Crosslink Density Distributions in NR/BR Blends: Effect of Cure Temperature and Time

1998 ◽  
Vol 71 (5) ◽  
pp. 958-965 ◽  
Author(s):  
Sally A. Groves
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Initial Rate ◽  
Density Distributions ◽  
Cure Temperature ◽  
Lower Cure ◽  
Crosslink Densities

Abstract Crosslink distributions in gum natural rubber (NR)/cis-poly(butadiene) (BR) blend vulcanizates have been studied previously for cure states ranging from times shortly after the onset of cure to over-cure at 150 and 175 °C, respectively. The effects of lower cure temperatures on the crosslink distributions through the cure in NR/BR blend vulcanizates are considered here. The results of this and the previous work indicate that at temperatures above 140 °C the BR phase in gum NR/BR blends begins curing before and at a faster initial rate than the NR phase. Below 140 °C it is the NR phase which attains high crosslink densities first and maintains this increased level over BR until over-cure. The effect of cure temperature on crosslink distribution at maximum state of cure is also presented.

Applications of FT-NMR to Crosslink Density Determinations in Natural Rubber Blend Vulcanizates

1992 ◽  
Vol 65 (4) ◽  
pp. 744-760 ◽  
Author(s):  
Paul S. Brown ◽  
M. John ◽  
R. Loadman ◽  
Andrew J. Tinker
Keyword(s):  
Nmr Spectroscopy ◽  
Carbon Black ◽  
Natural Rubber ◽  
Small Molecules ◽  
Crosslink Density ◽  
Chemical Shifts ◽  
Reference Position ◽  
Line Widths ◽  
Good Agreement ◽  
Crosslink Densities

Abstract Previously 90 MHz CW-NMR spectroscopy has been used to estimate the crosslink density in individual components of elastomer blends. Transfer of the technique to a 300 MHz FT instrument is not straightforward. Chemical shifts of polymer resonances in spectra of single-polymer vulcanizates are dependent on crosslink densities of the vulcanizates. Additionally, two resonances are observed for small molecules such as TMS and residual protonated solvent. The smaller resonance of each pair changes in shape and position in synchrony with the polymer signals and is considered to originate from solvent within the swollen polymer. The secondary TMS peak is used as the reference position from which to locate polymer signals in the spectrum. The position of these secondary peaks, and thus the polymer spectrum, relative to the “free” TMS is a function of crosslink density and also of carbon-black loading and type in filled vulcanizates. 13C-NMR line widths are observed to increase with crosslink density and this effect was used to study blends of NR with EPDM or a maleic acid modified EPDM. NR crosslink densities determined from 13C line-width analyses were in good agreement with those obtained from 1H-NMR and increased crosslinking in the modified EPDM was confirmed.

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.

Stress Relaxation of Natural Rubber During Irradiation

1970 ◽  
Vol 43 (2) ◽  
pp. 262-269
Author(s):  
D. Evans ◽  
J. T. Morgan ◽  
R. Sheldon ◽  
G. B. Stapleton
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Crosslink Density ◽  
Chain Scission ◽  
Crosslinking Reaction ◽  
Small Contribution ◽  
Relaxation Data ◽  
Strain Measurements ◽  
Random Scission ◽  
Crosslink Densities

Abstract The site of chain scission and crosslinking in vulcanized natural rubber irradiated with 4 MeV electrons has been determined by analysis of stress relaxation data. Sulfur and peroxide vulcanizates of different crosslink densities were prepared and the crosslink densities determined from stress—strain measurements. Stress relaxation was measured during irradiation using modified commercial relaxometers. The specimens were maintained in an atmosphere of nitrogen to minimize oxidative side effects. Scission is deduced to take place in the vicinity of crosslinks, since the rate of continuous stress relaxation is independent of crosslink density. Scission may be associated both with crosslinks initially present and with those subsequently introduced by irradiation. Crosslinking by radiation is largely a random process. However, there is a crosslinking reaction dependent to a slight extent on crosslink density as well as a small contribution from random scission reactions. G values for the random reactions are given.

EFFECT OF DEVULCANIZATION ON CROSSLINK DENSITY AND CROSSLINK DISTRIBUTION OF CARBON BLACK FILLED NATURAL RUBBER VULCANIZATES

2016 ◽  
Vol 89 (4) ◽  
pp. 653-670 ◽  
Author(s):  
Anu Mary Joseph ◽  
Benny George ◽  
Madhusoodanan K. N. ◽  
Rosamma Alex
Keyword(s):  
Carbon Black ◽  
Natural Rubber ◽  
Crosslink Density ◽  
Morphological Properties ◽  
Original Sample ◽  
Ambient Conditions ◽  
Absolute Value ◽  
Roll Mill ◽  
Percentage Retention ◽  
The Absolute

ABSTRACTCarbon black filled natural rubber (NR) vulcanizates were devulcanized at ambient temperature in a two roll mill. The effect of cure system, that is, conventional vulcanization (CV), semiefficient vulcanization (semi EV), and efficient vulcanization (EV) systems, used for vulcanization of the original sample, on the efficiency of devulcanization was studied. The efficiency of devulcanization expressed as percentage devulcanization of the samples calculated from residual crosslink density measurements was correlated with the sol fraction of the devulcanized samples based on Horikx analysis. Using chemical probe analysis, we determined (i) the crosslink distribution pattern of the original sample, (ii) the extent to which the different types of crosslinks—that is, polysulfidic, disulfidic, and monosulfidic crosslinks—have been debonded or broken during the shearing process in the two roll mill, and (iii) the pattern of bond formation during revulcanization. Mechanical shearing predominantly breaks the majority crosslink type (polysulfidic crosslinks in CV and semi EV cure systems and disulfidic crosslinks in EV samples). Irrespective of the significant reduction in total crosslink density in all three sets of samples, chain shortening reactions similar to the post-crosslinking chemical reactions at curing temperatures also occur during mechanical shear at ambient conditions, which increased the absolute value of monosulfidic links in CV and semi EV systems. However, in the devulcanized EV system, the absolute value of polysulfidic crosslinks increased, which might be due to the re-crosslinking of the cleaved bonds. All the devulcanized samples were revulcanized, and the mechanical and morphological properties were analyzed. The percentage retention of the vulcanizate properties after revulcanization of the devulcanized samples correlated very well with efficiency of devulcanization.

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.

The Dependence of Dielectric Properties on Crosslink Density of Rubbers

1978 ◽  
Vol 51 (1) ◽  
pp. 72-80 ◽  
Author(s):  
R. Bakule ◽  
A. Havránek
Keyword(s):  
Dielectric Properties ◽  
Natural Rubber ◽  
Crosslink Density ◽  
Unit Volume ◽  
Volume Distribution ◽  
Dicumyl Peroxide ◽  
Frequency Range ◽  
Polar Groups ◽  
Main Transition ◽  
Macroscopic Parameters

Abstract The dielectric properties of natural rubber, synthetic polyisoprene, andpolybutadiene samples crosslinked with sulfur and of natural rubber samplescrosslinked simultaneously with sulfur and dicumyl peroxide were studied. Inthe investigated systems, the number of polar groups in unit volume and thecrosslink density may be changed independently over relatively wide ranges.The measurements were performed in the frequency range from 101 to 105 Hzat various temperatures, and macroscopic parameters describing the dielectricproperties of the samples were evaluated. The position and intensity of thedielectric dispersion peak in the main transition zone is only slightly dependenton the crosslink density of the samples. These two values are mainly influencedby the amount of combined sulfur, or more generally, by the number and thedipole moments of polar groups in the sample. The influence of crosslink densityon the width of the absorption curve is very strong; the width increases withincreasing crosslink density. The possibility of explaining this effect in termsof the dependence of the free volume distribution function on crosslink densityis discussed.

Effect of vulcanization time on crosslink density and aging performance of natural rubber composites

2020 ◽  
Vol 62 (8) ◽  
pp. 858-862
Author(s):  
Ece Unur Yilmaz ◽  
Ahu Kor Dayioglu ◽  
Seda Balaban
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Elevated Temperatures ◽  
Mechanical Performance ◽  
Operating Conditions ◽  
Rubber Composites ◽  
Rubber Mixture ◽  
Natural Rubber Composites ◽  
Different Temperatures ◽  
Auto Parts

Abstract Natural rubber composites are widely used in the automotive industry because of their improved viscoelastic characteristics that are mostly governed by crosslink density. However, rubber parts suffer deterioration of performance over long service lives. Therefore, optimization of crosslink density and prediction of changes in physico-mechanical properties over time at elevated temperatures is extremely important for the production of safe auto parts. In this work, the effect of vulcanization time on crosslink density and thus the performance and lifetime of natural rubberbased auto parts was investigated. The natural rubber mixture prepared in this context was vulcanized for 3, 5, 10 and 15 minutes at a constant temperature of 160 °C. The crosslink density of each vulcanizite was determined by equilibrium swelling tests and the Flory-Rehner equation. The maximum crosslink density (10.75 × 10-5 mol × cm-3) and the minimum permanent compression set values (10 % at 70 °C and 25 % at 100 °C) were recorded for the sample vulcanized for 10 minutes (v10). Aging behavior of the samples were investigated by stress relaxation tests performed at 85 °C, 100 °C and 120 °C. The service lives of the vulcanizites at different temperatures were predicted by linear Arrhenius fits of degradation times. The sample vulcanized for 10 minutes (v10) was shown to exhibit a service life of 2282 hours at 70 °C in air and the optimum physico-mechanical performance under real operating conditions. The performance and lifetime prediction procedure used in this work could be employed in an early design of rubber components for specific applications.

In-situ dielectric cure monitoring as a method of measuring the influence of cure temperature on natural rubber vulcanization

2020 ◽  
Author(s):  
Narong Chueangchayaphan ◽  
Nattapong Nithi-Uthai ◽  
Kittiphan Techakittiroj ◽  
Hathaikarn Manuspiya
Keyword(s):  
Natural Rubber ◽  
Cure Monitoring ◽  
Cure Temperature
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