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.

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.

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.

Cut Growth in Vulcanizates of Natural Rubber, cis-Polybutadiene, and a 50/50 Blend: Part II. Cracking Patterns in the Strained State

1999 ◽  
Vol 72 (5) ◽  
pp. 895-909 ◽  
Author(s):  
G. R. Hamed ◽  
H. J. Kim
Keyword(s):  
Natural Rubber ◽  
Strain Energy ◽  
Crack Opening ◽  
Longitudinal Crack ◽  
Butadiene Rubber ◽  
Loading Direction ◽  
Steady Decrease ◽  
Crack Tips ◽  
Catastrophic Fracture ◽  
Simple Growth

Abstract The tensile strengths, σb, and apparent fracture energies, G, of edge-cut strip specimens (28 mm wide) of carbon black-filled vulcanizates of natural rubber (NR), cis-butadiene rubber (cis-BR), and a 50/50 blend have been determined. The BR vulcanizate exhibited a rather steady decrease in σb with increasing cut size, c, and fractured by simple growth of the original cut tip. NR and the NR/BR blend exhibited much higher strengths as well as a drop in σb at a critical cut size, ccr≈2.2 mm. High strengths are attributed, at least in part, to substantial longitudinal cracking prior to catastrophic fracture, especially when c<ccr. When strengths of edge-cut specimens were normalized by the regular (uncut) tensile strength, similar values were found for all three vulcanizates, when c>ccr. Below ccr, normalized strengths of the NR and NR/BR were comparable and exceeded those of BR. For all three vulcanizates, calculated fracture energies depended on cut size. Photographs of a deformed NR/BR specimen, which had developed the auxiliary cracking, revealed that longitudinal crack tips appear as "corners" propagating along the loading direction. As a longitudinal crack progresses, strain energy is released by the retraction of (sheared) material into the unstressed zone at the extremity of crack opening.

Effect of Crosslink Density on Cut Growth in Black-Filled Natural Rubber Vulcanizates

2002 ◽  
Vol 75 (5) ◽  
pp. 935-942 ◽  
Author(s):  
G. R. Hamed ◽  
N. Rattanasom
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Crack Growth ◽  
Crosslink Density ◽  
Longitudinal Crack ◽  
Test Pieces ◽  
Filled Rubber ◽  
Longitudinal Cracks ◽  
Natural Rubber Vulcanizates ◽  
High Crosslink Density

Abstract Tensile strengths, σb, of gum and N115-filled natural rubber test pieces, with and without edge pre-cuts, have been determined. At low crosslink density, the regular (uncut) σb of filled and gum vulcanizates is similar. However, at high crosslink density, the gum NR becomes brittle, while the corresponding filled rubber remains strong and resistant to cut growth. It is proposed that the tightly linked gum does not strain-crystallize appreciably during stretching, but that its filled counterpart does. Carbon black appears capable of inducing crystallization in a network that alone remains amorphous during extension. Filled vulcanizates of various crosslink densities have similar normal tensile strengths ( ≈ 30 MPa), but strengths differ, sometimes more than twofold, if a pre-cut is present. Lightly crosslinked specimens containing a small cut have strengths that depend very weakly on cut size, c. Furthermore, these develop long longitudinal cracks from which catastrophic rupture initiates. With larger cuts, strength decreases more rapidly with increasing c, there is less longitudinal crack growth, and rupture initiates near the original cut tip. In contrast, the strength of a highly crosslinked vulcanizate is sensitive to small cuts and test pieces exhibit minimal longitudinal cracking before failure.

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

The Determination of Network Chain Density and the Chemical Stress Relaxation of Crosslinked Polymers

1973 ◽  
Vol 46 (2) ◽  
pp. 477-482
Author(s):  
Saburo Tamura ◽  
Kenkichi Murakami
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Main Chain ◽  
Chemical Stress ◽  
Dicumyl Peroxide ◽  
Constant Independent ◽  
Crosslinked Polymers ◽  
Network Chain ◽  
The Difference ◽  
Entanglement Network

Abstract Both initial network chain densities nM(0) and nS(0) of dicumyl peroxide- cured natural rubbers were determined from the tensile stress and swelling method, respectively. The difference between nM(0) and nS(0) was usually constant, independent of the magnitude of network chain density. That is, it was found that the number of entanglement network chains in the crosslinked natural rubber was usually constant, independent of network chain density. The entanglement network chain density nII(0) was 0.7×10−4 mole/cc. This led to the supposition that the molecular weight between entanglement points Me would be about 9000. Although this value is far from exact, it does not differ too greatly from the value found for noncrosslinked natural rubber. Next, in order to calculate the number of main-chain scissions of crosslinked polymers from their chemical stress relaxation, we proposed our modification of Tobolsky's equation. Using our equation, it was found that the scission of dicumyl peroxide-cured natural rubber occurred in the main chain only. Furthermore, this value agreed with the one obtained from the oxidation of toluene solution of noncrosslinked rubber under the same conditions.

Effect of modified carbon black on the properties of natural rubber vulcanizate

1997 ◽  
Vol 66 (4) ◽  
pp. 683-693 ◽  
Author(s):  
A. K. Ghosh ◽  
S. Maiti ◽  
B. Adhikari ◽  
G. S. Ray ◽  
S. K. Mustafi
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Rubber Vulcanizate
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