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.

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.

STUDY ON NANOMORPHOLOGY OF HIGH-STRUCTURE CARBON BLACK AND ITS BOUND RUBBER BY AFM

2012 ◽  
Vol 19 (01) ◽  
pp. 1250003
Author(s):  
JIAN CHEN ◽  
YONGZHONG JIN ◽  
JINGYU ZHANG ◽  
YAFENG WU ◽  
CHUNCAI MENG
Keyword(s):  
Carbon Black ◽  
Cluster Structure ◽  
Chemical Activity ◽  
Styrene Butadiene Rubber ◽  
Butadiene Rubber ◽  
Atomic Force ◽  
Filled Rubber ◽  
Bound Rubber ◽  
Styrene Butadiene ◽  
High Structure

Bound rubber in carbon black (CB) filled rubber (natural rubber (NR) and styrene–butadiene rubber (SBS)) was prepared by the solvent method. The nanomorphology of CB and rubber/CB soluble rubber was observed by atomic force microscope. The results show that high-structure CB DZ13 has a "grape cluster" structure which consists of many original particles with the grain size of about 30–50 nm. Graphitizing process of CB decreases the amount of bound rubber. The NR/DZ13 soluble rubber with island–rim structure has been obtained, where the islands are DZ13 particles and the rims around the islands are occupied by NR film. But when the graphitized DZ13 particles were used as fillers of rubber, we have only observed that some graphitized DZ13 particles were deposited on the surface of the globular-like NR molecular chains, instead of the spreading of NR molecular chains along the surface of DZ13 particles, indicating that graphitized DZ13 has lower chemical activity than ungraphitized DZ13. Especially, we have already observed an interesting unusual bound rubber phenomenon, the blocked "bracelet" structure with the diameter of about 600 nm in which CB particles were blocked in ring-shaped SBS monomer.

scholarly journals Inducible overexpression and secretion of int-1 protein.

1989 ◽  
Vol 9 (8) ◽  
pp. 3377-3384 ◽  
Author(s):  
J Papkoff
Keyword(s):  
Molecular Weight ◽  
Cho Cells ◽  
Secretory Pathway ◽  
Mammary Tissue ◽  
Neural Tubes ◽  
Molecular Weights ◽  
Activation Of Transcription ◽  
Mouse Mammary Tumor ◽  
Tumor Virus ◽  
Very High

The int-1 proto-oncogene is a target for insertional activation of transcription by mouse mammary tumor virus in many murine mammary tumors. Whereas no expression of int-1 is seen in normal mammary tissue, int-1 RNA can be detected in normal mice in the neural tubes of midgestation embryos and in postmeiotic spermatocytes from adult testes. I report here the results of a study in which several different antibodies against synthetic peptides were produced and used to characterize the processing and secretion of int-1 protein. CHO cells were transfected with an inducible int-1 expression vector that was subsequently amplified to generate cell lines expressing very high levels of int-1 protein. Immunoprecipitation of [35S]cysteine-labeled cell lysates from these CHO cells yielded large amounts of four immature forms of int-1 glycoprotein (molecular weights of 36,000, 38,000, 40,000, and 42,000). A significant fraction of these int-1 species formed disulfide-linked multimers. Pulse-chase and glycosidase digestion studies demonstrated that some of the immature species of int-1 protein move through the secretory pathway and are processed to a mature heterogeneous glycoprotein with a molecular weight of about 44,000. Suramin treatment of the CHO cells during pulse-chase experiments increased the amount of 44,000-molecular-weight int-1 protein in the culture medium.

Immobilization of Elastomers at the Carbon Black Particle Surface

1970 ◽  
Vol 43 (5) ◽  
pp. 973-980 ◽  
Author(s):  
A. K. Sircar ◽  
A. Voet
Keyword(s):  
Carbon Black ◽  
Particle Surface ◽  
Carbon Black Particle ◽  
High Energy ◽  
Molecular Weights ◽  
Boiling Points ◽  
Furnace Black ◽  
Bound Rubber ◽  
Black Surface ◽  
Black Particle

Abstract Determinations have been made of the amount of elastomer unextractable from unvulcanized masticated mixes with carbon black by a given solvent at boil, expressed as immobilized elastomer. Saturated and unsaturated elastomers varying in molecular weights from 2000 to 325,000, were used, while solvents of greatly differing boiling points and solvent power were employed. It could be shown that the bonding between elastomers and carbon black is not a simple adsorption, but involves a higher energy interaction, defined as chemisorption. At successively higher temperatures elastomer is increasingly removed from the carbon black surface. The temperature Tm, obtained by extrapolation of the linear relationship between amounts immobilized and temperature of extraction, represents the temperature theoretically required to eliminate all bonds between carbon black and elastomer and is therefore indicative of the bond strength. Data suggest the existence of a bonding energy spectrum. Upon graphitization, blacks show a considerable decline in high energy bonding ability for elastomers. Saturated elastomers show less bonding than unsaturated elastomers with the same furnace black. “Bound rubber” represents the sum total of physically adsorbed, mechanically entangled, and chemisorbed elastomer. The actual values are greatly dependent upon the procedure used. “Immobilized rubber”, indicating chemisorbed elastomer, is easily determined, is not influenced by the method, and is more significant as an indicator of reinforcement.

Effect of Mechanical Shear on the Structure of Carbon Black in Reinforced Elastomers

1970 ◽  
Vol 43 (5) ◽  
pp. 943-959 ◽  
Author(s):  
A. M. Gessler
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Related Result ◽  
Critical Factor ◽  
Aggregate Structure ◽  
Carbon Black Concentration ◽  
Roll Mill ◽  
Total Structure ◽  
High Structure ◽  
High Shearing

Abstract The primary aggregate structure in high structure blacks is broken down when the blacks are milled in rubber. The breakdown, it is shown further, involves the disruption initially of more easily disrupted forces, and then subsequently of more difficultly disrupted forces. If the total structure breakdown is segmented accordingly, one finds that carbon blacks differ markedly in the proportion of the breakdown which occurs in each segment. But only the breakage of more difficultly disrupted structure is identified with chemical changes in the black and with concomitantly increased carbon—polymer interaction activity, i.e., with enhanced reinforcement. In studying the breakage of aggregate black structure which occurs when the blacks are milled in rubber, the following factors are considered: (1) Carbon Black Concentration: Breakage increases continuously, though not steadily, with carbon black concentration. This result is used to emphasize the merits of concentrated black masterbatching as the means for producing high quality products from SBR, BR, and EPDM rubbers. (2) Carbon Black Structure: Taking the total structure breakage over a broad range of carbon black concentrations, the extent of the breakage increases with the extent of the primary aggregate structure in the original black. (3) Polymer Viscosity or Molecular Weight: The extent to which breakage occurs on milling increases with the polymer viscosity or molecular weight. Since this result clearly cites the need for high shearing forces during milling, the severe limitations which must attend the use of plasticizing oils is implied. (4) Open Mill vs Banbury Mixing: The extent to which breakage occurs in the Banbury is significantly less than that on the two roll mill. Evidence is presented to show that this, clearly, is a temperature related result and, as in (3) above, that the magnitude of the shearing forces is the critical factor.

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.

The direct observation of polymer molecules and determination of their molecular weight

1964 ◽  
Vol 279 (1376) ◽  
pp. 50-61 ◽  
Keyword(s):  
Molecular Weight ◽  
Direct Observation ◽  
Particle Diameter ◽  
Dilute Solution ◽  
Crystalline Polymers ◽  
Polymer Molecules ◽  
Molecular Weights ◽  
Preferential Evaporation ◽  
Poor Solvent

An experimental investigation of the conditions necessary for the production of compact, single polymer molecules, in a form suitable for direct observation in the electron microscope, is described. Molecules are isolated by dispersing a dilute solution of the polymer as fine droplets on to a suitable substrate: ideally each droplet should contain either one or no polymer molecules. The solution is a mixture of two solvents, a good one and a poor one. Initially the good solvent predominates so that the probability of polymer aggregation is low. Preferential evaporation of the relatively volatile solvent on the substrate itself gives the poor solvent conditions needed for the formation of well-defined molecular spheres. Factors determining the choice of solvent, precipitant, and the composition of the mixture are discussed. There is little difficulty in obtaining single molecules with glassy amorphus polymers; rubbery polymers collapse and spherical molecules are formed only if the entire preparation is carried out at a temperature below that of the glass transition; crystalline polymers are not amenable to this technique. To obtain sufficient contrast the particles have to be shadowed and it is shown that, although certain dimensions are distorted by the metal coating, the shadow length faithfully represents the true particle diameter. Molecular weights, and their distribution, when of the order of a million and above, can readily be accurately determined. Conventional methods are unreliable in this region of high molecular weight.

Chromatographic Fractionation of Some Synthetic Elastomers

1948 ◽  
Vol 21 (3) ◽  
pp. 682-683 ◽  
Author(s):  
Ivan Landler
Keyword(s):  
Molecular Weight ◽  
Cellulose Acetate ◽  
Active Carbon ◽  
Low Molecular Weight ◽  
High Polymer ◽  
Acrylonitrile Copolymer ◽  
Molecular Weights ◽  
The Mean ◽  
Mean Molecular Weight ◽  
Poor Solvent

Abstract Mark and Saito were the first to fractionate a high polymer (cellulose acetate) by chromatographic adsorption on blood carbon. They found that molecules of low molecular weight were adsorbed first, and that the mean molecular weight of the product which remained unadsorbed was higher than the original molecular weight. Levi and Giera confirmed this result, but did not succeed in fractionating Buna-S or polyisoprene, for these polymers were eluted by the solvent during the washing operation in the column. The present authors have carried out further experiments in this field with a study of three commercial synthetic elastomers, viz., GR-S (butadienestyrene copolymer), Perbunan-N (butadiene-acrylonitrile copolymer), and Visitanex (polyisobutylene). The polymer was adsorbed by starting with a poor solvent composed of a mixture of toluene and methanol ; the quantity of alcohol added was just below the threshold of precipitation. The adsorbent used was a mixture of 75 per cent of lamp black (80 square meters per gram) and 25 per cent of coarse active carbon. The latter served to prevent agglomeration of the lamp black. The adsorbent was divided into three layers, of 10 grams each. At the end of the tube was a filter of fritted glass. Filtration was carried out under pressure, the rate of flow thereby being maintained constant, The polymers were characterized by their intrinsic viscosities. The molecular weights which were estimated by means of the relation, found experimentally between the molecular weight and viscosity, are only approximate, for this relation holds true only for narrow fractions.

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