Oxidation of Vulcanized Rubber. Effect of Temperature, State of Cure, and Thickness

1940 ◽  
Vol 13 (2) ◽  
pp. 375-388
Author(s):  
A. R. Kemp ◽  
J. H. Ingmanson ◽  
G. S. Mueller

Abstract 1. A previous investigation of the rate of oxidation of rubber over the temperature range of 60° to 80° C. has been extended to 90°, 100° and 110° C. 2. The rate of oxidation over the range which accounts for substantial deterioration of tensile strength appears to be a straight-line function of the time of aging from 60° up to an including 90° C. The rate of oxidation at 100° C. appears to diverge somewhat from a straight-line function of time decreasing as oxidation proceeds. 3. The rate of oxidation increases with increased temperature. Over the range of 60° to 110° C, the rate is doubled for each 7.5° increase in temperature, corresponding to a temperature coefficient of oxidation of 2.5. 4. Tensile strength decreases as a straight-line function of the time of aging and of the quantity of oxygen absorbed. 5. The quantity of absorbed oxygen, determined by weight gain corresponding to a 50 per cent decrease in tensile strength, varies with the temperature of oxidation. At 60° C. the oxygen requirement for 50 per cent deterioration is about 1.30 per cent, and at 110° C. about 0.65 per cent on the rubber hydrocarbon content. 6. Tensile strength increases, probably due to a mild curing effect, when specimens of the compound are heated in an atmosphere where the oxygen is replaced with carbon dioxide for the same periods of time at 80° and 110° C, were required to cause a 50 per cent deterioration in tensile strength in an oxygen atmosphere. 7. With increased time of vulcanization, the rate of oxidation increases. Oxidation appears to be autocatalytic in the case of overvulcanized rubber. 8. As time of vulcanization increases, there is a decrease in the quantity of oxygen required to cause a given decrease in tensile strength. 9. Thickness variations of 0.43 to 1.90 mm. in test-specimens of a compound containing an antioxidant do not affect quantity of oxygen absorbed or degree of tensile strength deterioration when aging is conducted at 80° C. and 3.5 kg. per sq. cm. oxygen pressure. 10. When tetramethylthiuram disulfide is used for vulcanization in place of sulfur, there appears to be no change in the mechanism of oxidation, but the rate of oxidation is reduced.

1942 ◽  
Vol 15 (1) ◽  
pp. 83-90
Author(s):  
Robert H. Johnson

Abstract An apparatus can be set up in laboratory glassware that will confirm the results obtained by Dufraisse in his manometric test for oxygen absorption. It has been shown that different rubber compounds possess different tendencies to absorb oxygen. It has also been shown that the differences in the rate at which rubber compounds absorb oxygen are comparable with those differences found in the rate of tensile-strength deterioration of the same compounds aged in the oxygen bomb. This modified Dufraisse manometric method is convenient, efficient, accurate and, above all, a speedy method for measuring the relative aging behavior of vulcanized rubber compounds. Within two hours it is possible to have the results by this method, whereas it is necessary to wait from four days to two weeks for such information by the oxygen bomb method.


1939 ◽  
Vol 31 (12) ◽  
pp. 1472-1478 ◽  
Author(s):  
A. R. Kemp ◽  
J. H. Ingmanson ◽  
G. S. Mueller

2012 ◽  
Vol 85 (1) ◽  
pp. 120-131 ◽  
Author(s):  
Md. Najib Alam ◽  
Swapan Kumar Mandal ◽  
Subhas Chandra Debnath

Abstract Several zinc dithiocarbamates (ZDCs) as accelerator derived from safe amine has been exclusively studied in the presence of thiazole-based accelerators to introduce safe dithiocarbamate in the vulcanization of natural rubber. Comparison has been made between conventional unsafe zinc dimethyldithiocarbamate (ZDMC) with safe novel ZDC combined with thizole-based accelerators in the light of mechanical properties. The study reveals that thiuram disulfide and 2-mercaptobenzothiazole (MBT) are always formed from the reaction either between ZDC and dibenzothiazyledisulfide (MBTS) or between ZDC and N-cyclohexyl-2-benzothiazole sulfenamide (CBS). It has been conclusively proved that MBT generated from MBTS or CBS reacts with ZDC and produces tetramethylthiuram disulfide. The observed synergistic activity has been discussed based on the cure and physical data and explained through the results based on high-performance liquid chromatography and a reaction mechanism. Synergistic activity is observed in all binary systems studied. The highest tensile strength is observed in the zinc (N-benzyl piperazino) dithiocarbamate-accelerated system at 3:6 mM ratios. In respect of tensile strength and modulus value, unsafe ZDMC can be successfully replaced by safe ZDCs in combination with thiazole group containing accelerator.


1985 ◽  
Vol 132 (2) ◽  
pp. 181-191 ◽  
Author(s):  
G.A.C. Boyd ◽  
J. Harding ◽  
P.A. Bleasdale ◽  
K. Dunn ◽  
G.I. Turner

2005 ◽  
Vol 21 (3) ◽  
pp. 183-199
Author(s):  
G.K. Jana ◽  
C.K. Das

De-vulcanization of vulcanized elastomers represents a great challenge because of their three-dimensional network structure. Sulfur-cured gum natural rubbers containing three different sulfur/accelerator ratios were de-vulcanized by thio-acids. The process was carried out at 90 °C for 10 minutes in an open two-roll cracker-cum-mixing mill. Two concentrations of de-vulcanizing agent were tried in order to study the cleavage of the sulfidic bonds. The mechanical properties of the re-vulcanized rubber (like tensile strength, modulus, tear strength and elongation at break) were improved with increasing concentrations of de-vulcanizing agent, because the crosslink density increased. A decrease in scorch time and in optimum cure time and an increase in the state of cure were observed when vulcanized rubber was treated with high amounts of de-vulcanizing agent. The temperature of onset of degradation was also increased with increasing concentration of thio-acid. DMA analysis revealed that the storage modulus increased on re-vulcanization. From IR spectroscopy it was observed that oxidation of the main polymeric chains did not occur at the time of high temperature milling. Over 80% retention of the original mechanical properties (like tensile strength, modulus, tear strength and elongation at break) of the vulcanized natural rubber was achieved by this mechanochemical process.


2005 ◽  
Vol 21 (4) ◽  
pp. 319-331 ◽  
Author(s):  
G.K. Jana ◽  
C.K. Das

The de-vulcanization of rubber waste poses a challenging economical, environmental and social problem. We propose a new de-vulcanization process to re-use the rubber waste. It is a mechano-chemical process (MCP), where the waste is de-vulcanized by a combination of mechanical shearing, heat (110 °C) and the use of a de-vulcanizing agent (diallyl disulfide). A new look at the de-vulcanization mechanism and the influence of the de-vulcanizing agent on the mechanical properties of the ultimate re-vulcanized rubber is also presented. One of the most interesting observations is that the retention of tensile strength of the re-vulcanized rubber with respect to the original tyre was 34.9% when de-vulcanized in the absence of diallyl disulfide and 72.4% in its presence. The formation of extra crosslinks in those re-vulcanized rubbers containing disulfide was confirmed from crosslink density data and from TGA results. DMA analysis revealed that the storage modulus also increased for re-vulcanized rubber containing the disulfide.


2020 ◽  
Vol 990 ◽  
pp. 262-266
Author(s):  
Prathumrat Nu-Yang ◽  
Atiwat Wiriya-Amornchai ◽  
Jaehoon Yoon ◽  
Chainat Saechau ◽  
Poom Rattanamusik

Thermoplastic vulcanizates or TPVs is a type of materials exhibiting excellent properties between thermoplastic and elastomer by combining the characteristics of vulcanized rubber with the processing properties of thermoplastics. This research aims to study the effect of thermal aging on the morphology and mechanical properties of thermoplastic vulcanizates (TPVs) based on a mixture of natural rubber (NR) and polystyrene (PS). TPVs samples were prepared using the internal mixer at a mass ratio of NR/PS 70/30, 50/50, 30/70 and 0/100. Tensile properties and impact strength showed that when the amount of NR increased tends of impact strength and elongation at break increased but tends of tensile strength decreased. On the other hand, tends of tensile strength for thermal aging at 70°C for 3 days increased when the amount of PS increase. The blending ratio of NR / PS at 70/30 is the best. It gave a worthy increase from 19.94 MPa to be 25.56 MPa (28.18%).


1953 ◽  
Vol 26 (1) ◽  
pp. 152-155
Author(s):  
Ira Williams

Abstract The use of oils and liquid softeners to assist in the mastication and processing of rubber or to produce softer vulcanized stocks has been standard practice since the early commercial use of rubber. More recently certain synthetic rubbers, polymerized under special conditions, have been treated with rather large amounts of mineral oils, with a resulting decrease in the cost of the rubber and apparently with no unfavorable effect on the rubber in most instances. A number of investigators have reported the effect of swelling agents on the properties of vulcanized rubber. Busse discusses the effect of solvents in a general way. Tiltman and Porritt conclude that the decrease in modulus caused by swelling in benzene is caused by a “loosening of cohesive forces.” Tire treads of natural rubber containing such softeners as pine tar and mineral rubber decrease in wear resistance in proportion to the softener content. Well vulcanized rubber of high modulus is most resistant to swelling in oils. Naunton, Jones, and Smith find that unaccelerated stocks lose the most tensile strength after being swollen, that milling of the raw rubber increases swelling, and that the presence of softeners in the rubber during vulcanization reduces the oil resistance. A limited amount of swelling has been reported to have little effect on the tensile strength of vulcanized natural rubber. Bourbon points out that separating the rubber molecules with solvent decreases the rate of vulcanization.


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