The properties of styrene-butadiene rubber (SBR) reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized ...The properties of styrene-butadiene rubber (SBR) reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized geome-tries of molecular modified silica reinforced SBR were obtained by using B3LYP calculation of density functional theory with the 6-31+G basis sets. The natural bond orbital analyses were carried out. The Si—O bond length of silica modified by KH-792 was the shortest and the electronegative of O was the highest. It indicated that the connection between silica and KH-792 was the tightest. Higher tensile strength and elongation of reinforced SBR was obtained by silica modified with the KH-792. It was caused by large delocalization of lone pair electrons of the two N atoms in KH-792. The S—C bond length in silica modified by KH-590 was longer than the ordinary S—C bond length. Then the sulfur free radical (·S·) was produced more easily in vulcanization. The degree of crosslink was increased by the cross-linkage of the rubber molecule and the sulfur free radical. That was why the highest stress and tear strength of reinforced SBR was produced when silane coupling agent KH-590 was used. The calculation results was in accord with experimental data.展开更多
A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH)...A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix at ...展开更多
Styrene-butadiene rubber(SBR)is widely used in tires in the automotive segment and vulcanization using sulfur is a common process to enhance its mechanical properties.However,the addition of sulfur as the cross-linkin...Styrene-butadiene rubber(SBR)is widely used in tires in the automotive segment and vulcanization using sulfur is a common process to enhance its mechanical properties.However,the addition of sulfur as the cross-linking agent usually results in impurities in pyrolysis products during rubber recycling,and thus the desulfurization during tire pyrolysis attracts much attention.In this work,the pyrolysis of vulcanized SBR is studied in detail with the help of Reax FF molecular dynamics simulation.A series of crosslinked SBR models were built with different sulfur contents and densities.The following Reax FF MD simulations were performed to show products distributions at different pyrolysis conditions.The simulation results show that sulfur products distribution is mainly controlled by sulfur contents and temperatures.The reaction mechanism is proposed based on the analysis of sulfur products conversion pathway,where most sulfur atoms are bonded with hydrocarbon radicals and the rest transfer to H_(2)S.High sulfur contents tend to the formation of elemental sulfur intermediate,and temperature increase facilitates the release of H_(2)S.展开更多
A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were ...A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.展开更多
Styrene-butadiene rubber(SBR)is an indispensable material in modern society,and the necessity for enhanced mechanical properties in SBR persists,particularly to withstand the rigors of challenging environmental condit...Styrene-butadiene rubber(SBR)is an indispensable material in modern society,and the necessity for enhanced mechanical properties in SBR persists,particularly to withstand the rigors of challenging environmental conditions.To surmount the limitations of conventional cross-linking modes,mechanical bonds stabilized by host-guest recognition are incorporated as the cross-linking points of SBR to form mechanically interlocked networks(MINs).Compared with covalently cross-linked network,the representative MIN exhibits superior mechanical performance in terms of elongation(1392%)and breaking strength(4.6 MPa),whose toughness has surged by 17 times.Dissociation of host-guest recognition and subsequent sliding motion provide an effective energy dissipation mechanism,and the release of hidden length is also beneficial to enhance toughness.Furthermore,the introduction of the rotaxane cross-links made the network more pliable and possess damping and elastic properties,which can return to initial state with one minute rest interval.We aspire that this direct introduction method can serve as a blueprint,offering valuable insights for the enhancement of mechanical properties in conventional commercial polymer materials.展开更多
The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine(4010NA)was dissolved in ethanol and impregnated into silica aerogel(SAG)via vacuum-pressure cycles,yielding composite particles(A-N)with enhanced sustained-...The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine(4010NA)was dissolved in ethanol and impregnated into silica aerogel(SAG)via vacuum-pressure cycles,yielding composite particles(A-N)with enhanced sustained-release and reinforcing capabilities.The effect of A-N on the mechanical properties and thermal-oxidative aging resistance of styrene-butadiene rubber(SBR)vulcanizates was investigated.TGA and BET assessments indicated that the loading efficiency of 4010NA in SAG reached 14.26%within ethanol's solu bility limit.Incorporating A-N into SBR vulcanizates significantly elevated tensile strength by 17.5%and elongation at break by 41.9%over those with fumed silica and free4010NA.Furthermore,A-N notably enhanced the thermal-oxidative aging resistance of SBR.After aging for 96 h at 100℃,the tensile strength and elongation at break of SBR with A-N sustained 70.09%and 58.61%of their initial values,respectively,with the retention rate of elongation at break being 62.8%higher than that of SBR with fumed silica and free antioxidant.The study revealed that A-N composite particles significantly inhibited the crosslinking in SBR's molecular chains,reducing hardening and embrittlement during later thermal-oxidative aging stages.展开更多
During hydraulic fracturing operations of low-permeability reservoirs,packers are the key component to ensure the success of multistage fracturing.Packers enable sections of the wellbore to be sealed off and separatel...During hydraulic fracturing operations of low-permeability reservoirs,packers are the key component to ensure the success of multistage fracturing.Packers enable sections of the wellbore to be sealed off and separately fractured by hydraulic pressure,one at a time,while the remainder of the wellbore is not affected.However,reliable sealing properties of the packer rubber are required to meet the high-pressure and high-temperature(HPHT)conditions of reservoirs(such as 70 MPa and 170 ℃).In this study,the structures of the packer rubber with two different materials are optimized numerically by ABAQUS and validated by experiments.The optimization process starts from the packer rubber with a conventional structure,and then,the weakest spots are identified by ABAQUS and improved by slightly varying its structure.This process is iterative,and the final optimized structure of a single rubber barrel with expanding back-up rings is achieved.For the structure of three rubber barrels with metallic protective covers,both HNBR and AFLAS fail under HPHT conditions.For the final optimized structure,the packer rubber made of AFLAS can work better under HPHT than that made of HNBR which ruptures after setting.The results show that the optimized structure of a single rubber barrel with expanding back-up rings and the material AFLAS are a good combination for the packer rubber playing an excellent sealing performance in multistage fracturing in horizontal wells.展开更多
As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical ...As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical behaviors for styrene-butadiene rubber(SBR)/CB compounds and CB gel(CBG) during large deformation/recovery to investigate the contribution of conductive CB network evolution to the Payne effect of the compounds. In the highly filled compounds, the frequency dependence of their strain softening behavior is much more remarkable than that of their CB network breakdown during loading, while during unloading the unrecoverable filler network hardly affects the complete recovery of modulus, both revealing that their Payne effect should be dominated by the disentanglement of SBR matrix. Furthermore,the bound rubber adjacent to CB particles can accelerate the reconstruction of continuous CB network and improve the reversibility of Payne effect. This may provide new insights into the effect of filler network, bound rubber, and free rubber on the Payne effect of CB filled SBR compounds.展开更多
A novel technology to prepare styrene-butadiene rubber （SBR）/carbon nanotubes （CNTs） composites was developed by combining a spray drying method and a subsequent mechanical mixing process. The cross-linking degree...A novel technology to prepare styrene-butadiene rubber （SBR）/carbon nanotubes （CNTs） composites was developed by combining a spray drying method and a subsequent mechanical mixing process. The cross-linking degrees of the vulcanized composites increased gradually with the additive CNTs contents. By comparing with those of the pure SBR composites, the mechanical properties such as tensile strength, tear strength and hardness of the composites filled with CNTs at certain contents were dramatically improved almost by 600%, 250% and 70%, respectively. The fabrication of the CNTs filled with SBR composites by combination of the spray drying method and subsequent mechanical mixing process was effective for enhancing the reinforcement effects of CNTs in rubbers. The novel technology can also open a new route for the modification and reinforcement on the nanocomposites with large amount of CNTs.展开更多
文摘The properties of styrene-butadiene rubber (SBR) reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized geome-tries of molecular modified silica reinforced SBR were obtained by using B3LYP calculation of density functional theory with the 6-31+G basis sets. The natural bond orbital analyses were carried out. The Si—O bond length of silica modified by KH-792 was the shortest and the electronegative of O was the highest. It indicated that the connection between silica and KH-792 was the tightest. Higher tensile strength and elongation of reinforced SBR was obtained by silica modified with the KH-792. It was caused by large delocalization of lone pair electrons of the two N atoms in KH-792. The S—C bond length in silica modified by KH-590 was longer than the ordinary S—C bond length. Then the sulfur free radical (·S·) was produced more easily in vulcanization. The degree of crosslink was increased by the cross-linkage of the rubber molecule and the sulfur free radical. That was why the highest stress and tear strength of reinforced SBR was produced when silane coupling agent KH-590 was used. The calculation results was in accord with experimental data.
基金supported by the National Natural Science Foundation of China(Nos.50573021 and 50603005)
文摘A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix at ...
基金The authors would like to express appreciation for the support of National Key Research and Development Program of China(Grant No.2018YFC1902601).
文摘Styrene-butadiene rubber(SBR)is widely used in tires in the automotive segment and vulcanization using sulfur is a common process to enhance its mechanical properties.However,the addition of sulfur as the cross-linking agent usually results in impurities in pyrolysis products during rubber recycling,and thus the desulfurization during tire pyrolysis attracts much attention.In this work,the pyrolysis of vulcanized SBR is studied in detail with the help of Reax FF molecular dynamics simulation.A series of crosslinked SBR models were built with different sulfur contents and densities.The following Reax FF MD simulations were performed to show products distributions at different pyrolysis conditions.The simulation results show that sulfur products distribution is mainly controlled by sulfur contents and temperatures.The reaction mechanism is proposed based on the analysis of sulfur products conversion pathway,where most sulfur atoms are bonded with hydrocarbon radicals and the rest transfer to H_(2)S.High sulfur contents tend to the formation of elemental sulfur intermediate,and temperature increase facilitates the release of H_(2)S.
基金supported financially by the National Natural Science Foundation of China (Project No.51273071)
文摘A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.
基金the financial support of the National Natural Science Foundation of China(22071152 and 22122105)the financial support of the National Natural Science Foundation of China(22305150)+4 种基金the financial support from the National Natural Science Foundation of China(22101175 and 52333001)Natural Science Foundation of Shanghai(22dz1207603)supported by the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(SN-ZJU-SIAS-006)State Key Laboratory of Polyolefins and Catalysis and Shanghai Key Laboratory of Catalysis Technology for Polyolefins(SKL-LCTP-202301)the Shuguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22SG11)。
文摘Styrene-butadiene rubber(SBR)is an indispensable material in modern society,and the necessity for enhanced mechanical properties in SBR persists,particularly to withstand the rigors of challenging environmental conditions.To surmount the limitations of conventional cross-linking modes,mechanical bonds stabilized by host-guest recognition are incorporated as the cross-linking points of SBR to form mechanically interlocked networks(MINs).Compared with covalently cross-linked network,the representative MIN exhibits superior mechanical performance in terms of elongation(1392%)and breaking strength(4.6 MPa),whose toughness has surged by 17 times.Dissociation of host-guest recognition and subsequent sliding motion provide an effective energy dissipation mechanism,and the release of hidden length is also beneficial to enhance toughness.Furthermore,the introduction of the rotaxane cross-links made the network more pliable and possess damping and elastic properties,which can return to initial state with one minute rest interval.We aspire that this direct introduction method can serve as a blueprint,offering valuable insights for the enhancement of mechanical properties in conventional commercial polymer materials.
基金financially supported by Natural Science Foundation of Shanxi Province(No.202303021211075)Shanxi Province Science and Technology Key Research and Development Project(No.201903D321065)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2021SX-TD011)。
文摘The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine(4010NA)was dissolved in ethanol and impregnated into silica aerogel(SAG)via vacuum-pressure cycles,yielding composite particles(A-N)with enhanced sustained-release and reinforcing capabilities.The effect of A-N on the mechanical properties and thermal-oxidative aging resistance of styrene-butadiene rubber(SBR)vulcanizates was investigated.TGA and BET assessments indicated that the loading efficiency of 4010NA in SAG reached 14.26%within ethanol's solu bility limit.Incorporating A-N into SBR vulcanizates significantly elevated tensile strength by 17.5%and elongation at break by 41.9%over those with fumed silica and free4010NA.Furthermore,A-N notably enhanced the thermal-oxidative aging resistance of SBR.After aging for 96 h at 100℃,the tensile strength and elongation at break of SBR with A-N sustained 70.09%and 58.61%of their initial values,respectively,with the retention rate of elongation at break being 62.8%higher than that of SBR with fumed silica and free antioxidant.The study revealed that A-N composite particles significantly inhibited the crosslinking in SBR's molecular chains,reducing hardening and embrittlement during later thermal-oxidative aging stages.
基金financial support from the Fundamental Research Funds for the Central Universities under Grant nos. 17CX05020 and 17CX06002the Research Funds for Introducing Talent (PhD) of China University of Petroleum under Grant no. YJ20170026+1 种基金the National Science and Technology Major Project under Grant no. 2016ZX05042004the Joint Funds of the National Natural Science Foundation of China under Grant no. U1762104
文摘During hydraulic fracturing operations of low-permeability reservoirs,packers are the key component to ensure the success of multistage fracturing.Packers enable sections of the wellbore to be sealed off and separately fractured by hydraulic pressure,one at a time,while the remainder of the wellbore is not affected.However,reliable sealing properties of the packer rubber are required to meet the high-pressure and high-temperature(HPHT)conditions of reservoirs(such as 70 MPa and 170 ℃).In this study,the structures of the packer rubber with two different materials are optimized numerically by ABAQUS and validated by experiments.The optimization process starts from the packer rubber with a conventional structure,and then,the weakest spots are identified by ABAQUS and improved by slightly varying its structure.This process is iterative,and the final optimized structure of a single rubber barrel with expanding back-up rings is achieved.For the structure of three rubber barrels with metallic protective covers,both HNBR and AFLAS fail under HPHT conditions.For the final optimized structure,the packer rubber made of AFLAS can work better under HPHT than that made of HNBR which ruptures after setting.The results show that the optimized structure of a single rubber barrel with expanding back-up rings and the material AFLAS are a good combination for the packer rubber playing an excellent sealing performance in multistage fracturing in horizontal wells.
基金financially supported by the National Natural Science Foundation of China(Nos.51790503 and 51873181)。
文摘As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical behaviors for styrene-butadiene rubber(SBR)/CB compounds and CB gel(CBG) during large deformation/recovery to investigate the contribution of conductive CB network evolution to the Payne effect of the compounds. In the highly filled compounds, the frequency dependence of their strain softening behavior is much more remarkable than that of their CB network breakdown during loading, while during unloading the unrecoverable filler network hardly affects the complete recovery of modulus, both revealing that their Payne effect should be dominated by the disentanglement of SBR matrix. Furthermore,the bound rubber adjacent to CB particles can accelerate the reconstruction of continuous CB network and improve the reversibility of Payne effect. This may provide new insights into the effect of filler network, bound rubber, and free rubber on the Payne effect of CB filled SBR compounds.
基金supported by the Foundation of Cadreman Talent Support Project of Tsinghua University,China (053288002)
文摘A novel technology to prepare styrene-butadiene rubber （SBR）/carbon nanotubes （CNTs） composites was developed by combining a spray drying method and a subsequent mechanical mixing process. The cross-linking degrees of the vulcanized composites increased gradually with the additive CNTs contents. By comparing with those of the pure SBR composites, the mechanical properties such as tensile strength, tear strength and hardness of the composites filled with CNTs at certain contents were dramatically improved almost by 600%, 250% and 70%, respectively. The fabrication of the CNTs filled with SBR composites by combination of the spray drying method and subsequent mechanical mixing process was effective for enhancing the reinforcement effects of CNTs in rubbers. The novel technology can also open a new route for the modification and reinforcement on the nanocomposites with large amount of CNTs.
