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.

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.

CURE CHARACTERISTICS OF DEVULCANIZED RUBBER:THE ISSUE OF LOW SCORCH

2017 ◽  
Vol 90 (3) ◽  
pp. 536-549 ◽  
Author(s):  
Anu Mary Joseph ◽  
Benny George ◽  
K. N. Madhusoodanan ◽  
Rosamma Alex
Keyword(s):  
Solvent Extraction ◽  
Natural Rubber ◽  
Main Chain ◽  
Process Safety ◽  
Original Sample ◽  
Vulcanized Rubber ◽  
Sulfur Vulcanization ◽  
Natural Rubber Vulcanizates ◽  
Devulcanized Rubber

ABSTRACT We investigate the reasons behind the observed low scorch during the revulcanization of devulcanized rubber. Mechanically devulcanized carbon black filled natural rubber vulcanizates originally cured by conventional vulcanization (CV), semiefficient vulcanization (semi EV), efficient vulcanization (EV), and peroxide systems as well as buffing dust obtained from pre-cured tread with known formulation were used. Revulcanization of these devulcanized samples using sulfur/sulfonamide system led to the following observations; irrespective of the type of sulfur cure system used for the initial vulcanization of the rubber, (i) the devulcanized samples cured without pre-vulcanization induction time and (ii) devulcanized samples prepared from peroxide vulcanized rubber cured with scorch safety. Based on the earlier reports that solvent extraction of devulcanized rubber did not improve the scorch time during revulcanization, the role of zinc bound non-extractable moieties was investigated using devulcanized rubber prepared from activator-free vulcanizates, which disproved the role of such moieties. This confirmed that the scorch reducing moieties should be attached to the rubber main chain, which can be unreacted crosslink precursors and cyclic sulfides left after the initial accelerated sulfur vulcanization of the original sample. The ability of pre-vulcanization inhibitor to induce scorch safety when devulcanized rubber is revulcanized as such, without adding any virgin rubber, proved that mercaptobenzothiazole (MBT) generated from crosslink precursors is the cause of low scorch. Acetone extracted devulcanized rubber samples prepared from tetramethyl thiuramdisulfide (TMTD) cured natural rubber, which does not follow the MBT pathway when revulcanized, cured with scorch safety, which further proved the role of MBT. Based on the previous reports and our results, it is obvious that powdering of rubber vulcanizate and devulcanization processes have no role on the low process safety of these materials, but it is inherent to the initial accelerated sulfur vulcanization chemistry undergone by these materials.

The Destructive Dissolution of Vulcanized Rubbers

1951 ◽  
Vol 24 (3) ◽  
pp. 616-620
Author(s):  
B. Dogadkin ◽  
Z. Tarasova
Keyword(s):  
Molecular Structure ◽  
Natural Rubber ◽  
Partial Pressure ◽  
Experimental Method ◽  
Molecular Oxygen ◽  
Surface Area ◽  
Synthetic Polymers ◽  
Vulcanized Rubber ◽  
Hydrocarbon Medium ◽  
Constant Rate

Abstract In previous work the process of destructive dissolution of vulcanized natural rubber was described, and it was shown that, in the strict absence of oxygen, a vulcanizate cannot be dissolved in a hydrocarbon medium at temperatures up to 140° C. Only in the presence of molecular oxygen does heating bring about dissolution of vulcanized rubber in the solvent, under which conditions the process proceeds along this pattern: union of oxygen with the double bonds → disintegration of the molecular chains where oxygen has combined → dissolution. if the surface area of the vulcanizate remains constant, the process takes place at a constant rate which depends on the temperature and the partial pressure of the oxygen in solution. In the following, experiments are described, the results of which show that vulcanized synthetic polymers also undergo destructive solution. The experimental method was the same as that described previously. The vulcanizates were prepared from recipes adapted to the particular synthetic rubbers. As was expected, the rate of destructive solution depends on the molecular structure of the rubbers (see Figure 1).

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.

The Dynamic Properties of Carbon Black-Loaded Natural Rubber Vulcanizates. Part I

1963 ◽  
Vol 36 (2) ◽  
pp. 432-443 ◽  
Author(s):  
A. R. Payne
Keyword(s):  
Thermal Treatment ◽  
Carbon Black ◽  
Natural Rubber ◽  
Dynamic Modulus ◽  
Dynamic Properties ◽  
Viscosity Change ◽  
Vulcanized Rubber ◽  
Elastic Responses ◽  
Natural Rubber Vulcanizates

Abstract The dynamic properties of a natural vulcanized rubber containing carbon black were studied for dynamic tensions of amplitude varying greatly. It was shown that both the elastic responses and viscosity change with amplitude of oscillation and with concentration and type of carbon black. The effects of thermal treatment on the dynamic modulus were also studied. Beginning with conditions of equilibrium between the hard and soft regions of the vulcanizate for very weak stresses, the values for the formation of hard regions from soft regions were determined by means of the Van't Hoff isochore.

Studies of the Heat Deterioration of Specially Prepared Natural Rubber Vulcanizates

1954 ◽  
Vol 27 (2) ◽  
pp. 459-467
Author(s):  
Donald J. Metz ◽  
Robert B. Mesrobian
Keyword(s):  
Natural Rubber ◽  
Elevated Temperatures ◽  
Experimental Methods ◽  
Oxygen Absorption ◽  
Cross Linking ◽  
Vulcanized Rubber ◽  
Chemical Agents ◽  
Complex Process ◽  
Cross Linkage ◽  
Natural Rubber Vulcanizates

Abstract In 1949, Flory, Rabjohn, and Shaffer presented an article describing the dependence of the elastic properties of vulcanized rubber on the degree of cross-linking. In order to prepare rubber vulcanizates characterized by known degrees of cross-linkage recently developed, disazodicarboxylate vulcanizing reagents were employed. These reagents react quantitatively with rubber, one cross-linkage being introduced for each molecule of the reagent. Whereas the conventional vulcanization of rubber with sulfur and accelerators is a complex process and it does not appear possible at the present time to specify the exact number of cross-linkages present in sulfur vulcanizates, the use of disazodicarboxylate vulcanizing reagents presents an opportunity to investigate the changes that occur in the physical properties of vulcanized rubber, characterized by known degrees of cross-linkage, on exposure to oxygen at elevated temperatures. Furthermore, the effect of heat deterioration of various chemical agents commonly employed in sulfur vulcanization recipes may be investigated in a unique way by incorporating such chemical agents in the free state into natural rubber previously vulcanized by disazodicarboxylate reagents. Recent studies of the deterioration of rubber vulcanizates at elevated temperatures have been reported by several workers. In this article, the experimental methods employed to study heat deterioration involve measurements of oxygen absorption, stress relaxation, and changes of 100 per cent modulus of natural rubber vulcanized to known extents of cross-linkage by decamethylene-dismethyl azodicarboxylate.

Tearing of Vulcanized Rubber

2005 ◽  
Vol 78 (3) ◽  
pp. 548-553 ◽  
Author(s):  
G. R. Hamed
Keyword(s):  
Natural Rubber ◽  
High Resistance ◽  
Short Review ◽  
Critical Value ◽  
Strength Anisotropy ◽  
The Past ◽  
Vulcanized Rubber ◽  
Loading Direction ◽  
Natural Rubber Vulcanizates ◽  
Very High

Abstract This short review summarizes some results of studies of rubber fracture carried out in the author's laboratory over the past several years. Particular attention has been focused on the details of cracking in technically important natural rubber vulcanizates with very high resistance to tearing. Such rubbers develop auxiliary cracks that grow essentially parallel to the loading direction and inhibit the main tear front from advancing. This crack splitting is attributed to oriented structure at the tear front and is predicted to occur when strength anisotropy at a tear tip reaches a critical value.

Relaxation Processes in Vulcanized Rubber. I. Relations between Stress Relaxation, Creep, Recovery, and Hysteresis

1963 ◽  
Vol 36 (2) ◽  
pp. 377-388 ◽  
Author(s):  
A. N. Gent
Keyword(s):  
Experimental Study ◽  
Stress Relaxation ◽  
Relaxation Rate ◽  
Creep Recovery ◽  
Relaxation Processes ◽  
Creep And Recovery ◽  
Vulcanized Rubber ◽  
Deformation Relationship ◽  
Good Agreement

Abstract An experimental study is described of stress relaxation, creep, recovery, and hysteresis in vulcanized rubbers under moderate deformations. The measurements indicate that the rate of stress relaxation is substantially independent of the amount or type of deformation for moderate deformations, and is simply related to the hysteresis. The rates of creep and recovery are found to be in good agreement with values calculated from the form of the load—deformation relationship and the (constant) value of the relaxation rate.

Some Chemical Effects in Fatigue Cracking of Vulcanized Rubbers

1963 ◽  
Vol 36 (2) ◽  
pp. 399-406 ◽  
Author(s):  
A. N. Gent
Keyword(s):  
Fatigue Life ◽  
Natural Rubber ◽  
Crack Growth ◽  
Crack Tip ◽  
Fatigue Cracking ◽  
Substantial Proportion ◽  
Oxidative Deterioration ◽  
Chemical Effects ◽  
Oxidation Inhibitors ◽  
Mechanical Rupture

Abstract An apparatus is described for studying the fatigue of rubber strips under repeated simple extensions in different atmospheres. The fatigue life is shown to be greatly increased in vacuo for vulcanizates of natural rubber and SBR. The effect of oxidation inhibitors and radical acceptors has been examined; they are found to prolong the life in air, but have little effect in vacuo. The results suggest that a substantial proportion of crack growth in air is due to oxidative deterioration of the rubber at the crack tip, probably initiated by mechanical rupture.

Sign in / Sign up

Export Citation Format

Share Document