HEAT AGING OF A BROMOBUTYL TIRE INNER LINER UNDER AEROBIC AND ANAEROBIC CONDITIONS

2021 ◽  
Author(s):  
M. Yerxa ◽  
C. Porter ◽  
R. J. Pazur
Keyword(s):  
Crosslink Density ◽  
Chain Scission ◽  
Double Quantum ◽  
Elongation At Break ◽  
Small Areas ◽  
Diffusion Limited ◽  
Low Field ◽  
Aging Conditions ◽  
Crosslinking Reactions ◽  
Aerobic And Anaerobic

ABSTRACT A bromobutyl tire inner liner compound was prepared and subjected to aerobic and anaerobic heat aging at a temperature of 100 °C for seven aging times up to 8 weeks. Hardness and mechanical properties were monitored, and the evolution of the crosslink density was followed using equilibrium solvent swell and low field double quantum (DQ) nuclear magnetic resonance (NMR). The hardness and the 300% tensile stress increased with heat aging, while both tensile strength and elongation at break dropped. Both chain scission and crosslinking reactions were taking place. Equilibrium swelling and DQ NMR results confirmed that a larger crosslink density increase was seen under aerobic versus anaerobic aging conditions. The network distribution consisting of a dominant low crosslinking zone and small areas of higher crosslinking slowly broadened and shifted toward higher crosslink densities upon heat aging. The compounds aged heterogeneously. Attenuated total reflectance–Fourier transform infrared spectroscopy confirmed the presence of an oxidized surface layer, and therefore diffusion-limited oxidation effects, but only under aerobic aging conditions. Reaction mechanisms are proposed to explain the net crosslink rise with heat aging.

CHARACTERIZATION AND CORRELATION OF THE NETWORK CHAIN DENSITY TO THE PROPERTIES OF FLUOROELASTOMER RUBBER

2020 ◽  
Vol 93 (2) ◽  
pp. 274-285 ◽  
Author(s):  
M. Boyd ◽  
I. Therrien ◽  
Richard. J. Pazur
Keyword(s):  
Crosslink Density ◽  
Double Quantum ◽  
Steady Increase ◽  
Intensity Data ◽  
Network Chain ◽  
Elongation At Break ◽  
Compression Set ◽  
Low Field ◽  
Subsequent Application ◽  
Corrected Intensity

ABSTRACT The concentrations of triallyl isocyanurate (TAIC) in a peroxide-curable fluoroelastomer terpolymer containing 67 wt% of fluorine were varied to generate compounds of differing crosslink densities. Experimental analysis was undertaken using rheometry, hardness, stress–strain (Mooney–Rivlin), equilibrium solvent swell, and low-field nuclear magnetic resonance (NMR) using the double quantum (DQ) technique. Increasing the TAIC concentration caused a systematic rise in rheometry elastic torque, hardness, and tensile strength, whereas both elongation at break and swelling levels decreased. These results are concurrent with an enhanced overall level of crosslinking, which was confirmed by the steady increase of the Mooney–Rivlin C1 values. DQ NMR analysis using hydrogen and fluorine probes and subsequent application of fast Tikhonov regularization to the corrected intensity data were particularly useful in discerning the inhomogeneous nature of the compound morphology. The spatial distribution of the crosslink density suggests that the compound consists of small, highly crosslinked/entangled polymerized TAIC domains embedded within the elastic crosslinked matrix. A concentration of 3 phr of TAIC is optimal according to compression set testing.

EXPERIMENTAL DETERMINATION OF THE QUANTITY AND DISTRIBUTION OF CHEMICAL CROSSLINKS IN UNAGED AND AGED NATURAL RUBBER. II: A SULFUR DONOR SYSTEM

2019 ◽  
Vol 92 (3) ◽  
pp. 513-530 ◽  
Author(s):  
Samantha Howse ◽  
Christopher Porter ◽  
Tesfaldet Mengistu ◽  
Ivan Petrov ◽  
Richard J. Pazur
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Heat Stability ◽  
Chain Scission ◽  
Dynamic Mechanical Properties ◽  
Double Quantum ◽  
Chain Entanglement ◽  
Tetramethylthiuram Disulfide ◽  
Entanglement Density ◽  
Chemical Crosslinks

ABSTRACT A series of unfilled and stabilized natural rubber compounds varying in concentration of tetramethylthiuram disulfide (TMTD) was analyzed using rheometry, hardness, dynamic mechanical properties, stress–strain (Mooney–Rivlin), equilibrium solvent swell (Flory–Rhener), and low-field nuclear magnetic resonance (NMR) by the double quantum (DQ) technique. Crosslinking level increased proportionately with TMTD concentration, and the reaction ratio of three TMTD molecules producing one crosslink was generally upheld. Unreacted TMTD acted as a pseudo-plasticizer and lowered the chain entanglement density with increasing TMTD content. DQ NMR confirmed that the elastic network was homogeneous and that the absolute chemical crosslink distributions broaden with increasing curative level. Upon mild heat aging, zinc complexes based on TMTD/ZnO are likely responsible for causing additional crosslinking, explaining the rise in crosslink density by equilibrium solvent swell and DQ NMR. The amine-based antioxidant, the generation of thiocarbamate radicals from TMTD, and the heat stability of the predominant monosulfide crosslinking system helped to limit network breakdown through chain scission. The chain entanglement increase is likely due to reduction of the plasticizing effect caused by unreacted curative. The distribution of crosslinks slightly broadens toward higher total crosslink density because of the generation of additional chemical crosslinks and chain entanglement densification.

ACTIVATION ENERGIES OF THERMO-OXIDIZED NITRILE RUBBER COMPOUNDS OF VARYING ACRYLONITRILE CONTENT

2019 ◽  
Vol 92 (1) ◽  
pp. 129-151 ◽  
Author(s):  
Richard J. Pazur ◽  
T. Mengistu
Keyword(s):  
Chain Scission ◽  
Activation Energies ◽  
Nitrile Rubber ◽  
Network Chain ◽  
Elongation At Break ◽  
Diffusion Limited ◽  
Rubber Compounds ◽  
Nitrile Rubbers ◽  
Oxidative Behavior ◽  
Recombination Reactions

ABSTRACT The thermo-oxidative behavior of carbon black–reinforced sulfur-cured nitrile rubber compounds with varying acrylonitrile (ACN) content (18–49 wt%) was investigated. Accelerated heat aging was carried out from 40 °C to 115 °C for various aging times. Ambient aging was also included. Samples were tested for hardness, 10% tensile stress, tensile strength, elongation at break, network chain density by equilibrium solvent swell, and toluene-soluble fraction. Diffusion-limited oxidation affected data at high temperatures and was eliminated for time-temperature superposition. Linear Arrhenius kinetic behavior was confirmed throughout the whole temperature range, and calculated activation energies varied from 75 to 93 kJ/mol. Activation energies calculated through the hardness data were found to increase steadily with ACN concentration, whereas the other test responses showed less direct correlation, likely because of the influence of the underlying NBR microstructure, which changes as a function of ACN content. The high-temperature thermo-oxidative process consists of both oxidative crosslinking and chain scission reactions. Sulfur reversion and alkyl radical recombination reactions are likely prevalent at low temperatures during the buildup of hydroperoxides up to 60 °C. The shelf life of nitrile rubbers strongly depends on their ACN level, with lower ACN nitriles being more susceptible to degradation, leading to shorter shelf lives, than higher ACN-containing nitriles.

scholarly journals The effects of alkanolamide addition on cure characteristics, swelling behaviour and tensile properties of silica-filled natural rubber (NR) / chloroprene rubber (CR) blends

2018 ◽  
Vol 34 ◽  
pp. 01030 ◽  
Author(s):  
Indra Surya ◽  
Syahrul Fauzi Siregar ◽  
Hanafi Ismail
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Tensile Properties ◽  
Crosslink Density ◽  
Tensile Modulus ◽  
Palm Stearin ◽  
Swelling Behaviour ◽  
Elongation At Break ◽  
Cure Characteristics ◽  
Chloroprene Rubber

Effects of alkanolamide (ALK) addition on cure characteristics, swelling behaviour and tensile properties of silica-filled natural rubber (NR)/chloroprene rubber (CR) blends were investigated. The ALK was synthesized from Refined Bleached Deodorized Palm Stearin (RBDPS) and diethanolamine, and incorporated into the silica-filled NR/CR blends as a non-toxic rubber additive. The ALK loadings were 0.0, 1.0, 3.0, 5.0 and 7.0 phr. It was found that the ALK exhibited shorter scorch and cure times and higher elongation at break of the silica-filled NR/CR blends. The ALK also exhibited higher torque differences, tensile modulus and tensile strength at a 1.0 phr of ALK loading and then decreased with further increases in the ALK loading. The swelling measurement proved that the 1.0 phr loading of ALK caused the highest degree in crosslink density of the silica-filled NR/CR blends.

scholarly journals Curing and mechanical properties of chlorosulphonated polyethylene rubber blends

2011 ◽  
Vol 17 (3) ◽  
pp. 315-321 ◽  
Author(s):  
Gordana Markovic ◽  
Vojislav Jovanovic ◽  
Suzana Samarzija-Jovanovic ◽  
Milena Marinovic-Cincovic ◽  
Jaroslava Budinski-Simendic
Keyword(s):  
Mechanical Properties ◽  
Crosslink Density ◽  
Hydraulic Press ◽  
Elongation At Break ◽  
Rubber Blends ◽  
Tensile Tester ◽  
Roll Mill ◽  
Cure Time ◽  
Chlorosulphonated Polyethylene ◽  
Scanning Electron

In this paper the curing and mechanical properties of two series of prepared blends, i.e., chlorosulphonated polyethylene (CSM)/isobutylene-co-isoprene (IIR) rubber blends and chlorosulphonated polyethylene (CSM)/chlorinated isobutylene-co-isoprene (CIIR) rubber blends were carried out. Blends were prepared using a two roll-mill at a temperature of 40-50?C. The curing was assessed by using a Monsanto Oscillating Disc Rheometer R-100. The process of vulcanization accelerated sulfur of pure rubbers and their blends was carried out in an electrically heated laboratory hydraulic press under a pressure of about 4 MPa and 160?. The stress-strain experiments were performed using tensile tester machine (Zwick 1425). Results indicate that the scorch time, ts2 and optimum cure time, tc90 increase with increasing CSM content in both blends. The values of modulus at 100% and at 300% elongation and tensile strength increases with increasing CSM content, whereas elongation at break shows a decreasing trend. The enhancement in mechanical properties was supported by data of crosslink density in these samples obtained from swelling measurement and scanning electron microscopy studies of the rubber blends fractured surfaces.

scholarly journals Ionic Liquids and Calcium Oxide Grafted with Allylmalonic Acid Applied to Support the Peroxide Crosslinking of an Ethylene–Propylene Copolymer

Materials ◽  
2020 ◽  
Vol 13 (15) ◽  
pp. 3260
Author(s):  
Magdalena Maciejewska
Keyword(s):  
Ionic Liquids ◽  
Silica Nanoparticles ◽  
Calcium Oxide ◽  
Crosslink Density ◽  
Ethylene Propylene ◽  
Rubber Compounds ◽  
Curing Characteristics ◽  
And Performance ◽  
Crosslinking Reactions ◽  
Thermal Stability Of

Nanosized calcium oxide (CaO) featuring a surface grafted with allylmalonic acid (ALA) was used to increase the efficiency of the peroxide crosslinking of an ethylene–propylene copolymer (EPM) filled with silica nanoparticles. In this study, 1-butyl-3-methylimidazolium ionic liquids (ILs) with different anions were applied to improve the dispersion of CaO/ALA and silica nanoparticles in the EPM copolymer, as well as to catalyze the interfacial crosslinking reactions. In this article, we discuss the effects of CaO/ALA and ILs on the curing characteristics, vulcanization temperature, crosslink density, mechanical properties, and thermal stability of EPM, as well as the resistance of EPM to weather aging. The CaO/ALA with ILs reduced the vulcanization time of the rubber compounds without a significant effect on the vulcanization temperature. Their application resulted in an increased vulcanizate crosslink density, as well as improved tensile strength compared to the pure peroxide system. The influence of 1-butyl-3-methylimidazolium ILs on EPM vulcanization and performance depends on the anion present in the molecules of the ionic liquid. The most active IL seems to be that with the tetrafluoroborate anion.

Correlation between Curing Temperature and the Properties of Conductive Composites

2013 ◽  
Vol 750-752 ◽  
pp. 119-122 ◽  
Author(s):  
Xiao Ya Wang ◽  
Zhi Dong Xia ◽  
Zhe Li
Keyword(s):  
Mechanical Properties ◽  
Electrical Conductivity ◽  
Crosslink Density ◽  
Fracture Morphology ◽  
Curing Temperature ◽  
Tensile Fracture ◽  
Elongation At Break ◽  
Conductive Composites ◽  
The Stability ◽  
Better Than

This study was carried out to discuss the influence of curing temperature on the performance of conductive composites filled with nickel-coated graphite (NCG). The electrical conductivity, crosslink density, mechanical properties and tensile fracture morphology have been investigated. The results indicated that curing temperature had great impact on the electrical conductivity and mechanical properties. Voluem resistivity decreased from 43.1 to 0.08 ohm-cm at 125°C-205°C, and the reason was discussed in light of formation and break of the conductive network in the composites. The stability of SR-NCG cured at 165°C-205°C were also better than those cured at other curing temperature. Besides, tensile strength increased from 2.41 to 7.19Mpa at 125°C-225°C, elongation at break have a 56% increase, and Shore A hardness also incresed from 74 to 82.

scholarly journals Devulcanization of ground tire rubber: microwave and thermomechanical approaches

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Dániel Ábel Simon ◽  
Dávid Zoltán Pirityi ◽  
Tamás Bárány
Keyword(s):  
Microwave Treatment ◽  
Chain Scission ◽  
Polymer Chains ◽  
Tire Rubber ◽  
Ground Tire Rubber ◽  
Elongation At Break ◽  
Link Density ◽  
Cross Links ◽  
Cross Link Density ◽  
Internal Mixer

Abstract We devulcanized ground tire rubber (GTR) in a laboratory microwave oven and an internal mixer, measured the soluble content and the cross-link density of the samples, and then used Horikx’s analysis. The results showed that microwave treatment caused severe degradation of the polymer chains, while in the case of thermomechanical devulcanization, the selective scission of covalent cross-links is more common. Four devulcanized ground tire rubber (dGTR) samples were chosen for further study and three groups of samples were produced: dGTR samples containing vulcanizing agents and different amounts of paraffin oil (dGTR-based mixtures), natural rubber-based rubber mixtures with different dGTR contents and reference rubber mixtures with dGTR-based mixtures (increased vulcanizing agent contents). Cure characteristics showed a plasticizer-like effect of dGTR. Tensile and tear strength decreased drastically with increasing dGTR content; however, elongation at break values did not follow such a trend. Mechanical properties improved with increased vulcanizing agent contents. The examined properties of the samples improved even further with the use of thermomechanically devulcanized samples. Horikx’s analysis showed that this is attributable to moderate polymer chain scission.

Mechanical Chain-Scission in Rubber Vulcanizate at Low Temperatures

1979 ◽  
Vol 52 (4) ◽  
pp. 773-780 ◽  
Author(s):  
T. Kusano ◽  
K. Kobayashl ◽  
K. Murakami
Keyword(s):  
Free Radicals ◽  
Chain Length ◽  
Low Temperatures ◽  
Crosslink Density ◽  
Glassy State ◽  
Chain Scission ◽  
Molecular Chain ◽  
Yield Strain ◽  
Air Stream ◽  
Intermolecular Reaction

Abstract When vulcanized natural rubbers are forced to extend in the glassy state, free radicals are produced by the scission of the primary chain. The amount of the free radicals increases with the strain. The tensile yield strain decreases with the decrease of the molecular chain length between crosslinks. This behavior is explainable on the basis of the limited chain extensibility. The extended chains are broken with further increases of the strain. The mechanically produced free radicals are quite stable below about −40°C. The crosslink density of the chain-ruptured material increases about 2∼3×10−5 mol/cm3. This fact shows that the free radicals are consumed not only by recombination but by the intermolecular reaction. In both sulfur and DCP vulcanizates, the network chains rather than the crosslinks are broken by stretching. In an air stream, some free radicals react with oxygen and others form crosslinks.

Antioxidant Properties of Carbon Black in Unsaturated Elastomers. Studies with cis-Polybutadiene

1965 ◽  
Vol 38 (3) ◽  
pp. 636-646
Author(s):  
J. T. Gruver ◽  
K. W. Rollmann
Keyword(s):  
Antioxidant Activity ◽  
Carbon Black ◽  
Antioxidant Properties ◽  
Chain Scission ◽  
Oxygen Absorption ◽  
Hydroxyl Groups ◽  
Carbon Blacks ◽  
Crosslinking Reactions ◽  
Absorption Measurements

Abstract The thermal antioxidant behavior of carbon black was studied in vulcanized cis-polybutadiene and related to the surface chemistry of the black. Continuous and intermittent stress relaxation and oxygen absorption measurements were employed to determine the antioxidant ability of the carbon blacks. The blacks were characterized by the surface concentrations of oxygen-containing functional groups, using methods described in the literature. Antioxidant activity was found to be highest in carbons containing relatively large amounts of bound oxygen. These carbons are also acidic and decompose peroxides by the ionic mechanism. This was demonstrated with cumyl peroxide. However, even though the acidity and ability to decompose cumyl peroxide to phenol and acetone could be destroyed by methylation, this treatment did not seriously impair the antioxidant activity, so that the role of acidic groups appears to be minor. Evidence is presented which suggests strongly that the antioxidant behavior of carbon blacks is due to surface quinones, possibly hydrogen-bonded with adjacent hydroxyl groups. Measurements made on samples vulcanized in peroxide and sulfur curing systems indicate that the antioxidant behavior of carbon black is independent of the method of vulcanization in the absence of other antioxidants. A characteristic feature of the antioxidant action of carbon blacks is their tendency to repress the oxidative crosslinking reactions, the relative amount of compensation of chain scission by crosslinking being smaller than in gum vulcanizates.

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