Determination of Degree of Crosslinking in Natural Rubber Vulcanizates. Part III

1961 ◽  
Vol 34 (1) ◽  
pp. 279-289 ◽  
Author(s):  
L. Mullins
Keyword(s):  
Molecular Weight ◽  
Natural Rubber ◽  
Physical Properties ◽  
Intrinsic Viscosity ◽  
Stress Strain ◽  
Strain Behavior ◽  
Equilibrium Volume ◽  
Volume Swelling ◽  
Natural Rubber Vulcanizates

Abstract The two previous parts of this series described an attempt to relate the physical properties of natural rubber vulcanizates to their network structure. The first established an empirical relationship between the stress-strain behavior of highly swollen natural rubbers in simple extension, and their equilibrium volume swelling in n-decane. It also examined the effect of changes in initial molecular weight of the unvulcanized masticated rubber on these properties, and an empirical correction making allowance for network flaws due to chain-segments terminated by a crosslink at only one end was obtained. The second part gave measurements of the equilibrium volume swelling and the intrinsic viscosity before vulcanization for each of a range of natural rubber vulcanizates which had been prepared by a method which enabled the number of crosslinks to be determined by chemical analysis. These measurements permitted a comparison to be made between (i) the chemical estimate of the actual number of crosslinks introduced and (ii) the number derived from the data on equilibrium volume swelling, by means of the empirical relations derived in Part I. For this purpose, an assumption was made that the stress-strain behavior of highly swollen rubbers was in accord with the predictions of the statistical theory. Recent studies of both the stress-strain properties of highly swollen rubbers and the method of determining number-averaged molecular weight from intrinsic viscosity measurements have provided an improved basis for the quantitative determination of the degree of crosslinking from measurements of physical properties. The results described in Parts I and II of this series are reinterpreted here to take account of both of these developments ; in addition, the effect of the introduction of a correction for a network defect equivalent to chain entanglements is examined.

Relation between Stress Strain Behavior and Equilibrium Volume Swelling for Peroxide Vulcanizates of Natural Rubber and cis-1,4-Polyisoprene

1967 ◽  
Vol 40 (2) ◽  
pp. 673-678 ◽  
Author(s):  
G. M. Bristow
Keyword(s):  
Natural Rubber ◽  
Elastic Behavior ◽  
Stress Strain ◽  
Strain Behavior ◽  
Equilibrium Volume ◽  
Equilibrium Swelling ◽  
Tentative Evidence ◽  
Volume Swelling ◽  
Natural Rubber Vulcanizates

Abstract Data are reported for the elastic behavior, as described by the parameters C1 and C2, and the equilibrium swelling in n-decane, νr, for cumyl peroxide vulcanizates of natural rubber and cis-1, 4-polyisoprene. For natural rubber vulcanizates the correlation between C1 and νr can be described in terms of the original Flory Rehner equation with χ= 0.41. Tentative evidence is presented which favors this equation rather than the later modified form in which the term in νr1/3 is replaced by one in (νr1/3− νr/2).

Determination of Degree of Crosslinking in Natural Rubber Vulcanizates. Part I

1957 ◽  
Vol 30 (1) ◽  
pp. 1-10 ◽  
Author(s):  
L. Mullins
Keyword(s):  
Natural Rubber ◽  
Empirical Relationship ◽  
Interaction Constant ◽  
Empirical Correction ◽  
Equilibrium Volume ◽  
Self Consistent ◽  
Volume Swelling ◽  
Natural Rubber Vulcanizates ◽  
The Relationship

Abstract This paper examines the relationship between the stress-strain properties of highly swollen natural rubber vulcanizates and their equilibrium volume swelling. It is shown that the empirical relationship obtained can be described equally well by either the Flory-Huggins equation or the Flory Modification of this equation, and values of the interaction constant µ for natural rubber in decane are determined. Observed differences in the values of µ obtained for sulfur and peroxide vulcanizates are interpreted in terms of the diluent effect of nonrubber constituents in the former. The effect of the initial molecular weight of the unmasticated rubber on these physical properties is examined and an empirical correction making allowance for chain segments terminated by a crosslink at only one end is obtained. The correction is larger than that derived by previous workers and possible sources of the observed differences are discussed. It is considered that internally self-consistent estimates of the degree of crosslinking of natural rubber vulcanizates may be obtained using the methods developed.

Influence of Crosslink Characteristics Induced by Aromatic-Based Antioxidants on the Swelling and Stress-Strain Behavior of Natural Rubber Vulcanizates

2003 ◽  
Vol 76 (2) ◽  
pp. 334-347 ◽  
Author(s):  
Tarek M. Madkour ◽  
Rasha A. Azzam
Keyword(s):  
Natural Rubber ◽  
Crosslinking Agent ◽  
Oxidative Degradation ◽  
Thermal Oxidative Degradation ◽  
Stress Strain ◽  
Strain Behavior ◽  
Strain Induced Crystallization ◽  
Elastomeric Chains ◽  
Natural Rubber Vulcanizates ◽  
Induced Crystallization

Abstract Stress-strain measurements were performed on dry and swollen natural rubber vulcanizates prepared using both sulfur as the crosslinking agent and aromatic-based bound antioxidants acting as a second crosslinking agent. The aromatic-based antioxidants were synthesized and analyzed spectroscopically in order to relate the final behavior of the vulcanizates to the nature of the crosslink characteristics. The anomalous upturn in the modulus values of these networks in response to the imposed stress was shown to persist in the dry as well as the swollen state. Since the swollen elastomeric chains cannot undergo a strain-induced crystallization, the abnormal upturns in the modulus values in an absence of a filler were explained on the basis of the limited extensibility of the short chains of networks prepared using two different crosslinking agents in line with earlier modeling predictions. Remarkably, the swelling experiments revealed the increase in the crosslink density of the networks in the early stages of the thermal oxidative degradation procedure indicating a post-cure of the chemically bound antioxidants to the elastomeric chains, which incidentally corresponds to a maximum in the modulus values of the networks. The rheological and other mechanical properties such as the hardness were shown not to have been affected as a result of the incorporation of the chemically bound antioxidants.

Behavior of Different Fractions of Purified Hevea Rubber during Vulcanization

1949 ◽  
Vol 22 (4) ◽  
pp. 994-999
Author(s):  
G. T. Verghese
Keyword(s):  
Molecular Weight ◽  
Natural Rubber ◽  
The Other ◽  
Stress Strain ◽  
Strain Behavior ◽  
Other Hand ◽  
The Difference

Abstract Considerable data on the vulcanization characteristics of molecular fractions of ordinary (unpurified) natural rubber are available. There is, on the other hand, little information of any systematic work on the vulcanization of purified rubber and of its fractions. Pummerer and Pahl vulcanized the sol and gel fractions obtained from purified Hevea rubber, and also the purified whole rubber. But apart from a statement that whole rubber vulcanized much faster than the two fractions obtained from it, no details have been published. Vulcanization of purified whole rubber and of its sol and gel fractions was studied also by Smith and Holt. They concluded that the difference which they observed in the stress-strain behavior of the fractions and whole rubber was due to differences in the rubber which persisted through vulcanization. The present paper deals with a study of the vulcanization characteristics of different fractions of purified rubber prepared by a method described in a previous paper. Also, for comparative purposes a similar study was made of the corresponding fractions of unpurified rubber. As the difference in molecular weight of some of the fractions obtained by the above method was rather small, a grouping of the fractions was made as follows :

scholarly journals RUBBER ELASTICITY AT LARGE DEFORMATION (II) STRESS-STRAIN BEHAVIOR OF NATURAL RUBBER VULCANIZATES

1976 ◽  
Vol 49 (8) ◽  
pp. 620-627 ◽  
Author(s):  
Hiroshi OKAMOTO ◽  
Junji FURUKAWA ◽  
Shinji INAGAKI
Keyword(s):  
Natural Rubber ◽  
Large Deformation ◽  
Rubber Elasticity ◽  
Stress Strain ◽  
Strain Behavior ◽  
Natural Rubber Vulcanizates

Effect and Detection of Loose Chain Ends in Crosslinked Polyurethane Elastomers

1971 ◽  
Vol 44 (1) ◽  
pp. 152-165 ◽  
Author(s):  
A. E. Oberth
Keyword(s):  
Crosslink Density ◽  
Volume Fraction ◽  
Present Theory ◽  
Swelling Ratio ◽  
Polyurethane Elastomers ◽  
Equilibrium Volume ◽  
Equilibrium Swelling ◽  
Volume Swelling

Abstract The effect of loose chain ends on tensile properties and equilibrium swelling of crosslinked polyurethane rubbers is studied. As in plasticized elastomers, tensile strength and elastic modulus are reduced approximately by a factor (1−νE,P)2, where νE,P is the volume fraction of loose chain ends, plasticizer, or both. This effect is much larger than predicted by present theory. Also the equilibrium volume swelling ratio, V0/V, of rubbers having terminal chains or an equal volume of plasticizer is the same, provided they do not differ in crosslink density. However, the volume fraction of “network rubber” in the equilibrium swollen specimen, ν2, differs owing to the non-extractability of terminal chains. On this basis a method is proposed which allows experimental determination of the volume fraction of loose ends. Elastomers abounding in loose chain ends show markedly less long term stress relaxation. This effect is not clearly understood but is useful to detect the presence of non load-bearing network.

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