Академический Документы
Профессиональный Документы
Культура Документы
Tudalen® 5138 US
Industry standard for (RAE)high viscous
plasticizers
Vivatec®
Industry standard for high
performance label free
plasticizers (MES, TDAE)
Hansen & Rosenthal is the Producer of Anti Ozone Waxes and Plasticizers
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
Technical Service:
Six rules for rubber release agents
@rubberworld
FU LL-CY CLE F A ST E R FORMULATED
S ER V ICE D E V E L O PM E N T F O R YO U
RUBBER REIMAGINED
We reimagine rubber’s possibilities every day. For longer-lasting belts and
treads. Tighter seals and stronger hoses. Better- performing infrastructure
FRPSRQHQWVDQGWRXJKHURLOȴHOGHTXLSPHQW(YHU\FRPSRXQGLVFXVWRP
formulated, A2LA-tested onsite, and expedited from start to delivery as if
your business is our top priority. Which it is.
NATURAL
BUTYL EPDM FKM HNBR
RUBBER
AIRBOSSRUBBERCOMPOUNDING.COM
$872027Ζ9(ȏ7Ζ5( 75$&.ȏ%8Ζ/'Ζ1* &216758&7Ζ21ȏ(1(5*< 2Ζ/ȏ0Ζ1Ζ1*ȏ$(5263$&(
:$7(575($70(17Ȑ$1':+(5(9(5(/6(58%%(5:25.6
UÊÊ-/,1/"®Ê/ÊÓÇÈ
UÊÊ-/,1/"®Ê6Ê{È
UÊÊ-/,1/"®Ê< Ê{
Struktol Additive Solutions – let our team improve the functionality, quality and performance
values in your business. When it comes to polymer additives, Struktol’s vast chemical experience is translated
into the most intelligent solutions available anywhere. Our sales and technical staff are the industry’s most
knowledgeable polymer additive experts and are dedicated to improving your processing performance.
7RJHWKHUZHQRZSURYLGH\RXZLWKLQFUHDVHGÁH[LELOLW\DQGVHFXULW\RIVXSSO\DQGWKHPRVW
HIIHFWLYHRLOVIRU\RXUUXEEHUSRO\PHUSODVWLFDQGDGKHVLYHSURGXFWV1RWRQO\GRZHEULQJ
\RXDEURDGHUUDQJHRIRLOVZHVXSSRUW\RXZLWKDQH[SDQGHGWHDPRIH[SHUWVRQFDOOWR
KHOSFUHDWHDQ\WKLQJ\RXQHHGWRÀW\RXUFULWLFDODSSOLFDWLRQV7ROHDUQPRUHDERXWZKDWWKLV
SRZHUIXOFRPELQDWLRQFDQPHDQIRU\RXFRQWDFW3URFHVV2LO7HDP#KROO\IURQWLHUFRPRU
3URFHVV2LO7HDP#SHWURFDQDGDOVSFRP
hollyfrontierlsp.com lubricants.petro-canada.com
+ROO\PDUNV//&XVHGZLWKSHUPLVVLRQE\+ROO\)URQWLHU5H¿QLQJ 0DUNHWLQJ//&
Contents Vol. 257, No. 5 February 2018
FEATURES
FEBRUARY
2018
129
The technical
24 Reinforcement of rubber
n of the
of very high silica/polymer int
in the case
surface silica erface
Technical Se
.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
ISO 9001
Business Briefs VESTENAMER ®
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.
7KHRGRULVJRQH
:HOLVWHQHGWR\RXDQGRXUSURGXFWLVEHWWHUIRULW
x ^D'ZdWZKhd͕EKDKZ^D>>
x /EW>DK>>E/E'
x D/E/D/WZ^^KtEd/D
x Dy/D/WZKhd/s/dz
ttt͘'>KͲDK>͘KD
;ϴϬϬͿϮϲϮͲϳϲϮϲ
KEddh^/E&KΛ'>KͲDK>͘KD
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:
Lin Bradley is technical market manager, rubber, Jose Briones, Ph.D., is marketing manager for
Americas, for Orion Engineered Carbons. Re- Orion Engineered Carbons in the rubber carbon
sponsible for technical interactions with rubber black segment. His responsibilities include achiev-
carbon black tire customers, Bradley oversees ing strategic sales goals and development of busi-
market research, coordination of technical ap- ness strategy, pricing policies and business cases
provals of ASTM and non-ASTM carbon blacks, for new product development. He has helped de-
and new product and solution introductions. velop more than 40 new products for Orion.
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.
Rubber composition for tire tread from 60 to 150 parts by mass per 100 Modified conjugated diene-based
and pneumatic tire parts by mass of the rubber compo- polymer, modified rubber composi-
U.S. patent: 9,834,661 nent, and a content of the alkyl- tion containing same, and method
Issued: December 5, 2017 triethoxysilane (C) being from 2.5 to for preparing modified conjugated
Inventors: Masaki Sato and Makoto 8.0 mass % relative to the silica (B). diene-based polymer
Ashiura U.S. patent: 9,834,619
Assigned: Yokohama Rubber 3 7 Issued: December 5, 2017
Key statement: A rubber composition Inventors: Moon-Seok Chun, Soo-
for a tire tread of the present technolo- Yong Lee and Seong-Du Lee
gy comprises a rubber component con- Assigned: LG Chem
taining not less than 30 mass % of a Key statement: Disclosed are a method
4
conjugated diene-based rubber (A), a of preparing a modified conjugated
silica (B), and a predetermined alkyl- diene-based polymer, a modified con-
triethoxysilane (C), the conjugated 2 jugated diene-based polymer prepared
diene-based rubber (A) containing not thereby, a rubber composition includ-
less than 5 mass % of a specified ing the modified conjugated diene-
structural member (a), the silica (B) based polymer, and a tire including the
having a nitrogen adsorption specific rubber composition. The method of
surface area (N2SA) from 194 to 225 6 preparing the modified conjugated
m2/g and a CTAB adsorption specific 5 diene-based polymer includes (a)
1
surface area (CTAB) from 180 to 210 polymerizing a vinyl aromatic mono-
m2/g, a content of the silica (B) being 8 mer and a conjugated diene monomer
RSS, LLC
6075A Lee’s Mill Road, Forest Park, GA 30297
Gilsonite ® is a registered trademark of the American Gilsonite Company.
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.
Table 2 - filler amount in phr of composites about 50°C. Peroxide was added, mixing was performed for
based on SBR, with CNT(N) and CB as the three minutes with rotors rotating at 60 rpm, and the composite
carbon allotropes; other ingredients: SBR was finally discharged. Composites were finally further ho-
100 phr, dicumyl peroxide 1.40 phr 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
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
back roll rotating at 38 rpm, and 1 cm as the nip between the
CB N326 ~10 + CNT(N): from 0 to 14 rolls.
(vol. fraction: 0.05) Crosslinking reaction was performed at 170°C for 10 minutes
CB N326 ~22 + CNT(N): from 0 to 14 for IR compounds, and at 170°C for 20 minutes for SBR com-
(vol. fraction: 0.10) pounds using a Monsanto oscillating disc rheometer (MDR
CB N326 ~35 + CNT(N): from 0 to 14
(vol. fraction: 0.15)
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
CNT(N) are Nanocyl NC7000 series from Nanocyl (Sambre- and 100 mm edge.
ville, Belgium), with carbon purity of 90%, average length of
about 1.5 μm and BET surface area of 275 m2/g. Characterization
Carbon black N326 (CB) from Cabot is characterized by 30 Dynamic mechanical characterization
nm as the mean diameter of spherical primary particles, a nitro- For SBR and IR based composites, dynamic shear moduli were
gen adsorption number of 77 m2/g and a DBP adsorption number measured by a Monsanto RPA 2000 rheometer (Alpha Technolo-
of 85 mL/100 g. gies, Heilbron, Germany) in the torsion mode. For each sample,
In IR based systems, composites with only CB, only CNT(B) a first strain sweep (0.1-25% shear strain amplitude) was per-
or hybrid fillers (CB+CNT) were prepared. The composition in formed at 50°C and 1 Hz, then the sample was kept in the instru-
phr (weight parts per hundred parts of rubber) is reported in table PHQW DW WKH PLQLPXP VWUDLQ DPSOLWXGH Ȗmin = 0.1%) for 10
1. In hybrid filler composites, the filler content was divided into minutes, to achieve fully equilibrated conditions. Finally, dy-
two equal parts of the two fillers. namic tests were performed at 50°C at increasing strain ampli-
Composites based on SBR are filled with CNT(N), CB or tude (0.1-25% shear strain amplitude) with a frequency of 1 Hz.
hybrid fillers (table 2). In this case, hybrid fillers were prepared Dynamic moduli of NR based composites were measured by a
by adding to the fixed contents of CB increasing amounts of dynamic mechanical analyzer Q800 (TA Instruments) in a shear
CNT(N). The contents were chosen to uniformly cover a wide sandwich configuration, in strain sweep mode. Parallelepiped
range of total filler surface area. specimens were cut from cured sheets of rubber with dimensions
Finally, NR based composites were prepared by adding only of about 3 x 3 x 8 mm3. Figure 1a shows a schematic representa-
CNT(N) or CB, as shown in table 3. tion of the test configuration. Two specimens are compressed
between the fixed plates and the moving plate of the machine.
Preparation Strain sweeps were carried out in the range 0.02% to 25% of
Composites, based on either IR, SBR or NR, were prepared strain amplitude, at room temperature and 1 Hz. Thanks to the
using a Brabender type internal mixer (Brabender PL-2000 small dimensions of the specimens, different directions of strain
Plasti-Corder torque rheometer, Brabender GmbH & Co. KG, could be applied in order to study the variation of material prop-
Duisburg, Germany), with a 50 mL mixing chamber. The fol- erties with the loading direction.
lowing procedure was adopted for the preparation of all the The various strain directions applied are shown in figures 1b
samples: 50 g of the polymer were introduced into the Braben- and 1c, where the rubber plate is sketched with a broken line, and
der type internal mixer and masticated at 80°C for one minute Cartesian coordinates are displayed: Plane 1-2 corresponds to the
with rotors rotating at 60 rpm. The filler was then added, mix- main plane of the rubber sheet, and direction 3 is the direction
ing was performed for four minutes, and the composite was perpendicular to such plane and also the direction of the pressure
then discharged at a temperature of about 90°C. The compos- applied during the compression molding phase. Two main con-
ite, so prepared, was left to reach room temperature and was figurations are shown, including through-thickness (TT) and in
fed again to the Brabender mixer kept at a temperature of plane (IP). In TT configuration, the shear strain is applied as in
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
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)
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&171ZKLFKDUH 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.
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
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
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, 3URWRQ+UHDFWLYHZLWKRUJDQLFLQRUJDQLFVXEVWUDWHVRIDOO
while silanes are not catalysts. Ti or Zr catalytic functionality types.
works in unfilled polymers (ref. 6) and changes the morphology $GGGLUHFWO\LQWRPL[IRULQVLWXFRXSOLQJDQGSRO\PHU
of the polymer at the nano-interface of a filled polymer, resulting catalysis for repolymerization (ref. 6) and copolymerization/
in polymers with slightly higher tensile strength (F/A) and sig- compatibilization (ref. 7) of dissimilar polymers.
nificantly higher elongation (e/l), which produces a tougher (de- )RUPQDQRPHWHUDWRPLFPRQROD\HUVIRUFRPSOHWH
fined as the area under the plot of stress vs. strain) polymer, adhesion.
which results in coatings on metal with higher reverse impact 5HVLVWDJLQJDQGSURYLGHQDQRSKRVSKRUXVDQWLFRUURVLRQDW
strength and greater mandrel flexibility. the nano-interface.
Polymer alloying to take advantage of the performance prop-
erties of different polymers can be a challenge. For example, al- References
WKRXJK33DQG+'3(DUHERWKROHILQVPRUHWKDQ33EOHQGHG 1. Edwin P. Plueddemann, 1982, “Silane Coupling Agents,”
LQWR +'3( ZLOO FDXVH GHODPLQDWLRQ GXULQJ PROGLQJ$GGLWLRQ http://www.springer.com/us/book/9780306434730.
and condensation polymers tend to delaminate. Silanes do not 2. http://www.gelest.com/wp-content/uploads/Goods-PDF-bro-
catalyze, but titanates catalyze to compatibilize both addition (PP, chures-couplingagents.pdf.
3((35DQGFRQGHQVDWLRQ3(7SRO\PHUVUHIILJXUH 3. Int. SAMPE Technical Conference (1988), 20 (Mater.-Process-
Figure 8 shows that 0.2 phr titanate has the same effect as es: Intercept Point), 423-37 CODEN: ISTCEF; ISSN: 0892-
adding 15 phr of process oil. 2624: “Enhanced bonding of fiber reinforcements to thermoset
A white paper on compatibilizers discussing thermoplastic resins,” General Dynamics/Kenrich Petrochemicals, Inc.
copolymers, maleated polymers and subject organometallics is 4. http://www.compositesworld.com/articles/advances-in-siz-
available (ref. 8). (continued on page 40)
The temperature sweep curve is done on specific samples (2 several methods with the objective to correlate it with some
x 4 mm2 of section, 14 mm of height) tested in elongation mode rubber properties and silane activity.
at 10 Hz under a dynamic strain amplitude of 0.1% from -80°C The silanol quantification is commonly considered as an
to 80°C (speed rate: 5°C/minute). appropriate way to predict the surface reactivity.
To study the Payne effect, the samples (double sandwich of The silanol content from TGA of the silica (figure 1) covers
specific form with a section of 2 x 4 mm2 and a height of 7 mm) a large spectra of values from 8.7 for Premium 200 MP to 14.6
DUHWHVWHGLQSXUHVKHDUȖPRGH7KHG\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
ORVVIDFWRUWDQįDUHUHFRUGHGEHWZHHQȖ 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.
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,
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
0.250
Tan (į) maximum
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.
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.
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
$270.00
Titanates and zirconates
(continued from page 34)
Manufacturing rubber products requires the use of ings-and-surface-treatments-for-carbon-fibers.
many additives. 5. Journal of Materials Science 28 (1993) 4,047-4,052, “Acous-
tic emission analysis and small-angle x-ray scattering from mi-
Therefore, mixing of the additives with the rubber
crocracks during deformation of ETFE composites,” R. Kraus,
is a very important step in the processing of rubber. A. Payer, W. Wilke, Abteilung Experimentelle Physik, Universitat
There has been extensive research to try to under- Ulm, Albert-Einstein-Allee 11, 7900 Ulm, Germany.
6. U.S. Patent 4,657,988, “Repolymerization.”
stand the relationships between the formulation
7. PIA Global Plastic Summit 2015, Chicago, IL, October 28,
and the properties of the final product. 2015: “New titanium-mixed metal catalyst for multi-polymer
compatibilization and post consumer recycle (PCR),” S.J.
Monte.
ISBN-13: 9781859572078
8. http://www.plasticsindustry.org/sites/plastics.dev/files/com-
Pages: 422
patibilizers%20whitepaper%20(version%201.0)_0.pdf.
Order Online: www.rubberworld.com/bookstore
9. KR 2012078860 Kumho Tires Co., Ltd., S. Korea.
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
HB
CHEMICAL
Ph:
Twinsburg, OH 44087
P (800) 991-2436 F: (330) 920-0971
www.hbchemical.com
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.
&Žƌ/ŶĨŽƌŵĂƟŽŶŽŶƚĂĐƚ:ĞƌƌLJDŝŬĞƐĞůůĂƚ
574.784.3409 ŽƌĞŵĂŝů͗ũŵŝŬĞƐĞůůΛŚŽŽƐŝĞƌƟƌĞ͘ĐŽŵ
tĞďƐŝƚĞ͗ǁǁǁ͘ŚŽŽƐŝĞƌƟƌĞĐƵƐƚŽŵŵĨŐ͘ĐŽŵ
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
SPRINTER MARKING
D UROMETERS
Offering a full
range of ink code- Rubber Hardness Testers
marking machines. AFLAS Fluoroelastomers
Shore A Normal rubber
FEPM SERIES: 100, 150 and Latex grades Asker C Soft rubber & sponge
Quick drying inks for high strength, general purpose use,
in a range of colors Shore D Hard rubber & plastics
are stocked to linings, extrusions coatings & binders. Shore E Soft rubber & sponge
support machine FKM: 200P specialty FKM for improved And More Scales Available
sales. performance at cold temps. FFKM SERIES: ● ASTM D2240 compliant
www.agcchem.com 866-527-4666
FLUOROELASTOMERS
FE P M S E R I E S
www.hoto-instruments.com
Neoprene
560 Highway 44
LaPlace, LA70068
1 985-536-7400
Sales@denka-pe.com
3N International, Inc.
Flame retardants, smoke suppressants,
UV stabilizers; CPE, PVC plasticizers,
ISO9001 process aids, impact modifiers, etc.
FOR SALE: VALUE PRICED
Certified Stocked in multiple locations in US.
Polyethylene Glycol 3350, 4000, and
8000 for rubber compounding
Allchem, Dalton GA.,706-226-4080,
Phone: (330) 665-3821 Fax: (330) 665-3823
paul@allchem-inc.com Web: www.3ninc.com Email: info@3ninc.com
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
E
CTIV
TIVE ONDU
DUC A -C
CON LACK EXTR N BLACK
A R B ON B A R B O
C C
imerys-graphite-and-carbon.com
Powerful
RPA technology
The RPA elite is part of the new line of rubber testing products from TA Instruments
and is backed by our world-renowned, global, direct support network.
rubber.tainstruments.com
“MORE THAN A
DISTRIBUTOR”
Lianda Corporation is a leading importer and distributor of specialty polymers
and chemicals for the rubber and plastics industries. For over 23 years, we have
established ourselves as a proven and reliable resource of quality products and
a provider of unsurpassed service to our customers.
From our extensive range of performance products, our leading product lines
include:
s #0% s (."2
s &+- s 0%2/8)$%3
s #2 s #52!4)6%3
s %#/ s #/!'%.43
s #3- s 3),)#!
s %0$- s ",/7).'