Structural Characterization of Natural Rubber Vulcanizates

1963 ◽  
Vol 36 (2) ◽  
pp. 547-557 ◽  
Author(s):  
C. G. Moore ◽  
M. Porter
Keyword(s):  
Natural Rubber ◽  
Main Chain ◽  
Structural Complexity ◽  
Chain Scission ◽  
Reaction Products ◽  
Chemical Reagents ◽  
Pendent Groups ◽  
Cure Time ◽  
Conjugated Triene ◽  
Natural Rubber Vulcanizates

Abstract The three principal approaches used in the structural resolution of sulfur vulcanizates of natural rubber are described and exemplified by their application to three systems: an unaccelerated sulfur system and two mercaptobenzothiazole (MBT)-accelerated sulfur systems, one of which makes very efficient use and the other inefficient use of the sulfur crosslinking. The ultimate aim of such studies is to relate vulcanizate structure to the physical properties and aging behavior of the vulcanizates during service. The first approach, which gives an overall measure of the structural complexity of the network, involves the determination of the crosslinking efficiency, (E), that is, the number of sulfur atoms combined in the network for each physically-effective, chemical crosslink formed. Crosslinking efficiencies of networks vary with increasing cure time from ca. 6-1.16 for the efficient-MBT system to 55-40 for the unaccelerated sulfur system. Between these extremes, it is found that variations of reactant concentrations and of temperature and time of cure lead to large variations in crosslinking efficiency and therefore of network complexity. Related work not reported here indicates that the latter features are also dependent on the type of accelerator used. More detailed information on network structure is obtained from analysis of reaction products of low molecular weight analogs of natural rubber with the vulcanizing agent and ancillary ingredients. Such studies reveal that the poor efficiency of the unaccelerated sulfur system is due to sulfur being combined wastefully in (i) long polysulfidic crosslinks of alkenyl t-alkyl structure, (ii) vicinal crosslinks which behave physically as one crosslink, and (iii) a large proportion of cyclic monosulfide groups which constitute an important modification of the main rubber chains. Conjugated triene groups, cis, trans-isomerized isoprene units, and main chain scission represent other possible types of modification. In contrast with this complex network, efficiently-cured MBT-accelerated sulfur vulcanizates contain, at early stages of cure, polysulfidic crosslinks of dialkenyl type which decrease with time to mainly monosulfide crosslinks; conjugated triene units are also present but little or no cyclic monosulfides, vicinal crosslinks, or main chain scission. Other accelerated sulfur vulcanizates possess structures intermediate between these two extremes, except that the crosslinks are generally of dialkenyl type and pendent groups terminated by accelerator residues constitute an additional possible type of modification. Knowledge from model olefin studies of the different types of sulfurated groups present in vulcanizates has led to the development of the third experimental approach, i.e. use of chemical reagents (‘chemical probes’) to determine specific groups. This approach is exemplified by reaction with actual vulcanizates of triphenylphosphine which removes sulfur atoms in excess of one or two from polysulfides; as cure proceeds in unaccelerated sulfur vulcanization, the proportion of combined sulfur present in cyclic sulfide groups rises from 75% to 95% while the average number of sulfur atoms in each crosslink unit falls from 12–13 to 2–4. Comparable data for the efficient MBT system confirm the essential simplicity of the network in this case.

Effect of Curing Systems on Fatigue of Natural Rubber Vulcanizates

1966 ◽  
Vol 39 (3) ◽  
pp. 785-797 ◽  
Author(s):  
W. L. Cox ◽  
C. R. Parks
Keyword(s):  
Fatigue Life ◽  
Natural Rubber ◽  
Main Chain ◽  
Accelerated Aging ◽  
Chain Scission ◽  
Rapid Loss ◽  
Effective Antioxidant ◽  
Natural Rubber Vulcanizates ◽  
Aging In Air ◽  
Oxidative Effect

Abstract The fatigue life of natural rubber-HAF black vulcanizates showed maxima when plotted as a function of crosslink concentration as did other properties related to a tearing process such as tensile strength, crack growth, and tear strength. Accelerated-sulfur vulcanizates were superior to peroxide and nonelemental-sulfur cures; this can be attributed to an exchange of polysulfide crosslinks under stress. An effective antioxidant was essential for maximum fatigue resistance. Accelerated-sulfur systems, although having a higher original fatigue life than peroxide or nonelemental-sulfur cures, showed a rapid loss on accelerated aging in air. This would indicate that an oxidative effect was involved. Sulfur group analyses of the flexed samples showed an increase in the concentration of RSSxSR linkages but a decrease in the total polysulfide sulfur, Sx, with no change in the crosslink densities. This suggests that the polysulfide linkages not only underwent exchange during the fatigue process but also homolytic cleavage to polythiyl radicals. These radicals can add to double bonds and in the presence of oxygen initiate oxidation chains which would lead to main chain scission.

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 .

EFFECT OF CURE EFFICIENCY ON PROPERTIES OF GUM AND BLACK FILLED NATURAL RUBBER VULCANIZATES

2011 ◽  
Vol 84 (2) ◽  
pp. 229-242 ◽  
Author(s):  
Gary R. Hamed ◽  
Kanoktip Boonkerd
Keyword(s):  
Electron Microscopy ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Crosslink Density ◽  
Cure Time ◽  
Cracking Pattern ◽  
Natural Rubber Vulcanizates ◽  
Scanning Electron ◽  
Fracture Specimens ◽  
Strength Effect

Abstract Effects of the sulfur cure efficiency on the reversion behavior and the normal and edge-cut tensile strength of gum and black filled natural rubber (NR) vulcanizates were studied. N, N-dicyclohexyl-2-benzothiazole sulfenamide (DCBS) was used as an accelerator. A series of five vulcanizates with high to low cure efficiencies was prepared by increasing the sulfur (S) to DCBS ratios within the range of 0.26–6.66. All vulcanizates were formulated to have the same crosslink density. The degree of reversion (%) calculated from cure curves of gum and black filled NR at 20 min above the cure time (tc100) passed through maximum with decreasing cure efficiencies. For both gum and black filled NR, the highest degree of reversion (%) was observed at the S/DCBS ratio of 1.17. The normal tensile strengths of gum and black filled NR were directly proportional to the cure efficiency. For gum NR vulcanizates, the edge-cut tensile strength was markedly influenced by cure efficiency. Similar to the normal tensile strength, the gum NR vulcanizates cured with the lowest cure efficiency showed the lowest edge-cut tensile strength. Effect of the cure efficiency on the edge-cut tensile strength was less in the case of black filled NR vulcanizates. However, the black filled NR vulcanizates cured with the lowest cure efficiency also showed the lowest edge-cut tensile strength. The cut tip characteristics of the fracture specimens were investigated using scanning electron microscopy. The gum specimens showed only the simple lateral cracking pattern, while all black filled specimens showed the longitudinal cracking pattern. Four different cracking patterns of the black filled specimens were identified. The distribution of cracking patterns depended strongly on the size of precut and the cure efficiency.

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.

Mechanisms Involved in the Recycling of NR and EPDM

1999 ◽  
Vol 72 (4) ◽  
pp. 731-740 ◽  
Author(s):  
M. A. L. Verbruggen ◽  
L. van der Does ◽  
J. W. M. Noordermeer ◽  
M. van Duin ◽  
H. J. Manuel
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Main Chain ◽  
Chain Scission ◽  
Ethylene Propylene ◽  
Temperature Range ◽  
Lower Reactivity ◽  
Ethylene Propylene Diene Rubber ◽  
Diene Rubber ◽  
Crosslink Densities

Abstract The thermochemical recycling of natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) vulcanizates with disulfides was studied. NR sulfur vulcanizates were completely plasticized when heated with diphenyldisulfide at 200 °C. It could be concluded that both main chain scission and crosslink scission caused the network breakdown. NR peroxide vulcanizates were less reactive towards disulfide at 200 °C, and only reacted through main chain scission. For EPDM a temperature range of 200–275 °C was studied. In the presence of diphenyldisulfide at 200 °C there was almost no devulcanization of EPDM sulfur vulcanizates, and at 225 and 250 °C there was only slightly more devulcanization. A decrease in crosslink density of 90% was found when 2×10−4 mol diphenyldisulfide/cm3 vulcanizate was added and the EPDM sulfur vulcanizates were heated to 275 °C. EPDM peroxide vulcanizates showed a decrease in crosslink density of ca. 40% under the same conditions. The lower reactivity of EPDM towards disulfide compared with NR is the result of higher crosslink densities, the presence of a higher percentage of more stable monosulfidic crosslinks and the fact that EPDM is less apt to main chain scission relative to NR.

Influence of Pyrolytic Carbon Black Prepared from Waste Tires on Mechanical Properties of Natural Rubber Vulcanizates

2017 ◽  
Vol 751 ◽  
pp. 332-336 ◽  
Author(s):  
Sarawut Prasertsri ◽  
Sansanee Srichan
Keyword(s):  
Mechanical Properties ◽  
Carbon Black ◽  
Natural Rubber ◽  
Pyrolytic Carbon ◽  
Filler Loading ◽  
Elongation At Break ◽  
Cure Time ◽  
Mooney Viscosity ◽  
Heat Build Up ◽  
Natural Rubber Vulcanizates

This research aimed to investigate the possibility of pyrolytic carbon black (PCB) used as filler in natural rubber (NR) and its effect on Mooney viscosity, cure characteristics and mechanical properties compared with commercial carbon black (N774). The results revealed that Mooney viscosity, stiffness and heat build-up tended to increase with increasing both PCB and N774 loading, whereas elongation at break decreased. However, the maximum tensile and tear strengths appeared at the optimum filler loading for both PCB and N774. At similar filler content, PCB-filled NR compounds have higher cure time, heat build-up and thermal resistance. Nevertheless, they exhibited lower Mooney viscosity and mechanical properties compared to N774-filled NR. Finally, it can be concluded that PCB could be utilized as filler in NR compound to act as semi-reinforcing filler and was classified as a filler to reduce costs.

The CBS-Accelerated Sulfuration of Natural Rubber and Cis-1,4-Polybutadiene

1972 ◽  
Vol 45 (1) ◽  
pp. 182-192 ◽  
Author(s):  
T. D. Skinner
Keyword(s):  
Natural Rubber ◽  
Zinc Sulfide ◽  
Chain Length ◽  
Network Formation ◽  
Reaction Times ◽  
Substantial Fraction ◽  
Chemical Complexity ◽  
Cure Time ◽  
Natural Rubber Vulcanizates

Abstract The results of characterization of the natural rubber vulcanizates are consistent with the results of characterization of the sulfidic products from 2-methylpent-2-ene. In both the model olefin system and the rubber system the initially formed crosslinks are polysulfidic but these are subsequently reduced to di- and monosulfidic crosslinks as the cure time is increased. Similar amounts of zinc sulfide are formed during the sulfuration of 2-methylpent-2-ene and during the vulcanization of natural rubber. The efficiency of sulfur utilization for crosslinking in natural rubber is approximately half that in comparable sulfurations of 2-methylpent-2-ene, i.e. approximately twice as many sulfur atoms are needed to obtain a chemical crosslink in natural rubber as are needed to obtain a crosslink in 2-methylpent-2-ene. This is presumed to be a consequence of the intra-molecular sulfuration that occurs in natural rubber. There is no evidence to indicate the presence of vicinal crosslinks in the natural rubber vulcanizates. Hence in agreement with the views of other workers it is concluded that the crosslinks present in accelerated sulfur vulcanizates of natural rubber are tetrafunctional and dialkenyl. The results of the characterization of the polybutadiene vulcanizates are not fully supported by the results of the model olefin studies. In the vulcanization of polybutadiene the initially formed crosslinks are polysulfidic. As vulcanization proceeds, the chemical complexity of the network increases. After long reaction times, however, no significant amount of monosulfidic crosslinks are present in the network and very little of the reacted sulfur is present in the form of zinc sulfide. Nitrogen analyses of the polybutadiene vulcanizates showed that a substantial fraction of the accelerator, equivalent to 80–90% of the available 2-thiobenzothiazole groups, become combined in the network during vulcanization. It is proposed that the combination of accelerator with polybutadiene prevents the desulfuration of dialkenyl polysulfides to dialkenyl monosulfides (the normally observed pathway of accelerated sulfuration of natural rubber) and allows vicinal crosslinking to proceed. Some support for this proposal is that vicinal crosslinks and a substantial amount of nitrogenous product are formed during the accelerated sulfuration of cyclohexene. The findings of Gregg and Katrenick on the MBTS accelerated sulfuration of cis-cis-1,5-cyclooctadiene are also consistent with this proposal. The nitrogen analyses of the polybutadiene vulcanizates indicate that very little of the accelerator is permanently combined in the network during the initial stages of network formation. Hence by comparison with the observed pattern of sulfuration of hex-3-ene, where it was shown that negligible amounts of nitrogenous product are present, it is proposed that dialkenyl (tetrafunctional) polysulfidic crosslinks are initially introduced into the polybutadiene network. The polysulfidic crosslinks then presumably undergo desulfuration reactions leading to dialkenyl crosslinks of reduced sulfur chain length until the desulfurating agent is, in effect, removed from the system by the 2-thio-benzothiazole groups becoming combined in the network. Once most of these groups have combined, after ca. 60 min. at 140° C, the desulfuration reactions are probably less important than the reactions leading to vicinal crosslinking, and it is likely that a well cured-polybutadiene vulcanizate contains a substantial fraction of vicinal crosslinks.

Aging with Applied Strain of A Black-Filled Natural Rubber Vulcanizate. Part I: Network Changes

2008 ◽  
Vol 81 (4) ◽  
pp. 650-670 ◽  
Author(s):  
Crittenden J. Ohlemacher ◽  
Gary R. Hamed
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Network Formation ◽  
Main Chain ◽  
Chain Scission ◽  
Tensile Behavior ◽  
Applied Strain ◽  
Chain Orientation ◽  
Double Network ◽  
Double Networks

Abstract Black-filled natural rubber, with an inefficient sulfur cure, was aged at 90 °C and 110 °C under nitrogen, with and without applied strain. Samples aged under strain became “double networks” and retained a residual extension ratio. The crosslink density of samples passed through a maximum with increasing severity of aging. Presumably this arises because the thermally labile, polysulfidic crosslinks break, and new crosslinks of lower rank form, resulting in increased crosslink density; but, when aged at 110 °C, this is offset by chain scission and other main-chain modifications. For double networks, it is proposed that a second network, which tends to keep samples extended, is formed at the expense of crosslinks in the original, first network. Unaged and single network samples were isotropic in tensile behavior and only slightly anisotropic in swelling behavior. For double networks, swelling and tensile properties were anisotropic, and there was some evidence that parallel specimens have increased ability to strain-crystallize. The observed anisotropies in double networks are proposed to arise from the chain orientation that persisted after double network formation.

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