The Effect of Ozone on Neoprene Vulcanizates and the Influence of Some Protective Agents and Fillers

1956 ◽  
Vol 29 (1) ◽  
pp. 166-175 ◽  
Author(s):  
A. Hartmann ◽  
F. Glander

Abstract In this investigation an attempt was made to show a certain analogy between the nature of the phenomenon of the crystallization of an undercooled melt and ozone crack formation in stretched natural or synthetic rubber, in order in this way perhaps to have some starting point for a more detailed experimental investigation of these interesting problems. At the same time the observed qualitative differences in the effects of ozone on natural rubber vulcanizates and on Neoprene vulcanizates might be explained. In the experimental part it is first shown, with the help of a simplified experimental method, that the rate of crack growth can be considerably reduced by the presence of protective agents. In addition, a great change in the temperature dependence of crack growth is observed under certain conditions. It can not yet be decided whether or not the rate of nuclei formation is similarly influenced. Furthermore, vulcanizates containing different fillers and different Neoprene contents have been examined.

1951 ◽  
Vol 24 (4) ◽  
pp. 999-1016
Author(s):  
George W. Blum ◽  
J. Reid Shelton ◽  
Hugh Winn

Abstract Safe limits of sample thickness for rubber oxidation and aging studies, such that the chemical reaction rather than the rate of diffusion will be rate-controlling have been investigated for natural-rubber vulcanizates and for four synthetic-rubber types. For studies involving the entire range of oxidation, including the autocatalytic stage of rapid oxygen absorption, the conventional 0.075-inch thickness is frequently not satisfactory for accelerated aging and oxidation studies if it is desired to avoid limitation by diffusion. Only in the GR-S black stock was this thickness found to be satisfactory up to a temperature of 100° C. The other stocks, including natural rubber, Butaprene-NXM, and Neoprene black and gum stocks all require thinner samples to ensure that the observed rate of oxygen absorption is free of limitation by diffusion. A method of calculating the probable limiting value of sample thickness, above which the rate of oxidation in the autocatalytic stage is limited by diffusion, has been developed on the basis of volumetric oxygen absorption data obtained with GR-S. The method has also been applied to natural-rubber vulcanizates and to other synthetic-rubber types to locate the approximate limiting values at various temperatures for oxidation and aging studies which extend into the autocatalytic stage of rapid reaction. The constant-rate period of oxidation is more important from a practical point of view than the autocatalytic stage, since properties are so seriously degraded as to make the rubber of little value before it reaches the final stage of rapid oxidation. Somewhat thicker samples may be used for studies that are confined to the earlier stages of oxidation. A 0.075-inch sample is free of limitation by diffusion in the constant-rate stage in the following cases: GR-S black and gum stocks at 110° C; Hevea black with added antioxidant at 100° C; and uninhibited Hevea black and gum stocks at 60° C. A 0.040-inch sample is satisfactory in this range for: uninhibited Hevea black at 100° and gum at 80° C; Butaprene-NXM black at 100° and gum at 90° C; and Neoprene black and gum stocks at 100° C.


2002 ◽  
Vol 75 (5) ◽  
pp. 935-942 ◽  
Author(s):  
G. R. Hamed ◽  
N. Rattanasom

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.


1982 ◽  
Vol 55 (4) ◽  
pp. 1055-1062 ◽  
Author(s):  
A. K. Bhowmick

Abstract Scanning electron microscopy studies have been carried out on gum and filled natural rubber vulcanizates to investigate the ridge formation in the abrasion of elastomers. The first step of the ridge formation is the occurrence of small particles on the smooth abrading surface by a process of microtearing. Their size and shape depend upon the frictional force per unit length of the abrader in contact with the rubber and the nature of the rubber and the abrasive. These particles are not loose, and, hence, are not removed easily if the strength of the matrix is high. Further particles appear on the surface with continued abrasion. These particles coalesce to form fine ridges on the surface which become progressively thicker. Removal of these ridges depends upon the crack growth resistance and strength of the vulcanizate as well as on the dissipation of sliding energy in the matrix. Gum and filled natural rubber vulcanizates follow similar mechanisms of ridge formation. Due to low strength and crack growth resistance of the gum natural rubber, the abrasion resistance is poor compared to the filled ones.


The effect of thermal aging and cyclic loading on mechanical properties and development of cracks in natural rubber vulcanizates was studied. After aging at 70oC and 110oC vulcanizates were subjected to cyclic loading. At a certain number of loading cycles, the samples were conducted in a tension test. At the aging condition of 70oC, the static tensile properties of material stay almost unchanged even after 88 aged hours and 8000 loading cycles. On the contrary, the dynamic fatigue resistance of vulcanizates decreases with increasing aging time. These results are attributed to the post-curing and the development of microcracks that might be caused by Mullins effect: in the case of static loading, the strain-induced crystallization may prevent cracks growth, but in the case of cyclic loading the strain-induced crystallization does not occur, so cracks develop without hindrance. However, at 110oC both static properties and dynamic fatigue resistance of material reduced dramatically because at high temperature the heat degradation exceeds both post-curing and strain-induced crystallization. Crack formation and propagation were examined by a digital optical microscope in the progress of cyclic loading. Results showed that natural rubber vulcanizate filled with carbon black has the best crack growth resistance (CGR) while the addition of modified and unmodified silica reduces CGR of materials. Moreover, the vulcanizate with unmodified silica has the lowest CGR.


1955 ◽  
Vol 28 (1) ◽  
pp. 153-185 ◽  
Author(s):  
P. Kainradl ◽  
F. Händler

Abstract The classification of various mixtures of natural rubber and of synthetic rubber and of synthetic rubbers with respect to heat build-up under dynamic stress depends on the experimental conditions under which the vulcanizates are tested. In many cases a reversal of the order of the mixtures is found when the latter are compared at constant deformation instead of at constant periodic stress. This is true also of flexing to the point of destruction of various types of vulcanizates. The dependence of the dynamic properties on the temperature and on the stress is characteristic of the type of vulcanizate. Hence, any classification of various mixtures depends not only on the character, but also on the magnitude of the stress. These differences were found within the temperature range encountered in practice, as in tires. Consequently, no definite conclusions about the temperature rise in the range of heat build-up extending to the point of destruction can be drawn from measurements of the dynamic properties at room temperature. Changes of the dynamic properties can also take place during dynamic stressing without any considerable rise of temperature. In general, the temperature rise in the static state and the flex life are related in the sense that the higher the temperature, the shorter is the flex life, if the preceding facts are taken into consideration. However, the experiments on the temperatures of destruction show that the flex life of different vulcanizates differs even when the rise of temperature is the same. For a flex life of 100 minutes, natural-rubber vulcanizates containing active carbon blacks were destroyed at higher temperatures (170°–185° C) than was the base mixture containing no filler (about 160° C). The synthetic-rubber mixtures showed greater heat build-up (190°–220° C). These differences are found with different, as well as with equal, mechanical stress on the vulcanizate. The nature of the destruction for a given stress depends to a considerable degree on the structure of the vulcanizate. When flexed to the point of destruction, natural-rubber vulcanizates containing zinc oxide or SRF carbon blacks, and all synthetic-rubber vulcanizates, crack from the core outward, without showing any extensive thermal decomposition. On the other hand, natural-rubber vulcanizates containing active carbon blacks or Aerosil showed definite evidence of heat decomposition in the center, i.e., stickiness and porosity. This distinction in the destruction patterns gives the impression that the cause of destruction in the first case is chiefly a mechanical attack, whereas in the latter, it is chiefly thermal decomposition. It must be concluded from all the experimental results that several chemical reactions of destruction, having different temperature coefficients, proceed simultaneously, and that direct mechanical attack by the external forces is, to a greater or less extent, added to the heat effect.


2018 ◽  
Vol 84 (12) ◽  
pp. 68-72
Author(s):  
A. B. Maksimov ◽  
I. P. Shevchenko ◽  
I. S. Erokhina

A method for separating the work of impact into two parts - the work of the crack nucleation and that of crack growth - which consists in testing two samples with the same stress concentrators and different cross-sectional dimensions at the notch site is developed. It is assumed that the work of crack nucleation is proportional to the width of the sample face on which the crack originates and the specific energy of crack formation, whereas the work of the crack growth is proportional to the length of crack development and the specific crack growth energy. In case of the sample fracture upon testing, the crack growth length is assumed equal to the sample width. Data on the work of fracture of two samples and their geometrical dimensions at the site of the notch are used to form a system of two linear equations in two unknowns, i.e., the specific energy of crack formation and specific energy of crack growth. The determined specific energy values are then used to calculate the work of crack nucleation and work of crack growth. The use of the analytical method improves the accuracy compared to graphical - extrapolative procedures. The novelty of the method consists in using one and the same form of the notch in test samples, thus providing the same conditions of the stress-strain state for crack nucleation and growth. Moreover, specimens with different cross-section dimensions are used to eliminate the scale effects. Since the specific energy of the crack nu-cleation and specific energy of the crack growth are independent of the scale factor, they are determined only by the properties of the metal. Introduction the specific energy of crack formation and growth makes possible to assign a specific physical meaning to the fracture energy.


1959 ◽  
Vol 32 (3) ◽  
pp. 739-747 ◽  
Author(s):  
J. R. Dunn ◽  
J. Scanlan

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.


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