Curing Characteristics,Fatigue and Hysteresis Behaviour of Feldspar Filled Natural Rubber Vulcanizates

Curing characteristics, fatigue, and hysteresis behaviour of feldspar filled SMR L vulcanizates and feldspar filled ENR 50 vulcanizates were studied. Two different types of natural rubber, SMR L and ENR 50 having 0 and 50 mol% of epoxide groups were used. The feldspar filled natural rubber vulcanizates were compared at similar filler loading which were used at 0, 10, 20, and 30 phr of filler loading. The curing characteristics such as scorch time (t ₂) and cure time (t ₉₀) slightly increased with increasing feldspar loading for both rubber vulcanizates. Besides t ₂ and t ₉₀, maximum torque (M _HR) significantly increased for both rubbers with increasing feldspar loading. The fatigue test showed that fatigue life decreased with increasing extension ratio, strain energy and filler loading. As the filler loading increased, the poor wetting of the feldspar by the rubber matrix gave rise to poor interfacial adhesion between filler and rubber matrix. Results also indicate that the vulcanizates with the highest feldspar loading exhibited the highest hysteresis. The feldspar filled SMR L vulcanizates showed higher fatigue life and lower hysteresis compare to feldspar filled ENR 50 vulcanizates.     

Cure and mechanical properties of filled SMR L/ENR 25 and SMR L/SBR blends

The effect of blend ratio of natural rubber/epoxidized natural rubber (SMR L/ENR 25) and natural rubber/styrene‐butadiene rubber (SMR L/SBR) blends on scorch time (t₂), cure time (t₉₀), resilience, hardness, and fatigue properties were studied in the presence of carbon black and silica. An accelerated sulfur vulcanization system was used throughout the investigation. The scorch and cure times of the rubber compound were assessed by using a Moving‐Die Rheometer (MDR 2000). Resilience, hardness, and fatigue life were determined by using a Wallace Dunlop Tripsometer, a Wallace Dead Load Hardness Tester, and a Fatigue to Failure Tester, respectively. The results indicate that t₂ and t₉₀ decrease with increasing ENR 25 composition in the SMR L/ENR 25 blend whereas both values increase with increasing SBR content in the SMR L/SBR blend. This observation is attributed to faster cure in ENR 25 and higher saturation in SBR. Resilience decreases with increase in % ENR and % SBR but hardness shows the reverse behavior in their respective blends. The fatigue life increases with % ENR, but it passes through a maximum with % SBR in the respective blends. In all cases, aging lowers the fatigue life, a phenomenon that is caused by the breakdown of crosslinks in the vulcanizate. Differences in all the observed values between carbon black‐filled and silica‐filled blends are associated with the varying degrees of interaction and dispersion of the two fillers in the rubber blend matrix. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 47–52, 2001     

The Effect of Filler Loading and Epoxidation on Paper-Sludge-Filled Natural Rubber Composites

The effect of filler loading and epoxidation on curing characteristics, dynamic properties, tensile properties, morphology, and rubber-filler interactions of paper-sludge-filled natural rubber compounds have been studied. Two different types of natural rubber, SMR L and ENR 50, having 0% and 50% of epoxidation and conventional vulcanization were used. Paper sludge was used as a filler and the loading range was from 0 to 40 phr. Compounding was carried out using a laboratory-sized two-roll mill. The scorch time for both rubber compounds decreased with filler loading. The cure time was found to decrease with increasing filler content for SMR L vulcanizates, whereas for ENR 50, the cure time seemed to be independent of the filler loading. Dynamic properties, i.e., maximum elastic torque, viscous torque, and tan delta, increase with filler loading in both grades of natural rubber. Results also indicate that both rubbers show increment in tensile modulus but inverse trend for elongation at break and tensile strength. However, for a fixed filler loading, ENR 50 compounds consistently exhibit higher maximum torque, modulus at 100% elongation, and modulus at 300% elongation, but lower elongation at break than SMR L compounds. In the case of tensile strength, ENR 50 possesses higher tensile strength than SMR L at 10 to 20 phr, but the difference is quite small at 30 and 40 phr. These findings might be associated with better rubber-filler interaction between the polar hydroxyl group of cellulose fiber and the epoxy group of ENR 50.     

Dependence of Mooney scorch time of SMR L,ENR 25, and ENR 50 on concentration and types of antioxidants

The effect of concentration of antioxidants on the Mooney scorch time of two grades of epoxidized natural rubbers (ENR 25 and ENR 50) and one grade of natural rubber (SMR L) was studied using a Monsanto automatic Mooney viscometer (MV 2000). Three types of antioxidants, viz., 2,2′‐methylene‐bis(4‐methyl, 6‐tertbutylphenol) (AO 2246), N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine (IPPD) and poly‐2,2,4‐trimethyl‐1,2‐dihydroquinoline (TMQ) were used, and the concentration range was varied from 0 to 5 phr. The conventional vulcanization system with 2‐mercaptobenzothiazole (MBT) as the accelerator was used throughout the study. Results show that increasing the phenol‐based antioxidant (AO 2246) concentration will increase the scorch time of ENR at a lower temperature of vulcanization while its effect on SMR L is not significant. This retardation effect is attributed to the “solvation” of epoxide group by the phenolic group in AO 2246, thus reducing the activation of adjacent double bond in ENR. The scorch time, however, is shortened by the amine‐based antioxidants (IPPD and TMQ) for the three rubbers studied, a phenomenon associated with the ability of the amine group to enhance the formation of more active sulfurating agent and subsequently increases the cure rate as the concentration of the amine‐based antioxidants is increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2940–2946, 1999     

The Effect of Rice Husk Powder on Standard Malaysian Natural Rubber Grade L (SMR L) and Epoxidized Natural Rubber (ENR 50) Composites

The effects of rice husk powder (RHP) loading and two types of natural rubber matrix (SMR L and ENR 50) on curing characteristics and mechanical properties were studied. The scorch time and cure time decreased with increasing RHP loading whereas maximum torque showed an increasing trend. SMR L composites possessed longer scorch time and cure time than ENR 50 composites. Incorporation of RHP into both rubbers improved tensile modulus significantly but decreased tensile strength and elongation at break. SMR L composites exhibited the lower tensile modulus and higher tensile strength and elongation at break than ENR 50 composites.     

Palm oil fatty acid as an activator in carbon black filled natural rubber compounds: effect of vulcanization system

Carbon black filled natural rubber compounds were cured using conventional vulcanization (CV) and semi-efficient vulcanization (semi-EV) systems. The effect of palm oil fatty acid on cure characteristics and mechanical properties was examined. It was found that the cure time t₉₀, and scorch time increased with increasing palm oil fatty acid concentration in both systems. At fixed acid concentration, semi-EV compounds show shorter t₉₀ and scorch time than CV compounds. Results from tensile modulus, hardness, maximum torque-minimum torque M_HR-M_L, and swelling measurements indicate that palm oil fatty acid has some effect on crosslink density. At fixed palm oil fatty acid concentration, CV compounds have better mechanical properties (tensile modulus, hardness, tear and tensile strengths) compared with semi-EV compounds. ©1997 SCI     

Concentration effect of stearic acid on scorch behavior of epoxidized natural rubber

The effect of stearic acid on Mooney scorch time of epoxidized natural rubber (ENR 25 and ENR 50) and one grade of unmodified natural rubber (SMR L) was investigated in the concentration range of 0.5 to 14.5 phr. Other parameters, namely accelerator systems, temperature, and fillers (carbon black and silica), on the scorch property of ENR 25 in the presence of excess loading of stearic acid were also studied. Results indicate that scorch time increases with stearic acid loading for all the rubbers investigated, the rate of increase being fastest in ENR 50, followed by ENR 25 and SMR L. Mooney scorch time of ENR shows strong dependence on stearic acid loading for delay-action accelerators and at lower temperature of vulcanization. For a fixed filler loading, the dependence of scorch time on stearic acid concentration is similar to that of gum stock. The retardation effect exhibited by excess stearic acid on the vulcanization of ENR may be attributed to complex formation of chelates and the reduction in activation of adjacent double bonds in ENR resulting from interaction between stearic acid and the epoxide group of ENR. © 1995 John Wiley & Sons, Inc.     

Cure characteristics of unaccelerated sulfur vulcanization of epoxidized natural rubber

The curing characteristics of unaccelerated sulfur vulcanization of ENR 25 and ENR 50 were studied in the temperature range from 100–180°C. The range of sulfur loading was from 1.5 to 6.5 phr. The scorch time was determined by Mooney Shearing Disk Viscometer whereas the initial cure rate, maximum torque, and reversion properties were obtained from the Moving Die Rheometer (MDR 2000). Results shows that ENR 25 gives a longer scorch time than ENR 50, an observation similar to that in an accelerated system reported earlier. For temperature < 120°C, scorch time depends exponentially on sulfur loading for both rubbers. However, this dependence diminishes as temperature is increased. This observation is attributed to the availability of activated sulfur molecules for vulcanization. The initial cure rate and maximum torque increases with increasing sulfur loading. ENR 50, however, exhibits higher value than ENR 25, suggesting faster cure in the former. For a fixed sulfur loading, reversion is a time and temperature-dependent phenomenon. It decreases with increasing sulfur loading because of the increase of cross-linking density for both rubbers stuided. © 1996 John Wiley & Sons, Inc.     

Palm Oil Fatty Acid as an Activator in Natural Rubber Gum Compounds

The potential of palm oil fatty acid as an activator in natural rubber gum compounds has been studied. The curing characteristics and mechanical properties of natural rubber gum compounds with palm oil fatty acid as an activator were not much different compared to commercial stearic acid, especially at concentrations below 3 phr. Incorporation of both acids increased the scorch and cure times, t ₉₀, and the M _HR — M _L(maximum torque — minimum torque) passed through a maximum value and decreased slightly with increasing amounts of acids. Tensile modulus and hardness for stearic acid increased up to 5 phr and then decreased with increasing acid concentration. However, for palm oil fatty acid, these properties showed an optimum value at 3 phr and then started to decrease. The fracture properties (i.e., tear and tensile strengths) also passed through a maximum as the concentration of both acids increased.     

Properties of Halloysite Nanotube (HNT) Filled SMR L and ENR 50 Nanocomposites

Various HNTs loading filled SMR L and ENR 50 were prepared. Addition of HNTs caused increments in scorch time, cure time, tensile modulus, and thermal stability of nanocomposites. Optimum tensile strength of nanocomposites was achieved at 20 phr loading. Elongation at break, swelling percentage, and fatigue life decreased with increasing HNTs loading. ENR 50 nanocomposites show shorter scorch time, longer cure time, and lower curing rate index than SMR L nanocomposites. ENR 50 nanocomposites also show higher tensile modulus and thermal stability than SMR L nanocomposites. SEM images show that HNTs can be dispersed more uniformly at lower filler loading.     

Mooney scorch time of epoxidized natural rubber

The scorch property of accelerated sulfur vulcanization of three grades of expoxidized natural rubber (viz. ENR 10, ENR 25, and ENR 50) was studied by using Mooney Shearing Disk Viscometer in the temperature range of 100–180°C. Effects of accelerator types, concentration of accelerator, and carbon black on ENR 10 were also determined. Results obtained indicate a similar scorch behavior as that reported earlier for SMR L. However, some differences in the magnitude of scorch times in the temperature and concentration studies are observed between ENR and SMR L. These differences are attributed to the activation of a double bond by the adjacent epoxide group in ENR, the effect being more significant for a higher degree of epoxidation of natural rubber. In the case of ENR 50, differential scanning calorimetry measurement suggests that additional crosslink occurs via a ring-opening reaction at about 155°C. Based on first-order reaction kinetics, the apparent activation energy of vulcanization for the rubbers studied is estimated and discussed.     

Effect of blend ratio on Mooney scorch time of rubber blends

The Mooney scorch times of three rubber blends [epoxidized natural rubber (ENR) 50/SMR L, ENR 50/styrene butadiene rubber (SBR), and Standard Malaysian Rubber SMR L/SBR] were studied in the temperature range of 120–160°C using an automatic Mooney viscometer. N-Cyclohexyl-2-benzothiazyl sulfenamide was used as the accelerator, and the rubber formulation was based on the conventional vulcanization system. Results for the blends investigated indicate that a negative deviation of scorch time from the interpolated value was observed, especially for temperatures lower than 130°C. This observation was attributed to the induction effect of the ENR 50 in the ENR 50/SMR L and ENR 50/SBR blends to produce more activated precursors to crosslinks, thus enhancing interphase crosslinking. To a lesser extent, SMR L also exhibited such an induction effect in the SMR L/SBR blend. At 120°C, maximum induction effect occurred at around a 40% blend ratio of ENR 50 and SMR L in the respective blends. For the filled stock at 140°C, carbon black exhibited less effect on the scorch property of the blends compared to silica. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1301–1305, 1998     

The Comparison Effects of Palm Oil Fatty Acid and Stearic Acid on Dynamic Properties,Curing Characteristics and Mechanical Properties of Carbon Black Filled Epoxidized Natural Rubber Compounds

Abstract

The effects of palm oil fatty acid and stearic acid on dynamic properties, curing characteristics and mechanical properties of carbon black filled epoxidized natural rubber compounds were studied. It was found that the scorch time, t ₂ and cure time, t ₉₀ increased with increasing both acids concentrations. For dynamic properties, the maximum elastic torque, increased with acids concentration, whereas the minimum elastic torque shows a decreasing trend. Results also indicate that the decrease in viscous torque and tan δ is significant with increasing acids concentration. For tensile modulus, hardness, maximum torque-minimum torque and swelling index, results indicate that both acids have some effects on crosslink density. However tensile and tear strength pass through a maximum as the concentration of both acid increased.     

The Effect of Accelerator/Sulphur Ratio on the Cure Time and Torque Maximum of Epoxidized Natural Rubber

Abstract

The cure time of accelerated sulphur vulcanization of Epoxidized Natural Rubber (ENR 25) was studied while one grade of unmodified natural rubber– Standard Malaysian Rubber Light (SMR L) was used as a control. Five accelerators, viz. 2-mercaptoben-zothiazole (MBT), tetramethylthiuram disulphide (TMTD), zinc dimethyldithiocarbamate (ZDMC), N-tert-butyl-2-benzothiazylsulphenamide (TBBS) and diphenylguanidine (DPG) were used in the study and the vulcanization systems used were conventional vulcanization (CV), semi-efficient vulcanization (semi-EV) and efficient vulcanization (EV). Monsanto Moving-Die Rheometer (MDR 2000) was used to determined the cure time in the temperature range of 100-180°C. The results indicate that cure time decreases exponentially with increasing temperature for the two rubbers studied. At a fixed curing temperature, ENR 25 shows shorter cure time compared to that of SMR L. This has been attributed to the activation of the double bond by the adjacent epoxide group in ENR 25. Studies of the effect of varying amounts of M Bata a fixed sulphur concentration show that cure time decreases as the accelerator concentration increases. ENR 25 shows higher torque maximum than SMR L. This observation can be related to the oxirane group which is bulky and thus accounts for increased glass; transition temperature with increase in the level of epoxidation. Of the vulcanization systems, CV shows the highest torque maximum followed by semi-EV and than EV. This trend can be attributed to the amount of active sulphurating agent which increases with increasing accelerator concentration. It was also found that the influence of accelerator/sulphur ratio becomes less significant as vulcanization temperature increases.     

Palm Oil Fatty Acid Additive (POFA) Filled Natural Rubber Compounds ‐ The Effects of Temperature on Curing Characteristics,Dynamic Properties and Reversion

Abstract

The effects of temperature on curing characteristics, dynamic properties and reversion behaviour of palm oil fatty acid additive (POFA 2) filled natural rubber compounds were studied. The scorch time, t₂ and cure time, t₉₀ were found decrease with increasing POFA 2 concentration. At similar POFA 2 concentration the t₂ and t₉₀ also decreased with increasing cure temperature. For dynamic properties compared to control compound, the compounds with POFA 2 show higher maximum elastic torque but lower minimum elastic torque. At similar POFA 2 concentration, the maximum and minimum elastic torque decrease with increasing cure temperature. Results also indicate that the incorporation of POFA 2 and increment in cure temperature decrease the loss tan delta. Reversion decreased with increasing POFA 2 concentration whereas increasing the cure temperatures exhibits opposite trend.     

Vinyl acetate ethylene copolymer and nanosilica reinforced epoxidized natural rubber: Effects of sulfur curing systems on cure characteristics,tensile properties,thermal stability,dynamic mechanical properties and oil resistance

This study aimed at preparing nanocomposite from epoxidized natural rubber with about 40 mol% epoxidation (ENR40), vinyl acetate ethylene copolymer (VAE) contained about 70 wt% acetate groups and nanosilica (nSiO₂). Two parts by weight per hundred parts of rubber/resin of nSiO₂ were assembled to 80/20 (w/w) ENR40/VAE blend via latex blending. The resulting nanocomposite latex was coagulated before compounding with curing agents in an internal mixer. Tetrabenzylthiuram disulphide was used as a non‐carcinogenic accelerator in three sulfur vulcanization/curing systems, namely conventional (CV), semi‐efficient (semi‐EV) and efficient (EV) systems. The rubber compounds were sheeted on a two‐roll mill and press‐cured using a compression molding machine. Influence of curing systems on cure characteristics, tensile properties, thermal stability, dynamic mechanical properties and oil resistance of the nanocomposites was investigated. The results revealed that the CV system exhibited the highest crosslink density, tensile properties and storage modulus, while the EV system exhibited the longest scorch and cure time and the highest thermal stability and oil resistance. Moreover, the percentage retention of the tensile properties after thermal aging for CV system was lower than that of semi‐EV and EV systems. However, the pristine ENR40 and 80/20 (w/w) ENR40/VAE blend were also prepared for comparison. J. VINYL ADDIT. TECHNOL., 25:E28–E38, 2019. © 2018 Society of Plastics Engineers     

Effect of filler loading on cure time and swelling behaviour of SMR L/ENR 25 and SMR L/SBR blends

The effect of filler loading on the cure time (t₉₀) and swelling behaviour of SMR L/ENR 25 and SMR L/SBR blends has been studied. Carbon black (N330), silica (Vulcasil C) and calcium carbonate were used as fillers and the loading range was from 0 to 40 phr. Results show that for SMR L/ENR 25 blends the cure time decreases with increasing carbon black loading, whereas silica shows an increasing trend, and calcium carbonate does not show significant changes. For SMR L/SBR blends, the cure time of carbon black, silica and calcium carbonate generally decreases with increasing filler loading. The percentage swelling in toluene and ASTM oil no 3 decreases for both blends with increasing filler loading, with calcium carbonate giving the highest value, followed by silica‐ and carbon black‐filled blends. At a fixed filler loading, SMR L/ENR 25 blend shows a lower percentage swelling than SMR L/SBR blends. © 2003 Society of Chemical Industry     

Fatigue and hysteresis behavior of halloysite nanotubes‐filled natural rubber (SMR L and ENR 50) nanocomposites

The effect of various halloysite nanotubes (HNTs) loading on fatigue life, stress–strain behavior, and hysteresis of HNTs/Standard Malaysian Rubber (SMR) L and HNTs/epoxidized natural rubber (ENR) 50 nanocomposites were studied. The addition of HNTs caused decrement in fatigue life for both nanocomposites at any extension ratio. Generally, HNTs/SMR L nanocomposites showed higher fatigue life than ENR 50 nanocomposites. Addition of more HNTs caused decrement of stress for HNTs/SMR L nanocomposites, whereas HNTs/ENR 50 nanocomposites showed vice versa at any strain. This result was supported by the graph of accumulated strain energy against extension ratio. Hysteresis values increased with addition of HNTs in both nanocomposites where of HNTs/ENR 50 nanocomposites exhibited higher hysteresis than HNTs/SMR L nanocomposites at any HNTs loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A Comparative Study on Curing Characteristics,Mechanical Properties,Swelling Behavior,Thermal Stability,and Morphology of Feldspar and Silica in SMR L Vulcanizates

Abstract

Comparison studies on effects of feldspar and silica (Vulcasil C) as a filler in (SMR L grade natural rubber) vulcanizates on curing characteristics, mechanical properties, swelling behavior, thermal analysis, and morphology were examined. The incorporation of both fillers increases the scorch time, t ₂, and cure time, t ₉₀, of SMR L vulcanizates. At a similar filler loading, feldspar exhibited longer t ₂ and t ₉₀ but lower values of maximum torque, M_HR, and torque difference, M_HR–M_L than did silica-filled SMR L vulcanizates. For mechanical properties, both fillers were found to be effective in enhancing the tensile strength (up to 10 phr), tensile modulus, and hardness of the vulcanizates. However, feldspar-filled SMR L vulcanizates showed lower values of mechanical properties than did silica-filled SMR L vulcanizates. Swelling measurement indicates that swelling percentages of both fillers-filled SMR L vulcanizates decrease with increasing filler loading whereas silica shows a lower swelling percentage than feldspar-filled SMR L vulcanizates. Scanning electron microscopy (SEM) on fracture surface of tensile samples showed poor filler–matrix adhesion for both fillers with increasing filler loading in the vulcanizates. However, feldspar-filled SMR L vulcanizates showed poorer filler–matrix adhesion than did silica-filled SMR L vulcanizates. Thermogravimetric analysis (TGA) results indicate that the feldspar-filled SMR L vulcanizates have higher thermal stability than do silica-filled SMR L vulcanizates.     

THE EFFECTS OF A MULTIFUNCTIONAL ADDITIVE ON CURING CHARACTERISTICS,MECHANICAL PROPERTIES,AND SWELLING BEHAVIOR OF NATURAL RUBBER/POLYCHLOROPRENE RUBBER BLENDS

The effects of a diamine salt of fatty acid of general structure [RNH₂ ⁺[CH₂)₃NH⁺] [R′COO^?]₂ referred to as a multifunctional additive (MFA) on curing characteristics and mechanical properties and swelling behavior of natural rubber (SMR L) and polychloroprene (CR) rubber blends were studied. Compared to SMR L/CR blends without MFA, the incorporation of 2 phr (parts per hundred parts of rubber) of MFA in the blends increased mechanical properties, i.e., tensile strength, tensile modulus and hardness, and improved swelling resistance toward toluene and ASTM oil No. 1. However the scorch time, t ₅ and cure index, Δt _L decrease with incorporation of MFA into the blends.