Relaxation Processes in Vulcanized Rubber. III. Relaxation at Large Strains and the Effect of Fillers

1963 ◽  
Vol 36 (3) ◽  
pp. 697-708 ◽  
Author(s):  
A. N. Gent
Keyword(s):  
Stress Relaxation ◽  
Carbon Black ◽  
Natural Rubber ◽  
Progressive Failure ◽  
Large Strains ◽  
Relaxation Processes ◽  
Vulcanized Rubber ◽  
Rubber Vulcanizate ◽  
Finite Extensibility ◽  
Creep And Stress Relaxation

Abstract Some experimental measurements are described of stress relaxation and creep at room temperatures in vulcanizates of natural rubber, butyl, and SBR. In an unfilled natural rubber vulcanizate the rate of stress relaxation is found to rise sharply for extensions of more than about 200%. Reasons are given for attributing this to the growth of a crystalline phase. Similar rates are observed at all extensions for a carbon black filled natural rubber vulcanizate. This is shown to be in satisfactory accord with the Mullins-Tobin model structure for filled vulcanizates, when the whole of the observed relaxation occurs in “softened” regions at rates appropriate to the high local deformations. The failure of rubber-carbon black associations with time does not appear to constitute a major relaxation process. In noncrystallizing unfilled vulcanizates the rate of relaxation is found to decrease somewhat with extension, possibly due to finite-extensibility effects. Preliminary measurements on a filled SBR vulcanizate suggest that a significant contribution to the observed relaxation arises from progressive failure of rubber-filler associations in this case. The relation derived previously between the rates of creep and stress relaxation at equivalent deformations is confirmed in all cases, within experimental error. Its validity in highly-irreversible systems is thus established experimentally.

Longitudinal Cracking in a Carbon Black Filled Natural Rubber Vulcanizate during Chemical Stress Relaxation

1998 ◽  
Vol 71 (2) ◽  
pp. 157-167 ◽  
Author(s):  
G. R. Hamed ◽  
J. Zhao
Keyword(s):  
Stress Relaxation ◽  
Carbon Black ◽  
Natural Rubber ◽  
Longitudinal Crack ◽  
Chemical Stress ◽  
Loading Direction ◽  
Rubber Vulcanizate ◽  
Edge Cracks ◽  
Forced Air ◽  
Oxidative Attack

Abstract Thin specimens of a black-filled, natural rubber vulcanizate have been held in uniaxial tension at 72°C and 200% elongation in a forced air oven. After substantial oxidative attack (inferred from stress relaxation), small edge cracks formed. Initially, these cracks grew perpendicular to the loading direction, but, upon reaching about 0.1 mm in depth, longitudinal crack growth commenced and fracture progressed by a kind of 0°-peel process with “splitting-off” of successive strands of rubber. This phenomenon is attributed to anisotropy in strength caused both by straining and by oxidative attack.

Aging of Natural Rubber Vulcanizates in the Presence of Dithiocarbamates

1959 ◽  
Vol 32 (3) ◽  
pp. 739-747 ◽  
Author(s):  
J. R. Dunn ◽  
J. Scanlan
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Protective Action ◽  
Dicumyl Peroxide ◽  
Vulcanized Rubber ◽  
Aging Properties ◽  
Photochemical Aging ◽  
Natural Rubber Vulcanizates

Abstract The thermal and photochemical aging of extracted dicumyl peroxide-, TMTD (sulfurless)- and santocure-vulcanized rubber, in presence of a number of metal and alkylammonium dithiocarbamates, has been investigated by measurements of stress relaxation. The dithiocarbamates have a considerable protective action upon the degradation of peroxide- and TMTD-vulcanizates, but they accelerate stress decay in santocure-accelerated vulcanizates. The reasons for this behavior are discussed. It is suggested that the excellent aging properties of unextracted TMTD vulcanizates are due to the presence of zinc dimethyldithiocarbamate formed during vulcanization.

Relaxation Processes in the Deformation of Unloaded Rubbers and the Influence of the Degree of Vulcanization

1951 ◽  
Vol 24 (4) ◽  
pp. 810-819
Author(s):  
B. A. Dogadkin ◽  
M. M. Reznikovskii˘
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Elastic Deformation ◽  
Relaxation Processes ◽  
Spatial Network ◽  
Relaxation Properties ◽  
Constant Rate ◽  
Different Temperatures ◽  
Kinetics Of

Abstract 1. It is shown that the process of stress relaxation at different initial elongations as well as the process of deformation at constant rate for unloaded rubbers at different temperatures (20–70° C) can be represented quantitatively by equations suggested in earlier works. Likewise the possibility of expanding the theories proposed for the kinetics of high-elastic deformation of spatial polymers is substantiated. 2. It is shown that the relaxation properties of soft unloaded vulcanizates of natural rubber and many synthetic rubbers do not undergo essential changes during vulcanization. 3. The conjecture is expressed that the invariability of the relaxation properties during vulcanization continues until the bonds of the spatial network are distributed sufficiently widely not to influence the activity or heat movement of the chain segments between them.

Influence of Chemical Structure on the Dynamic Properties of Sulfur-Vulcanized, Carbon Black-Reinforced Natural Rubber

1972 ◽  
Vol 45 (4) ◽  
pp. 1051-1063 ◽  
Author(s):  
G. M. Doyle ◽  
R. E. Humphreys ◽  
R. M. Russell
Keyword(s):  
Service Life ◽  
Carbon Black ◽  
Natural Rubber ◽  
High Temperatures ◽  
Network Structure ◽  
Thermal Aging ◽  
Chemical Structure ◽  
Dynamic Properties ◽  
Rubber Vulcanizate ◽  
Operating Temperatures

Abstract A comparison is made of the composition and properties of the different rubber vulcanizate networks obtained by varying the ratio of sulfur to sulfenamide accelerator and by the thermal aging of vulcanizates containing predominantly polysulfide crosslinks. It is concluded that the changes in network structure which can take place, for example, during the service life of natural rubber tires are not the direct cause of failures of the type associated with rubber fatigue at high temperatures. However, a reduction in the total number of crosslinks can accelerate failure by increasing the amount of heat generated during flexing. More stable networks giving improved resistance to fatigue at high operating temperatures are obtained by the use of higher ratios of accelerator to sulfur than are conventionally employed.

Oxidative Stress Relaxation of Natural Rubber Vulcanized with Di-Tertiary-Butyl Peroxide

1956 ◽  
Vol 29 (3) ◽  
pp. 1043-1046 ◽  
Author(s):  
Svein Ore
Keyword(s):  
Oxidative Stress ◽  
Stress Relaxation ◽  
Carbon Black ◽  
Natural Rubber ◽  
First Grade ◽  
Main Reaction ◽  
Reaction Products ◽  
Hydrogen Atoms ◽  
Tertiary Butyl ◽  
Butyl Peroxide

Abstract It has been shown by Farmer and Moore that natural rubber can be vulcanized with di-tert.-butyl peroxide (DTBP), Presumably the free radicals formed by the unimolecular decomposition of the peroxide abstract some of the more labile (e.g., α-methylenic) hydrogen atoms, leading to direct C—C crosslinks between the rubber molecules, with tert.-butanol and acetone as the main reaction products. This preliminary communication presents some of the results of an investigation of the oxidative stress relaxation of the following types of DTBP vulcanizates. (A) First grade pale crepe, DTBP, and carbon black (MPC) mixed on the mill and vulcanized in a press. The carbon black was added to minimize the deleterious effect of impurities. (B) Purified rubber vulcanized: (1) in aqueous heating media; (2) in the press; (3) in DTBP vapor.

Relaxation Processes in Vulcanized Rubber. II. Secondary Relaxation Due to Network Breakdown

1963 ◽  
Vol 36 (2) ◽  
pp. 389-398 ◽  
Author(s):  
A. N. Gent
Keyword(s):  
Molecular Structure ◽  
Experimental Study ◽  
Natural Rubber ◽  
Relaxation Process ◽  
Relaxation Processes ◽  
Secondary Relaxation ◽  
Oxidative Deterioration ◽  
Vulcanized Rubber ◽  
Oxidation Inhibitors ◽  
Natural Rubber Vulcanizates

Abstract An experimental study is described of a “secondary” relaxation process in stretched vulcanizates, which becomes dominant after long periods at normal temperatures. It is shown to be affected markedly by the temperature, the atmosphere in which the test is conducted, and the presence of oxidation inhibitors. It is therefore attributed to oxidative deterioration of the molecular structure. In some vulcanizates, however, a similar or even greater relaxation is found to occur in vacuo, and this is attributed to the failure of specific crosslink structures. The extent of recovery on releasing the extended testpieces has also been investigated for a number of natural rubber vulcanizates.

Thermal destruction of carbon black network structure in natural rubber vulcanizate

2011 ◽  
Vol 122 (2) ◽  
pp. 1300-1315 ◽  
Author(s):  
Atsushi Kato ◽  
Toshiya Suda ◽  
Yuko Ikeda ◽  
Shinzo Kohjiya
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Network Structure ◽  
Thermal Destruction ◽  
Rubber Vulcanizate

Heats of Vulcanization of Synthetic Rubbers

1944 ◽  
Vol 17 (2) ◽  
pp. 404-411 ◽  
Author(s):  
P. L. Bruce ◽  
R. Lyle ◽  
J. T. Blake
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Chemical Reactions ◽  
Side Reaction ◽  
Heat Evolution ◽  
Butyl Rubber ◽  
Vulcanized Rubber ◽  
Principal Reaction ◽  
Low Sulfur ◽  
Quantity Of Heat

Abstract 1. The heats of vulcanization for natural rubber and Buna-S are nearly equal. The data for both materials indicate two different chemical reactions during vulcanization. At low sulfur percentages, the principal reaction forms soft vulcanized rubber and is accompanied by little or no heat evolution. Above the 2 per cent sulfur region, a second reaction predominates, forming hard rubber and producing a relatively large quantity of heat. 2. The presence of an accelerator (Santocure) in Buna-S has little, if any, effect on heat of vulcanization. 3. The addition of carbon black to Buna-S lowers the heat of vulcanization in the region above 4 per cent sulfur. The calories evolved in a 10 per cent sulfur compound decrease linearly with percentage of carbon black. 4. The heats of vulcanization of Buna-N (Hycar OR-15) indicate the presence of two chemical reactions. Unlike natural rubber and Buna-S, the ebonite reaction does not predominate until the sulfur concentration is raised above 10 per cent. 5. The heat of vulcanization of Butyl rubber with sulfur is equal to the heat evolved with natural rubber containing 0.6 per cent sulfur. If one sulfur atom reacts per double bond, the maximum amount combining would be 0.72 per cent sulfur. During the vulcanization of Butyl rubber with p-quinone dioxime and lead peroxide, a large amount of heat is evolved by a side reaction between the vulcanizing agents. The reaction involving the Butyl rubber produces about 6 calories per gram, a considerably higher value than the 1 calorie produced by sulfur vulcanization. 6. The heat of vulcanization of Neoprene-GN without added agents corresponds to a value for smoked sheet rubber containing 4.5 per cent sulfur. The addition of zinc oxide and magnesia decreases the heat of vulcanization.

Poisson's Ratio for Stretched Vulcanized Natural Rubber

1969 ◽  
Vol 42 (2) ◽  
pp. 547-556 ◽  
Author(s):  
H. Sekiguchi ◽  
M. Kakiuchi ◽  
T. Morimoto ◽  
K. Fujimoto ◽  
N. Yoshimura
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Large Deformation ◽  
Poisson’S Ratio ◽  
Poisson Ratio ◽  
Poisson's Ratio ◽  
Elongation Ratio ◽  
Infinitesimal Deformation ◽  
Carbon Black Content ◽  
Vulcanized Rubber

Abstract Changes in the Poisson's ratio of natural vulcanized rubber due to elongation were investigated experimentally. The following results were obtained: If infinitesimal deformation at any instant during elongation is considered, it appears to be correct to take the Poisson's ratio at such instants as 0.5. If the apparent Poisson ratio when a certain standard mark is taken and a large deformation imparted is considered, and the elongation ratio is made α, the Poisson's ratio decreases from 0.5 in accordance with the equation log10 (1/m)=0.0204α2−0.261α−0.0628. This equation is valid for subsequent elongations, no matter what elongation situation is taken for the standard marks. These two results do not vary with the carbon black content or on repeated stretching.

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