Mixing of Carbon Black with Rubber. II. Mechanism of Carbon Black Incorporation

1985 ◽  
Vol 58 (4) ◽  
pp. 774-784 ◽  
Author(s):  
George R. Cotten
Keyword(s):  
Molecular Weight ◽  
Particle Size ◽  
Carbon Black ◽  
Cross Section ◽  
Effective Cross Section ◽  
Rubber Content ◽  
Narrow Channels ◽  
Second Stage ◽  
Bound Rubber ◽  
Average Size

Abstract The present study leads to postulating the following mechanism for carbon black incorporation. During the first stage of incorporation, carbon black agglomerates become encapsulated by the polymer. At this stage, the interstices within these agglomerates are still filled with air, giving a very weak, crumbly composite. The rubber becomes forced into these interstices during the second stage of incorporation. As the rubber is being forced through the narrow channels between the aggregates, bound rubber is being formed. The immobilized layer of the polymer tends to reduce the effective cross section of the channels through which more rubber must pass before reaching the inner part of the agglomerates. Thus, as the activity of carbon black increases, e.g., higher bound rubber, the incorporation time increases. At a given carbon black activity, the effective thickness of the immobilized polymer layer would increase with increasing molecular weight of polymer, but be independent of the oil loading. This agrees with experimental observation that the incorporation time increases with molecular weight of the polymer, while oil loading has no effect other than that associated with the lowering of bound rubber content. The average size of channels through which rubber must pass depends also on the carbon black morphology. The size of these channels would be expected to increase with increasing structure of carbon black, and (to a lesser extent) with increasing particle size. These parameters have the expected influence on the incorporation time; since the incorporation time decreases with increasing DBPA value and decreasing tint.

Influence of Carbon Black on Process-Ability of Rubber Stocks. I. Bound Rubber Formation

1975 ◽  
Vol 48 (4) ◽  
pp. 548-557 ◽  
Author(s):  
G. R. Cotten
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Polymer Degradation ◽  
Processing Conditions ◽  
Rubber Content ◽  
High Molecular Weight Polymer ◽  
Molecular Weight Polymer ◽  
Bound Rubber ◽  
Wide Range ◽  
Process Ability

Abstract 1. A direct correlation between bound rubber content and molecular weight of soluble polymer was found for a wide range of carbon black samples and processing conditions in SBR. 2. No significant polymer degradation occurred during the ineorporation of carbon black into SBR rubber. 3. A theory was proposed to explain the observed changes in viscosity and extrusion shrinkage of rubber stocks. This theory is based on the concept of occluded rubber which is rich in high molecular weight polymer and behaves as a part of filler volume during viscous flow.

Sorption of GR-S Type of Polymer on Carbon Black. III. Sorption by Commercial Blacks

1953 ◽  
Vol 26 (1) ◽  
pp. 102-114 ◽  
Author(s):  
I. M. Kolthoff ◽  
R. G. Gutmacher
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Intrinsic Viscosity ◽  
Benzene Solution ◽  
Weight Fraction ◽  
High Molecular Weight Fraction ◽  
Molecular Weights ◽  
Bound Rubber ◽  
Flow Through ◽  
Peculiar Behavior

Abstract The sorption capacities toward GR-S five commercial carbon blacks are in decreasing order: Spheron-6, Vulcan-1, Philblack-0, Sterling-105, Philblack-A. Apparently, the sorption is not related to surface area. The sorption on Vulcan-1 of GR-S from its solutions in seven different solvents or mixtures of solvents increases with decreasing solvent power for the rubber. The sorption curves of two “cold rubbers,” polymerized at −10 and +5° respectively, showed little difference from that of 50° GR-S. Previous heating of carbon black in nitrogen at 500 or 1100° increased the sorption by about 20 per cent over unheated carbon. Air-heating of carbon black at 425° did not cause a difference in the sorption from benzene solution, but produced an increase in the sorption of rubber from n-heptane solution. In the range 75% butadiene-25% styrene to 5% butadiene-95% styrene, there is practically no effect of the degree of unsaturation on the sorption. Polystyrene of high intrinsic viscosity exhibits a peculiar behavior with furnace blacks. Vulcan-1 sorbed microgel as well as the sol fraction from n-heptane solutions of GR-S containing microgel (conversion 74.7 and 81.5 per cent). There was no appreciable difference in the amount of sorption of rubber fractions having average molecular weights varying from 433,000 to 85,000. There is little change in the amount sorbed after two hours of shaking, but the intrinsic viscosity of the residual rubber decreases with time. The low molecular-weight rubber is sorbed more rapidly, but is slowly replaced by the more tightly sorbed high molecular weight fraction. Partial fractionation of a rubber sample can be achieved by allowing the rubber solution to flow through a column of weakly sorbing carbon black. A large portion of the sorbed rubber can be recovered from the column by washing it with a good solvent such as xylene. Bound rubber is produced by intimate mixing of equal parts of carbon black and rubber swollen in chloroform, when the mixture is dried in vacuum at 80° or at room temperature. Milling is not essential to get bound rubber.

Mixing of Carbon Black with Rubber. VI. Analysis of NR/SBR Blends

1988 ◽  
Vol 61 (4) ◽  
pp. 609-618 ◽  
Author(s):  
George R. Cotten ◽  
Lawrence J. Murphy
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
High Molecular Weight ◽  
Surface Area ◽  
Bound Rubber ◽  
Very High

Abstract The distribution of carbon black in NR/SBR blends was determined through the analysis of bound rubber. The NR/SBR blends were found to be very different from the previously studied SBR/BR compounds: these differences were assigned to mutual insolubility of the two polymers and a very high molecular weight of NR. In NR/SBR blends, it was found that changes in molecular weight of the polymer has no effect on the carbon black distribution in the blend. While the “activity” of carbon black did not affect the distribution, the loading of the black in NR decreased linearly with increasing surface area of the black. Approximately 35% of normal tread blacks (surface area 80–100 m2/g) was found in the NR phase. However, the bond between NR and carbon black is quite weak, and black continues to migrate into the SBR phase on prolonged mixing or during blending of NR and SBR masterbatches.

Bound—Rubber Formation in Diene Polymer Stocks

1958 ◽  
Vol 31 (2) ◽  
pp. 369-373 ◽  
Author(s):  
P. B. Stickney ◽  
E. E. McSweeney ◽  
W. J. Mueller ◽  
S. T. Palinchak
Keyword(s):  
Particle Size ◽  
Carbon Black ◽  
Recent Work ◽  
Experimental Approach ◽  
Polymer Gel ◽  
Fine Powders ◽  
Bound Rubber ◽  
Close Relationship ◽  
Static Extraction ◽  
Rubber Filler

Abstract The phenomenon of insolubilization of rubber by carbon black has been known for at least twenty-seven years. There have been many attempts during this time to establish a relationship between insolubilization, or bound rubber formation, and reinforcement of rubber by carbon black. It was postulated, as far back as 1925, that there was a parallelism between particle size and insolubilization. This in spite of the fact that the methods available for determining particle size of very fine powders at that time were relatively crude. It was postulated at that time that there was a close relationship between the phenomena of vulcanization and reinforcement. This concept has had recurrent periods of popularity since that time. The insolubilization of rubber by carbon black, or other pigments, has been estimated by various techniques by the early investigators in the field. In more recent work, the trend has been toward a very straightforward experimental approach. Bound rubber in an uncured rubber-filler compound is usually determined by static extraction using the same apparatus and techniques used in determining the gel content of unfilled polymers. It follows that, using this method, polymer insoluble because of crosslinking, or gel, cannot be distinguished from polymer insolubilized by incorporation of fine fillers. In investigating the formation of bound rubber, therefore, the presence of gel in the polymer being used, or formation of polymer gel during processing must be taken into account.

Ozonolytic Degradation of Interpolymers of Natural Rubber with Methyl Methacrylate and Styrene

1958 ◽  
Vol 31 (1) ◽  
pp. 82-85
Author(s):  
D. Barnard
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Natural Rubber ◽  
Accurate Determination ◽  
Synthetic Polymers ◽  
Polymer Chains ◽  
Low Molecular Weight ◽  
Rubber Content ◽  
Tert Butyl Hydroperoxide

Abstract The preparation of graft and block interpolymers of natural rubber and synthetic polymers has made it desirable that the number and size of polymer chains attached to rubber be readily determinate. The degradation of unsaturated polymers with tert-butyl hydroperoxide in the presence of osmium tet oxide has been used for the determination of free polystyrene in SBR and carbon black in several elastomers, and has recently been applied to the present problem. The accurate determination of the rubber content of interpolymers by quantitative ozonolysis essentially according to the method of Boer and Kooyman suggested that this might be made the basis of isolation of the attached polymer, the rubber being degraded into fragments of low molecular weight, from which the polymer could be separated by conventional techniques. The method should be applicable to any interpolymer, or mixture, of a polyunsaturated and a saturated polymer and is illustrated with reference to interpolymers of natural rubber (NR)-polymethyl methacrylate (PMM) and NR-polystyrene (PS).

Studies on Carbon Black. III. Theory of Bound Rubber

1957 ◽  
Vol 30 (1) ◽  
pp. 157-169
Author(s):  
D. S. Villars
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Selective Adsorption ◽  
General Sense ◽  
Polymer Molecules ◽  
Naturally Occurring ◽  
High Molecular Weight Material ◽  
Chemical Type ◽  
Bound Rubber ◽  
Set Up

Abstract Theories of reinforcement may be grouped into two general classes, mechanical and chemical. The mechanical type of theory attempts to explain reinforcement by alteration of direction of tear or by mechanieal entrainment. The chemical type of theory invokes the formation of bonds between the filler and rubber. Because of its implication with respect to the latter, Fielding of Goodyear developed a “bound rubber” test. The amount of rubber bound to carbon black was defined as that unextractable from the raw masterbatch by benzene. Some ten years ago, Baker and Walker reported an insolubilization of GR-S, on mixing with carbon black, over and above the amount of naturally occurring gel. The amount of insolubilized polymer increases with increasing molecular weight of the GR-S, and a selective adsorption of the high molecular weight material was found. Since this phenomenon was obtained also in polymers where they believed chemical gelation to be impossible, the conclusion was drawn by them that it is purely physical—this notwithstanding the fact that they found that extractions at higher temperatures failed to remove the insolubilized polymer. Because the method of analysis for insolubilized polymer used by Baker and Walker was essentially a bound-rubber analysis, interest in the latter was revived and it became desirable to set up a hypothesis to explain the mechanism of bound-rubber formation. (Let us understand the term “rubber” as applying in its more general sense as synonymous with “elastomer”.) The present paper reports a theory developed by the writer about ten years ago to explain various observations on the hypothesis that bound rubber is a gel of carbon black particles, the bonding agent of which consists of the longer polymer molecules. The theory interprets the observed linear dependence of bound rubber on loading in terms of an elemental area associated with the segmental adsorption of elastomer molecules, the molecular weight of these segments, and the functionality of the carbon black particles.

Molecular Weight Effects in Adsorption of Rubbers on Carbon Black

1968 ◽  
Vol 41 (5) ◽  
pp. 1256-1270 ◽  
Author(s):  
Gerard Kraus ◽  
J. T. Gruver
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Large Particle ◽  
Molecular Weights ◽  
Molecular Weight Dependence ◽  
Bound Rubber ◽  
Sieve Effect ◽  
High Structure ◽  
Very High ◽  
Poor Solvent

Abstract The molecular weight dependence of the adsorption of polybutadiene on carbon black from a poor solvent, n-heptane, and bulk, i.e., the phenomenon of “bound rubber”, was investigated. For narrow distribution polymers the adsorption is proportional to Mn, where n = 0.14 for adsorption from n-heptane solution; n = 0.5 for adsorption from bulk. Anomalously low solution adsorption was observed for polymers of very high molecular weight (> 500,000). This is ascribed to a sieve effect by aggregates of carbon black particles which cannot be penetrated by the large molecular coils. In high structure blacks, which pack more loosely, and in large particle blacks, which form larger interstices between particles, onset of anomalous adsorption is shifted toward higher molecular weights.

Filler—Elastomer Interactions. Part IV. The Effect of the Surface Energies of Fillers on Elastomer Reinforcement

1992 ◽  
Vol 65 (2) ◽  
pp. 329-342 ◽  
Author(s):  
Siegfried Wolff ◽  
Meng-Jiao Wang
Keyword(s):  
Carbon Black ◽  
Small Strain ◽  
Rubber Content ◽  
Specific Component ◽  
Dispersive Component ◽  
Surface Energies ◽  
Precipitated Silica ◽  
Bound Rubber ◽  
High Elongation ◽  
Polymer Interaction

Abstract Carbon black N110 and a precipitated silica, which have comparable surface area and structure, were selected as model fillers to study the effect of filler surface energies on rubber reinforcement. In comparison with carbon black, the surface energies of silica are characterized by a lower dispersive component, γsd, and higher specific component, γssp. It was found that the high γssp of silica leads to strong interaggregate interaction, resulting in higher viscosity of the compounds, higher αƒ, and higher moduli of the vulcanizates at small strain. The higher γsd of carbon black, in contrast, causes strong filler—polymer interaction, which is reflected in a higher bound-rubber content of the compounds and higher moduli of the vulcanizates at high elongation.

PROPERTIES OF SBR FILLED WITH CARBON BLACK AND ARAMID PULP HYBRID FILLER: COMPARISON BETWEEN PREDISPERSED ARAMID PULP AND CONVENTIONAL ARAMID PULP

2016 ◽  
Vol 89 (4) ◽  
pp. 640-652 ◽  
Author(s):  
Manuchet Nillawong ◽  
Pongdhorn Sae-oui ◽  
Krisda Suchiva ◽  
Chakrit Sirisinha
Keyword(s):  
Carbon Black ◽  
Hybrid Composites ◽  
Aramid Fiber ◽  
Rubber Content ◽  
Hybrid Filler ◽  
Fiber Loading ◽  
Bound Rubber ◽  
Extended Range ◽  
Heat Buildup ◽  
Rubber Filler

ABSTRACT Compounds of SBR incorporated with hybrid filler of carbon black (CB) and aramid pulp were prepared. The ratio of CB to aramid pulp was varied and its effects on viscoelastic and mechanical properties of the rubber were investigated. Two aramid pulp types were used in this study: conventional aramid pulp (CAP) and the predispersed aramid pulp (PAP). The rubber–filler interaction as indicated by bound rubber content decreases with increasing aramid pulp loading, regardless of the aramid pulp type. This results in a decrease in tensile and abrasion properties with increasing fiber loading. The energy dissipation properties of the hybrid composites are also poorer than those of the CB/SBR composite, as reflected by the heat buildup values. Use of predispersed aramid fiber resulted in improved dispersion of the fiber in SBR. Thus, Mooney viscosities of the PAP-filled systems are lower than those of the CAP-filled systems, but the percentages of elongation at breaks are higher. The distinct feature of aramid fiber/CB hybrid SBR composites is their high moduli over an extended range of temperatures up to 80°C that is unattainable with the use of CB alone.

A Method for Evaluation of Carbon Blacks and Correlation with Road Wear Ratings

1974 ◽  
Vol 2 (3) ◽  
pp. 211-228 ◽  
Author(s):  
G. R. Cotten ◽  
E. M. Dannenberg
Keyword(s):  
Carbon Black ◽  
Abrasion Resistance ◽  
Laboratory Tests ◽  
The Other ◽  
Rubber Content ◽  
Carbon Blacks ◽  
Heat Treated ◽  
Bound Rubber ◽  
Normal Production

Abstract Prediction of tread wear from laboratory tests can be a valuable guide in the development of improved carbon blacks and controlling the quality of normal production. We have developed two tests which give good correlation with actual road wear data on over 100 experimental blacks. One test involves running Akron angle abrasion on a compound with only 30 phr of carbon black where differences in abrasion resistance are magnified. The other test measures surface activity towards the polymer by determining bound rubber content of a heat-treated nonproductive mix. By using both tests together, tread wear ratings of blacks used in this study could be predicted almost as well as by a single, controlled, multisectional road test with five tires run for 8000–10,000 miles.

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