colloidally similar in surface area and structure to
N134, but with an adjusted ASD that better balances rolling resis-
tance and tread wear. Both grades have been available in other re-
gions, and now we produce them for the North American market.
We have also developed other HP grades for specialized
applications. For off-the-road trucks, such as those in mining,
agriculture and forestry, HP 1125 addresses chip and chunk
failures seen in the difficult environment in which these tires
operate. Our racing grade concepts (HP 160, HP 170S, HP 180
and HP 200S) are not intended to optimize or balance rolling
resistance and tread wear, but to maximize dry traction.
and the ability to blend carbon blacks to achieve reinforcement
in between tread and carcass grades created little availability
or demand for such carbon blacks.
Now, many tire producers have realized that evolving per-
formance requirements of the tire market may require such an
“in between” grade. In response, we have developed Ecorax S
470 carbon black which features a high structure and surface
area between the reinforcing (tread) and semi-reinforcing (car-
cass) grades to bridge the reinforcement gap. Use of Ecorax S
470, alone or in blends with standard ASTM grades, reduces
energy dissipation in the tire body and consequently reduces
rolling resistance.
What factors should rubber compounders be considering
when selecting rubber carbon black for tire applications?
Bradley: Tire design engineers need more flexibility in their
component designs to allow them to meet a variety of evolving
performance requirements. When considering which carbon
blacks to select, the engineer should consider how a particular
grade might allow changes to, for example, initial tread thick-
ness, which might allow achievement of another goal, such as
weight or energy dissipation reductions. Because all parts of a
tire act in concert, a change in one tire component affects the
performance of the others. We urge our customers to look at
our non-ASTM carbon black grades as parts of a package to
optimize overall tire performance.
Evidence has shown that maximizing dispersion of fillers
improves tire performance; this is especially true of tire tread
compounds, where incremental improvements in dispersion

What do you see as the “next big thing” in rubber carbon

black for tires?
Bradley: We are currently seeing intense interest in several
non-ASTM carbon black grades that reduce energy dissipation
within the body of the tire. For many years, carbon black
manufacturers focused solely on reducing the rolling resistance
of tread compounds in response to increasing use of silica.
After many years of working to optimize tread designs and
compounds, many tire companies have shifted their focus to
the body of the tire. In response, we developed the carbon black
grades Ecorax S 204, S 206 and S 470 to assist in these efforts.
I believe that “the next big thing” will be significant chang-
es in the tire carcass to reduce weight and energy dissipation.
These will require the use of carbon blacks with surface areas
and structure outside of the conventional range of ASTM
grades. In the past, higher surface area carbon blacks were
mostly used in tread compounds, and lower surface area car-
bon blacks were used in the carcass. Between these tread and
carcass blacks, there were few to no commercial offerings.
Technically, these grades would have been ASTM N400 series
carbon blacks, but reactor technology, end-user requirements

FOLLOW US ON TWITTER @rubberworld 19

 Perspective
lead to meaningful improvements in abrasion resistance. In
turn, improved tread wear can reduce initial tread thickness,
while maintaining tread life. Carbon blacks such as our narrow
ASD grades can assist in these efforts. By reducing the number
of very small aggregates, nASD grades improve dispersion at
a given surface area at equal mix times. The end result is im-
proved tread life.
Optimizing tread compounds is only a small part of overall
tire design changes that can help tire producers meet their fuel
efficiency improvement goals. Our Ecorax carcass grades
offer additional opportunities for gains in terms of reducing the
overall weight of tires by allowing adjustments to inner liner
and sidewall thickness. A low surface area, high structure car-
bon black, such as Ecorax S 204, enables tire designers to re-
duce sidewall thickness, while maintaining the required stiff-
ness to meet the other requirements.
Further, a low surface area, low structure grade (such as
Ecorax S 206) used in an inner liner in place of a commonly
used grade such as N660 will reduce air permeability, allowing
reduced inner liner thickness, while maintaining the required
level of air retention.
We believe that combining these grades with the latest tire
design concepts enables tire designers to achieve higher levels
of performance, while meeting the wide range of market and
regulatory requirements.
Do electric cars change anything for tire manufacturers in
terms of carbon black?
Bradley: Interestingly, the requirements of the electric car
market have split into two distinct segments. The first electric
car segment could be considered the high-performance car
market, where vehicle acceleration and top speeds approach or
even exceed those of gasoline-powered sports cars. This mar-
ket segment has the same requirements as those for the highest
speed rated tires already on the market.
The second electric car segment is focused on energy effi-
ciency. Tires for electric cars in this segment tend to have
much narrower tread footprints, but sidewalls that are within
the typical height range for existing tire configurations. How-
ever, because of the decreased ratio of tread width to sidewall
height, the rolling losses due to energy dissipation from the
sidewalls become even more prominent. Grades such as Eco-
rax S 204 and S 470 are good solutions for reducing sidewall
energy dissipation to achieve the highest energy efficiency.
These tires tend to have higher recommended inflation pres-
sures, which require low permeability inner liner compounds.
In this case, Ecorax S 206 is a good choice to minimize perme-
ability with the thinnest practical inner liners to reduce weight.
As a single carbon black supplier, how does Orion respond to
the tire market demand for multiple sourcing?
Bradley: We understand customers' concerns about being
single-sourced and their desire for multiple sources of supply.
To that end, we are constantly adjusting our manufacturing
footprint to make our new grades available upon demand. We
have developed local production capability, and we have mul-
tiple facilities that can produce the same grade to provide
greater security of supply.

Polymer Extrusion 5th Edition

New
Boo
Author: : Chris Rauwendaal k
ISBN: 978-1-56990-516-6
934 pages
©2014, hardcover
$199.95 USD + SH
This book bridges the gap between theory and practice in the extrusion field. Now in its
fifth edition, the best-selling Polymer Extrusion continues to provide valuable, up-to-date
information for polymer engineers and chemists who need both theoretical and practical
tools for successful extrusion operations. Since the last edition in 2001, there have been
many new developments in the field and are incorporated in this edition.

New, Updated Content

Chapter 2: A discussion on high speed single screw extruders has been added.
Chapter 7: An innovative theory is presented that allows prediction of melt temperatures
without having to result to numerical techniques and computer simulation.
Chapter 8: Now includes information on the efficient extrusion of medical devices;
this section discusses optimal manufacturing practices, screw designs, and processing
conditions.
Chapter 11: The section on gels has been expanded and now includes information on
discolored specks, how to predict their occurrence and frequency, as well as instruments to
detect defects in pellets.
New information has been added throughout and references have been updated.

To order visit: www.rubberworld.com/bookstore

or call 330.864.2122

20 RUBBERWORLD.COM ‡ FEBRUARY 2018

 Patent News
Rubber composition for tire tread
and pneumatic tire
U.S. patent: 9,834,661
Issued: December 5, 2017
Inventors: Masaki Sato and Makoto
Ashiura
Assigned: Yokohama Rubber
Key statement: A rubber composition
for a tire tread of the present technolo-
gy comprises a rubber component con-
taining not less than 30 mass % of a
conjugated diene-based rubber (A), a
silica (B), and a predetermined alkyl-
triethoxysilane (C), the conjugated
diene-based rubber (A) containing not
less than 5 mass % of a specified
structural member (a), the silica (B)
having a nitrogen adsorption specific
surface area (N2SA) from 194 to 225
m2/g and a CTAB adsorption specific
surface area (CTAB) from 180 to 210
m2/g, a content of the silica (B) being
For additional industry patent
information click here:
from 60 to 150 parts by mass per 100 Modified conjugated diene-based
parts by mass of the rubber compo- polymer, modified rubber composi-
nent, and a content of the alkyl- tion containing same, and method
triethoxysilane (C) being from 2.5 to for preparing modified conjugated
8.0 mass % relative to the silica (B). diene-based polymer
U.S. patent: 9,834,619
3 7 Issued: December 5, 2017
Inventors: Moon-Seok Chun, Soo-
Yong Lee and Seong-Du Lee
Assigned: LG Chem
Key statement: Disclosed are a method
4
of preparing a modified conjugated
diene-based polymer, a modified con-
2 jugated diene-based polymer prepared
thereby, a rubber composition includ-
ing the modified conjugated diene-
based polymer, and a tire including the
rubber composition. The method of
6 preparing the modified conjugated
5 diene-based polymer includes (a)
1
polymerizing a vinyl aromatic mono-
8 mer and a conjugated diene monomer
Using Harmonite instead of Gilsonite saved an
® ®
SBS membrane maker over $100,000 last year.
And it blends better too.
Harmonite’s ideal for other rubber compounds and modified bitumen
formulations as well.
That’s because Harmonite is a unique, high-performance, economical
alternative for organic and inorganic additives and fillers, offering —
U Reduced mixing time — up to 50% in some cases — and
accompanying reductions in power consumption.
U Sealants and coatings with ideal viscosity for easy ‘spreadability’,
spraying and trowelling.
Build it better with Harmonite.
Visit www.rssharmonite.com
RSS, LLC
6075A Lee’s Mill Road, Forest Park, GA 30297
Gilsonite ® is a registered trademark of the American Gilsonite Company.
FOLLOW US ON TWITTER @rubberworld 21
 Patent News
through continuous solution polymer-
ization using a multifunctional anionic
polymerization initiator in the pres-
ence of a hydrocarbon solvent, thus
forming an active polymer having a
reactive end; and (b) coupling or link-
ing the reactive end of the active poly-
mer with an alkylamino alkoxy silane
compound.
Run flat tire
U.S. patent: 9,834,043
Issued: December 5, 2017
Inventor: Shinsaku Kamada
Assigned: Toyo Tire & Rubber
Key statement: A run flat tire having a
side reinforcing rubber part is dis-
closed. The side reinforcing rubber
part is formed by a rubber composition
having a ratio (M50H/M50N) of ten-
sile stress (M50H) in 50% elongation
at a measurement temperature of
100°C to tensile stress (M50N) in 50%
elongation at a measurement tempera-
ture of 23°C of from 1.0 to 1.3. A
cushion rubber layer interposed
between the side reinforcing rubber
part and a bead filler is provided, and
tensile stress in 50% elongation at a
measurement temperature of 23°C of a
rubber composition forming the cush-
ion rubber layer is larger than tensile
stress in 50% elongation at a measure-
ment temperature of 23°C of the rub-
ber composition forming the side rein-
forcing rubber part, and is smaller than
tensile stress in 50% elongation at a
measurement temperature of 23°C of a
rubber composition forming the bead
filler.
CL
9 1 10 11
5 Key statement: Disclosed is a rubber
6 composition for tire treads and a tire
8 2
5A
5B
12 7 weight of a wet masterbatch prepared
3 carbon black and a liquid styrene-buta-
4
22 RUBBERWORLD.COM ‡ FEBRUARY 2018
Natural rubber outsoles and foot-
wear
U.S. patent: 9,833,037
Issued: December 5, 2017
Inventor: Thomas W. Wilson, III
Assigned: Nike
Key statement: An elastomer composi-
tion includes guayule rubber and a
butadiene rubber, with at least about 5
phr guayule rubber based on 100 phr
elastomer. The cured rubber has a
higher coefficient of friction as com-
pared to a cured rubber of the same
formulation except using Hevea rubber
rather than guayule rubber.
7 2
23
22
21 8 compound including a virgin rubber
9 component and a reclaimed rubber
20
10
19
60 11
12 24
33
13
14
18
17
62
63 15
16
61
Rubber composition for tire tread
and tire manufactured by using the
same
U.S. patent: 9,828,494
Issued: November 28, 2017
Inventor: Byung Lip Kim
Assigned: Hankook Tire
manufactured using the same. More
particular, the rubber composition for
tire treads includes 50 to 200 parts by
by reacting a styrene-butadiene latex, a
diene copolymer at 50 to 95°C for
three to nine hours according to a
batchwise method, 60 to 70 parts by
weight of a raw rubber, and 50 to 200
parts by weight of a carbon black.
Accordingly, the rubber composition
for tire treads has enhanced grip and
anti-wear performances under a condi-
tion of heavy load, high slip and high
speed, and thus, may be usefully used
in manufacturing an ultra-high perfor-
mance tire.
Tire tread and method of making
the same
U.S. patent: 9,827,726
Issued: November 28, 2017
Inventor: Craig B. Norton
Assigned: Bridgestone Bandag
Key statement: A method of making a
tire tread includes mixing a tire tread
component, forming a green sheet
from the tire tread compound, and cur-
ing the green sheet to form a cured tire
tread. The reclaimed rubber compo-
nent may have a Mooney viscosity
(ML [1+4] @ 100°C) of greater than
65. The reclaimed rubber component
may also have a crosslink density that
is between 20 and 50% of the cross-
link density of the reclaimed rubber
prior to reclaiming.
Rubber composition comprising a
polyphenylene ether resin as plasticizer
U.S. patent: 9,822,247
Issued: November 21, 2017
Inventor: Vincent Abad
Assigned: Michelin
Key statement: A rubber composition
is based on at least one predominant
vinylaromatic diene elastomer, a rein-
forcing filler, a crosslinking system
and a thermoplastic resin comprising
optionally substituted polyphenylene
ether units, said resin having a com-
patibility with said vinylaromatic
diene elastomer such that a mixture of
said vinylaromatic diene elastomer and
said resin creates a composition hav-
ing less than 10% of its volume in the
form of particles greater than 2
 Patent News
micrometers in size. The rubber com-
position may be used in semi-finished
tire articles and tires.
Process for producing rubber com-
position
U.S. patent: 9,822,246
Issued: November 21, 2017
Inventors: Seiichi Katou and Satoshi
Horie
Assigned: Bridgestone
Key statement: Process for producing
a rubber composition comprising a
rubber component (A) comprising at
least one selected from natural rubbers
and synthetic diene rubbers, a filler
containing an inorganic filler (B), a
silane coupling agent (C), and at least
two kinds of chemical agents (D) and
(E) selected from guanidines, sulfen-
amides, thiazoles, thiurams, dithiocar-
bamates, thioureas and xanthates,
wherein the rubber composition is ation on the tire surface. The present
kneaded in a plurality of stages where- invention relates to a studless winter
in, in the first stage (X) of kneading, tire including a tread formed from a
the rubber component (A), all or a por- rubber composition containing a pre-
tion of the inorganic filler (B), all or a determined amount of a farnesene
portion of the silane coupling agent resin obtained by polymerizing farne-
(C), and at least two kinds of the sene. The present invention relates to a
chemical agents (D) and (E) are added studless winter tire including a tread
and kneaded. formed from a rubber composition
containing a predetermined amount of
Studless winter tire at least one myrcene resin selected
U.S. patent: 9,822,245 from the group consisting of myrcene
Issued: November 21, 2017 polymers with a Mw of 1,000-
Inventors: Takahiro Mabuchi, Ken- 500,000, myrcene-butadiene copoly-
suke Washizu, Toshifumi Haba and mers with a Mw of 1,000-500,000, and
Kenya Watanabe myrcene-styrene copolymers with a
Assigned: Sumitomo Rubber Mw of 1,000-150,000; and a predeter-
Key statement: Provided is a studless mined amount of a silica with an N2SA
winter tire which provides good per- of 40-400 m2/g, the rubber component
formance on ice and snow and good containing a predetermined amount of
abrasion resistance, and suffers little a high-cis polybutadiene with a cis
change in hardness and little discolor- content of 95% by mass or more.
A Grade II conveyor cover made with Harmonite ®
needed 32% less aromatic oil, no powdered coal
at all, and had better abrasion resistance.
And it cost $.025 less per pound to formulate.
It’s ideal for other rubber compounds and CASE formulations as well.
That’s because Harmonite is a unique, high-performance, economical
alternative for organic and inorganic additives and fillers, offering —
U Reduced mixing time — up to 50% in some cases — and
accompanying reductions in power consumption.
U An economical replacement for other expensive ingredients like
® ®
petroleum pitch, titanium dioxide, Austin Black and Gilsonite .
Build it better with Harmonite.
Visit www.rssharmonite.com
RSS, LLC
6075A Lee’s Mill Road, Forest Park, GA 30297
Austin Black® is a registered trademark of Coal Fillers, Inc. Gilsonite® is a registered trademark of the American Gilsonite Company.
FOLLOW US ON TWITTER @rubberworld 23
Mechanical reinforcement of rubber by sp2
carbon allotropes such as carbon black and
carbon nanotubes: The role of interfacial
area and filler orientation
by Maurizio Galimberti, Giuseppe Infortuna, Vincenzina Bar-
bera, Silvia Guerra and Andrea Bernardi, Politecnico di Mi-
lano; and Silvia Agnelli and Stefano Pandini, Universitá degli
Studi di Brescia, Italy
The large variety of reinforcing fillers nowadays available proves
their importance for enhancing the properties of rubber com-
pounds (refs. 1-4).
Besides the so-called traditional fillers, such as the nanostruc-
tured carbon black and silica (refs. 5 and 6), new generations of
fillers are being developed, as for example nanofillers, i.e., par-
ticles with at least one dimension below 100 nm (ref. 7). Such a
low size results in a very high surface to volume ratio, and there-
fore in a higher reinforcing efficiency in a rubber-based compos-
ite (refs. 8-11). Major interest is for carbon nanofillers: carbon
nanotubes (CNT), both single-walled and multi-walled (refs. 7, 8
and 12), and graphene and graphene related materials (GRM),
such as graphene nanoplatelets made by a few stacked layers of
graphene (nanoG) (refs. 13-16). It is indeed worth underlining
that new types of carbon nanofillers are continuously appearing
(refs. 17 and 18).
It is clear nowadays that, particularly for large scale applica-
tions, nanofillers cannot replace CB. Indeed, increasing interest
is for hybrid systems based on CB-CNT and CB-graphene re-
lated materials (refs. 19-22), developed by partially substituting
CB with nanometric carbon allotropes.
In spite of such large interest for carbon nanofillers and for
hybrid filler systems, the theoretical study of their effects on the
properties of a rubber compound does not have the same space,
and this limits their rational use and exploitation.
Some of the authors studied the effects of sp2 carbon allo-
tropes on the mechanical properties of a rubber matrix: a single
filler or hybrid filler systems were used (refs. 9 and 23-26). A
common rationalization of the mechanical reinforcement by dif-
ferent families of sp2 carbon allotropes has been proposed re-
cently by the authors (refs. 9 and 24). A common correlation was
found between the composites’ modulus and the surface made
available by the filler per unit volume of composite, meaning
with the specific interfacial area.
In such a common frame for the behavior of sp2 carbon allo-
tropes, it is definitely interesting to identify the distinctive fea-
tures of the nanometric ones, mainly CNT and GRM. They are
characterized by a high aspect ratio (or shape anisotropy); i.e., the
ratio of the maximum over the minimum dimension of the par-
ticle. Hence, CNT and GRM can present a preferential orienta-
tion in the elastomeric matrix and, as a consequence, they can
impart anisotropic properties, which means directionally depen-
dent properties. Preferential orientation and alignment of
24 RUBBERWORLD.COM ‡ FEBRUARY 2018
nanoparticles is an effective way to selectively improve the
composite properties along specific directions. However, in soft
matrices such as rubbers, anisotropic effects promoted by
nanoparticles have never been thoroughly analyzed. A remark-
able anisotropic behavior of the dynamic moduli has been docu-
mented by some of the authors for composites based on natural
rubber (NR), filled with either CNT or a nanosized graphite
(nanoG) (refs. 23 and 26). Properties along transversal directions
were experimentally measured, and it was found that the struc-
turing of nanofillers induced an orthotropic and transversally
isotropic response. As a result, the dynamic moduli were very
similar to each other when measured in the sheet plane, and
nearly twice as much when measured in the orthogonal direction
(i.e., perpendicular to the sheet plane).
The aim of this work was to go more in depth into such inves-
tigation: The separate and combined effects of filler surface area
and filler orientation were studied. Comparison was made be-
tween a nanostructured and a nanometric filler, CB and CNT,
respectively. Common features and differences in their influence
on the mechanical behavior are highlighted and explained on the
basis of their main parameters.
Experimental
Materials
Composites were prepared with three different matrices: iso-
prene rubber (IR), styrene butadiene rubber (SBR) and natural
rubber (NR).
Synthetic poly(1,4-cis-isoprene) (IR) was SKI3 (Nizhnekam-
skneftechim Export, Nizhnekamsk, Russia), with 70 Mooney
units (MU) as Mooney viscosity (ML [1+4] 100°C).
Synthetic poly(styrene-co-butadiene) (SBR) was from solu-
tion anionic polymerization: Nipol NS 522 (Zeon Corporation,
Düsseldorf, Germany), with 39 mass% of bound styrene, 37.5
mass% of extension oil and 62 Mooney units (MU) as Mooney
viscosity (ML [1+4] 100°C).
Poly(1,4-cis-isoprene) from Hevea brasiliensis (natural rub-
ber, NR) was SMR GP, with 65 Mooney units as Mooney viscos-
ity (ML [1+4] 100°C), from Lee Rubber.
Organic peroxide was 2,5-dimethyl-2,5-di(tert-butylperoxy)
hexane supported on silica/CaCO3 (45 mass %), from Arkema
Inc.
Two types of multiwall carbon nanotubes were used.
CNT(B) are Baytubes C150 P from Bayer Material Science.
7KH\DUHFKDUDFWHUL]HGE\FKHPLFDOSXULW\•ZWOHQJWKRI
ȝPQXPEHURIZDOOVRIRXWHUDQGLQQHUGLDPHWHUVRI
10-16 and 4 nm, respectively, according to the technical data
sheet. Their surface area, measured by the BET method, is 200
m2/g.
 Table 1 - filler amount in phr of composites
based on IR, with CNT(B) and CB as the
carbon allotropes; other ingredients: IR 100
phr, dicumyl peroxide 1.40 phr
CNT(B) 0 1.25 2.50 5.00 10.00 15.00 30.00
CNT(B)/CB - - 1.25/ 2.50/ 5.00/ 7.50/ 15.00/
1.25 2.50 5.00 7.50 15.00
CB N326 0 1.25 2.50 5.00 10.00 15.00 30.00
Table 2 - filler amount in phr of composites
based on SBR, with CNT(N) and CB as the
carbon allotropes; other ingredients: SBR
100 phr, dicumyl peroxide 1.40 phr
CNT(N) 0; 1; 2; 3; 4; 5; 6; 6.5; 7.5; 10; 11; 14; 18; 20
CB N326 0; 10; 15; 20; 22; 30; 35; 45; 50; 60
CB N326 ~10 + CNT(N): from 0 to 14
(vol. fraction: 0.05)
CB N326 ~22 + CNT(N): from 0 to 14
(vol. fraction: 0.10)
CB N326 ~35 + CNT(N): from 0 to 14
(vol. fraction: 0.15)
CNT(N) are Nanocyl NC7000 series from Nanocyl (Sambre-
ville, Belgium), with carbon purity of 90%, average length of
about 1.5 μm and BET surface area of 275 m2/g.
Carbon black N326 (CB) from Cabot is characterized by 30
nm as the mean diameter of spherical primary particles, a nitro-
gen adsorption number of 77 m2/g and a DBP adsorption number
of 85 mL/100 g.
In IR based systems, composites with only CB, only CNT(B)
or hybrid fillers (CB+CNT) were prepared. The composition in
phr (weight parts per hundred parts of rubber) is reported in table
1. In hybrid filler composites, the filler content was divided into
two equal parts of the two fillers.
Composites based on SBR are filled with CNT(N), CB or
hybrid fillers (table 2). In this case, hybrid fillers were prepared
by adding to the fixed contents of CB increasing amounts of
CNT(N). The contents were chosen to uniformly cover a wide
range of total filler surface area.
Finally, NR based composites were prepared by adding only
CNT(N) or CB, as shown in table 3.
Preparation
Composites, based on either IR, SBR or NR, were prepared
using a Brabender type internal mixer (Brabender PL-2000
Plasti-Corder torque rheometer, Brabender GmbH & Co. KG,
Duisburg, Germany), with a 50 mL mixing chamber. The fol-
lowing procedure was adopted for the preparation of all the
samples: 50 g of the polymer were introduced into the Braben-
der type internal mixer and masticated at 80°C for one minute
with rotors rotating at 60 rpm. The filler was then added, mix-
ing was performed for four minutes, and the composite was
then discharged at a temperature of about 90°C. The compos-
ite, so prepared, was left to reach room temperature and was
fed again to the Brabender mixer kept at a temperature of
Table 3 - filler amount in phr (and volume
fraction in brackets) of composites based
on NR, with CNT(B) and CB as the carbon
allotropes; other ingredients: NR 100 phr,
dicumyl peroxide 1.40 phr
CNT(B) 0 4 15 35
(0.02) (0.07) (0.15)
CB N326 0 4 15 35
(0.02) (0.07) (0.15)
about 50°C. Peroxide was added, mixing was performed for
three minutes with rotors rotating at 60 rpm, and the composite
was finally discharged. Composites were finally further ho-
mogenized by passing them five times through a two-roll mill
operating at 50°C, with the front roll rotating at 30 rpm and the
back roll rotating at 38 rpm, and 1 cm as the nip between the
rolls.
Crosslinking reaction was performed at 170°C for 10 minutes
for IR compounds, and at 170°C for 20 minutes for SBR com-
pounds using a Monsanto oscillating disc rheometer (MDR
2000) (Alpha Technologies, Heilbron, Germany).
NR sheets were compression molded for 10 minutes at 170°C
with 3.5 MPa pressure into square plates with 3 mm thickness
and 100 mm edge.
Characterization
Dynamic mechanical characterization
For SBR and IR based composites, dynamic shear moduli were
measured by a Monsanto RPA 2000 rheometer (Alpha Technolo-
gies, Heilbron, Germany) in the torsion mode. For each sample,
a first strain sweep (0.1-25% shear strain amplitude) was per-
formed at 50°C and 1 Hz, then the sample was kept in the instru-
PHQW DW WKH PLQLPXP VWUDLQ DPSOLWXGH Ȗmin = 0.1%) for 10
minutes, to achieve fully equilibrated conditions. Finally, dy-
namic tests were performed at 50°C at increasing strain ampli-
tude (0.1-25% shear strain amplitude) with a frequency of 1 Hz.
Dynamic moduli of NR based composites were measured by a
dynamic mechanical analyzer Q800 (TA Instruments) in a shear
sandwich configuration, in strain sweep mode. Parallelepiped
specimens were cut from cured sheets of rubber with dimensions
of about 3 x 3 x 8 mm3. Figure 1a shows a schematic representa-
tion of the test configuration. Two specimens are compressed
between the fixed plates and the moving plate of the machine.
Strain sweeps were carried out in the range 0.02% to 25% of
strain amplitude, at room temperature and 1 Hz. Thanks to the
small dimensions of the specimens, different directions of strain
could be applied in order to study the variation of material prop-
erties with the loading direction.
The various strain directions applied are shown in figures 1b
and 1c, where the rubber plate is sketched with a broken line, and
Cartesian coordinates are displayed: Plane 1-2 corresponds to the
main plane of the rubber sheet, and direction 3 is the direction
perpendicular to such plane and also the direction of the pressure
applied during the compression molding phase. Two main con-
figurations are shown, including through-thickness (TT) and in
plane (IP). In TT configuration, the shear strain is applied as in
FOLLOW US ON TWITTER @rubberworld 25

Figure 1 - schematic representation of test
configurations, a) parallelepiped samples
were taken from a crosslinked
nanocomposite sheet and tested in the
shear sandwich configuration by a
dynamic mechanical analyzer,
b) representation of direction of shear
strains applied to specimens in b) “through-
thickness” and c) “in-plane” configurations;
the coordinates of the reference system
(long arrows) and the applied strain
directions (short arrows) are also displayed
Fixed clamps
Results
Structural chemical characterization of fillers
Both CB and CNT were characterized to get their morphological,
chemical and structural characteristics.
In brief, CNT(B) was characterized in (ref. 9), and has: BET
surface area equal to 200 m2/g, DBP absorption number of 316
mL/100 g and number of layers stacked in crystalline domain of
about 10, measured by WAXD analysis.
CB and CNT(N) were characterized and compared in (ref.
24). Carbon purity was investigated by means of thermogravi-
metric analysis and was found to be larger for CB (about 98%)
than for CNT(N) (about 90%). Indeed, infrared spectra of
CNT(N) showed features compatible with hydrocarbon, as well
as oxygenated functional groups, and Boehm titration revealed a
larger amount of acidic oxygenated groups. Disordered structure
was shown for both CB and CNT(N) by Raman spectroscopy
and WAXD analysis.

Rubber plate
Role of filler interfacial area for the mechanical reinforcement
6WRUDJHPRGXOXVDWVPDOOVWUDLQV*¶Ȗmin, was selected as the
Moving clamp parameter to study the mechanical reinforcement of rubber
Rubber
specimen composites. It can be reasonably expected that different fillers
Picture of DMA Q800 -
(a) TA Instruments clamp provide different initial modulus values, hence different levels
of mechanical reinforcement. As an example, figure 2 shows
Surfaces of the results obtained for SBR based composites, listed in table
strain 3 Through-thickness 3 In-plane
application J21 2.
J31 2
J32 2 At the same filler volume fraction, CNT(N) leads to a modu-
J12
lus much higher than that obtained only with CB. It is indeed
(c) worth observing the dramatic increase of modulus of a CB based
1 (b) 1
composite by adding even a low CNT(N) amount. The graph in
figure 2 clearly shows the higher reinforcing efficiency of CNT
figure 1b, i.e., through the sheet thickness; while in IP configura- and the fact that CNT is able to impart its higher efficiency also
tion, the shear strain is applied as in figure 1c and lies in the 1-2 to hybrid filler composites.
plane. One of the main reasons for the higher efficiency of CNT is
It is worth pointing out that TT configuration is similar to the its higher surface area. To support this claim, the data obtained
test configuration carried out by the RPA, in the sense that the for systems with different filler type and matrix type are plotted
strain is applied on a surface perpendicular to the pressure ap- as a function of the specific interfacial area in figure 3. The spe-
plied during the curing phase. cific interfacial area is the total surface area of filler normalized

Figure 2 - G'Jmin versus total filler volume Figure 3 - (G'/G'm)Jmin versus specific
% of composites based on SBR filled with interfacial area for composites based on
only CB, only CNT(N) or hybrid filler systems SBR or IR; black line indicates the
(CB+CNT[N]) master curve

10 25
CB (SBR)
Hybrid CNT(N) (SBR)
8 (ICB = 10%) Hybrid 20 CB + CNT(N) (SBR) (ICB = 5%)
CB + CNT(N) (SBR) (ICB = 10%)
G’Jmin (MPa)

(G’/G'm )Jmin

CNT(N) (ICB = 15%) CB + CNT(N) (SBR) (ICB = 15%)

6 Hybrid 15 CNT(B) (IR)
(ICB = 5%) CB (IR)
4 CB 10 CB + CNT(B) (IR) (ICB = ICNT)

2 5 y = e0.043x
R2 = 0.943
Matrix: SBR
0 0
0% 10% 20% 30% 0 10 20 30 40 50 60
Total filler volume % Specific interfacial area (m2/cm3)

26 RUBBERWORLD.COM ‡ FEBRUARY 2018

 The role of filler orientation on the mechanical properties
Figure 4 - G'Jmin versus filler volume % of Correlation discussed in the previous paragraph is based on the
composites based on NR filled with CB or assumption that the specific interfacial area can be representative
CNT(B), tested in two different of the interaction between the polymer and the filler. This as-
configurations: in-plane (triangles) or sumption could be disputed. However, the correlation was based
through-thickness (squares) (figure 1) on experimental data and the fit was remarkable. Other parame-
ters to represent the polymer filler interaction, such as CTAB or
25
CNT(B)-IP DBP absorption, are under investigation. A question could arise:
20 CNT(B)-TT
Whatever the parameter is to represent the polymer-filler interac-
tion, can the reinforcing effects of the fillers be modeled only on
G'Jmin (MPa)

CB-IP
15 the basis of this parameter? As mentioned in the Introduction,
CB-TT nanometric fillers such as CNT are characterized by high aspect
10 ratio. It was commented that fillers with high aspect ratio could
have preferential orientation in the rubber composite, and could
5 thus promote anisotropic effects. In this work, anisotropic effects
were investigated by dynamic mechanical tests carried out on
0
parallelepiped specimens. As shown in figure 1, different loading
0% 5% 10% 15% 20%
directions were applied: They can be classified with two test
Filler volume %
configurations, i.e., TT and IP configurations.
Systems based on NR filled with CB or CNT(B) were inves-
over the volume of the composite, calculated according to equa- WLJDWHGDQG*¶Ȗmin values are reported in figure 4 as a function
tion 1: of filler volume %.
Figure 4 shows anisotropic properties of CNT(B) filled com-
 6SHFLILFLQWHUIDFLDODUHD ȡ $CB ࢥCBȡ $CNT ࢥCNT (1) posites. In fact, for systems filled with CNT(B), the modulus is
higher in IP configuration than in TT configuration. On the other
:KHUHȡLVWKHILOOHUGHQVLW\HTXDOWRJFP3 for both CB and hand, the same values of moduli were measured for composites
&17$LVWKHVXUIDFHDUHDPHDVXUHGE\%(7PHWKRGDQGࢥLV with CB in TT and IP configurations, and curves are overlapped:
the filler volume fraction in the composite. As, for example, for This reveals an isotropic behavior. The anisotropy index of
an SBR based composite filled with 0.1 CB and 0.06 CNT(N)
as the volume fractions, the specific interfacial area is
         PFP3. Equation 1 pro- Figure 5 - schematic representation of the
vides an estimation of the filler-polymer interfacial area under hypothesized organization of CB (left side)
the hypothesis that all the filler surface is available to contact and CNT (right side) with a lateral view in
the polymer. “through-thickness” tests and with a top
 ,QILJXUHDUHUHSRUWHGERWKWKHGDWDVKRZQLQILJXUHZLWK view in “in-plane” tests
SBR as the elastomer, and the data of IR based composites
(listed in table 1). In order to compare data with different matri- In-plane
ces, the stiffness values reported in figure 3 were normalized over
the modulus of the neat matrix (G’m).
 )LJXUH  VKRZV WKDW XS WR DERXW  PFP3, the storage
modulus values seem to follow a common trend, irrespective of
the different fillers used, nanostructured or nanometric, single or
hybrid, and even irrespective of the polymer matrix. By fitting
the data with an exponential curve, a sort of master curve was Through-thickness
calculated, displayed by a black curve in figure 3. The master
FXUYHLVFDOFXODWHGXSWRPFP3, a remarkable content, which
FRUUHVSRQGVWRSKURI&%DQGSKURI&171ZKLFKDUH In-plane
contents typical of many elastomer composites reported in the
scientific literature and also available at the commercial scale.
The calculated master curve establishes a quantitative correla-
tion between moduli at low strain amplitude, and could be used
as a tool for the rationalization of reinforcement, with many po-
WHQWLDO DGYDQWDJHV )RU H[DPSOH LQ UHI  LW ZDV XVHG DV D
quantitative tool to design lightweight elastomeric materials. Through-thickness
 $WFRQWHQWVKLJKHUWKDQPFP3, the data are more scat-
tered. This could be due to an increased difficulty of dispersion
at such high contents, particularly with CNT.

FOLLOW US ON TWITTER @rubberworld 27

CNT(B) filled composites, i.e., the ratio of IP modulus over TT
modulus, is: 1.88 ± 0.04 (4 phr), 2.25 ± 0.04 (25 phr) and 2.07 ±
0.04 (35 phr).
Therefore, for a tubular filler characterized by a high aspect
ratio (CNT[B]), the stiffness measured by the application of the
strain in the plane of the rubber plate is about twice as much as
the stiffness measured by the application of strain through the
thickness. This effect is due to filler structuring in the rubber
matrix. Figure 5 shows a schematic representation of hypothe-
sized filler structuring.
CB particles are nearly isometric and are randomly distribut-
ed in the whole volume of rubber. CNT(B)s are flexible tubes
and present a planar random orientation inside parallel layers,
partially interconnected and structured through the sheet thick-
ness. Only for CNT(B), therefore, different moduli values are
obtained as a function of applied stress direction.
The hypothesis of filler structuring depicted in figure 5 was
confirmed by the analysis with a transmission electron micro-
scope (TEM) applied on sections, allowing one to observe the
filler structure through the sheet thickness. The application of an
electron diffraction technique to TEM images allows one to
Figure 6 - a) G’Jmin and b) (G’/G’m)Jmin versus
specific interfacial area of composites
based on NR filled with CB or CNT(B),
tested in two different configurations:
in-plane (triangles) or through-thickness
(squares) (revisit figure 1); in b) black circles
are data of composites based on SBR or IR
25
a)
CNT(B)-IP
20 CNT(B)-TT
G'Jmin (MPa)
identify CNT(B) preferential orientation, and to highlight their
layered structuring, with alternate layers having high or low filler
concentration (ref. 23). Such filler structuring is in agreement
with the transversally isotropic mechanical behavior revealed by
dynamic mechanical tests.
Master curves and anisotropic properties
In the previous paragraph, the anisotropy of the mechanical rein-
forcement of rubber compounds based on an anisometric filler
such as CNT(B) has been documented. The question which
arises is how to combine this finding with the results which led
to the master curve shown in figure 3. Why CB and CNT give
the same initial modulus at the same specific interfacial area
(figure 3) and the same filler, CNT gives different values of initial
modulus as a function of the direction of the applied stress? As a
matter of fact, the question could be the following: Is it possible
to take into account both the role of filler surface area and of
filler orientation?
To answer these questions, the data of figure 4 were plotted in
figure 6a as a function of the specific interfacial area.
In the graph in figure 6a, the points due to CB, both in TT and
IP configuration, and to CNT(B) in TT configuration, lie on the
same master curve. Only the points due to CNT(B) in IP con-
figuration are above this curve, as the composite revealed higher
modulus for a same specific interfacial area, when stress was
applied in IP configuration. At least for TT configuration, the
concept of a master curve common to both CB and CNT, based
on specific interfacial area, still seems to also be valid for an an-
isometric filler such as CNT.
It is interesting, therefore, to compare the new master curve
found for NR based systems in TT configuration with the master
curve obtained with IR and SBR based systems (shown in figure
3). At this aim, the data of NR of figure 6a were normalized over
the matrix modulus and plotted in figure 6b, where the original
data of IR and SBR based systems are also displayed as black

CB-IP
15 circles, without distinction of filler or matrix type. They are very
CB-TT
close to the data of NR composites in TT configuration, at least up
10 to 25 m2/cm3, as already observed for the SBR/IR mastercurve.
The data of the SBR/IR mastercurve were obtained by a tor-
5
sional rheometer (Monsanto RPA 2000 rheometer). This test con-
figuration has similarities with the TT test realized in shear sand-
0
0 10 20 30 40 50 60
wich configuration: In both cases, the strain is applied on a surface
perpendicular to the pressure applied during the curing phase.
Specific interfacial area (m /cm3)
2

50 Conclusions
IR or SBR based composites b) This work is a contribution for the rationalization of the me-
40 CNT(B)-IP (NR) chanical reinforcing effects of a rubber matrix promoted by sp2
CNT(B)-TT (NR) carbon allotropes, both nanostructured, such as CB, and nano-
(G’/G'm)Jmin

30 CB-IP (NR) metric, such as CNT. CB and CNT, which were used as the only
CB-TT (NR)
filler or as a hybrid filler system.
20 Differently from a nearly isometric filler such as CB, fillers
with high aspect ratio, such as CNT, promote anisotropic proper-
10 ties. This is due to filler structuring: CNT presents a planar ran-
dom orientation inside parallel layers, partially interconnected,
0 and structured through the sheet thickness.
0 10 20 30 40 50 60 In spite of the anisotropic properties of CNT filled compos-
Specific interfacial area (m /cm3)
2
ites, a common equation (master curve), able to correlate the

28 RUBBERWORLD.COM ‡ FEBRUARY 2018

mechanical reinforcement (initial modulus) with the interfacial
area made available by fillers, was obtained for composites based
on CB, CNT or hybrid filler systems, and isoprene or styrene/
butadiene rubber. This occurs when the load acts parallel to the
orientation of filler particles. In this case, there is no dependence
of moduli on filler aspect ratio. On the other hand, if the load acts
perpendicular to the fibers' direction, the modulus depends not
only on filler volume fraction and interfacial area, but also on
filler aspect ratio.
A master curve for the mechanical reinforcement could be
used as a predictive tool for designing composites with target
modulus and density values. Moreover, the possibility to selec-
tively increase composites’ reinforcement along specific direc-
tions could be exploited in advanced design of rubber composites.
References
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FOLLOW US ON TWITTER @rubberworld 29
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Why titanates and zirconates may be better
adhesion promoters than silanes for silica and
carbon reinforced polymeric composition
by Salvatore J. Monte, Kenrich Petrochemicals Figure 2 from the Gelest technical bulletin, Silane Coupling
Agents (ref. 2), shows silane effectiveness on inorganics. The
The reason why titanates and zirconates may be better adhesion effectiveness on carbon black is poor, and on sulfur is not even
promoters than silanes lies in the intrinsic multi-functional chem- mentioned. Charles Goodyear would have been stymied if he
istry of neo-alkoxy titanium and zirconium organo-metallics tried silanes, yet the silica-silane mindset permeates today’s com-
compared to trisalkoxy silanes at the nano-interface where dis- pounding and obviates interfacial surface modification innova-
similar materials meet.
A nanometer is the length your fingernail grows in a second.
You can’t “see” it with a scanning electron microscopic photo, Figure 2 - silane effectiveness on inorganics
but it is where the “rubber hits the road” in polymeric composite
performance. Substrates
The six titanate/zirconate functions (F1-F6) as compared to Excellent Silica
the three silane functions (F1, F2, F5), shown in figure 1, will Quartz
frame the discussion. Glass
Function 1, hydrolysis coupling of silanes, requires hydroxyl Aluminum (AIO[OH])
Alumino-silicates (e.g., days)
groups, which do not exist on carbon black interfaces. Nor, do Silicon
hydroxyls exist on graphite or aramid fibers or sulfur, sulfides, Good Copper
sulfates, carbonates, nitrides, nitrates and a host of other inorgan- Tin (SnO2O3)
ics and organics used in polymeric compositions. Talc
We like to think that the IT (information technology) of things Inorganic oxides
(e.g. Fe2O3, TiO2, Cr2O3)
and Industry 4.0 (with software and robotics control) have freed Steel, iron
us from the “old” ways of doing things. But, the pioneers who Asbestos
went before us still influence how we compound. Nickel
Zinc
Function 1 “coupling”: Ti vs. Si difference Lead
Slight Marble, chalk (CaCO3)
Until his death in 1991 at the age of 75, Dr. Edwin P. Plued- Gypsum (CaSO4)
demann was considered the world’s foremost expert on silane Barytes (BaSO4)
coupling agents. In 1982, Plueddemann wrote the book, Silane Graphite
Coupling Agents (ref. 1) and said on page 114: “… Surfaces that Poor Carbon black
showed little or no apparent response to silane coupling agents
include calcium carbonate, graphite and boron….”

Figure 3 - the use of titanate in situ to

Figure 1 - a comparison of the titanates/ compatibilize oil, water, BaSO4 and type 1
zirconates with silanes according to their Portland cement
functionalities

Titanates and zirconates

They are different than silanes
Titanate/zirconate six Silane three functions
functions
(F1) (F2) (F3) (F4) (F5) (F6) (F1) (F2) (F5)
(RO)n-Ti-(-O-X--R’-Y)4-n (RO)n-Si-(R’-Y)1
F1. (RO)n = proton (H+) reactive = Hydroxyl (OH-) reactive
F2. -Ti-(-O = catalytic reactive = -Si- stable carbon bond
F3. -X- = heteroatom = None
15 16
F4. - R’ = thermoplastic = Carbon bond to -Y
F5. - Y) = thermoset = Thermoset
F6. )4-n = hybrid, quat, = Monofunctional No titanate Titanate
chelate coordinate BaSO4/oil BaSO4/oil
Water/cement Water/cement

FOLLOW US ON TWITTER @rubberworld 31

 Figure 4 - initial, during and final (top to
bottom) - conductive carbon black
(Cabot XC-72R) placed on water with no
coupling agent (left) and same amount of
same carbon black placed on water
containing directly emulsifiable neoalkoxy
titanate (right) with no mechanical stirring
of the ingredients at any time
Conductive carbon black on water
No titanate LICA 09
Conductive carbon black on water
No titanate LICA 09
Conductive carbon black on water
No titanate LICA 09
tion using non-hydroxyl bearing materials like vulcanizing
agents, accelerators, blowing agents, organic fibers, and even
Portland cement, which is 74% trimethylene sulfide and carbon
disulfide, with the balance being tricalcium aluminate, Ca, Mg,
Al and S oxides.
Space limits providing a reference for every titanate or zir-
conate reactable interface, so thinking outside the “silica-silane
32 RUBBERWORLD.COM ‡ FEBRUARY 2018
Table 1 - resistivity of 3.75% XC-72R
conductive black in styrene butadiene block
copolymer/PS 10 mm thick test slab
Weight % LICA 09 Resistivity
carbon black Surface, :/sq. Volume, :.cm
Control >10e16 7.8 x 10e14
0.67 1.7 x 10e12 3.0 x 10e12
1.00 2.1 x 10e8 4.3 x 10e7
2.00 5.7 x 10e7 3.7 x 10e7
box,” figure 3 is taken from the author's thirty-first patent, EP 2
614 040 B1, granted in the EU April 12, 2017, in which a titanate
was added to water and dispersed, followed by spent drilling
mud (oil saturated BaSO4), and then ASTM C150-Type 1 Port-
land cement admixed to make a useful composition out of non-
silane reactable inorganic and organic materials.
Neoalkoxy titanates and zirconates couple via function 1
proton (H+) coordination coupling without hydrolysis or alcohol
condensation by-products. Therefore, a non-polar olefin polymer
having surface hydrogens (protons) becomes a reactive substrate,
or an aliphatic process oil with titanate “wets” CaCO3 filler like
an aromatic oil.
The effect of the titanate used in figure 4 on an XC-72R
3.75% carbon black/thermoplastic elastomer is shown in table 1.
Carbon black can be mixed atomically with no mechanical
stirring in water containing an emulsified titanate (LICA 09-neo-
alkoxy tri-dodecylbenzene sulfonyl titanate), as opposed to phase
separating without titanate (figure 4).
The fiberglass interface - Si vs. Zr - zirconates yield better
aged compositions
Practical commercial use of “coupling agents” began in 1953
using silane-sized fiberglass reinforced unsaturated polyester
parts for the Corvette automobile. Let us revisit fiberglass where
silanes are proven performers and discuss function 1 coupling at
the glass interface. Fiberglass has up to 16% hydroxyl groups.
The degree of silane coupling is dependent on the percentage of
Figure 5 - ETFE with fibers (E-glass) not
treated with coupling agent
20Pm
 Figure 6 - ETFE with fibers treated with Figure 8 - (left) 1,000 g of unfilled EPR
NZ 44 sheeted off a two-roll mill (right) catalysis
effect of 0.2 phr titanate

20Pm

Figure 7 - the catalytic effect of a neoalkoxy plex trade secret coupling agent containing coatings used on
titanate pellet masterbatch on PP/PET/PE glass and carbon fiber reinforcements (ref. 4).
R. Kraus et al. (ref. 5) stated: “The ETFE matrix was a copo-
Brabender plasticorder blends of three recycled polymers:
PP/PET/PE lymer of ethylene (38.5%) and tetrafluoroethylene (61.5%), with
a low fraction (0.4%) of perfluoropropylvinylether (PPVE) pro-
duced by Hoechst.
The fibers were glass fibers (E-glass) with an average diam-
eter of 10 μm and an average length of L = 60 μm. One fraction
of the fibers was treated with the coupling agent NZ 44
(neopentyl[diallyl]oxytri[N-ethylenediamino] ethylzirconate) to
improve the fiber-matrix interface. The specimens were prepared
by melting the mixture of matrix and a weight fraction of 10% of
Incompatible PP/PET/PE Compatibilized PP/PET/PE - fibers under pressure (p = 25 bar) at a temperature of 295°C, fol-
No additive 1.5% Ken-React CAPS KPR
12/LV pellets lowed by cooling to RT (cooling rate ~ 3 K min-1).
The influence of the coupling agent on the fiber-matrix inter-
face was studied by breaking composites at low temperature (T
(OH-) groups. = -190°C, liquid nitrogen) and analyzing the fracture surface by
Neoalkoxy titanates and zirconates react with more abundant scanning electron microscopy. Electron micrographs (figures 5
surface protons (H)+, which provides a greater degree of linkage, and 6) show that in the composite made of fibers without cou-
thus providing a performance
advantage in long term aging
maintenance of original func- Table 2 - evaluation of various coupling agents in glass fiber
tional properties when compared reinforced epoxy composites (original/aged properties)
to the interfacial deterioration
Formulation Parts by weight
data obtained using silanes in 100.0
Resin, DEN 438 (Novalak - Dow)
such tests as 240- hour 10% salt Hardener, methyl nadic anhydride 87.5
water boil used in advanced Glass fiber as shown (short - 5 mm) 40.0
composites protocol testing. Additive(s) 0.4
Table 2 (ref. 3) shows the aged Brookfield viscosity measured at 80°C, cure 30 minutes at 150°C, post cure: four hours at
amino silane maintains 65% and 180°C.
the aged amino zirconates 93% Aging 240 hours in boiling 10% aqueous salt solution.
of original properties. The aged Additive Long fiber Short fiber vehicle only
amino silane is 2.9 times better Tensile Viscosity Flexural Compressive Falling ball
and the aged amino zirconate is pullout 0.2 rpm/2 strength, strength, Impact strength
6.1 times better than the control energy, J rpm: mega gPa gPa kJ/m
Original/aged poise Original/aged Original/aged Original/aged
long fiber tensile strength. Control 54/14 0.67 : 0.43 0.82/0.40 1.54/1.21 1.7/1.0
Fiberglass reinforcements Amino silane 63/41 0.63 : 0.48 0.96/0.69 1.69/1.43 1.9/1.5
(E-glass) are sold with a silane Epoxide silane 65/37 0.58 : 0.45 0.92/0.74 1.58/1.51 1.9/1.6
sizing. These sizings are com- Amino zirconate 92/86 0.39 : 0.34 1.31/1.23 1.92/1.80 1.9/1.7

FOLLOW US ON TWITTER @rubberworld 33

 Function 3 nano-Ti/Zr phosphatization - flame retardance
Figure 9 - one inch to quarter inch mandrel and anti-corrosion
flexibility and anti-corrosion using a Silanes do not have phosphorus heteroatom functionality and
neoalkoxy pyrophosphato zirconate in an thus cannot nano-intumesce an interface. Two of the author’s
unfilled WB acrylic patents were held under DoD secrecy orders using phosphato
and pyrophosphato titanates to control the burn rate and burn rate
Clear water based acrylic (Joncryl RC 537) containing QB exponent of AL/AP/PU solid rocket fuel and RDX/CAB Insensi-
012 applied to Q panels and baked 10 minutes at 65°C,
conditioned in air for one hour and then immersed eight tive Munitions LOVA propellant for the Abrams A1A tank
hours in 5% NaCl solution at 3.27 pH rounds.
Figure 9 shows the use of a neoalkoxy titanate:zirconate 1:2
No additive QB 012 Quat NZ 38 co-solvated quat blend (QB 012) having a function 3 nano-heteroatom pyro-
phosphato group improves the mandrel flexibility of an unfilled
WB acrylic (Joncryl RC 537) coating from 1" to ¼" and im-
proves corrosion resistance at the bend. The amine used to quat-
ernize the otherwise water insoluble Ti/Zr blend caused a degree
of hydrophilicity, so it was decided to co-solvate the neat neoalk-
oxy pyrophosphate zirconate (NZ 38) with Texanol, resulting in
improved anti-corrosion performance at the scribe.
In plasticized systems, 0.2 phr of subject organometallics will
No additive - QB 012 - LICA NZ 38 ester replace up to 18% process oil or plasticizer to equivalent elonga-
control 38J, NZ 38J - alcohol - 1:9 tion, while increasing tensile strength independent of filler. This
1” mandrel bend 1:2 1/4” mandrel option does not exist with silanes.
causes com- 1/4” mandrel bend causes no The author believes that the application of the six functions
plete delamina- bend causes no delamination,
tion, severe dis- delamination, no discolor-
would appear to allow for more effective transfer of impact
coloration and no discolor- ation and little forces such as experienced by aircraft tires. See Kumho Tires
little corrosion at ation and mild corrosion at the Co., Ltd., S. Korean patent (ref. 9), summarizing the new and
the scribe corrosion at the scribe novel effects of a neoalkoxy aromatic amino zirconate’s six func-
scribe tions in a tire rubber composition.

pling agent, the matrix is removed from the fibers. In the com- Summary
posite made of the fibers treated with coupling agent NZ 44, Subject titanates and zirconates may be better adhesion promot-
most of the fibers are covered with polymer matrix. This indi- ers than silanes because their six function chemistry works dif-
cates that the fiber-matrix interface is improved by the coupling ferently:
agent.  ‡1RK\GUR[\O2+JURXSVRU+2QHHGHGDVZLWKVLODQHV
 ‡1RS+VHQVLWLYLW\VSHFLDOSUHWUHDWPHQWFRQGLWLRQVQHHGHG
Function 2 catalysis add directly to the organic or water phase.
Titanium and zirconium based organometallics are catalysts,
while silanes are not catalysts. Ti or Zr catalytic functionality
works in unfilled polymers (ref. 6) and changes the morphology
of the polymer at the nano-interface of a filled polymer, resulting
in polymers with slightly higher tensile strength (F/A) and sig-
nificantly higher elongation (e/l), which produces a tougher (de-
fined as the area under the plot of stress vs. strain) polymer,
which results in coatings on metal with higher reverse impact
strength and greater mandrel flexibility.
Polymer alloying to take advantage of the performance prop-
erties of different polymers can be a challenge. For example, al-
WKRXJK33DQG+'3(DUHERWKROHILQVPRUHWKDQ33EOHQGHG
LQWR +'3( ZLOO FDXVH GHODPLQDWLRQ GXULQJ PROGLQJ$GGLWLRQ
and condensation polymers tend to delaminate. Silanes do not
catalyze, but titanates catalyze to compatibilize both addition (PP,
 ‡3URWRQ+UHDFWLYHZLWKRUJDQLFLQRUJDQLFVXEVWUDWHVRIDOO
types.
 ‡$GGGLUHFWO\LQWRPL[IRULQVLWXFRXSOLQJDQGSRO\PHU
catalysis for repolymerization (ref. 6) and copolymerization/
compatibilization (ref. 7) of dissimilar polymers.
 ‡)RUPQDQRPHWHUDWRPLFPRQROD\HUVIRUFRPSOHWH
adhesion.
 ‡5HVLVWDJLQJDQGSURYLGHQDQRSKRVSKRUXVDQWLFRUURVLRQDW
the nano-interface.
References
1. Edwin P. Plueddemann, 1982, “Silane Coupling Agents,”
http://www.springer.com/us/book/9780306434730.
2. http://www.gelest.com/wp-content/uploads/Goods-PDF-bro-
chures-couplingagents.pdf.
3((35DQGFRQGHQVDWLRQ3(7SRO\PHUVUHIILJXUH
Figure 8 shows that 0.2 phr titanate has the same effect as
adding 15 phr of process oil.
A white paper on compatibilizers discussing thermoplastic
copolymers, maleated polymers and subject organometallics is
available (ref. 8).
34 RUBBERWORLD.COM ‡ FEBRUARY 2018
3. Int. SAMPE Technical Conference (1988), 20 (Mater.-Process-
es: Intercept Point), 423-37 CODEN: ISTCEF; ISSN: 0892-
2624: “Enhanced bonding of fiber reinforcements to thermoset
resins,” General Dynamics/Kenrich Petrochemicals, Inc.
4. http://www.compositesworld.com/articles/advances-in-siz-
(continued on page 40)
Optimization of the silica/polymer interface
in the case of very high surface silica: New
methods to support formulation adjustments
for passenger car and truck tire treads
by Laurent Guy and Thomas Chaussée, Solvay, France (M = 538 g/mol with two atoms of silicone in one molecule
structure able to interact with the silica surface). The amount of
Precipitated silica, used as a reinforcing filler, appears to be a silane will cover a large range. The following equation gives an
key enabler to help in the reduction of CO2 emissions of vehi- indication regarding the number of Feet_Si/nm2 on the silica
cles through improvement of the tire performance (ref. 1), such surface in order to compare all silicas:
as rolling resistance. Number of Feet_Si/nm2 = 2 x ([TESPT_quantity_phr]/538)
In the early 1990s, Solvay (formerly Rhodia) created a new x 6.02e23)/(silica_quantity_phr x SSA_fromCTAB_m2/g
standard with the development of HDS Zeosil 1165 MP silica. x 1e18) (2)
Thanks to optimum dispersion in rubber, wear resistance is
much improved as compared to conventional silica. On the
other hand, wet grip and rolling resistance are improved and Table 1 - filler characteristics
lead to better performance than carbon black tread compounds
Typical analysis Zeosil Zeosil HRS Premium
(refs. 2 and 3). 1165 MP 1200 MP 200 MP
Today, the main challenge is not only to continue the exten- BET (specific surface 156 201 212
sion of the magic triangle (wear, rolling resistance and wet area – m2/g )
grip), but also to afford better processing and compounding of CTAB (specific surface 154 196 196
the silica technology, not only for passenger car tires, but also area – m2/g)
Moisture 7.1 6.6 5.6
for truck tires. (2 hours at 105°C) – %
To reach new performances for the compromise reinforce-
ment and hysteresis, the use of silica with high specific surface
area like Premium 200 MP, Zeosil HRS 1200 MP and Premium
SW is key. But in this case, we need for premium silica to de- Table 2 - tire tread recipes (in phr)
fine new optimization rules, likely linked to the difference in
All silica
surface chemistry and activity. sSBR (Buna VSL 4526-2) 137.5
The first section of this article will describe the surface activ- Silica 80
ity of these silicas. The second part will highlight some examples Silane TESPT Variable
of optimization in the case of passenger car tire tread recipes. TDAE oil (Vivatec 500) 2.5 (or 17.5 for Zeosil
HRS 1200 MP)
N330 3
Materials and methods 6-PPD 1.9
Materials Stearic acid 2
For fuel efficient passenger car (PC) tire tread compounds, the ZnO 2.5
elastomer matrix is based on a solution styrene butadiene rub- CBS 1.5
ber (s-SBR). A solution styrene butadiene rubber with oil ex- DPG Variable
TBzTD 0.2
tension has been used in our experiments. To investigate only S 1.1
the pure effect, there was no addition of other elastomers.
Solvay HDS Zeosil 1165 MP, Premium 200 MP and Zeosil
HRS 1200 MP are compared. The main physico-chemical char-
acteristics of these silicas are presented in table 1. Rubber for- Table 3 - Feet_Si/nm2 values as a function of
mulations are presented in table 2 for passenger car tire tread. silica nature (80 phr) linked to silane amount
Some ingredients are adjusted in order to take into account
Feet_Si/nm2 0.3 0.6 0.9 1.2 1.5 1.8 2.1
the variation of the total polymer/filler contact area and the Zeosil 1165 Phr - 3.2 4.8 6.4 7.9 9.5 -
adsorption on the silica surface. MP
The DPG molecule level is adjusted with the total engaged SSA = 160 m2/g Phf - 4.0 6.0 8.0 9.9 11.9 -
surface in order to compensate for the adsorption on the silica Premium 200 MP Phr - - 6.1 8.1 10.1 12.1 14.1
surface (refs. 4 and 5), with the following equation: SSA = 200 m2/g Phf - - 7.6 10.1 12.6 15.1 17.6
Zeosil HRS 1200 Phr 2.0 4.0 6.1 8.1 10.1 - -
Amount of DPG (phr) = 0.00012 * Q(silica quantity in phr) MP
* SSA (from BET in m²/g) (1) SSA = 200 m2/g Phf 2.5 5.0 7.6 10.1 12.6 - -
The only coupling agent in this study is the silane TESPT

FOLLOW US ON TWITTER @rubberworld 35

 There is no standard protocol for this measurement. There
Table 4 - typical mixing cycle for the are different methods (refs. 11 and 12). We apply the following
non-productive stages used in passenger one: The Sears number is here the volume of sodium hydroxide
car tires (NaOH) 0.1 M which is necessary to increase the pH of a sus-
pension of silica (1.5 g in 150 mL of a 200 g/l NaCl solution)
Phase 1 (NP1) Temperature Ingredient
0’ 80°C SBR from 4 to 9.
0’30 - 2/3 silica + silane The dispersion is done in a beaker placed in an ice bath
1’30 - 1/3 silica + oil + stearic acid using a 1,500 W ultrasonic probe (Branson, 19 mm) for eight
2’30 - Outgassing minutes. After stirring, the pH of the solution is measured. If
2’45 - Rotor speed increase to pH is more than 4, a 1 M HCl solution is added to decrease pH
get 150°C
3’30 - Plateau at 150°C below 4. From this point, a 0.1 M NaOH solution is added to
5’30 155°C Dump reach pH 9 with a titrator (for example, Titrando 808 Me-
Phase 2 (NP2) trohm). V1 and V2 are the volume of NaOH corresponding to
0’ 90°C Masterbatch pH 4 and 9, respectively.
0’30 - ZnO + anti-aging The Sears number for 1.5 gram of dry silica is calculated
0’45 - Rotor speed increase to
get 150°C following the equation (3):
2’ - Plateau @ 150°C [(V2 - V1) x 150]/[(100-moisture) x m] (3)
4’ 150°C Dump With V1: volume of 0.1 M sodium hydroxide solution at pH
Phase 3 (NP3) = 4 in ml; V2: volume of 0.1 M sodium hydroxide solution at
0’ 90°C Masterbatch pH = 9 in ml; m: mass of silica (g); and moisture: two hours at
3’ 150°C Dump
105°C (table 1).
The experimental values are expressed in table 3, and a
For the three silicas, the Feet_Si/nm2 values are described in conversion of sodium hydroxide volume in terms of exchange-
table 3. The curing system is based on the association of CBS- able protons per nm2 is calculated following the equation (4):
TBzTD-DPG-sulfur.
The mixing process (table 4), in three steps for non-produc-
tive stages, is carried out in a Brabender 0.380 liter internal
mixer (speed rate: 100 rpm; fill factor: 0.6).
Using those conditions, a final plateau above 150-155°C is
reached at the end of the NP Step 1. The productive stage (ad-
dition of the DPG-CBS-TBzTD-sulfur cure system) is per-
formed on an open mill.
After calendering, the compounds are cured at 160°C for
passenger car tire tread and according to their own t98 (based on
the rheological data from ODR).
Methods
To characterize the silica surface chemistry and reactivity, a lot
of methods have been inventoried (ref. 6).
In addition to the standard characterizations (BET, CTAB,
pH and moisture) (table 1), additional measurements have been
performed.
To get a first estimation of the silanol density (SiOH/nm2),
a thermogravimetric analysis (TGA) from ambient temperature
to 1,000°C (ref. 7) and a chemical dosage using methanol have
been performed (ref. 8).
The IRFT experiments (Bruker Equinox 55) give informa-
tion on the silanol repartition. The spectra are presented in fig-
ure 1 after desorption under vacuum (10-7 mbar) for one hour
at 25°C. Attribution of the absorption bands has been published
(ref. 9).
Other methods are used to evaluate the surface reactivity of
the silica. One is the Sears method, based on a dosage of the
 QE6L2+»QP2 from Sears number) = 60 *
([Sears number for 1g]/SBET) (4)
To determine the optimal silane quantity as a function of the
silica nature, a robotization system has been developed to allow
fast screening and different test condition evaluations using
silica, silane and solvent (xylene) (ref. 13). The unreacted silane
amount is quantified by the HPLC method. The optimal quan-
tity will be expressed in Feet_Si/nm2.
Rubber compounds are described by the rheological, me-
chanical and dynamic properties.
Rheological properties are measured using a MV2000E
rheometer at 100°C (ISO 289) for the Mooney viscosity ML
(1+4) and an ODR Monsanto R100S at 160°C (ISO 3417) for
the vulcanization curve and its associated main criteria (mT,
MT, TS2, T90, T98).
Mechanical properties are performed using an Instron 5564
for the tensile tests on cured compounds. Characteristics ex-
tracted from stress-strain curves are the modulus at x% (M10,
M100 and M300), as well as the ultimate properties of tensile
strength (TS) and elongation at break (EB) (NF ISO 37). Tear
resistance (ASTM C - NF ISO 33) is measured on the same
equipment.
Hardness (durometer A) is measured at room temperature
(ASTM D2240), and DIN abrasion is carried out according to
NF ISO 4649.
To study the dynamic properties (ASTM D5992), Metravib
VA3000 and VA2000 analyzers are used. We selected three
different deformation modes in line with the tire behavior.
 )RUWKHVWDQGDUGFKDUDFWHULVWLFV(
(¶(¶¶DQGWDQįWKH
silica surface by sodium hydroxide (ref. 10), initially developed
to define the specific surface area of colloidal silica in 1956
(ref. 11), and later extended to qualify the specific surface area
of precipitated silica or mesoporous silica (ref. 12).
36 RUBBERWORLD.COM ‡ FEBRUARY 2018
samples (cylinders with a section of 95 mm2 and a height of 14
mm) are tested in compression mode at 10 Hz at a temperature
of 60°C. Testing is done after a static pre-strain of 10% and a
dynamic double strain amplitude of 4%.
 Figure 1 - quantification of silanols/nm2 for Figure 3 - Payne effect at 40°C as a function
the three silicas of the number of feet per nm2 from silane
for Zeosil 1165 MP, Premium 200 MP and
16 Zeosil HRS 1200 MP
14
12 3.00
10

Delta G’ (MPa) -40°C

2.50
8
2.00
6
4 1.50
2 1.00
0
Zeosil Zeosil HRS Premium 0.50
1165 MP 1200 MP 200 MP
Si-OH/nm2 exchangeable (Sears) 0.00
0.0 0.5 1.0 1.5 2.0 2.5
Si-OH/nm2 surface (MeOH) Number of Si Feet/nm2
Si-OH/nm2 total (TGA)
Number of Si atoms from TESPT reacted on silica
surface/nm2 (or Feet_Si/nm2) Zeosil 1165 MP Premium 200 MP Zeosil HRS 1200 MP

The temperature sweep curve is done on specific samples (2
x 4 mm2 of section, 14 mm of height) tested in elongation mode
at 10 Hz under a dynamic strain amplitude of 0.1% from -80°C
to 80°C (speed rate: 5°C/minute).
To study the Payne effect, the samples (double sandwich of
specific form with a section of 2 x 4 mm2 and a height of 7 mm)
several methods with the objective to correlate it with some
rubber properties and silane activity.
The silanol quantification is commonly considered as an
appropriate way to predict the surface reactivity.
The silanol content from TGA of the silica (figure 1) covers
a large spectra of values from 8.7 for Premium 200 MP to 14.6
DUHWHVWHGLQSXUHVKHDUȖPRGH7KHG\QDPLFPHDVXUHPHQWV for Zeosil 1165 MP of Si-OH/nm2.
are carried out at 10 Hz under different temperatures. The varia- The chemical dosage (via esterification with methanol)
tions of the storage modulus (G'), the loss modulus (G") and the gives an estimate of the surface silanol quantity. For all silica
ORVVIDFWRUWDQįDUHUHFRUGHGEHWZHHQȖ DQGȖ  (figure 1), the values are always lower than the values obtained
The data are plotted as a function of the simple strain amplitude. from TGA, which confirms that precipitated silica includes in-
The following abbreviations are used: G’0 (elastic modulus at ternal silanols (ref. 15).
YHU\ORZVWUDLQȖ *¶’ (elastic modulus at high strain The Sears method is supposed to give access to the specific
Ȗ ¨*¶ >*¶0 - G’’@DQGWDQįPD[WKHPD[LPXPRI surface area via a dosage of the weakly acidic silanol groups
ORVVIDFWRUEHWZHHQȖ DQGȖ 7KHH[SORLWDWLRQRI (ref. 12). As seen in figure 1, the comparison at the same sur-
the results is done after a first strain sweep between 0.001 and face (200 m2/g) induces lower Sears number values for Pre-
0.5 (in order to remove any irreversible effects) (ref. 14). mium 200 MP (1.8) against 2.5 for Zeosil HRS 1200 MP.

Experimental results - silica surface and interface

characterization Figure 4 - Mooney viscosity at 100°C (ML
The surface reactivity of the silica has been investigated by [1+4] in mu) as a function of the number of
feet per nm2 from silane for Zeosil 1165 MP,
Premium 200 MP and Zeosil HRS 1200 MP
Figure 2 - spectra in IRFT for the three silicas
140
1.0 120
Zeosil 1165 MP
ML (1+4) -100°C

Zeosil HRS 1200 MP 100

0.8
Absorbance units

Premium 200 MP
80
0.6 60
40
0.4
20
0.2 0
0.0 0.5 1.0 1.5 2.0 2.5
0.0 Number of Si Feet/nm2
0

0
00

80

60

40

20

00
4,

3,

3,

3,

3,

3,

Wavenumber cm-1 Zeosil 1165 MP Premium 200 MP Zeosil HRS 1200 MP

FOLLOW US ON TWITTER @rubberworld 37

 So there is no direct link between the specific surface area A variation in terms of silane amount will be introduced and
and the Sears number. For this reason, we prefer to express the adapted to each silica (table 3) in order to use common values:
Sears values as a number of exchangeable protons on the silica number of Feet_Si/nm2.
surface. The obtained values (figure 1) are always lower than The optimization of the silane content is based on the
the surface silanols quantity. measurement of the Payne effect at 40°C. From figure 3, we
After the quantification, the silanols profiles are obtained can observe that the minimum values are quite equivalent for
through the use of IRFT. Zeosil 1165 MP and Zeosil HRS 1200 MP, with values close
As seen in figure 2, the distributions in terms of associated, to 1.1-1.2 Si_Feet/nm2. This value is quite close to the model
internal and terminal silanols are quite the same for Zeosil 1165 measurement (part 2) using only silica and silane in a non-
MP and Zeosil HRS 1200 MP. The silica Premium 200 MP polar solvent.
induces a different distribution for terminal and internal silan- In the case of Premium 200 MP, a higher value close to 1.5-
ols. 1.6 Si_Feet/nm2 is measured. This result is also aligned with
The lower values in terms of surface silanols (chemical dos- the previous model method (1.8 Feet_Si/nm2).
age) can explain the lower content of geminated silanols (and In conclusion for this section, from two different methods
more isolated silanols) for Premium 200 MP (5.0) in compari- we validate that for standard silica, such as Zeosil 1165 MP or
son to Zeosil 1165 MP (7.5). An ideal amorphous silica like Zeosil HRS 1200 MP, the standard equation to adapt the silane
cristobalite induces a surface silanols value of 4.6 SiOH/nm2 dosage is enough (equation [5]). But in the case of advanced
(ref. 16).
After the characterization of the silanol nature on
silica surface, the next step is the reactivity of this Figure 5 - dynamic performance indicators for
surface with a standard silane like TESPT. rolling resistance (tan į maximum at 40°C) and for
Thanks to the model setup and the analysis of the wet grip (maximum of tan į during temperature
unreacted silane by HPLC, it is possible to access the sweep) for Zeosil 1165 MP
quantity of silane reacted on the silica surface. 0.270
1.10
Based on the fact that the TESPT molecule has 1.05
temperature sweep

Tan (į) maximum

0.250
Tan (į) maximum

two silicone atoms, we are able to determine the num- 1.00

Payne, 40°C
ber of silicon (Si) atoms from TESPT reacted on the 0.95 0.230
0.90
silica surface/nm2 (or number of Feet_Si/nm2). 0.85 0.210
As seen in figure 1, the first key result is to find a 0.80
0.190
similar value of 1.1-1.2 at Si/nm2 for both Zeosil 1165 0.75
0.70 0.170
MP and Zeosil HRS 1200 MP. This value is in ac- 0.65
cordance with the standard silane dosage proposed for 0.60 0.150
precipitated silica by Wolff (ref. 17) and following the 0.0 0.5 1.0 1.5 2.0 2.5
equation (5): Number of Si feet/nm2
TESPT_amount (phr) = 0.0005 x
quantity_silica_phr x SSA_CTAB_m2/g (5) Wet grip (temperature sweep - maximum tan į)
Rolling resistance (Payne - 40°C)
In the case of Premium 200 MP, the value is quite
a bit higher with 1.8 at Si_TESPT/nm2. It seems that
the silica surface nature impacts the silane activity,
despite a specific surface area identical to Zeosil HRS Figure 6 - dynamic performance indicators for
1200 MP. The consequence is the need to adapt the rolling resistance (tan į maximum at 40°C) and for
silane content to the silica nature, and less to the spe- wet grip (maximum of tan į during temperature
cific surface area, in this case. sweep) for Zeosil HRS 1200 MP
An additional point is that there is no correlation 0.270
1.10
between these values in terms of silane reactivity and 1.05
temperature sweep

Tan (į) maximum

0.250
Tan (į) maximum

the silanol quantity on the silica surface. 1.00

Payne, 40°C

To check this hypothesis, the next section will de- 0.95 0.230
0.90
fine in real compounds the optimal dosage of TESPT 0.85 0.210
silane. 0.80
0.190
0.75
0.70 0.170
Optimization of the silane amount as a function of 0.65
silica nature in a passenger car tire tread recipe 0.60 0.150
Global approach: Definition of optimal silane content 0.0 0.5 1.0 1.5 2.0 2.5
To define the optimal silane content, a simplified Number of Si feet/nm2
recipe (based on pure sSBR) and a mixing protocol to
optimize filler dispersion and distribution (tables 2 Wet grip (temperature sweep - maximum tan į)
Rolling resistance (Payne - 40°C)
and 4) are used.

38 RUBBERWORLD.COM ‡ FEBRUARY 2018

 silica technology like Premium 200 MP, an increase
Figure 7 - dynamic performance indicators for of the silane content (+20/50%) is required to try to
rolling resistance (tan į maximum at 40°C) and for optimize the overall performance.
wet grip (maximum of tan į during temperature The following section will share some results and
sweep) for Premium 200 MP benefits of adapting silane content.
1.10 0.270
1.05 Optimal silane content - impact on the rubber
temperature sweep

Tan (į) maximum

0.250
Tan (į) maximum

1.00 performance

Payne, 40°C
0.95 0.230 The benefit of the silane adjustment on rubber perfor-
0.90
0.85 0.210 mance has been studied for the three silicas. Regarding
0.80
0.190 the processing (figure 4), the variation of the Mooney
0.75 values as a function of the silane content confirms the
0.70 0.170
0.65 interest in adjusting the silane for silica at high specific
0.60 0.150 surface area (200 m2/g) like Premium 200 MP. Thanks
0.0 0.5 1.0 1.5 2.0 2.5 to the silane adjustment, the Mooney value can be re-
Number of Si Feet/nm2 duced by 10% in order to be close or similar to that of
Z1165 MP.
Wet grip (temperature sweep - maximum tan į) Regarding dynamic performance for all silicas
Rolling resistance (Payne - 40°C)
(figures 5, 6 and 7), the silane adjustment is con-
firmed in terms of the balance between the two de-
scriptors: rolling resistance (Payne - tan max - 40°C)
Figure 8 - mechanical performance indicators with and wet grip (temperature sweep - maximum of tan
M300 (MPa) and DIN abrasion (mm3) for Zeosil value). To reach the optimal level of the silane amount
1165 MP helps to optimize the two laboratory descriptors.
At the same high surface area (200 m2/g), Premium
20.0 220
200 MP allows users to reach the best balance thanks
18.0
200 to a special compromise between aggregate size and
DIN abrasion (mm3)

16.0
14.0 specific surface area (ref. 18).
M300 (MPa)

180
12.0 Regarding mechanical performance for all silicas
10.0 160 (figures 8, 9 and 10), the silane adjustment is con-
8.0
140 firmed in terms of balance between the two descrip-
6.0 tors: M300 and DIN abrasion. The silane adjustment
4.0 120 is a key parameter to manage the balance between the
2.0
0.0 100 two properties.
0.0 0.5 1.0 1.5 2.0 2.5 As before, Premium 200 MP gives a better com-
promise in terms of reinforcement and abrasion level.
Number of Si Feet/nm2
M300 DIN abrasion
In conclusion, the silane adjustment is the key to
obtaining the best performances from the silica/silane
association, including some benefits in processing.

Figure 9 - mechanical performance indicators with Conclusion

M300 (MPa) and DIN abrasion (mm3) for Zeosil HRS The goal is to get a step further in tire performance for
1200 MP safety, fuel saving and durability for passenger cars,
trucks and buses.
20.0 220
The actual development of silica with high or very
18.0
200 high surface is key to reaching the best compromise
DIN abrasion (mm3)

16.0
14.0 between wear, handling and rolling resistance without
M300 (MPa)

180
12.0 sacrificing wet traction: our safety.
10.0 160 The adaptation of the silane amount to the surface
8.0
140 activity of the silica and not to the silica surface is
6.0 critical to addressing overall performance.
4.0 120 In passenger car tire tread, silica with high surface,
2.0
0.0 100 like Premium 200 MP, and optimization of the silane
0.0 0.5 1.0 1.5 2.0 2.5 content (+20/50% of the standard dosage) allows for
an increase in the compromise between the rolling
Number of Si Feet/nm2
M300 DIN abrasion
resistance and wear resistance.
This article is based on a paper presented at the

FOLLOW US ON TWITTER @rubberworld 39

 meeting, October 27, 1994.
Figure 10 - mechanical performance indicators with 4. F. Bomo, Makromol. Chem., Macromol. Symp., 23,
M300 (MPa) and DIN abrasion (mm3) for Premium 321 (1989).
200 MP 5. J. Ramier, L. Chazeau, C. Gauthier, L. Guy and M.N.
Bouchereau, Rubber Chem. Technol., 80, 183 (2007).
20.0 220
6. A.P. Legrand, H. Hommel, A. Tuel, A. Vidal, H.
18.0
16.0 200 Balard, E. Papirer, P. Levitz, M. Czernichowski, R. Erre,

DIN abrasion (mm3)

14.0 H. Van Damme, J.P. Gallas, J.F. Hemidy, J.C. Lavalley,
180
M300 (MPa)

12.0 O. Barres, A. Burneau and Y. Grillet, Adv. in Coll. and

10.0 160 Interf. Sci., 33, 91 (1990).
8.0 7. J. Meier, J. Fritzsche, L. Guy, Y. Bomal and M. Klup-
140
6.0 pel, Macromolecules, 42, 2,127 (2009).
4.0 120 8. R. Valero and J. Hernandez (to Rhodia), Patent
2.0 WO2003016215 A1, August 13, 2002.
0.0 100
9. A. Burneau and J.P. Gallas, “The surface properties
0.0 0.5 1.0 1.5 2.0 2.5 of silica,” A.P. Legrand, editor, Wiley Ed., NY (1998).
Number of Si Feet/nm2 10. F. Heinroth, R. Munnekhoff, C. Panz, R. Schmoll, J.
M300 DIN abrasion Behnisch and P. Behrens, Microporous and Mesopo-
rous Materials, 116, 95 (2008).
11. G.W. Sears, Analytical Chemistry, 28, 1981 (1956).
192nd Technical Meeting of the Rubber Division, ACS, Octo- 12. T. Okel (to PPG), Patent WO2010/129518 A1, November 11,
ber 2017. 2010/S. Uhrlandt et al. (to Degussa), Patent US6180076, January
30, 2001/L. Gottlieb (to Degussa), Patent FR2824820, November
References 22, 2002/D. Luginsland et al. (to Degussa), Patent WO2004/065443
1. L. Guy, Workshop “WKS9 - energy efficient vehicles towards A2, August 5, 2004/A. Weihmeier et al. (to Evonik), Patent
50g CO2/km (or 2 liter/100 km),” Challenge Bibendum (Cheng- DE102008017747, October 10, 2009.
du, China), November 11, 2014. 13. T. Chaussée, “New method to support formulation adjustment
2. Y. Bomal, P. Cochet, B. Dejean, P. Fourre and D. Labarre, for optimized tire performance,” Tire Tech 2017.
Actua. Chim., 1-2, 42 (1996). 14. J. Ramier, C. Gauthier, L. Chazeau, L. Stelandre and L. Guy,
3. G. Agostini, J. Bergh and T. Materne, Akron Rubber Group J. of Polym. Sci., Part B: Polymer Physics, 45, 286 (2007).
15. The Chemistry of Silica, R.K. Iler, John Wiley & Sons, ed; first
edition (1978).
16. L.T. Zhuravlev, Colloids and Surfaces A: Physicochemical
and Engineering Aspects, 173, 1 (2000).
17. S. Wolff, M.J. Wang and E.H. Tan, Rubber Chem. Technol. 66,
The Science and 163 (1993).
Practice of 18. L. Guy, P. Cochet, Y. Bomal and S. Daudey, Kautschuk Gummi
Rubber Mixing Kunstoffe, 62, 383 (2009).

$270.00
Manufacturing rubber products requires the use of
many additives.
Therefore, mixing of the additives with the rubber
is a very important step in the processing of rubber.
There has been extensive research to try to under-
stand the relationships between the formulation
and the properties of the final product.
ISBN-13: 9781859572078
Pages: 422
Order Online: www.rubberworld.com/bookstore
Titanates and zirconates
(continued from page 34)
ings-and-surface-treatments-for-carbon-fibers.
5. Journal of Materials Science 28 (1993) 4,047-4,052, “Acous-
tic emission analysis and small-angle x-ray scattering from mi-
crocracks during deformation of ETFE composites,” R. Kraus,
A. Payer, W. Wilke, Abteilung Experimentelle Physik, Universitat
Ulm, Albert-Einstein-Allee 11, 7900 Ulm, Germany.
6. U.S. Patent 4,657,988, “Repolymerization.”
7. PIA Global Plastic Summit 2015, Chicago, IL, October 28,
2015: “New titanium-mixed metal catalyst for multi-polymer
compatibilization and post consumer recycle (PCR),” S.J.
Monte.
8. http://www.plasticsindustry.org/sites/plastics.dev/files/com-
patibilizers%20whitepaper%20(version%201.0)_0.pdf.
9. KR 2012078860 Kumho Tires Co., Ltd., S. Korea.

40 RUBBERWORLD.COM ‡ FEBRUARY 2018

 Meetings
Bangkok hosts GRTE 2018
GRTE (Global Rubber Technology
Forum) 2018 and the Global Rubber,
Latex and Tire Expo 2018 will be
held March 14-16 at the Bangkok
International Trade & Exhibition Center
in Bangkok, Thailand. The event is orga-
nized by TechnoBiz CURC United.
GRTE 2018 highlights will include
a trade exhibition, specialized training
courses, a global rubber technology
forum, a global rubber industry network-
ing dinner, a rubber and tire industry
consultants pavilion, reference publica-
tions, rubber technologists awards, a
rubber industry job corner and the rubber
technology education zone.
The theme of the event is “What
is New in Rubber Technology and
Markets.” Focus topics will include new
rubber raw materials and additives; cur-
ing and vulcanization of rubber; mix-
ing and compounding; rubber reinforce-
ment; nano composites; extrusion and
calendering; rubber mold design and
molding of rubber; rubber bonding; rub-
ber testing and rheology; tire technology
and retreading; recycling of rubber and
tires; latex dipped products technology;
and industry regulations.
Exhibitors will include suppliers and
manufacturers of natural and synthetic
Rubber Group News
The Bourbon Trail Elastomer Group will
hold its spring technical meeting April 19
in Cincinnati, OH. Details are available at
www.bourbontrailelastomergroup.org.
The Chicago Rubber Group will hold
the course, Basics of Rubber Technology,
March 13-15 at SKF Sealing Solutions in
Elgin, IL. The course fee is $375 and the
deadline to sign up is February 20. The
CRG is also taking applications and nomi-
nations, respectively, for the Harold Stark
Memorial Scholarship and Robert Kann
Education Award. The deadline is March
1. Further information is available at www.
chicagorubbergroup.org.
The Fort Wayne Rubber & Plastics
Group will hold a technical meeting on
April 12 at Ceruti's in Fort Wayne, IN.
42 RUBBERWORLD.COM ‡ FEBRUARY 2018
rubber; rubber chemicals and additives;
rubber machinery and testing equipment;
latex chemicals and machinery; dipped
latex products technology; tire technol-
ogy; rubber and latex products; tires and
automotive rubber parts; natural rubber
plantations; and rubber reclaim and recy-
cling.
Rubber industry training courses will
be held in conjunction with GRTE 2018.
On Tuesday, March 13, the fol-
lowing courses will be held: “Rubber
Compounding Formulation: Optimiza-
tion and Case Studies,” “Behavior of
Rubber Flow During Molding,” and
“Basic Process Troubleshooting.”
On Thursday, March 15, courses
will be held on “Latex Compounding
- Principles and Practice,” “Applied
Rubber Technology (Thai Version),” and
“Rubber Injection Molding.”
On Friday, March 16, courses will be
held on “Rubber Compression Molding”
and “Rubber-To-Metal Bonding: Science
and Practice.”
For more information and to regis-
ter for the Global Rubber Technology
Forum, and Latex and Tire Expo, contact
TechnoBiz CURC United, tel.: +66-2-
933 0077; fax: +66-2-955 9971; or visit
www.rubbertechnology-expo.com.
Further information is available at www.
fwrpg.org.
The Los Angeles Rubber Group will
hold its TIPS meeting and dinner April 3 at
the Knott's Berry Farm Hotel in Buena Park,
CA. Details are available at www.tlargi.org.
The Mexico Rubber Group will hold a
course on “Antioxidants and Antiozonants
for Rubber Compounds,” instructed by Jose
Gazano, in the Rubber Chamber Auditorium
in Mexico City, Mexico. Further informa-
tion is available at www.rubber.org/mexico-
rubber-group.
The Michigan Rubber Group will hold
a technical meeting March 7 at the Grand
River Hotel in Grand Rapids, MI. Details
are available from Keith Korthals (989) 435-
7400, or at www.michiganrubbergroup.com.
The Mid-Atlantic Rubber & Plastics
Group will hold its spring technical
TechnoBiz will hold its Plastic Films
Processing Training Week March 5-8 in
Atlanta, GA.
This four-day event is divided into
two separate seminars. One focuses on
polymer science and melt rheology, and
the second seminar focuses on blown
and cast films, including processing and
troubleshooting.
This program is aimed at owners, plant
managers, process engineers, floor super-
visors and operators from manufacturing
and research environments.
Further information is available at
www.plastics-industry.org.
TechnoBiz will host the train-
ing program, Rubber Compounding
& Processing, April 16-18 in Jakarta
Indonesia.
Course content will cover rubber prod-
ucts, raw materials and chemicals, includ-
ing specification, function, compatibility
and selection; compound formula design,
including ingredient-property relations,
functions of materials in a rubber com-
pound, polymer, filler and process oil
as the basic building block, and cross-
linking and accelerator systems in rela-
tion to part and processing performance;
compound performance optimization and
case studies, including formula develop-
ment methods and tools, usage of raw
material knowledge and formulation case
studies; mixing of rubber, including mix-
meeting May 10 at the Air Products &
Chemicals facility in Allentown, PA. In
addition to the technical program, the event
will feature a tour of the Air Products
facility. Further information is available at
www.marpg.org.
The New England Rubber & Plastics
Group will hold its 2018 spring technical
meeting on April 3. Further information is
available at www.nerpg.org.
The Ohio Rubber Group will hold
its spring technical meeting April 10 at
the Hilton Garden Inn in Twinsburg, OH.
Details are available at www.ohiorubber-
group.org.
The Twin Cities Rubber Group will
hold a technical meeting March 8 at the
Holiday Inn Hotel & Suites Arbor Lakes in
Maple Grove, MN. Further information is
available at www.twincitiesrubbergroup.org.
 Meetings
ing equipment, interaction of the mixing Rubber Division, ACS mediate to Advanced Compounding
process with rubber, and review of mix- and Testing of Rubber; Understanding
ing process design regarding polymer discounts courses Raw Materials, the Building Blocks of
changes and dispersion; extrusion of rub- The Rubber Division of the American Rubber Compounding; Compounding
ber; injection molding, including analysis Chemical Society is offering a $100 for Performance; Solving Problems in
from a compounder's perspective; rubber- discount on its online courses through Rubber Compounding and Process-
to-metal bonding; and cost management March 15. ing; Dynamic Rubber Design; An
and reduction. Online courses offered include: Introduction to Continuous Vulcani-
The course instructor is Hans-Joachim Basic Rubber Technology; Intermediate zation; An Introduction to Flexible
Graf. Further information is available at Rubber Technology; and Advanced Cellular Rubber; Chemistry and Tech-
www.rubber-industry.org. Rubber Technology. nology of Polyurethane Elastomers;
Upcoming training opportunities Failure Analysis of Rubber and Plastics
ARPM hosts plant taking place at the Rubber Division's by Physical and Chemical Analysis;
Elastomer Training Center in Akron, OH, Essentials of Rubber Technology;
tour of Zochem will include the following: Advanced Compound Mixing and Consistency;
The Association for Rubber Products Rubber Technology; Natural Polymers, Establishing a Rubber Molding Process;
Manufacturers will host a plant tour of Renewable Resources; Introduction and Applied Rubber Technology.
Zochem, located in Dickson, TN, on to Compounding, Testing and Mixing For more information on discounted
Thursday, March 29. Highlighted as the of Elastomers; Silicone Basics; Intro- online courses and upcoming training
newest zinc oxide production facility on duction to Rubber Technology for Non- opportunities, contact Christie Robinson
earth, rubber industry executives will Technologists; Molding of Rubber; (crobinson@rubber.org), or visit www.
have an opportunity to tour the newest, Introduction to Rubber Bonding; Inter- rubber.org/upcoming-training.
state-of-the-art zinc oxide manufacturer.
The Zochem leadership team has uti-
lized its more than 250 years of com-
bined experience in zinc oxide manufac-
turing to improve its plant's capabilities.
Cutting-edge imrovements in key steps
in the production process are said to have
significantly improved the end product,
such as a new pneumatic conveyor, new
control systems and a self-designed, high
efficiency product filter collector.
Additionally, the entire company's
culture is said to be safety-driven.
Zochem's safety record is said to stretch
back over 1,644 days without a medical
aid accident. The continuous improve-
ment culture has noticeably impacted
operational results, allowing Zochem to
significantly grow their business in just
three years from zero sales to being
North America's largest zinc oxide man-
ufacturer.
During this plant tour event, execu-
tives from ARPM member companies
and special guests will have the oppor-
tunity to tour the state-of-the-art facility,
while increasing their knowledge of how
instrumental zinc oxide is in general.
Further information on this ARPM
plant tour is available at www.arpminc.
com.

FOLLOW US ON TWITTER @rubberworld 43

2018 Rubber Division, ACS Events

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Visit rubberiec.org to Industry Professionals & Students - Call for Abstracts

learn more or to secure Rubber Division, ACS is accepting abstracts for the 194th Technical
your exhibit space today! Meeting, Student Colloquium & Poster Session. Deadline is April 16th,
2018. Visit rubberiec.org to view the Technical Meeting session topics
and to submit an abstract.
Calendar
Future
Meetings/
Expos
2018
Indianapolis May 8-10
Louisville October 9-11
2019
Cleveland October 7-10
www.rubber.org
Tire Industry Association, 63rd Off-
The-Road Tire Conference, Sawgrass
Marriott Golf Resort, Ponte Vedra, FL,
www.tireindustry.org - February 21-24.
Rubber Division, ACS, Natural Poly-
mers, Renewable Resources, Elastomer
Training Center, Akron, OH, www.rub-
ber.org/upcoming-training - February 27
- March 1.
March
JEC Group, JEC World 2018 Inter-
national Composites Show, Paris-Nord
Villepinte, Paris, France, www.jeccom-
posites.com - March 6-8.
Rubber Division, ACS, Introduction to
Compounding, Testing and Mixing of
Elastomers, Elastomer Training Center,
Akron, OH, www.rubber.org/upcoming-
training - March 6-8.
Michigan Rubber Group, techni-
cal meeting, Grand River Hotel, Grand
Rapids, MI, www.michiganrubbergroup.
com - March 7.
Rubber Division, ACS, Silicone Basics,
Elastomer Training Center, Akron, OH,
www.rubber.org/upcoming-training -
March 8.
Twin Cities Rubber Group, technical
meeting, Holiday Inn Hotel & Suites
Arbor Lakes, Maple Grove, MN, www.
twincitiesrubbergroup.org - March 8.
University of Akron, Akron Polymer
Technology Services, Rubber Bushing
Designing for Automotive and Commer-
cial Application course, Akron Polymer
Training Center, Akron, OH, www.uak-
ron.edu/apts/ - March 13-14.
Chicago Rubber Group, Basics of
Rubber Technology 2018, SKF College,
Elgin, IL, www.chicagorubbergroup.org
- March 13-15.
TechnoBiz, GRTE 2018 Global Rubber,
Latex & Tire Expo, Bangkok, Thailand,
www.rubbertechnology-expo.com
March 14-16.
Rubber Division, ACS, Introduction
to Rubber Technology for Non-
Technologists, Elastomer Training Center,
Akron, OH, www.rubber.org/upcoming-
training - March 20.
Rubber Division, ACS, Molding of
Rubber, Elastomer Training Center,
Akron, OH, www.rubber.org/upcoming-
training - March 21.
Rubber Division, ACS, Introduction
to Rubber Bonding, Elastomer Training
Center, Akron, OH, www.rubber.org/
upcoming-training - March 22.
April
Los Angeles Rubber Group, TIPS
meeting and dinner, Knott's Berry Farm
Hotel, Buena Park, CA, www.tlargi.org
- April 3.
Ohio Rubber Group, technical meeting,
Hilton Garden Inn, Twinsburg, OH, www.
ohiorubbergroup.org - April 10.
Automated Imaging Association, AIA
Vision Show, Hynes Convention Center,
Boston, MA, www.visionshow.org - April
10-12.
Fort Wayne Rubber & Plastics Group,
technical meeting, Ceruti's, Fort Wayne,
IN, www.fwrpg.org - April 12.
Institute of Scrap Recycling Industries,
ISRI Annual Convention and Exposition,
Mandalay Bay Resort and Casino, Las
Vegas, NV, www.isri2018.org - April
14-19.
Bourbon Trail Elastomer Group, spring
technical meeting, Cincinnati, OH, www.
bourbontrailelastomergroup.org - April
19.
Adsale Exhibition Services Ltd.,
Chinaplas 2018, National Exhibition and
Convention Center, Hongqiao, Shanghai,
China - www.chinaplasonline.com - April
24-27.
Rapid Medtech Communications
Ltd., Med-Tech Innovation Expo: The
Medical Technology Event, Ricoh Arena,
Coventry, U.K., www.med-techexpo.com
- April 25-26.
Mexico Rubber Group, course on
“Antioxidants and Antiozonants for
Rubber Compounds,” Rubber Chamber
Auditorium, Mexico City, Mexico, www.
rubber.org/mexico-rubber-group - April
26.
May
International Rubber Study Group,
World Rubber Summit 2018, Colombo,
Sri Lanka, www.rubberstudy.com - May
7-8.
- International Institute of Synthetic
Rubber Producers, 59th Annual General
Meeting, Madrid, Spain, www.iisrp.com
- May 7-10.
Plastics Industry Association, NPE
2018: The Plastics Show, Orlando, FL,
www.npe.org - May 7-11.
FOLLOW US ON TWITTER @rubberworld
For additional calendar
information click here:
Rubber Division, American Chemical
Society, 193rd Technical Meeting, Hyatt
Regency, Indianapolis, IN, www rubber.
org - May 8-10.
Mid-Atlantic Rubber & Plastics Group,
spring technical meeting, Air Products &
Chemicals, Allentown, PA, www.marpg.
org - May 10.
Chicago Rubber Group, spring techni-
cal meeting, Hawk's View Country Club,
Lake Geneva, WI, www.chicagorubber-
group.org - May 14.
VBRI Press, International Conference
on Plastics and Rubber Technology,
Stockholm, Sweden, www.vbripress.com
- May 14-17.
Messe Frankfurt, Techtextil North
America, Georgia World Congress
Center, Atlanta, GA, www.messefrank-
furt.com - May 22-24.
Urethanes Technology International,
Utech Europe 2018, MECC, Maastricht,
The Netherlands, www.utecheurope.eu -
May 29-31.
Koelnmesse GmbH, The Tire Cologne,
Northern Halls of Koelnmesse, Cologne,
Germany, www.thetire-cologne.com -
May 29 - June 1.
Michigan Rubber Group, golf outing,
East Lansing, MI, www.michiganrubber-
group.com - May 31.
June
Fort Wayne Rubber & Plastics Group,
annual golf outing, Maxwelton Golf
Club, Syracuse, IN, www.fwrpg.org -
June 14.
Fort Wayne Rubber & Plastics Group,
technical meeting, Ceruti's, Fort Wayne,
IN, www.fwrpg.org - June 14.
Ohio Rubber Group, golf outing, Yankee
Run Golf Course, Brookfield Twp., OH,
www.ohiorubbergroup.org - June 19.
July
Bourbon Trail Elastomer Group, sum-
mer technical meeting, Louisville, KY,
www.bourbontrailelastomergroup.org -
July 12.
French Socity for Composite Materials,
ICCE-26, International Conference on
Composites for Nano Engineering, Paris,
France, www.icce-nano.org - July 15-21.
Chicago Rubber Group, golf outing,
Village Links, Glen Ellyn, IL, www.chi-
cagorubbergroup.org - July 19.
Cvent, Latin Auto Parts Expo, Atlapa
Convention Center, Panama City, Panama,
www.latinpartsexpo.com - July 25-27.
Michigan Rubber Group, fishing out-
ing, Grand Haven, MI, www.michigan-
rubbergroup.com - July 27.
45
 Hotlinks Corporate Sponsor
RubberWorld Hotlinks
Wabash MPI (www.wabashmpi.com) is a leading interna-
tional supplier of standard and custom presses for aerospace,
medical, recreation, automotive, energy, education, ASTM,
and rubber and plastics testing, research and development
laboratories and other applications. Customers rely on
Wabash MPI for complete new equipment start-up, preven-
tative maintenance and other field service needs. Wabash
also offers calibration services with certifications for pres-
sure and temperature using devices traceable to NIST.
Since its modest beginnings in 1941, Wabash MPI has
emerged as a premier domestic and international supplier
of production and laboratory hydraulic, pneumatic and elec-
tric presses. With over 12,000 presses produced, its ISO
9001:2008 certified manufacturing facility in Wabash, IN,
has the experience and expertise to tackle the most challenging press applications.
Wabash MPI has expanded over the years into presses for production compression molding, transfer molding, c-frame, as well
as presses with vacuum assist. Several standard models are available to choose from, or Wabash MPI can custom build a press to
specifications. Presses can be produced in sizes from .5 to 1,200 tons, and bed sizes from 6” x 6” to 6’ x 12’, for molding, laminat-
ing, trimming, forming, bonding, sizing, etc. Customers may choose from a range of clamp force options, platen heating and cooling
options, enhanced control packages or from an exhaustive list of standard and custom options and accessories.
Products offered by Wabash MPI include compression presses (four-post, Genesis and Vantage), vacuum presses (slab side
and vacuum shroud), transfer presses, electric presses, ASTM presses (rubber and plastic), pneumatic presses, laboratory presses
(Genesis), custom engineered presses (compression molding, large platen and vacuum shroud), as well as used equipment.

CHEMICALS AND MATERIALS MACHINERY AND EQUIPMENT CUSTOM MIXING & COMPOUNDING
R. D. Abbott 2KM North America Inc. Airboss Rubber Compounding
Akrochem Corporation Deublin Cri-Tech, Inc.
Akron Dispersions, Inc. French Oil Mill Machinery Co., The
Eagle Elastomer
AkzoNobel Gomaplast Machinery
H.L. Blachford Ltd. Grieve Corporation Hexpol Compounding
R. E. Carroll, Inc. Guill Tool and Engineering Co. Hoosier Racing Tire
Cabot Corporation Guyson Soucy Techno Inc
Chem-Trend Hilma Div. of Carr Lane Roemheld Valley Processing
Cri-Tech, Inc. Hydratecs Injection Equipment Valley Rubber Mixing
Finite Fiber Maplan Machinery + Planning
Firestone Polymers Nerpco USA LLC
Goldsmith & Eggleton Reliable Rubber & Plastic Machinery Co. CUSTOM SERVICES
H&R Group REP Corp. Conitex Sonoco
HallStar Company Sprinter Marking
Harwick Standard Technical Machine Products MOLD RELEASES
Hydratecs Injection Equipment Troester Machinery Ltd.
Chem-Trend Limited Partnership
INTERBUSINESS USA, INC. VMI
McLube Wabash Franklynn Industries
Polychem Dispersions McLube
Polymer Valley Chemicals, Inc. TESTING EQUIPMENT / LABORATORIES Release Coatings of New York
Renkert Oil Akron Rubber Development Laboratory, Inc.
H.M. Royal DeFelsko Corporation
Endurica CUSTOM CALENDERING
RSS, LLC
Sid Richardson Carbon & Energy Hoosier Racing Tire Hoosier Racing Tire
Struktol Corporation Rex Gauge
Vanderbilt Chemicals LLC Standards Testing Laboratories
Wacker Silicones Corp. TA Instruments
Zeon Chemicals

46 RUBBERWORLD.COM ‡ FEBRUARY 2018

@ rubberworld.com
Hallstar (www.hallstar.com) is a global manufacturer of
innovative, leading-edge chemistry solutions for the indus-
trial polymer and personal care sectors. Hallstar’s hands-on
collaboration, unparalleled technical support and deep com-
petency in ester chemistry help its customers realize their
new product development vision.
Hallstar provides customized solutions and formulations
tailored to customer needs and problems, state-of-the-art
laboratories and region specific expertise on every continent,
and extensive scientific knowledge and unmatched technical
support.
Hallstar is a market leader in the design and synthesis of
new specialty ester chemistries with numerous products in commercial production, including specialty PVC fittings, polymerics and
other specialty chemistries. Decades of expertise on both the commercial and technical sides of ester plasticizers have given Hallstar
a vast storehouse of knowledge that the firm uses to modify or completely customize monomeric and polymeric solutions. Hallstar
can help customers keep up with changes and leverage opportunities in the industrial marketplace.
Industrial solutions provided by Hallstar include elastomer modifiers (industry standard specialty monomeric and polymeric
plasticizers for elastomers with diverse requirements, including next-generation critical applications and products), thermoplastic
modifiers (ester plasticizers, with emphasis on polymerics and non-phthalates, used for a range of flexible [PVC] applications and
designed to meet the stringent low temperature flexibility, extraction resistance and migration resistance required of special ther-
moplastic applications), adhesive/sealant modifiers (a range of high performing, innovative ester chemistries designed to meet the
specific needs of adhesives and sealant formulations), and coatings modifiers (with an emphasis on low VOC, ester-based coales-
cents and solvents that have been developed to support next generation regulatory requirements, providing low Tg, high efficiency
and excellent compatibility with a range of resins).

Akrochem Corporation (www.akrochem.com) has the right ingredients,

from simple fillers to unique rubber chemical blends and dispersions,
because the company offers the broadest line of materials anywhere. An
experienced technical staff always goes above and beyond the call of duty
to help customers find the most intelligent solutions.
Improving customer productivity has been the Akrochem goal since the
firm began serving the rubber and plastic industries in 1929. Akrochem
provides a comprehensive assortment of compounding materials and color
concentrates, from the basic to the most complex and customized, all sup-
ported by the industry’s best technical expertise and service. Akrochem
promotes professionalism through its ISO 9001-2008 and National
Association of Chemical Distributors (NACD) accreditations.
Akrochem’s product lines for rubber compounding include antifoams, carbon blacks, chemical dispersions, colors (powders),
colors (paste dispersions), colors (polymer dispersions - masterbatch), colors (thermoplastic color concentrates), cure blends and
chemical blends, elastomers, emulsions and fluids, fire retardants, flocks and wood flours, magnesia products, mineral fillers, plasti-
cizers, processing aids, release agents, resins and tackifiers, rubber chemicals, silicone products, silicone rubber additives, stearates,
sulfurs, vulcanized vegetable oils, waxes and zinc oxides.
Akroform MTT-80/EPR/P is a type of thiazole heterocyclic compound used for crosslinking halogen-containing polymers.
MTT-80 acts as a vulcanization accelerator to polychloroprene rubber, chlorinated or brominated butyl rubber. It is a non-thiourea
accelerator. MTT-80 is easily dispersed, non-staining and non-discoloring.
LG NBR 2860 is a copolymer of butadiene and acrylonitrile manufactured by advanced cold emulsion polymerization. It is a
non-staining, medium Mooney and medium/low acrylonitrile polymer designed to aid in processing operations such as extruding
and calendering. It also offers better abrasion resistance and gas permeability than the general purpose elastomers like natural rubber
and SBR.
If you would like your web site featured here contact your sales rep
Dennis Kennelly, dennis@rubberworld.com or Mike Dies, mike@rubberworld.com
FOLLOW US ON TWITTER @rubberworld 47
 Suppliers Showcase
Cradle to Cradle Certified carbon black
Carbon black from the company has received an official
Cradle to Cradle Certified Bronze Certificate, assessed by the
Environmental Protection Encouragement Agency. This is said
to be the first time that a carbon black has received this certi-
fication.
The company's carbon black is upcycled because the output
material is of higher quality than the input material (furnace
black in car tires). Its extremely low content of polycyclic
aromatic hydrocarbons (PAHs) means that it is of such good
quality that the firm recommends its use in all kinds of appli-
cations, including those involving a lot of skin contact, such
as bicycle handlebars, stroller handles, wheelchairs, and car
and bicycle tires, where abrasion and inhalation of carcino-
genic PAH-containing particles can be hazardous. The use of a
high-quality product like the company's carbon black is said to
have the potential to positively impact on the health and well-
Customized treated silica
PV-Sil customized treated silica products for the rubber indus-
try have been helping improve efficiency for decades, accord-
ing to the company. PV-Sil treated silicas are said to elimi-
nate or reduce VOC emissions, improve coupling efficiency,
reduce mixing cycle time, possibly reduce a pass in multi-
stage mixing, and provide for customer specific options. The
company also provides kaolin clays, silica products, carbon
black, custom treating and packaging, and value added ser-
vices, including material blending, bulk carbon black transfer
from super sacks to bulk trucks, de-densification of fillers,
vibratory screening to classify materials, pre-weighs and test-
ing. (Polymer Valley Chemicals)
www.polymervalleychemicals.com
Social value of carbon black examined
Carbon black is said to be a safe, highly engineered micro-
scopic carbon that plays an important role in many areas.
Carbon black is a virtually pure, elemental carbon in the
form of colloidal particles, which are microscopic and
arranged in a grape-like form. Its physical appearance is that
of a black, finely divided pellet or powder; individual par-
ticles of carbon black are invisible to the human eye.
The size of the particles and the way they are aggregated
provide specific properties to the carbon black and define
its use. For example, a large particle-sized soft carbon black
grade will contribute to the elasticity of the tire sidewalls,
while a small particle-sized hard carbon black grade will be
essential to ensure the durability of the tire's tread.
Whenever one uses something that is black, it probably
contains carbon black. From cars to computers, plumbing to
agriculture, and banknotes to shoes, carbon black is making
48 RUBBERWORLD.COM ‡ FEBRUARY 2018
Carbon Black/Silica
being of many people, and it is therefore said to be a beneficial
Cradle-to-Cradle product.
The Cradle-to-Cradle Certified products program is an
independent, third party verified certification program that
certifies products and materials that are developed to respect
human and environmental health, designed for future use
cycles, and that utilize clean energy and water throughout the
supply chain. Certified products are required to show continu-
ous improvement every two years.
One of the interesting findings of the certification activi-
ties was said to be a reconfirmation that the company's carbon
black has extremely low levels of harmful PAHs. A low level
of PAHs is increasingly becoming important, given health
considerations and increased REACH regulation, according to
the company. (Black Bear Carbon)
www.blackbearcarbon.com
Recycled carbon black
The value of the market for carbon blacks is said to be huge,
and as a material approved for use in rubber products by com-
panies such as Volvo cars, Enviro recycled carbon black is
said to find customers in many different industries. Vibration
damping, shock and collision protection, gaskets, seals and
rubber sheet are examples of products where Enviro recycled
material can replace new product. Recycled carbon black is
said to have the potential to replace newly produced carbon
black in the majority of these products, and the company is
seeking acceptance in more markets and sees potential in
products made from natural rubber and synthetic rubber com-
pounds such as EPDM. (Scandinavian Enviro Systems)
www.envirosystems.se
lives better, according to the company. It makes travel safer,
communication possible, and enables access to clean water
for drinking and irrigation.
This company is said to lead the way in the industry in
terms of pollution control technology, and aims to be as
efficient as possible in the carbon mass balance efforts and
sustainable practices, while providing a secure, consistent
supply of the highest quality to customers across the globe.
The company's campaign, called Social Value of Carbon
Black, is the beginning of an initiative started by the firm for
the industry at large.
The company's footprint extends across 12 countries
with 16 manufacturing facilities. The firm provides a com-
plete portfolio of products across ASTM grades and special-
ty blacks to meet specific end requirements. (Birla Carbon)
www.birlacarbon.com
 Suppliers Showcase
Specialty carbon products
Specialty carbons for rubber compounds provided by the com-
pany include Ensaco Timcal carbon black and Timrex Timcal
graphite. Properties of Ensaco Timcal 250G conductive carbon
black are said to include high structure/low surface area, soft
flakes, low oxygen content, high purity and high graphiticity.
It is said to provide electrical conductivity, excellent disper-
sion, low viscosity increase, low cure inhibition, easy mixing
and processing, some thermal conductivity, and it meets the
most stringent purity requirements, according to the company.
Properties of Timrex Timcal graphite are said to include high
crystallinity, high carbon content, lamellar structure, and
various shapes and sizes. It is said to provide self-lubrication,
thermal and electrical conductivity, and a gas barrier. (Imerys
Graphite & Carbon)
www.imerys-graphite-and-carbon.com
Pelletized carbon blacks
SR409 is a next generation high structure pelletized carbon
black. It is said to offer an effective surface area that places it
between the traditional tread and carcass carbon black groups.
Its broad aggregate size distribution, combined with high struc-
ture, provides elastomeric compounds with good processing,
reduced hysteresis and high physical properties, according to the
company. Typical applications for SR409 are said to include tire
components where low hysteresis, high physical properties and
good extrusion/calendering quality are required, and dynamic
mechanical rubber components requiring low heat build-up and
flex to fatigue resistance. Performance features of SR409 are
said to include low hysteresis, and good mixing, dispersion and
processing characteristics. (Sid Richardson Carbon & Energy)
www.sidrich.com
Precipitated silica solutions for rubber use
Precipitated silica solutions for industrial rubber applications
are provided by the company. Precipitated silica is colorless,
odorless and chemically inert, yet the interaction between
silica particles and rubber is said to be important for the per-
formance of composites that few rubber compounders regard
it as a commodity product.
With the introduction of chemically-modified Agilon per-
formance silica and other advanced products, the company
continues to develop products that enable rubber manufactur-
ers to create goods that last longer and perform better.
In addition to optimized processing characteristics, such
as faster cure rates, easier mixing, improved flow or more
flexible extrusion and color compounding capabilities, the
company's silica technologies also are said to impart specific
properties to finished high-performance products.
Compared to rubber compounds using carbon black fill-
ers with similar surface areas, these characteristics are said to
include increased stiffness and reinforcing strength, enhanced
Carbon Black/Silica
White reinforcing fillers
Rubbersil white reinforcing fillers include precipitated silicas
and synthetic sodium aluminum silicates. Rubbersil products
are said to be white reinforcing fillers that provide excellent
performance and processing properties to mechanical and
technical rubber goods, according to the company. Rubbersil
products are available in a wide range of surface areas to offer
required performance, from easiest processing to maximum
reinforcement. Applications for Rubbersil include conveyor
belts, hoses, translucent and colored shoe soles and rubber
articles, low hardness joints, piping, rollers, rubber support,
flooring, micro cellular plates, cables, boat dock bumpers, tank
lining and OTR tire tread. Rubbersil RS-250 is said to provide
outstanding reinforcement power compared to all precipitated
silica grades. Rubbersil RS-200 is said to impart excellent
reinforcing properties like hardness, tensile strength, tear and
abrasion resistance. (Glassven)
www.glassven.com
Reinforcement materials
Research, development, manufacturing and sale of carbon black
for tires and automotive, contruction and other industrial rub-
ber products are provided by the company. The firm's portfolio
of products includes reinforcing, semi-reinforcing, conductive,
ultra-clean and low-PAH products from the Vulcan, Sterling,
Regal, Spheron and Propel families. The company's additives
for industrial rubber products are said to allow manufacturers to
tailor mechanical, electrical and thermal properties to improve
product performance while maximizing production efficiency
in a wide range of applications, such as hoses and belts, automo-
tive weatherstripping and molded rubber products. (Cabot)
www.cabotcorp.com
resistance to heat build-up, better tear strength with equal
tensile strength, improved color retention and/or translucence,
superior chip and chunk resistance, and extended product life
in high-temperature environments, according to the company.
Hi-Sil reinforcing fillers are said to remain among the best
known and most trusted brands in the industry, encompass-
ing a broad range of materials engineered to help end-users
achieve specific processing and performance requirements.
Each Hi-Sil silica formulation is controlled by the company
for surface area, particle size and other physical properties to
regulate finished characteristics such as reinforcing strength,
dispersibility, viscosity, cure rate, compression set and abra-
sion, tear and temperature resistance.
The company's semi-reinforcing fillers are said to be
designed with lower surface areas to limit stiffness, lower
compression set, control heat build-up and improve dynamic
modulus and resilience. (PPG Silica Products)
www.ppgsilica.com
FOLLOW US ON TWITTER @rubberworld 49
 Suppliers Showcase
Vertical conveyor oven
The No. 933 is a gas-heated, 250°F vertical conveyor oven,
currently used for post-curing silicone rubber parts inside
cardboard boxes. Workspace dimensions measure 1' wide
by 13' deep by 12' high. Forty-
two trays, each 72" wide by 23"
long and rated for 100 pounds
loading on 34" centers, lower
vertically and pass back into
the heating zone, then exit at
the top of the heating zone and
pass downward through cooling. Two 6,000 cfm, 5 hp recir-
culating blowers provide a total 12,000 cfm vertical upward
airflow to the loads. Four 24" diameter tubeaxial fans are each
driven by a 5 hp motor to push/pull air through the cooling
zone on this conveyor oven. The No. 933 features 4" insulated
walls, a removable top-mounted heat chamber, an aluminized
steel interior, plus two independent doors for access to the
workspace. (Grieve)
www.grievecorp.com
Cure time reduction
TurboCure consists of the company's TempInverter and
FillBalancer technologies that can be applied in combina-
tion or independently, based on the application. By reversing
temperature distribution in the material flow, TempInverter is
said to reduce cure time by 30% or more, providing a 15% or
greater energy savings. Inside the mold, by rebalancing the
fill between the cavities, FillBalancer modifies the distribu-
tion of temperature in the flow as it approaches the cavities,
resulting in a reduction of cure time by up to 40%, according
to the company. (Rep)
www.repinjection.com
Injection molding machine
The tie-bar-less E-Victory 50/80 injection molding machine
with electric injection unit is used to process extremely low
viscosity liquid silicone rubber (LSR) with high precision and
high efficiency, according to the manufacturer. On the com-
pany's tie-bar-less injection molding machines, the patented
force-divider is said to ensure that the moving mold mounting
platen follows the mold exactly, while the clamping force is
building up, distributing the clamping force evenly across the
platen face. This is said to keep all the cavities closed with
exactly the same force, which ensures consistent compression
of the mold and consistently high product quality, according
to the company. (Engel)
www.engelglobal.com
For additional equipment
information click here
http://www.rubberworld.com/equipment
50 RUBBERWORLD.COM ‡ FEBRUARY 2018
Equipment
Micro-injection molding
The electric Allrounder 270 A with a size 5 micro-injection unit
produces silicone membranes as used in valves for the medical
technology or the automotive industry. The micro-injection unit
is equipped with a special 8 millimeter LSR screw for manu-
facturing the 0.05 grams LSR pre-molded part (70 durometer
A hardness). A servo-electric injection unit from Kipe Molds
integrated into the 1+1-cavity mold and into the Selogica con-
trol system is used for the 0.005 gram second LSR component
(30 durometer A hardness). A Kiki robotic system removes the
LSR/LSR diaphragm, feeds it to a camera inspection station,
and places it in a container. (Arburg)
www.arburg.com
3D printer technology
Evolv3D is three-dimensional printer technology that is said
to be opening up new ways silicone rubber parts are designed.
Using heat-curable liquid silicone rubber (LSR) through a liq-
uid additive manufac-
turing (LAM) process,
functional prototypes
can be made in just a
couple of days. The
technology can offer a
world of possibilities
and applications in the
manufacturing of ana-
tomically customized
devices, according to the company. Evolve3D technology,
developed by M.R. Mold & Engineering, uses heat-cured
liquid silicone rubber, allowing an easy transfer into injec-
tion molding processes for high-volume manufacturing. The
potential applications are many and useful to both the design
engineer and those in need of custom fitted type devices,
such as prosthetics and orthotics, according to the company.
Adaptability of the Evolv3D technology to making unique
one-off parts or anatomically customized devices is vast, with
few intellectual property restrictions so far, according to the
firm. (R.D. Abbott)
www.rdabbott.com
Multi-shaft mixers
VersaMix multi-shaft mixers are said to be ideal for pro-
cessing medium to high viscosity applications up to several
hundred thousand centipoise, including many slurries, pastes,
gels and suspensions. The 500 gallon VersaMix, Model
VMC-500, has been equipped with a custom combination
of independently driven agitators. The anchor agitator with
helical flights and the screw auger agitator work in tandem to
promote efficient product turnover, while bringing air pockets
to the surface. Two saw-tooth high-speed disperser blades
impart shear for fast powder wet-out and thorough deagglom-
eration. (Charles Ross & Son)
www.mixers.com
 Suppliers Showcase Instruments

Force measurement Thermal desorption

Entry level computer-based force testing solutions have
been introduced for applications ranging from load limit and
distance testing to break limit, time average, cyclic count
and duration testing, constant hold and
more. Optimized for production and qual-
ity control testing, the architecture of the
L1 system is designed for reliable, fast,
repeatable and easy operation, according
to the company. The L1 line of force solu-
tions consists of systems for computer con-
trolled force measurement, digital force
gages, FMM digital force tester motorized test stands, manual
test stands and load cell sensors. L1 systems are said to be
easy-to-use, computer-controlled testing systems designed for
high-volume, in-situ production testing. (L.S. Starrett)
www.starrett.com
The TD-30 thermal desorption system is available for use with
the company's Nexis GC-2030 gas chromatograph, as well as
its entire GCMS product line. With large sample capacities, an
efficient workflow and a robust design, it is said to be ideally
suited for the analysis of trace components in such industries as
environmental, chemical and automotive, according to the com-
pany. The TD-30 series consists of two models, the TD-30 and
TD-30R. The TD-30 is equipped with a 60-sample carousel. The
TD-30R has the ability to hold 120 samples, the largest capacity
in the industry, making it well-suited to large-volume automated
analysis, according to the company. Both are equipped with a
retrapping function that allows split samples desorbed from the
tube and loaded into the GCMS to be trapped again for potential
re-measurement. An overlap function is said to improve process-
ing functionality. (Shimadzu Scientific Instruments)
www.ssi.shimadzu.com

Tire uniformity testing For additional instruments

The Astec tire and wheel evaluation center measures tire unifor-
information click here
mity for passenger and light truck radial tires and wheel assem- http://www.rubberworld.com/instruments
blies. The purpose of the Astec tire and wheel evaluation center
is to assure product quality. This is done by measuring, grading,
marking and sorting tires according to force variation. Radial
runout, lateral runout and sidewall appearance capabilities are
available with the optional TGIS laser measurement system. Key
advantages are said to include the following: Runs all passenger
and light truck tire and wheel assemblies through on-screen real
time waveform analysis and on-line diagnostics or troubleshoot-
ing tools; ergonomically designed and easy to use, providing
quick maintenance and ease of use through touchscreen com-
mands; best machine performance specifications in the industry
through patented technology; and open framed design gives easy
access to all critical parts of the machinery, according to the com-
pany. (Ametek/Micro-Poise Measurement Systems)
www.micropoise.com

Extrusion control system

The updated DS-eTPC II controller is said to be engineered with
added flexibility to support a broader range of processes and
applications. Processors are said to enjoy a larger 15" viewing
screen with multi-touch capabilities
to enable zoom-in and out, as well as
extruder control for up to three extrud-
ers and real-time and historical data
trending. Other enhancements include
an increase of heat-only zones from
four to eight, with an option up to 20;
two auxiliary drives; a remote set-point; and speed trim via
discrete inputs from gauging equipment. The DS-eTOC II has a
modular design. Standard features include historical data collec-
tion, real-time and historical data trending, web interface, alarm
log and more. (Davis-Standard)
www.davis-standard.com

FOLLOW US ON TWITTER @rubberworld 51

 Suppliers Showcase Materials

Aromatic resin tackifiers Tire industry solutions

Aromatic resin tackifiers are said to offer improved perfor-
mance and a better environmental profile compared with cur-
rent market options. Tackifiers are chemicals used to increase
surface stickiness in adhesive formulations. In independent,
ISO 17025 certified third-party testing, the Resonance HF90-
300 series of tackifier resins performed better than the mar-
ket benchmark in tack, elongation and tear and tensile bond
strength, according to the company. These enhancements
should lead to improved stability and performance in tire, rub-
ber and adhesive applications, according to the firm. At the
same time, these resins are formulated without butyl, octyl or
nonylphenol monomers, and can be used to reduce or elimi-
nate alkylphenol monomer levels from adhesive formulations.
This is said to allow the development of a variety of formula-
tions. (Hexion)
www.hexion.com
For additional materials
information click here
http://www.rubberworld.com/materials
Solutions for the manufacture of tires provided by the company
include a range of environmentally friendly Rhenodiv release
agents, Rhenomark tire marking paints, Rhenoshape tire vul-
canization bladders, Rhenogran aramid fiber masterbatches
and additives. In addition to traditional silicone-based products
such as Rhenodiv BP-286 and Rhenodiv BP-2864, which
are removed after vulcanization from the tires in mechanical
washing systems or by means of laser technology, new 100%
silicone-free products such as Rhenodiv BP-166 and Rhenodiv
BP-9500 are now available. The company is said to provide
ideal solutions for nitrosamine-free and highly reinforced tire
compounds. Dithiophosphates, including Rhenogran TP-50
and Rhenogran SDT-50, are nitrogen-free accelerators that can
replace typical sulfenamide, thiuram and carbamate accelera-
tors. Under extreme mechanical, dynamic and thermal loads,
the aramid fiber masterbatches of the Rheogran P91-40 series
are said to provide outstanding reinforcing performance for tire
compounds. The addition of Vulkanol TOF to a silica-filled
compound for tire treads is said to significantly improve wet
grip performance. (Lanxess)
www.lanxess.com

DEREK KNOWS TIRES

Derek Berresford has 25 years of experience
solving tire manufacturers’ toughest problems.
He’s an expert on everything from Accelerators
and Carbon Black, to Sulfur, Stearic, and more,
delivering the right products and solutions.

Give Derek a call today to see how he and HB

Chemical can make your job easier and your
products better.

1665 Enterprise Pkwy.

HB
CHEMICAL
Ph:
Twinsburg, OH 44087
P (800) 991-2436 F: (330) 920-0971
www.hbchemical.com

Give us a call and let us help solve your biggest challenges.

Service you expect.

52 RUBBERWORLD.COM ‡ FEBRUARY 2018
 People in the News
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FOLLOW US ON TWITTER @rubberworld 53

Visit Us At The Show
July 2-5, 2018, the international rubber and
elastomer industry will meet for the
German Rubber Conference DKT 2018 in
Nuremberg.

Classifieds
In a world where
needs
are expanding Tire engineering and
specialty tire manufacturing.
MESGO expands ISO-registered custom
mixing, calendering and
solutions www.mesgo.it gum calendering processes.
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increased production of TESTING INSTRUMENTS
extrusions & APPLICATIONS
203-855-8755 cober.com

73 MAPLEHURST AVE.
PROVIDENCE, RI 02908
PH: 401.331.5650
SALES@BENZTESTERS.COM
WWW.BENZTESTERS.COM
Coming March 2018
Annual Custom Mixing & Custom Services www.rubberworld.com
Issue

54 RUBBERWORLD.COM ‡ FEBRUARY 2018

Classifieds
WANTED RUBBER EXCELLENCE
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Phone: (330) 665-3821 Fax: (330) 665-3823
paul@allchem-inc.com Web: www.3ninc.com Email: info@3ninc.com

FOLLOW US ON TWITTER @rubberworld 55

 Index To Advertisers
3N International, Inc. (www.3ninc.com) ............................................... 55
AGC Chemicals Americas (www.agcchem.com) .................12, 13, 55
AirBoss Rubber Compounding
(www.airbossofamerica.com) .................................................2nd cover
Akrochem (www.akrochem.com) ......................................................... 47
Allchem (www.allchem-inc.com) ........................................................... 55
APV Engineered Coatings (www.apvcoatings.com) .................55, 56b
Benz (www.benztesters.com) ................................................................ 54
Burgess Pigment Company (www.burgesspigment.com) .................... 6
Cober Microwave (www.cober.com) ........................................................54
Corporate Consulting, Service & Instruments, Inc.
(www.ccsi-inc.com) ............................................................................. 51
Denka Performance Elastomer LLC (sales@denka-pe.com) ........ 55
Gerlach Inc. (www.gerlachinc.com) .................................................... 54
Glo-Mold, Inc. (www.glo-mold.com) ........................................................ 8
H&R Group US, Inc. (www.hur.com) .........................................4th cover
Hallstar (www.hallstar.com) ................................................................... 47
Harwick Standard Distribution (www.harwick.com) ........................ 11
HB Chemical (www.hbchemical.com) ......................................... 7, 9, 52
Holly Frontier Lubricants & Specialty Products
(www.hollyfrontierlsp.com) ..................................................................... 2
Hoosier Custom Manufacturing
(www.hoosiertirecustommfg.com) .........................................................54
Hotlinks Directory (www.rubberworld.com) ..................................46, 47
Hoto Instruments (www.hoto-instruments.com) .................................. 55
Imerys (www.imerys-graphite-and-carbon.com).................................56e
Interbusiness USA, Inc. (www.interbusinessgroup.com) ......... 55, 56a
Kenrich (www.4kenrich.com) .............................................................. 54
Lianda (www.liandacorp.com) ..................................................3rd cover
LM Containers (www.lmcontainers.com)........................................... 55
Marvel Consultants (www.marvelconsultants.com) ........................... 55
Mesgo Compounding Solutions (www.mesgo.it) ..................... 54, 56h
McLube, Division of McGee Industries (www.mclube.com) 16, 55, 56d
NPE 2018 (www.npe.org) ..................................................................... 30
Polymerics (www.polymerics.com) ...................................................... 55
Polymer Valley Chemicals
(www.polymervalleychemicals.com) ......................................... 15, 17
Release Coatings of New York, Inc. (www.rcony.com) .................... 55
RSS Harmonite (www.rssharmonite.com) .........................................21, 23
Rubber Division, ACS (www.rubber.org) ........................................41, 44
Soltex, Inc. (www.soltexinc.com) ........................................................ 43
Sprinter Marking (www.sprintermarking.com) ............................55, 56c
Struktol Company of America (www.struktol.com) .............................. 1
TA Instruments (www.rubber.tainstruments.com) .............................. 56f
TechnoBiz (www.technobiz-asia.com) ............................................... 54
Vanderbilt Chemicals (www.vanderbiltchemicals.com)....................56g
IMI (www.vmi-group.com) ......................................................................... 5
Wabash MPI (www.wabashmpi.com) ................................................... 46

Rubber World
SALES STAFF
DENNIS J. KENNELLY UTPAL PAUL
Senior VP-Associate Publisher 203, Dheeraj Gaurave Heights-I
1741 Akron-Peninsula Rd. New Link Road, Andheri-West,
Akron, OH 44313-5157 Mumbai (Bombay) - 400053, India
Ph: 330-864-2122 - Fx: 330-864-5298 Ph: 91-22-26744747 - Mobile: 91-9892614102
Email: dennis@rubberworld.com Email: u_paul2002@yahoo.co.in

MIKE DIES RINGIER TRADE PUBLISHING

Sales Representative East China - VIVIAN SHANG
1741 Akron-Peninsula Rd. Phone: +86-21 6289-5533 EXT 169
Akron, OH 44313-5157 vivian@ringiertrade.com
Ph: 330-864-2122 - Fx: 330-864-5298
Email: mike@rubberworld.com North China and South China - MAGGIE LIU
Phone: +86-20 8732-3316 EXT 9332
ANDRE JAMAR maggieliu@ringiertrade.com
International Marketing Consultant
Avenue Nicolai 49 A / Bte 4 Hong Kong - MIKE HAY
4802 Heusy Phone: +852 2369 8788 ext 11
Belgium mchhay@ringier.com.hk
Ph: +32(0)-87-225385 Taiwan - KELLY WONG
Mobile: + 32(0)-496-510513 Phone: +886 4 2329 7318
Email: andrejamar1@gmail.com wangyujung@ringier.com.hk

56 RUBBERWORLD.COM • FEBRUARY 2018

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Rubber World full page 7x10.indd 1 7/9/15 1:39 PM

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