Oxidation of GR-S and Other Elastomers

1947 ◽  
Vol 20 (3) ◽  
pp. 747-759
Author(s):  
John O. Cole ◽  
James E. Field
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Physical Properties ◽  
Experimental Methods ◽  
Chain Scission ◽  
Cross Linking ◽  
Antioxidant Action ◽  
Mechanism Of Oxidation ◽  
Natural Rubber Vulcanizates

Abstract The effect of heat aging on the physical properties of an elastomer is generally considered the result of oxidation, which produces both chain scission and cross-linking in the polymer. Early in the development of GR-S, a marked difference in the aging of GR-S and natural rubber vulcanizates was observed. From the effect of aging on hardness, tensile strength, modulus, and elongation it appeared that cross-linking occurred more rapidly than chain scission with GR-S, but the reverse was true with natural rubber. The work reported here was undertaken to provide a better understanding of the differences in aging of GR-S and natural rubber and to introduce new experimental methods for studying the mechanism of oxidation and antioxidant action in elastomers.

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.

Dependence of Tensile Strength of Vulcanized Rubber on the Degree of Cross-Linking

1950 ◽  
Vol 23 (1) ◽  
pp. 27-43
Author(s):  
Paul J. Flory ◽  
Norman Rabjohn ◽  
Marcia C. Shaffer
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Chain Scission ◽  
General Character ◽  
Cross Linking ◽  
Vulcanized Rubber ◽  
Relationship Of ◽  
The Relationship ◽  
Considerable Detail ◽  
Proportionality Relationship

Abstract The suitability of disazodicarboxylates as quantitative cross-linking agents for the preparation of rubber vulcanizates of known degrees of cross-linking has been emphasized previously. In a recent paper we have presented the results of an investigation on the dependence of the equilibrium force of retraction on the elongation and degree of cross-linking of rubber and GR-S vulcanized with these compounds. The present paper reports an extension of these investigations of the relationship of physical properties of rubberlike materials to their network structure. Specifically, the tensile strength of azo vulcanized natural rubber has been explored as a function of the degree of cross-linking and of the extent of modification of the chain units. The tensile strengths of natural rubber specimens vulcanized to various extents using sulfur alone or sulfur in conjunction with various accelerators have been investigated in considerable detail recently by Gee, who has emphasized the critical dependence of the tensile strength on the degree of cross-linking. Values for the latter quantity, however, were deduced indirectly from the equilibrium force of retraction using the simple proportionality relationship between force of retraction and degree of cross-linking afforded by the theory of rubber elasticity. This relationship is known to be only approximately valid. Furthermore, the effects on the force of retraction of chain scission, which doubtless accompanied some of the vulcanizations to a considerable degree, were disregarded. For these reasons, Gee's values for the degrees of cross-linking occurring in his vulcanizates are only approximate estimates, and in a few cases they may be seriously in error. Nevertheless, the general character of the relationship between tensile strength and degree of cross-linking which he obtained is confirmed by our results on rubber samples quantitatively cross-linked with measured proportions of decamethylene-dismethyl azodicarboxylate.

Oxidative Aging of Natural Rubber Vulcanizates. Part III. Crosslink Scission in Monosulfidic Networks

1969 ◽  
Vol 42 (3) ◽  
pp. 924-935 ◽  
Author(s):  
T. Colclough ◽  
J. I. Cunneen ◽  
G. M. C. Hrggins
Keyword(s):  
Natural Rubber ◽  
Physical Properties ◽  
Chemical Structure ◽  
Spectroscopic Methods ◽  
Chemical Probes ◽  
Conjugated Diene ◽  
Strain Measurements ◽  
Oxidative Aging ◽  
Tert Butyl Hydroperoxide ◽  
Natural Rubber Vulcanizates

Abstract A natural rubber vulcanizate containing almost entirely monosulfidic crosslinks was oxidized in oxygen and with tert-butyl hydroperoxide. The changes in physical properties due to oxidation were followed by stress—strain measurements, and the changes in chemical structure were investigated with chemical probes, and by spectroscopic methods. The results show that when the oxidized vulcanizates are heated at 75° C, the monosulfidic crosslinks are broken, that crosslinks containing two sulfur atoms are formed, and that conjugated diene and triene structures are introduced into the main polyisoprene chains.

Influences of Particle Sizes on Properties of Natural Rubber/Waste Ground Rubber Powders Blends

2013 ◽  
Vol 773 ◽  
pp. 668-672
Author(s):  
Jun Liang Liu ◽  
Ping Liu ◽  
Xiao Qiang Tang ◽  
Dong Zeng ◽  
Xing Kai Zhang ◽  
...  
Keyword(s):  
Mechanical Properties ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Chemical Activation ◽  
Cross Linking ◽  
Particle Sizes ◽  
Elongation At Break ◽  
Tear Strength ◽  
Rubber Waste ◽  
Ground Rubber

In this paper, the blends of natural rubber with waste ground rubber powders have been prepared by mechano-chemical activation method. The influences of particle sizes on both processing performances and mechanical properties have been investigated. The results indicated that: the blends with waste ground rubber powders of smaller particle sizes approached to higher surface tensile and easily mechano-chemical activation, which led to the formation of complete homogenous re-vulcanization cross-linking structure and resulted in the improvements of the whole performances of the final products. The tensile strength, the elongation at break and tear strength approached to the highest value of 20.7MPa, 530% and 33.0 kN/m as the 100mesh waste ground rubber powders were used as the starting materials.

Effect of Oxygen Concentration on Aging of Rubber Vulcanizates. II. Effect of Partial Pressure of Oxygen on Changes in Physical Properties Accompanying Oxidation

1953 ◽  
Vol 26 (3) ◽  
pp. 643-654 ◽  
Author(s):  
J. Reid Shelton ◽  
William L. Cox
Keyword(s):  
Physical Properties ◽  
Partial Pressure ◽  
Oxygen Concentration ◽  
Chain Scission ◽  
Cross Linking ◽  
Partial Pressure Of Oxygen ◽  
Aging Behavior ◽  
Storage Temperatures ◽  
Normal Storage ◽  
Oxygen Concentrations

Abstract The over-all rate of deterioration of physical properties increases with the oxygen concentration, as would be expected from the increased rate of oxygen absorption: The nature of the deterioration resulting from a given amount of oxygen absorbed is influenced also by changes in the partial pressure of oxygen in the aging atmosphere. It appears that chain scission is favored at higher oxygen concentrations, while cross-linking becomes of greater relative importance at lower oxygen concentrations. These data suggest that R⋅ radicals are more effective than RO2⋅ radicals in reacting with double bonds to form crosslinks. Heat aging in the absence of oxygen, as observed by heating a vulcanizate in lamp-grade nitrogen, results in considerable stiffening, particularly in the case of a GR-S black stock. This effect is observed primarily in the first few hours of heating, and may account for some of the erratic behavior observed in the early stages of aging when changes in physical properties are compared on the basis of amount of oxygen absorbed. Higher oxygen concentration brings about a more rapid oxidation, and also results in a higher proportion of chain scission compared to cross-linking for a given amount of oxygen absorbed. As tensile decay is the most evident sign of deterioration of Hevea stocks, it follows that the aging behavior of natural rubber in air at normal storage temperatures will be better than that predicted by high temperature testing in oxygen. In the case of GR-S stocks, on the other hand, oxidative hardening is the most serious result of aging, and consequently, the aging behavior of GR-S stocks in air at normal storage temperatures is poorer than would be expected on the basis of comparative tests in oxygen at higher temperatures.

Correlation of Blooming and Tensile Properties in Surfactant-Loaded Natural Rubber Vulcanizates

2016 ◽  
Vol 705 ◽  
pp. 35-39 ◽  
Author(s):  
Bryan B. Pajarito ◽  
Jimyl Arabit
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Tensile Properties ◽  
Tensile Strain ◽  
Tensile Modulus ◽  
Adhesive Tape ◽  
Taguchi Design Of Experiment ◽  
Convection Oven ◽  
Maximum Tensile Strain ◽  
Natural Rubber Vulcanizates

Tensile properties of surfactant-loaded natural rubber (NR) vulcanizates are investigated in correlation with blooming. Rubber sheets are compounded using an L12 orthogonal array of Taguchi design of experiment, where ingredients are treated as factors varied at low and high loadings. Blooming experiments are carried out by placing NR sheets in a natural convection oven set at 50 °C for 20 days. The amount of bloom on the surface is removed using adhesive tape and is monitored with time. Tensile properties of rubber dogbone samples are also measured with time. Results show that 5 out of 12 formulations show blooming to be significantly related to tensile modulus (0.005 < p < 0.039). It is observed that the tensile modulus increases with blooming (0.898 < r < 0.973). Three formulations indicate significant correlation of blooming with tensile strength (0.022 < p < 0.047). As observed, tensile strength decreases with blooming (-0.884 < r < -0.930). Five formulations signify blooming to have significant correlation with maximum tensile strain (0.000 < p < 0.011), which decreases with blooming (-0.957 < r < -0.995). Two formulations imply significant negative (-0.960 < r < -0.963) correlation between blooming and tensile set (p= 0.009).

Aromatic and Epoxidised Oil Curing and Rebound Resilience Characteristic and their Humidity Effect of Hardness on NR Vulcanizates

2013 ◽  
Vol 812 ◽  
pp. 138-144 ◽  
Author(s):  
Mohamed Rahmah ◽  
Wan Zain Norazira ◽  
Shafie Nur Ashyikin ◽  
Mohd Nurazzi Norizan
Keyword(s):  
Natural Rubber ◽  
Physical Properties ◽  
Room Temperature ◽  
Rubber Compound ◽  
Humidity Effect ◽  
Humidity Level ◽  
Cure Time ◽  
Humidity Chamber ◽  
Overall Performance ◽  
Natural Rubber Vulcanizates

Recently, aromatic oil (AO) is one of the substances that is typically used as a processing aid especially for high filler loadings in formulating rubber compound. Aromatic oil has disadvantages in that, it is hazardous to environment, toxic and has been labeled as carcinogenic. In this research, an epoxidised oil (EO) and aromatic oil were used to investigate the effect incorporation of oil onto the SBR/NR natural rubber vulcanizates (NR). From the result obtained, EO showed shorter cure time and scorch time as the oil loading were increased up to 20 pphr of EO. Physical properties such as hardness and rebound resilience of NR/EO vulcanisate were also investigated upon exposure to different humidity level in humidity chamber. At room temperature, the hardness of EO loading onto the SBR/NR vulcanisate is lower than AO loadings. Hardness was slightly decreased with increasing rate of humidity. There is great difference in hardness and rebound resilience values between AO and EO. Both hardness and rebound resilience were not affected by humidity. This implies the existence of good filler interaction with EO and rubber which do not impart changes in the hardness and resilience properties of rubber compound. Epoxidised oil has great promising potential to replace the carcinogenic aromatic oil as it has good overall performance and renewable in nature .

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