Effects of hot‐air aging and dynamic fatigue on the structure and dynamic viscoelastic properties of unfilled natural rubber vulcanizates

The effects of hot‐air aging and dynamic tensile fatigue on the network structure and dynamic viscoelastic properties of unfilled natural rubber (NR) vulcanizates were investigated with magnetic resonance crosslink density spectrometry, Fourier transform infrared spectroscopy/attenuated total reflection (FTIR–ATR), and dynamic mechanical analysis. The results showed that there was a carbonyl weak absorption peak at 1723 cm^?1 in the FTIR–ATR spectra of unfilled NR vulcanizates after hot‐air aging; The crosslink density decreased continuously as the aging time increased. The dynamic modulus of an aged specimen declined considerably, and the value of tan δ after 72 h of aging greatly increased. There was a large difference in the FTIR–ATR spectra of unfilled NR vulcanizates before and after tensile fatigue. The peaks at 1597, 1415, and 1015 cm^?1 increased concurrently with the tensile fatigue time. Initial analysis suggested that structures such as conjugated dienes appeared in the network structure. The modulus declined sharply, whereas the value of tan δ increased noticeably, after tensile fatigue. The effects of hot‐air aging and tensile fatigue on the crosslink density and FTIR–ATR spectra of unfilled NR vulcanizates were different, but both affected the viscoelastic properties dramatically. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

反式-1,4-聚异戊二烯的结晶性对丁苯橡胶/反式-1,4-聚异戊二烯共混硫化胶动态力学性能的影响

用动态力学分析仪和差示扫描量热仪研究了丁苯橡胶(SBR)/反式-1,4-聚异戊二烯(TPI)共混硫化胶的动态力学性能和结晶性能。结果表明,SBR与TPI的两相相容性良好。随着TPI用量的增加,SBR/TPI共混硫化胶的玻璃化转变温度向低温方向移动,且损耗因子峰值逐渐降低。用炭黑填充CV体系硫化SBR/TPI共混胶的损耗因子峰值低于相应的未填充胶料;而当TPI晶体熔融后,炭黑填充胶料的损耗因子要大于未填充者。不同硫化体系硫化SBR/TPI共混胶的损耗因子峰值和玻璃化转变温度从大到小的变化依次为CV体系、EV体系和DCP体系。     

Influence of internal strain on change of crosslink density of natural rubber vulcanizates by thermal ageing

Change of crosslink density of natural rubber (NR) vulcanizates by thermal ageing at 60 °C has been studied under swollen conditions in solvents to investigate the influence of internal strain applied to the vulcanizate on the crosslink density change. The internal strain was controlled by swelling with various solvents such as n‐hexane, toluene, tetrahydrofuran (THF), methanol and water. The order of degree of the swelling is toluene ≈ THF > n‐hexane > methanol > water. The influence of curing system has been investigated with the vulcanizates cured by the conventional and EV cure systems. After thermal ageing, the apparent crosslink densities of the swollen vulcanizates in n‐hexane, toluene and THF decrease irrespective of the cure systems, while that of the swollen vulcanizate in water increases. For the swollen vulcanizates in methanol, the apparent crosslink density of the vulcanizate with the conventional cure system after thermal ageing increases while that of the vulcanizate with the EV cure system decreases. The decrement of the apparent crosslink density of the vulcanizate after thermal ageing becomes larger and larger upon increasing the internal strain. © 2001 Society of Chemical Industry     

Effect of liquid isoprene rubber on dynamic mechanical properties of emulsionpolymerized styrene/butadiene rubber vulcanizates

The effect of liquid isoprene rubber (LIR) on the dynamic mechanical properties of emulsion‐polymerized styrene/butadiene rubber (ESBR) vulcanizates was investigated by temperature sweep using dynamic mechanical analysis. The introduction of LIR led to ESBR vulcanizates having higher loss factor (tan δ) in the temperature range ? 30 to 0 °C, and lower tan δ in the range 60 to 80 °C. A small amount of LIR‐403 (LIR with carboxyl groups) led to a significant change in tan δ: the addition of LIR‐403 (3 phr) led to a 7.5% increase in tan δ from ? 30 to 0 °C, and a 24.9% decrease in tan δ from 60 to 80 °C. It was found that the introduction of LIR increased the bound rubber content in the ESBR compound. Equilibrium swelling experiments showed that the crosslink density of the vulcanizates increased after the introduction of LIR‐403 or LIR‐50 (general purpose LIR). The change in tan δ from 60 to 80 °C was related to polymer–filler interactions. The characteristic constant of filler–ESBR matrix interaction (m) was calculated. At a given filler volume fraction, the increase in m in the presence of LIR could be well related to the decrease in tan δ from 60 to 80 °C. The influence of LIR on filler network in the ESBR compound was also investigated by strain and temperature sweeps using a rubber processing analyzer. Copyright © 2011 Society of Chemical Industry     

不同硫化体系对NR抗硫化返原性的影响

研究了半有效硫化体系（SEV）、普通硫黄硫化体系（CV）、平衡硫化体系（EC）等对NR硫化特性、力学性能、交联密度的影响。结果表明：不同硫化体系硫化的NR胶料抗返原性从大到小顺序为EC〉SEV2〉SEV1〉CV。SEV2硫化胶力学性能优异,交联密度较大。SEV1和CV硫化胶在过硫化条件下力学性能降低显著。在不同硫化条件下,EC和SEV2硫化胶横向松弛时间t2变化较小,抗返原性较好;SEV1和CV硫化胶横向松弛时间t2变化较大,抗返原性较差。     

Chemical crosslink densit and network structure of natural rubber vulcanizates modified with phosphorylated cardnol prepolymer

The chemical crosslink density (CLD) and network structure of natural rubber (NR) vulcanizates, modified with phosphorylated cardanol prepolymer (PCP), have been studied by equilibrium swelling and other chemical methods. The PCP-modified NR vulcanizates showed lower CLD, as compared to the unmodified NR samples, the decrease being lesser for the semiefficient vulcanization (SEV) system, as compared to the conventional (CV) and efficient (EV) vulcanization system. The superior tensile characteristics of the PCP-modified vulcanizates of the SEV system is presumed to be partly due to the presence of an entangled network structure between the aliphatic segment of PCP and the isoprene chains, as evident from X-ray diffraction studies. The critical role of Zn⁺⁺ions in the crosslinking reactions, especially at higher concentrations of PCP, was evident from the increase in CLD at higher concentrations of ZnO. The reduction in the IR absorption intensity, in the presence of ZnO, indicated the probable complex formation of Zn⁺⁺ions with the phosphate groups of PCP. © 1994 John Wiley & Sons, Inc.     

硫化体系对EPDM耐热老化性能的影响

研究了普通硫化体系 (CV)、半有效硫化体系 (SEV)和有效硫化体系 (EV)的硫化特性及其对EPDM力学性能和耐热老化性能的影响 ,以及防老剂对EPDM耐热老化性能的影响。试验结果表明 ,采用SEV和EV体系硫化的硫化胶有较好的耐热老化性能 ,采用CV体系的硫化胶有较好的力学性能 ;防老剂对EPDM的耐热老化性能无明显影响。     

Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging

Variation of the crosslink density of a rubber vulcanizate depending on the rubber composition after the thermal aging was studied with single rubber, biblend, and triblend vulcanizates of natural rubber (NR), butadiene rubber (BR), and styrene‐butadiene rubber (SBR). The efficient vulcanization (EV) system was employed to minimize the influence of free sulfur in the vulcanizate on the change of the crosslink density. Thermal aging was performed at 40, 60, and 80°C for 20 days with 5‐day intervals. The crosslink densities of the vulcanizates after the thermal aging increase. For the single rubber vulcanizates, variation of the crosslink density by the thermal aging has the order: SBR > BR > NR. For the biblend vulcanizates, variations of the crosslink densities of the NR/SBR and SBR/BR blends are larger than that of NR/BR blend. Variation of the crosslink density of the vulcanizate increases by increasing the SBR content in the vulcanizate. Variation of the crosslink density of the rubber vulcanizate depending on the rubber composition was explained by miscibility of the blends, combination reaction of the pendent groups, and mobility of the pendent group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1378–1384, 2000     

Mechanical properties,chemical and aging resistance of natural rubber filled with nano‐Al2O3

Al₂O₃ nanoparticles were introduced to natural rubber (NR) to investigate its reinforcement effect on filled NR vulcanizates. The results show that Nano‐Al₂O₃/NR nanocomposites exhibit significantly improved tensile strength, elongation at break, modulus, and tearing strength. Scanning electron microscopy analyses indicate that nanoparticles dispersed in NR matrix at nanoscale and show nano‐reinforcement effect on NR vulcanizates. The aging resistances of filled NR vulcanizates improve. After aging test, tensile strength, tearing strength, and modulus improved, and elongation at break decreased. These attribute to the crosslink maturation reactions, which result in the conversion of polysulfidic linkages into disulfidic and monosulfidic ones. The acid and alkaline resistances of nano‐Al₂O₃‐filled NR vulcanizates improve compared with that of unfilled NR systems. After acid and alkaline test, tensile strength and elongation at break improve, and modulus decrease. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Cure behavior and antimicrobial performance of sulfur‐cured natural rubber vulcanizates containing 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate or silver‐substituted zeolite

This work used 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate (HPQM) or silver‐substituted zeolite (SSZ) as antibacterial agents for natural rubber (NR) compounds vulcanized by conventional vulcanization (CV), semi‐efficient vulcanization, and efficient vulcanization (EV) systems. The cure behavior and antibacterial performance of the NR vulcanizates were studied by varying the loadings of HPQM or SSZ, contact times, and vulcanization systems. The antibacterial performance of the rubber compounds was examined by halo test and plate‐count‐agar methods against Escherichia coli (E. coli, ATCC 25922) and Staphylococcus aureus (S. aureus, ATCC 25923) as the testing bacteria. The cure time and crosslink density were dependent on the vulcanization recipe used but were not affected by the addition of HPQM or SSZ. Diphenylguanidine at the level of 1.0 phr (parts by weight per hundred parts of resin) in NR vulcanized by the EV system had the ability to kill the E. coli and S. aureus bacteria. The NR vulcanized by the CV system showed the most pronounced antibacterial performance, as compared with the other two vulcanization systems, via migration and diffusion of HPQM or SSZ onto the NR surfaces, this being identified by the relatively large reduction of contact angle values. The HPQM showed the most preference for NR compounds vulcanized with the CV system with a contact time of 120 min or longer to achieve a bacteria‐killing efficacy of 99.0–99.9%, the efficacy being more pronounced for E. coli bacteria. J. VINYL ADDIT. TECHNOL., 19:123–131, 2013. © 2013 Society of Plastics Engineers     

Thermal aging properties and chemical resistance of blends of natural rubber and epoxidized low molecular weight natural rubber

Studies into solvent resistance and aging properties of blends of natural rubber and epoxidized low molecular weight natural rubber were carried out. Vulcanization of the blends using the semi‐efficient vulcanization (semi‐EV) system was found to have curing advantages over conventional vulcanization (CV) and efficient vulcanization (EV) systems. The rheological properties (cure time, t₉₀, and scorch time, t₂), solvent resistances, and aging properties of the vulcanizates were found to improve as the level of epoxidized low molecular weight natural rubber in the blends increases. The mechanical properties of the blends were also found to be within the accepted level for NR vulcanizates. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1733–1739, 2005     

Comparative study on natural antioxidant as an aging retardant for natural rubber vulcanizates

The research aim is mainly to investigate the effectiveness of natural antioxidant (NA) obtained from oil palm leaves (Elaeis guineensis) as an aging retardant in natural rubber (NR) vulcanizates. Comparison of NA with other commercial antioxidants, trimethyl quinoline (TMQ) and butylated hydroxy toluene (BHT), is investigated. The effect of natural and commercial antioxidants on NR vulcanizates was explored before and after aging. Aging test was carried out at 70°C for three different periods, 4, 7, and 14 days to determine aging property by performing the tensile and tear tests. NA shows lower tensile properties, crosslink density, tack strength but high tear strength compared to the commercial antioxidants, BHT and TMQ. However, upon aging NR vulcanizates with NA retains its properties equivalent to that of commercial antioxidants, BHT and TMQ. Thus, NA can be used as an aging retardant for short‐term protection in application requiring moderate tensile properties and can be used as alternative source for commercial antioxidant. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

平衡硫化体系硫化天然橡胶的平衡硫化性和化学应力松弛行为

<正>WOlff’‘,”采用双（3-三乙氧基甲硅烷基丙基）-四硫化物（St69）与硫黄组成的平衡硫化体系（EC）,既减少了硫化返原的产生,又保留了传统硫黄硫化体系（CV）的优点,同时克服了因采用有效硫化体系（EV）或半有效硫化体系（SEV）所导致的强度等     

Dynamic Mechanical Analysis of Amorphous-Phase Organization in Acrylic Polymers

Factors affecting polymer network organization were studied in highly crosslinked acrylics of the type used in dental adhesive resins. The variables tested were comonomer content and processing conditions. BisEMA (2,2,-bis[4-(2-methacryloyloxyethoxy)-phenyl]-propane) and BisEMA + TEGDMA (triethyleneglycol dimethacrylate) were cured with and without 25% comonomer. Comonomers had characteristics that are expected to influence intrachain organization in amorphous phases: TEGDMA, crosslinking; methyl methacrylate (MMA), monomer conversion; isobornyl methacrylate (IBM), low cure shrinkage; tetrahydrofurfuryl methacrylate (THFM), antiplasticization. Dynamic mechanical analysis temperature scans were run at 0.1 Hz 2h or 24h after ambient cure, or 24h postcure after heating at 75° or 125°C. After 24h, tan δ maxima occurred in ranges centering on approximately -30°, 75° and 150°C (T_g). Heating at 125°C nearly eliminated all peaks except T_g, reduced tan δ peaks and increased T_g by 0–14°. T_g increased in the order: TEGDMA>125°C>IBM>MMA>75°C>2h>24h>THFM. The ability to crosslink, and postcure heating at 125°C, were the more important factors found to increase intrachain organization in amine-promoted, unfilled BisEMA resins of the type used in dental sealants, luting cements and bulk-filling resin composite materials.     

Structural effect of phenalkamines on adhesive viscoelastic and thermal properties of epoxy networks

Phenalkamine, the Mannich reaction products from cardanol, formaldehyde, and polyamines were prepared using ethylene diamine, diethylene triamine and triethlene tetraamine. These products were characterized by high‐pressure liquid chromatography (HPLC), infrared spectroscopy, and nuclear magnetic resonance spectroscopy (1H NMR). Clearly resolved peaks due to presence of triene, diene, monoene, and saturated side chain containing species of cardanol were observed in HPLC. The presence of characteristic methylene linkages of Mannich bases at δ 3.5–4.0 ppm was observed by 1H NMR. These curing agents were reacted with diglycidyl ether of bisphenol‐A at room temperature and the curing times were optimized. The cured resins showed good adhesion with different metal surfaces particularly higher values were observed with copper due to its high surface energy. The viscoelastic properties of the cured samples were determined by dynamic mechanical thermal analysis. The storage modulus (E′) was found to be in the order of 10⁹ Pa and tan δ values are around 90°C. A reduction in storage modulus (E′) and an increase in tan δ values on postcuring were observed. Thermogravimetry analysis showed two‐stage degradation above 250°C for the cured samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4741–4748, 2006     

Effect of a small amount of sulfur on the physical and mechanical properties of peroxide‐cured fully saturated HNBR compounds

Sulfur can be used as crosslink coagent in unsaturated elastomer. In this work, a fully saturated HNBR with 39 wt % nitrile content was selected to investigate the effect of a small amount of sulfur acting as crosslink coagent on the physical and mechanical properties of peroxide‐cured vulcanizates. First, selective cleavage of polysulfide (? Sx? ) and monosulfide(? S? ) bond by combined thiol‐piperidine treatment were performed and the existence of poly/monosulfide bond in sulfur‐contained HNBR compounds was verified. Then, no‐filler HNBR compounds with various content of sulfur were investigated to detect the influence of sulfur on the crosslink density and cure kinetics. The MDR results showed that the crosslink density of HNBR compounds reduced only when the amount of sulfur is 0.25 phr and above. Besides, the curing rate of no‐filler HNBR compounds increased with the increasing of the amount of sulfur and reached a maximum at a dosage of 0.25 phr sulfur. Finally, physical and mechanical properties of fully formulated compounds were evaluated and it was found that the addition of small amounts of sulfur in fully saturated HNBR compounds could improve the dynamic properties of peroxide‐cured HNBR compounds remarkably but at a cost of slightly higher compression set values and a small loss in heat aging resistance. In a conclusion, small amount of sulfur can impart the peroxide vulcanizates some “sulfide properties” like dynamic property, tensile strength, but at the same time, due to the introduction of sulfur, some “peroxide vulcanizates property” like heat‐resistance property, hot air resistance were weakened slightly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41612.     

Analysis of unbound materials in carbon‐black‐filled NR vulcanizates

Extraction of unbound materials from carbon‐black‐filled natural rubber (NR) vulcanizates with different cure systems was studied using various solvents with different dielectric constants of n‐hexane, toluene, THF, acetone, and acetonitrile. The extraction was performed at room temperature and 40°C for 2 days and in the boiling solvent for 8 h. Amounts of extracted materials from the NR vulcanizates increase by increasing the temperature. Amounts of extracted materials from the NR vulcanizates with n‐hexane, toluene, and THF are more than those with acetone and acetonitrile. Amounts of extracted materials from the NR vulcanizate with a high crosslink density are less than those from the NR vulcanizate with a low one. Thermogravimetric analysis of the NR vulcanizates before and after the extraction were carried out to investigate components of the extracted materials. It was found that there were polymer components and metal complexes, as well as organic matters with a low molecular weight in the extracted materials. Abilities of the solvents to extract unbound materials from the NR vulcanizates were discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1995–2005, 1999     

Impact of aliphatic amine comonomers on DGEBA epoxy network properties

This study characterized the mechanical and thermal properties of the oligomer‐based formulations of the diglycidyl ether of bisphenol A (DGEBA) cured with series aliphatic amines (triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and O,O bis (2‐aminopropyl propylene glycol) (Jeffamine D230) with different functionalities in the glassy state. Impact Izod and three‐point bending tests were conducted to determine the networks' impact energy (E_i), elasticity modulus (E_y), yield stress (σ_y) and fracture toughness (K_IC) values. The same three‐point bending mode was also employed to characterize the systems' thermo‐mechanical properties (DMA) and storage modulus (E') and damping modulus (tan δ = E"/E') values. The DGEBA/D230 network showed greater flexibility, maximum impact energy, higher fracture toughness, and a lower yield stress than the DGEBA/TETA and DGEBA/TEPA networks. The fracture behavior of these epoxy systems was correlated to the molecular weight between the crosslink points, M_c, and the plastic zone size (r_p) at the crack tip carved in the samples. The DGEBA/D230 network had the highest storage modulus and tan δ intensity, together with higher toughness and deformation during the network's fracture. These results were a consequence of the structural characteristics of comonomers, including their chain segment flexibility, molecular weight between crosslink points and functionality. POLYM. ENG. SCI., 54:2132–2138, 2014. © 2013 Society of Plastics Engineers     

交联键类型对硫化丁苯橡胶拉伸应力松弛行为的影响

利用两相模型讨论了不同硫化体系的硫化丁苯橡胶的应力松弛行为。通过平衡溶胀法求得不同硫化体系中存在的几种不同交联网络结构的含量。普通硫化体系(CV)含有较多的多硫交联键,有效硫化体系(EV)含有较多的单硫交联键,而半有效硫化体系(SEV)的单硫、多硫交联键含量在前两者之间。考察了交联键类型、拉伸速率以及应变对应力松弛行为的影响。结果表明,CV体系的拉伸强度、不可松弛分量都要高于其它2种体系。交联键类型对可松弛分量的影响较小。     

Preparation and characterization of natural rubber/ultrafine full-vulcanized powdered styrene–butadiene rubber blends

In this paper, natural rubber (NR)/ultrafine full-vulcanized styrene–butadiene powdered rubber (UFPSBR) blends were prepared and studied for the first time. Scanning electron microscopy and thermogravimetric analysis were employed to characterize UFPSBR. Equilibrium swelling method was used to determine the crosslink density of NR/UFPSBR vulcanizates. The results on mechanical properties showed that when NR/UFPSBR ratio was 100/5, the formulation exhibited favorable performances compared to pure NR vulcanizates. The heat build-up temperature also decreased after adding UFPSBR into the NR formulation. In dynamic mechanical analysis, in the temperature range of ?10 to ?5 °C, loss factor (tanδ) values of NR/UFPSBR vulcanizates showed an increasing trend over the given temperature range and exhibited a peak value at approximate ?5 °C. This indicates that wet traction and rolling resistance of samples were improved after UFPSBR was added in NR. This research demonstrates that UFPSBR can be incorporated into a conventional NR formula to successfully improve the comprehensive performances and dynamic mechanical properties of NR formula.