On the Role of Bound Rubber in Carbon-Black Reinforcement

1989 ◽  
Vol 62 (1) ◽  
pp. 143-156 ◽  
Author(s):  
Gary R. Hamed ◽  
S. Hatfield

Abstract A simple model of filler dispersion has been used to approximate particle spacing and the portion of rubber that is restricted as a result of particulate reinforcement. For N330 black, which has an equivalent radius of 20.2 nm, the critical concentration (in SBR of Mw=344 000) for coherent carbon-gel formation upon solvent immersion is 30 phr. At this level of filler, particle-particle spacing is approximately the diameter of the average SBR random coil. In the second part of the study, compositions in which portions of free rubber had been extracted were compared to conventional mixes at the same black concentrations. Conventional and extracted vulcanizates had similar cure behavior and resistance to deformation, however, extracted samples, with excessive bound rubber had reduced strengths, consistent with the presence of inherent flaws. Apparently, the extracted samples, which are torn apart upon mastication are unable to fully reknit together even after compression molding and vulcanization.

1976 ◽  
Vol 49 (1) ◽  
pp. 126-139
Author(s):  
D. N. Schulz ◽  
L. E. Calihan ◽  
D. P. Tate

Abstract This paper describes the advantageous cross-fertilization of solution-masterbatch technology and powdered-rubber processing. A nonlatex method has been developed for the preparation of free-flowing solution-SBR powders. The factors affecting powder particle size and morphology have been identified. Optimization of the preparative variables has resulted in dry-blendable solution-SBR powders. As a consequence of a low shear history, the solution-SBR powder blends show distinctive rubber-filler, rheological, and physical properties. For example, unvulcanized solution-SBR powder compounds evince higher molecular weights and lower bound-rubber contents than conventional mixes. Yet, the microscopic filler dispersion of these two types of compounds appears similar. Uncured solution-SBR powder blends also exhibit stiffer rheological behavior than conventional mixes. Furthermore, this stiffness tends to persist in the vuleanizates derived from these powdered compounds. Vulcanizate excellence depends primarily upon fineness of the powder particles and absence of free filler. Conditions have been found which permit the direct ribbon extrusion of tire tread, without prior compacting or milling. Conventional single-screw ribbon- tread extruders are sufficient to produce treads of high quality.


2021 ◽  
Vol 22 (5) ◽  
pp. 2348
Author(s):  
Luka Mesarec ◽  
Mitja Drab ◽  
Samo Penič ◽  
Veronika Kralj-Iglič ◽  
Aleš Iglič

Biological membranes are composed of isotropic and anisotropic curved nanodomains. Anisotropic membrane components, such as Bin/Amphiphysin/Rvs (BAR) superfamily protein domains, could trigger/facilitate the growth of membrane tubular protrusions, while isotropic curved nanodomains may induce undulated (necklace-like) membrane protrusions. We review the role of isotropic and anisotropic membrane nanodomains in stability of tubular and undulated membrane structures generated or stabilized by cyto- or membrane-skeleton. We also describe the theory of spontaneous self-assembly of isotropic curved membrane nanodomains and derive the critical concentration above which the spontaneous necklace-like membrane protrusion growth is favorable. We show that the actin cytoskeleton growth inside the vesicle or cell can change its equilibrium shape, induce higher degree of segregation of membrane nanodomains or even alter the average orientation angle of anisotropic nanodomains such as BAR domains. These effects may indicate whether the actin cytoskeleton role is only to stabilize membrane protrusions or to generate them by stretching the vesicle membrane. Furthermore, we demonstrate that by taking into account the in-plane orientational ordering of anisotropic membrane nanodomains, direct interactions between them and the extrinsic (deviatoric) curvature elasticity, it is possible to explain the experimentally observed stability of oblate (discocyte) shapes of red blood cells in a broad interval of cell reduced volume. Finally, we present results of numerical calculations and Monte-Carlo simulations which indicate that the active forces of membrane skeleton and cytoskeleton applied to plasma membrane may considerably influence cell shape and membrane budding.


1962 ◽  
Vol 35 (5) ◽  
pp. 1308-1341 ◽  
Author(s):  
Jean LeBras

Abstract According to the partial conclusions drawn from the results given in each of the three chapters of this review, one can say that the question of reinforcement by resins, if it has not yet attained the aims sought for, has accumulated a great deal of useful information and now seems in a position to make rapid progress. The most significant point that seems to emerge is the necessity for the establishment of strong chemical bonds between the resin particle and the elastomer. This is undoubtedly not sufficient, and other characteristics of the particle must also intervene; but we have said above that one could now imagine a systematic study of the influence of these characteristics, and we need not return to it here. Many questions are still posed and the investigator will have the task of answering them. We consider it important to insist, however, in this conclusion, on some very recent results which it seemed preferable to us to mention here rather than to incorporate them in the text. In fact, they will either bring a confirmation on the influence of chemical bonds or show the possibility of preparing rubbers which should lend themselves remarkably well to this kind of reinforcement. In studying the crosslinking phenomena that involve the well known hardening of dry natural rubber on storage, Sekhar has shown that reactive groups are present as in integral part of the polyisoprene chain when it leaves the tree. These reactive groups have the characteristic property of carbonyl groups or, more specifically, aldehyde groups. They are responsible for crosslinking of the rubber molecules, and reactive monofunctional amines or other carbonyl reagents are capable of inhibiting this crosslinking effectively. From the critical concentration of reagent required to inhibit hardening, one has to postulate the presence of 9 to 29 aldehyde groups per polyisoprene molecule, assuming a molecular weight of 1,000,000). Because of the presence of these aldehyde groups on the chain of the rubber hydrocarbon, one was led logically to suppose that molecules of aminoplast resins formed in the latex might be fixed chemically on the rubber through the aid of these groups. This is what Sekhar and Angove realized with hydrazine-formalde-hyde resins. At a concentration of 5% and less of resin based on rubber, the latex remained fluid with no tendency to gel. Films and foam rubbers prepared from such resin latex showed considerable reinforcement: thus for a 3% resin content, for example, the tensile strength of a latex film passes from 285 kg/cm2 for the control to 362 kg/cm2 (the elongation in both cases being 925%), the 600% modulus from 32 to 75 kg/cm2, the tear resistance from 64 to 100 kg/cm. It is therefore with the greatest interest that one should consider such reinforcement results obtained with such a small proportion of resin; they emphasize the very important part that must be played by a strong chemical bond between the filler particle and the elastomer. It is evident, however, that the small proportion of aldehyde groups present on the rubber molecule limits the possibilities of such a fixation and must not permit to obtain the maximal reinforcing effects. That is why it seems necessary to pay a great attention to the reaction of glyoxal on rubber, which is endowing this latter with aldehyde-α alcohol side groups and gives it the reactivity toward the resins that seems to be desirable. We may therefore think that the years to come will bring into this field new and useful results, with a view toward the improvement of the characteristics of vulcanized rubber and ever-widening development of its application.


2017 ◽  
Vol 90 (1) ◽  
pp. 146-158 ◽  
Author(s):  
Chomsri Siriwong ◽  
Pongdhorn Sae-Oui ◽  
Chakrit Sirisinha

ABSTRACT Influence of the surface modifying agents (SMAs) polyethylene glycol (PEG), 3-aminopropyl triethoxysilane (APTES), and bis-(3-triethoxysilylpropyl)tetrasulfide (TESPT) on properties of silica-filled chloroprene rubber (CR) was investigated. Results reveal that the presence of SMAs greatly improves mechanical and dynamic properties of the silica-filled CR because of the reduced filler–filler interaction and improved rubber–filler interaction as evidenced by the Payne effect and bound rubber content results, respectively. When compared at the same SMA dosage, TESPT gives the best overall vulcanizate properties. This effect is attributed to high coupling efficiency of TESPT and its ability to donate sulfur atoms during vulcanization, leading to the improved filler dispersion, rubber–filler interaction, and cross-link density. APTES gives high coupling efficiency, but because of the lack of sulfur atoms, its performance is slightly inferior to that of TESPT. In contrast, PEG can only reduce filler–filler interaction, with no significant impact on rubber–filler interaction and cross-link density; therefore, PEG provides lower property improvement.


A detailed analytical investigation has been made of the reactions occurring during the early stages of the oxidation of ethyl alcohol (ethanol) in the temperature region 270 to 370° C. During an induction period the alcohol is converted quantitatively into acetaldehyde until a critical concentration of this intermediate has accumulated. The pressure then begins to rise autocatalytically, and methanol, formaldehyde and carbon monoxide become detectable; evidence is presented to show that these compounds arise from the further oxidation of acetaldehyde. The amount of ethanol consumed and of acetaldehyde formed at the end of the induction period are largely independent of the initial reactant pressures, except at low pressures of the alcohol. A study of the effect of added acetaldehyde shows that the minimum quantity required to eliminate the induction period is the same as that normally present at the end of the induction period. Hydrogen peroxide is the only product, other than acetaldehyde, detected during the induction period. Under optimum surface conditions the yields of hydrogen peroxide are equivalent to those of the aldehyde. A moderate increase in surface shortens the induction period, but a further increase retards reaction. In vessels of large surface: volume ratio, the yields of hydrogen peroxide are much reduced, while in a potassium chloride-coated vessel peroxides are invariably absent; in each case, the other products are unchanged. The mechanisms of the chain-initiating and propagating reactions are considered and the role of the surface in initiating and terminating chains is discussed.


1994 ◽  
Vol 67 (5) ◽  
pp. 834-844 ◽  
Author(s):  
Yu-Chun Ou ◽  
Zhong-Zhen Yu ◽  
A. Vidal ◽  
J. B. Donnet

Abstract Rubber reinforcement of silicas with different surface alkylation have been evaluated by studies of NH3-modified swelling, swelling volume fraction, stress-strain tests, and scanning electron microscopy. Effects of silica alkylation on filler dispersion has been explained on the basis of surface energy and acid-base interactions. Bound rubber reductions have been explained according to acid-base interactions and/or physical entanglements. Hysteresis losses have been interpreted based on the reductions of polymer-filler and filler-filler interactions. The results show that the extent of reinforcement in NR and SBR vulcanizates is reduced when the silicas are alkylated, especially in the case of the hexadecyl group. However, in NBR vulcanizates the alkylation seems to have less influence on the reinforcement characteristics of the silica.


Fractals ◽  
1993 ◽  
Vol 01 (04) ◽  
pp. 818-826 ◽  
Author(s):  
L.A.N. AMARAL ◽  
A.-L. BARABÁSI ◽  
S.V. BULDYREV ◽  
S. HAVLIN ◽  
H.E. STANLEY

We study the effect on interface roughening of a gradient ∇p in the density of pinning sites p. We identify a new correlation length, ξ, which is a function of ∇p: ξ~(∇p)−γ/α, where α=ν⊥/ν|| is the roughness exponent, and γ=ν⊥/(1+ν⊥). The exponents ν⊥ and ν|| characterize the transverse and longitudinal correlation lengths. To investigate the effect of ∇p on the scaling properties of the interface in (1+1) and (2+1) dimensions, we calculate the critical concentration, pc, and the exponents γ and α from which ν⊥ and ν|| can be determined. Our results are in qualitative agreement with some of the features of imbibition experiments.


Foods ◽  
2021 ◽  
Vol 10 (8) ◽  
pp. 1832
Author(s):  
Kali Kotsiou ◽  
Dimitrios-Diogenis Sacharidis ◽  
Anthia Matsakidou ◽  
Costas G. Biliaderis ◽  
Athina Lazaridou

Roasted yellow split pea (YSP) flours were used to substitute wheat flour, at 10–20% (flour basis) in wheat bread formulations. Rheometry showed that roasted YSP flour addition increased elasticity and resistance to deformation and flow of the composite doughs, particularly at 20% substitution; instead, at 10% addition (either raw or roasted YSP flour), there were no effects on dough rheology and bread textural properties. Breads fortified with roasted YSP flour at levels >10% exhibited lower loaf-specific volume and harder crumb compared to control (bread without YSP flour). Moreover, only breads with 20% roasted YSP flour displayed a significantly higher staling extent and rate, compared to control, as assessed by large deformation mechanical testing and calorimetry (starch retrogradation) of crumb preparations. This formulation also showed a large increase in β-sheets and β-turns at the expense of α-helix and random coil conformations in protein secondary structure as assessed by FTIR spectroscopy. Roasting of YSP effectively masked the “beany” and “grass-like” off-flavors of raw YSP flour at 10% substitution. Overall, roasted YSP flour at the 10% level was successfully incorporated into wheat bread formulations without adversely affecting dough rheology, bread texture, and shelf-life, resulting in final products with a pleasant flavor profile.


1961 ◽  
Vol 34 (2) ◽  
pp. 697-704 ◽  
Author(s):  
W. A. Ladd ◽  
M. W. Ladd

Abstract Until recently, the main role of the electron microscope in rubber research was the determination of particle size and shape of reinforcing pigments and fillers. The electron microscope proved its value in its first industrial problem in 1940 when it showed the particle size of Micronex to be 28 mµ. In 1942 it established the correlation between particle size of carbon and rubber properties. The next contribution was the establishment of reticulate chain structure, in 1945, using stereo-photomicrography. The electron microscope led the way to the carbon gel concept when carbons producing different road wear results were shown to have equal particle size and structure. Micrographs of carbon gel were published in 1951. Studies of rubber latexes, various pigments and fillers were also applications of the electron microscope in which the determination of particle size and shape was involved. Today, improvements in resolution, development of new techniques and accessory equipment have greatly expanded the application of the electron microscope. This paper is concerned mainly with describing these new developments ; first, as a help to electron microscopists in the rubber field; second, to illustrate what can be done with the electron microscope, so that research and production men can recognize possible applications of this discerning tool to the solution of their problems. Electron microscopes have come a long way in the short 20-year period. Figure 1 shows the microscope used in our laboratories. This instrument is currently resolving detail as fine as 10 A or 1 mµ in routine daily operation. Its design makes possible the development of special holders and thereby increases its value as a research tool. Another piece of equipment that is as important in microscope research as the electron microscope itself is the evaporating unit shown in Figure 2. This is used for shadowing and forming replication films under vacuum, thus making possible studies of rubber surfaces and surfaces of pigments and other rubber ingredients. In shadowing, detail is made visible by coating the specimen with metal evaporated at an angle from the tungsten basket at A. Carbon can be evaporated by the arc at B, forming a replicating film or mold of the specimen. This will be discussed under “preparation”. Today, the proper preparation of specimens is the most important step in successful microscopy. The various preparations used are as follows.


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