Flocculation in Silica Reinforced Rubber Compounds

2009 ◽  
Vol 82 (5) ◽  
pp. 524-540 ◽  
Author(s):  
S. Mihara ◽  
R. N. Datta ◽  
J. W. M. Noordermeer
Keyword(s):  
Activation Energy ◽  
Coupling Agent ◽  
Physical Phenomenon ◽  
Interfacial Interaction ◽  
Shielding Effect ◽  
Interaction Layer ◽  
Filled Rubber ◽  
Rubber Compounds ◽  
Bound Rubber ◽  
Flocculation Rate

Abstract Flocculation plays an important role in reinforcement of silica filled rubber compounds, even if coupling agents are applied. It is well known that silica tends to flocculate during the early stages of vulcanization, when no dense rubber network has been formed yet. In the present study, flocculation was monitored by following the change in storage modulus at low strain, the so-called Payne effect, using a RPA2000 dynamic mechanical tester. The kinetic parameters: the rate constant and the activation energy of the silica flocculation were calculated according to the well-known Arrhenius equation. On basis of the value of the activation energy obtained for flocculation, it can be concluded that the silica flocculation is a purely physical phenomenon. Bound rubber measurements were also done in order to estimate the interfacial interaction layer between silica and polymer resulting from the coupling agent. The silica flocculation rate decreases with increasing interfacial interaction layer on the silica surface. This indicates that the decrease of the flocculation rate is due to the shielding effect of the coupling agent. It is argued that the attractive flux from forces related to polarity differences between the silica and the rubber is the determining factor for silica flocculation.

REINFORCEMENT OF NATURAL RUBBER BY SILICA/SILANE IN DEPENDENCE OF DIFFERENT AMINE TYPES

2017 ◽  
Vol 90 (4) ◽  
pp. 651-666 ◽  
Author(s):  
C. Hayichelaeh ◽  
L. A. E. M. Reuvekamp ◽  
W. K. Dierkes ◽  
A. Blume ◽  
J. W. M. Noordermeer ◽  
...  
Keyword(s):  
Heat Capacity ◽  
Natural Rubber ◽  
Health And Safety ◽  
Aliphatic Amines ◽  
Shielding Effect ◽  
Processing Temperature ◽  
Rubber Content ◽  
Payne Effect ◽  
Rubber Compounds ◽  
Bound Rubber

ABSTRACT Diphenyl guanidine (DPG) is the most commonly used secondary accelerator in silica-reinforced rubber compounds because of its additional positive effect on the silanization reaction and deactivation of free silanol groups that are left over after the silanization. However, because of health and safety concerns about the use of DPG, which decomposes to give highly toxic aniline during high processing temperature, safe alternatives are required. This work investigates the effect of various types of aliphatic amines having alkyl or cyclic structures and similar pKa (i.e., hexylamine [HEX], decylamine [DEC], octadecylamine [OCT], cyclohexylamine [CYC], dicyclohexylamine [DIC], and quinuclidine [QUI]) on the properties of silica-reinforced natural rubber (NR) compounds by taking the ones with DPG and without amine as references. When compared with the compound without amine, the use of all amine types reduces filler–filler interaction (i.e., the Payne effect) and enhances filler–rubber interaction, as indicated by bound rubber content and decreased heat capacity increment. The amines with alkyl chains can reduce the Payne effect and enhance cure rate to a greater extent compared with the amines with cyclic rings as a result of better accessibility toward the silica surface and a shielding effect because of less steric hindrance. The longer carbon tails on linear aliphatic amines ranging from HEX, DEC, to OCT lead to a lower Payne effect, lower heat capacity increment, higher bound rubber content, and higher modulus as well as tensile strength. Overall, the use of OCT provides silica-reinforced NR compounds with properties closest to the reference one with DPG and can act as a potential alternative for DPG.

PROMOTING INTERFACIAL COMPATIBILITY OF SILICA-REINFORCED NATURAL RUBBER TIRE COMPOUNDS BY ALIPHATIC AMINE

2018 ◽  
Vol 91 (2) ◽  
pp. 433-452 ◽  
Author(s):  
C. Hayichelaeh ◽  
L. A. E. M. Reuvekamp ◽  
W. K. Dierkes ◽  
A. Blume ◽  
J. W. M. Noordermeer ◽  
...  
Keyword(s):  
Crosslink Density ◽  
Silica Surface ◽  
Shielding Effect ◽  
Polymer Layer ◽  
Vulcanized Rubber ◽  
Rubber Compounds ◽  
Bound Rubber ◽  
Interfacial Compatibility ◽  
Physical Interactions ◽  
Tan Δ

ABSTRACT Octadecylamine (OCT) as an alternative for diphenyl guanidine (DPG) in silica-reinforced NR tire compounds with bis-(triethoxysilyl-propyl)tetrasulfide (TESPT) as silane coupling agent was investigated with focus on the improvement of compatibility between the silica surface and rubber molecules, by taking the amine-free rubber compound as a reference. The quantity of OCT and DPG was varied in a range of 2.4–9.5 mmol per 100 parts of rubber by weight (i.e., 0.5–2.5 phr). Bound rubber contents, changes in heat capacity (ΔCp), and immobilized polymer layer (χim) data prove an enhanced interfacial compatibility as the amines are absorbed on the polar silica surface and catalyze the silanization reaction. Comparing the two different amine types, the rubber compounds with OCT show higher interfacial compatibility than the ones with DPG, because of an additional shielding effect promoted by the long alkyl chain that leads to more hydrophobicity. Thus, the rubber compounds with OCT show higher physically bound rubber contents and consequently higher total bound rubber, a higher immobilized polymer layer, as well as a lower Payne effect. However, the compounds with OCT show a higher flocculation rate constant because the physical interactions between amine and silanol groups decrease under thermal treatment. The compounds with OCT show a lower cure torque difference that indicates a lower crosslink density, but because of the good interfacial interaction combining both chemical and physical interactions, the vulcanized rubber with OCT at optimum loading shows better mechanical properties and tan δ at 60 °C when compared with the DPG counterpart. At high (excessive) loading of amines, the compounds with DPG clearly have higher crosslink density and thus higher modulus as well as tensile strength compared with the use of OCT.

SILICA-REINFORCED NATURAL RUBBER TIRE TREAD COMPOUNDS CONTAINING BIO-BASED PROCESS OILS. I: ASPECTS OF MIXING SEQUENCE AND EPOXIDE CONTENT

2019 ◽  
Vol 93 (2) ◽  
pp. 360-377
Author(s):  
C. Hayichelaeh ◽  
L. A. E. M. Reuvekamp ◽  
W. K. Dierkes ◽  
A. Blume ◽  
J. W. M. Noordermeer ◽  
...  
Keyword(s):  
Natural Rubber ◽  
Rate Constant ◽  
Silica Surface ◽  
Early Stage ◽  
Shielding Effect ◽  
Cure Reaction ◽  
Silanol Groups ◽  
Rubber Compounds ◽  
Tan Δ ◽  
Flocculation Rate

ABSTRACT A bio-based process oil for rubber compounds is one of the compounding ingredients to be used toward an eco-friendly and more sustainable rubber technology. This work investigates epoxidized palm oil (EPO) as an alternative for petroleum-based process oil in silica-reinforced natural rubber (NR) tire tread compounds. The effect of different incorporating steps of EPO on the properties of the rubber compounds is first studied, taking into account that the polar functional groups in the oil molecules may interact with the silanol groups on the silica surface. The properties of silica-reinforced NR compounds with EPO oil are compared with that of reference mixes with treated distillate aromatic extract (TDAE) and without oil. The compounds with EPO show a lower viscosity, filler–filler interaction, and flocculation rate constant but higher cure reaction rate constants compared with the compound with TDAE. The results indicate that the epoxide groups in EPO interact with the silanol groups on the silica surface, promoting a greater shielding effect on the polar surface and thus better silica dispersion and less interference with the vulcanization reaction. The different incorporating steps of EPO show no significant effect on the viscosity, filler–filler interaction, or flocculation rate constant but clearly affect the extent of crosslinking, as indicated by the cure torque difference. The presence of EPO in an early stage of the mixing together with the first half addition of silica and silane results in the lowest cure torque difference, modulus, and tensile strength (i.e., the highest tan δ at 60 °C), which indicates a possible obstruction for the interaction between the silanol groups and silane coupling agent by the EPO molecules. Comparing EPO with different epoxide contents in the range of 1–3 mol%, the increase in epoxide content gives similar Payne effects but enhances the cure reaction, resulting in improved tensile properties and tan δ at 60 °C. The results clearly prove that EPO can be used as a TDAE alternative.

Bound rubber morphology and loss tangent properties of carbon-black-filled rubber compounds

2015 ◽  
Vol 294 (3) ◽  
pp. 501-511 ◽  
Author(s):  
Dina Gabriel ◽  
Alexander Karbach ◽  
Doris Drechsler ◽  
Jochen Gutmann ◽  
Karlheinz Graf ◽  
...  
Keyword(s):  
Carbon Black ◽  
Loss Tangent ◽  
Filled Rubber ◽  
Rubber Compounds ◽  
Bound Rubber

Polybutadiene-g-polypentafluorostyrene as a coupling agent for lignin-filled rubber compounds

Polymer ◽  
2014 ◽  
Vol 55 (26) ◽  
pp. 6754-6763 ◽  
Author(s):  
Kushal Bahl ◽  
Nicole Swanson ◽  
Coleen Pugh ◽  
Sadhan C. Jana
Keyword(s):  
Coupling Agent ◽  
Filled Rubber ◽  
Rubber Compounds

scholarly journals THE ORIGIN OF MARCHING MODULUS OF SILICA-FILLED TIRE TREAD COMPOUNDS

2019 ◽  
Vol 93 (2) ◽  
pp. 378-394 ◽  
Author(s):  
J. Jin ◽  
J. W. M. Noordermeer ◽  
W. K. Dierkes ◽  
A. Blume
Keyword(s):  
Coupling Agent ◽  
Coupling Reaction ◽  
Coupling Agents ◽  
Key Factors ◽  
Silane Coupling Agents ◽  
Filled Rubber ◽  
Rubber Compounds ◽  
Silane Coupling ◽  
Filler Dispersion ◽  
Distinct Maximum

ABSTRACT Silica-reinforced S-SBR/BR tire tread compounds often show characteristic vulcanization profiles that do not exhibit a distinct maximum in the cure curve nor a plateau profile within acceptable time scales (marching modulus). In such a situation, it is difficult to determine the optimum curing time, and as a consequence, the physical properties of the rubber compounds may vary. Previous studies stated that the curing behavior of silica-filled rubber compounds is related to the degree of filler dispersion, the silanization, and the filler–polymer coupling reaction, as well as to the donation of free sulfur from the silane coupling agent. Such results imply that these are the key factors for minimization of the marching modulus. Various silane coupling agents with different sulfur ranks and functionalities were mixed at varied silanization temperatures. The correlation between these factors and their effect on the marching modulus intensity (MMI) were investigated. The MMI was monitored by measuring the vulcanization rheograms using a rubber process analyzer at small (approximately 7%) and large (approximately 42%) strains to discriminate the effects of filler–filler and filler–polymer interactions on the marching modulus of the silica-filled rubber compounds. Both factors have an intricate influence on the marching modulus, determined by the degree of filler–filler interaction and the coupling agent.

scholarly journals The Effect of Silanization Temperature and Time on the Marching Modulus of Silica-Filled Tire Tread Compounds

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 209 ◽  
Author(s):  
Jungmin Jin ◽  
Jacques W. M. Noordermeer ◽  
Wilma K. Dierkes ◽  
Anke Blume
Keyword(s):  
Styrene Butadiene Rubber ◽  
Butadiene Rubber ◽  
Filled Rubber ◽  
Mixing Parameters ◽  
Rubber Compounds ◽  
Bound Rubber ◽  
Strong Relation ◽  
Coupling Rate ◽  
Higher Temperature ◽  
Styrene Butadiene

Marching modulus phenomena are often observed in silica-reinforced solution styrene–butadiene rubber/butadiene rubber (S-SBR/BR) tire tread compounds. When such a situation happens, it is difficult to determine the optimum curing time, and as a consequence the physical properties of the rubber vulcanizates may vary. Previous studies have demonstrated that the curing behavior of silica compounds is related to the degree of silanization. For the present work, the effect of silanization temperature and time on the marching modulus of silica-filled rubber was evaluated. The correlations between these mixing parameters and their effect on the factors that have a strong relation with marching modulus intensity (MMI) were investigated: the amount of bound rubber, the filler flocculation rate (FFR), and the filler–polymer coupling rate (CR). The MMI was monitored by measuring the vulcanization rheograms using a rubber process analyzer (RPA) at small (approximately 7%) and large (approximately 42%) strain in order to discriminate the effects of filler–filler and filler–polymer interactions on the marching modulus of silica-filled rubber compounds. The results were interpreted via the correlation between these factors and their effect on the MMI. A higher temperature and a longer silanization time led to a better degree of silanization, in order of decreasing influence.

EFFECTS OF SILANE AGENTS AND CURING TEMPERATURES ON VULCANIZATE STRUCTURES

2019 ◽  
Vol 93 (2) ◽  
pp. 414-428 ◽  
Author(s):  
Byungkyu Ahn ◽  
Jong-Yeop Lee ◽  
Donghyuk Kim ◽  
Il Jin Kim ◽  
Sangwook Han ◽  
...  
Keyword(s):  
Coupling Agent ◽  
Crosslink Density ◽  
Silica Surface ◽  
Coupling Reaction ◽  
Rolling Resistance ◽  
Coupling Agents ◽  
Silane Coupling Agents ◽  
Filled Rubber ◽  
Rubber Compounds ◽  
Silane Coupling

ABSTRACT Silane coupling agents are commonly used in silica-filled rubber compounds to hydrophobize the silica surface and improve filler–rubber interaction. The coupling agent bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) is the most widely used coupling agent. The tetrasulfide is more reactive than the disulfide in bis[3-(triethoxysilyl)propyl]disulfide (TESPD) due to its low decomposition energy, resulting in more coupling reaction with rubber molecules. Meanwhile, vulcanization temperature affects chemical networks. Polysulfide is vulnerable to heat, so it can be easily broken to form shorter crosslinks. Compounds with TESPD or TESPT were vulcanized at 160 and 180 °C. In addition to the decomposition, the reactivity of the silanes was confirmed from the cure characteristics of the compounds without the curatives. TESPD could also cause a coupling reaction without the curatives such as TESPT known to release free sulfur. By analyzing vulcanizate structures, total crosslink density was separated into chemical crosslink density and filler–rubber networks. Applying TESPT or vulcanizing at 180 °C increased the filler–rubber networks, and the higher vulcanization temperature decreased the chemical crosslink density. By correlating physical properties, effects of the vulcanizate structures on performance of tread compounds were investigated. The filler–rubber interaction was dominant for wet traction and mechanical properties in tensile test. The chemical crosslink density affected rolling resistance.

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