Elastomers with outstanding strength,toughness and healing efficiency are highly promising for many emerging fields.However,it is still a challenge to integrate all these beneficial features in one elastomer.Herein,an...Elastomers with outstanding strength,toughness and healing efficiency are highly promising for many emerging fields.However,it is still a challenge to integrate all these beneficial features in one elastomer.Herein,an asymmetric alicyclic structure adjacent to aromatic disulfide was tactfully introduced into the backbone of polyurethane(PU)elastomer.Specifically,such elastomer(PU-HPS)was fabricated by polycondensing polytetramethylene ether glycol(PTMEG),isophorone diisocyanate(IPDI)and p-hydroxydiphenyl disulfide(HPS)via one-pot method.The molecular mobility and phase morphology of PU-HPS can be tuned by adjusting the HPS content.Consequently,the dynamic exchange of hydrogen and disulfide bonds in the hard segment domains can also be tailored.The optimized sample manifests outstanding tensile strength(46.4 MPa),high toughness(109.1 MJ/m^(3)),high self-healing efficiency after fracture(90.3%),complete scratch recovery(100%)and good puncture resistance.Therefore,this work provides a facile strategy for developing robust self-healing polymers.展开更多
Although synthetic rubbers show continuously improved mechanical properties,natural rubber (NR) remains irreplaceable in the rubber family due to its superior mechanical properties.A mainstream viewpoint regarding the...Although synthetic rubbers show continuously improved mechanical properties,natural rubber (NR) remains irreplaceable in the rubber family due to its superior mechanical properties.A mainstream viewpoint regarding the superiority of NR is that NR possesses a natural network formed by linking the poly(cis-l,4-isoprene) chain terminals to protein and phospholipid aggregates;after vulcanization,the natural network additionally contributes to rubber mechanics by both increasing the network density and promoting the strain-induced crystallization (SIC) behavior.However,the reason why the natural network promotes SIC is still unclear;in particular,only using the increased network density cannot explain our finding that the NR shows smaller onset strain of SIC than Gel (the gel component of NR with higher network density) and even vulcanized NR.Herein,we point out that the inhomogeneous chain deformation is the alternative reason why SIC of NR takes place at smaller strain than that of Gel.More specifically,although the natural network is homogenous on the subchain length scale based on the proton double-quantum NMR results,it is essentially inhomogeneous on mesoscale (100 nm),as revealed by the small angle X-ray scattering analysis.This inhomogeneous network also leads to the mesoscale deformation inhomogeneity,as detected by the orientation of stearic acid (SA) probe,thus resulting in the smaller onset strain of SIC of NR.Based on the experimental results,a mesoscale model is proposed to qualitatively describe the crucial roles of inhomogeneous structure and deformation of natural network in NR?s mechanical properties,providing a clue from nature to guide the development of high-performance rubbers with controlled structures at mesoscale.展开更多
It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances.Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer...It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances.Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer(MSMEV),which exhibits high mechanical properties,multi-shape memory property and malleability.The triple crosslinking network is formed by reacting diglycidyl ether of bisphenol F(DGEBF)with 4-aminophenyl disulfide,γ-aminopropyltriethoxysilane(APTS)and poly(propylene glycol)bis(2-aminopropyl ether)(D2000).The triple crosslinking manifests triple functions:the disulfide bonds and the silyl ether linkages enable malleability of the epoxy network;the silyl ether linkages impart the network with high heterogeneity and broaden the glass transition region,leading to multi-shape memory property;a small amount of D2000 increases the modulus difference between the glassy and rubbery states,thereby improving the shape fixity ratio.Meanwhile,the high crosslinking density and rigid structure provide the MSMEV with high tensile strength and Young’s modulus.Moreover,integrating carbon fibers and MSMEV results in shape memory composites.The superior mechanical properties of the composites and the recyclability of carbon fiber derived from the dissolvability of MSMEV make the composites hold great promise as structural materials in varied applications.展开更多
The integration of high strength and toughness concurrently is a vital requirement for elastomers from the perspective of long-term durability and reliability. Unfortunately, these properties are generally conflicting...The integration of high strength and toughness concurrently is a vital requirement for elastomers from the perspective of long-term durability and reliability. Unfortunately, these properties are generally conflicting in artificial materials. In the present work, we propose a facile strategy to simultaneously toughen and strengthen elastomers by constructing 3 D segregated filler network via a simple latex mixing method.The as-fabricated elastomers are featured by a microscopic 3 D interconnected segregated network of rigid graphene oxide(GO) nanosheets and a continuous soft matrix of sulfur vulcanized natural rubber(NR). We demonstrate that the interconnected segregated filler network ruptures preferentially upon deformation, and thus is more efficient in energy dissipation than the dispersed filler network. Therefore, the segregated filler network exhibits better reinforcing effects for the rubber matrix. Moreover, the excellent energy dissipating ability also contributes to the outstanding crack growth resistance through the release of concentrated stress at the crack tip. As a result, the strength, toughness and fatigue resistance of the nanocomposites are concurrently enhanced. The methodology in this work is facile and universally applicable, which may provide new insights into the design of elastomers with both extraordinary static and dynamic mechanical performance for practical applications.展开更多
Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mecha...Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.展开更多
The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the ...The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide)(PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene(PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe3+ ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.展开更多
It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene.In order to explore the function of phosphate groups on the mechanical pr...It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene.In order to explore the function of phosphate groups on the mechanical properties of polyisoprene rubber,a terminally functionalized compound(PIP-P)containing phosphate groups was synthesized and further vulcanized to prepare the model compound V-PIP-P.Through analyzing the test results,it was found that these phosphate groups formed polar aggregates in non-polar polyisoprene rubber matrix,serving as an additional dynamic cross-linking sites,which increases the cross-linking density and improves mechanical properties.The influence of the phosphate groups on the strain-induced crystallization(SIC)was further investigated via synchrotron wide-angle X-ray diffraction(WAXD)experiment.These phosphate group aggregates not only reduced the onset strain of SIC,but also slowed down the molecular chain mobility,which hinder the crystal lateral growth.The above results help us to gain a deeper understanding for the function of phosphate groups in the formation of"naturally occurring network"and guide the molecular design of next generation polyisoprene rubber.展开更多
基金supported by the National Natural Science Foundation of China(No.51873110)the Foundation of Guangdong Provincial Key Laboratory of Natural Rubber Processing and Key Laboratory of Carb on Fiber and Functio nal Polymers(Beijing University of Chemical Technology),Ministry of Educati on.
文摘Elastomers with outstanding strength,toughness and healing efficiency are highly promising for many emerging fields.However,it is still a challenge to integrate all these beneficial features in one elastomer.Herein,an asymmetric alicyclic structure adjacent to aromatic disulfide was tactfully introduced into the backbone of polyurethane(PU)elastomer.Specifically,such elastomer(PU-HPS)was fabricated by polycondensing polytetramethylene ether glycol(PTMEG),isophorone diisocyanate(IPDI)and p-hydroxydiphenyl disulfide(HPS)via one-pot method.The molecular mobility and phase morphology of PU-HPS can be tuned by adjusting the HPS content.Consequently,the dynamic exchange of hydrogen and disulfide bonds in the hard segment domains can also be tailored.The optimized sample manifests outstanding tensile strength(46.4 MPa),high toughness(109.1 MJ/m^(3)),high self-healing efficiency after fracture(90.3%),complete scratch recovery(100%)and good puncture resistance.Therefore,this work provides a facile strategy for developing robust self-healing polymers.
基金financially supported by the National Natural Science Foundation of China (No. 51333003)Special Fund for Agro-scientific Research in the Public Interest (No. 201403066-1)
文摘Although synthetic rubbers show continuously improved mechanical properties,natural rubber (NR) remains irreplaceable in the rubber family due to its superior mechanical properties.A mainstream viewpoint regarding the superiority of NR is that NR possesses a natural network formed by linking the poly(cis-l,4-isoprene) chain terminals to protein and phospholipid aggregates;after vulcanization,the natural network additionally contributes to rubber mechanics by both increasing the network density and promoting the strain-induced crystallization (SIC) behavior.However,the reason why the natural network promotes SIC is still unclear;in particular,only using the increased network density cannot explain our finding that the NR shows smaller onset strain of SIC than Gel (the gel component of NR with higher network density) and even vulcanized NR.Herein,we point out that the inhomogeneous chain deformation is the alternative reason why SIC of NR takes place at smaller strain than that of Gel.More specifically,although the natural network is homogenous on the subchain length scale based on the proton double-quantum NMR results,it is essentially inhomogeneous on mesoscale (100 nm),as revealed by the small angle X-ray scattering analysis.This inhomogeneous network also leads to the mesoscale deformation inhomogeneity,as detected by the orientation of stearic acid (SA) probe,thus resulting in the smaller onset strain of SIC of NR.Based on the experimental results,a mesoscale model is proposed to qualitatively describe the crucial roles of inhomogeneous structure and deformation of natural network in NR?s mechanical properties,providing a clue from nature to guide the development of high-performance rubbers with controlled structures at mesoscale.
基金by the State Key Scientific Special Project of China(No.2016ZX05017-002)the National Natural Science Foundation of China(No.51873110).
文摘It remains a challenge to use a simple approach to fabricate a multi-shape memory material with high mechanical performances.Here,we report a triple crosslinking design to construct a multi-shape memory epoxy vitrimer(MSMEV),which exhibits high mechanical properties,multi-shape memory property and malleability.The triple crosslinking network is formed by reacting diglycidyl ether of bisphenol F(DGEBF)with 4-aminophenyl disulfide,γ-aminopropyltriethoxysilane(APTS)and poly(propylene glycol)bis(2-aminopropyl ether)(D2000).The triple crosslinking manifests triple functions:the disulfide bonds and the silyl ether linkages enable malleability of the epoxy network;the silyl ether linkages impart the network with high heterogeneity and broaden the glass transition region,leading to multi-shape memory property;a small amount of D2000 increases the modulus difference between the glassy and rubbery states,thereby improving the shape fixity ratio.Meanwhile,the high crosslinking density and rigid structure provide the MSMEV with high tensile strength and Young’s modulus.Moreover,integrating carbon fibers and MSMEV results in shape memory composites.The superior mechanical properties of the composites and the recyclability of carbon fiber derived from the dissolvability of MSMEV make the composites hold great promise as structural materials in varied applications.
基金financially supported by the National Natural Science Foundation of China (No. 51673120)。
文摘The integration of high strength and toughness concurrently is a vital requirement for elastomers from the perspective of long-term durability and reliability. Unfortunately, these properties are generally conflicting in artificial materials. In the present work, we propose a facile strategy to simultaneously toughen and strengthen elastomers by constructing 3 D segregated filler network via a simple latex mixing method.The as-fabricated elastomers are featured by a microscopic 3 D interconnected segregated network of rigid graphene oxide(GO) nanosheets and a continuous soft matrix of sulfur vulcanized natural rubber(NR). We demonstrate that the interconnected segregated filler network ruptures preferentially upon deformation, and thus is more efficient in energy dissipation than the dispersed filler network. Therefore, the segregated filler network exhibits better reinforcing effects for the rubber matrix. Moreover, the excellent energy dissipating ability also contributes to the outstanding crack growth resistance through the release of concentrated stress at the crack tip. As a result, the strength, toughness and fatigue resistance of the nanocomposites are concurrently enhanced. The methodology in this work is facile and universally applicable, which may provide new insights into the design of elastomers with both extraordinary static and dynamic mechanical performance for practical applications.
基金financially supported by the National Natural Science Foundation of China (Nos. 51873110 and 51790501)State Key Laboratory of Polymer Materials Engineering (No. sklpme2019-2-14)the Fundamental Research Funds for Central Universities。
文摘Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers;however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.
基金financially supported by the National Natural Science Foundation of China(Nos.51973126 and 51333003)。
文摘The branching structures in natural rubber(NR) were believed to be critical for its superior mechanical properties. However, it is challenging to unravel the branching structure-function relationship of NR due to the complexity of the system. Herein, polyisoprene-(polyisoprene-g-polylactide)(PI-PLA) as model compound containing branching structure was designed and synthesized, which can improve the modulus, strength and viscoelasticity activation energy compared to those of the pristine polyisoprene(PI). The reason is that the branching structure contributes to the entanglement between polyisoprene chains. In order to probe the effect of branching structure on noncovalently crosslinked system, the polyisoprene block of PI-PLA was epoxidized and mixed with Fe3+ ions to introduce coordination bonds. Compared with the linear counterpart, the branching structure obviously enhanced activation energy of coordinated polyisoprenes, remarkably improving the mechanical properies of elastomer.
基金supported by the National Natural Science Foundation of China(Nos.51973126,51333003).The authors gratefully acknowledge the Shanghai Synchrotron Radiation Facility(SSRF).
文摘It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene.In order to explore the function of phosphate groups on the mechanical properties of polyisoprene rubber,a terminally functionalized compound(PIP-P)containing phosphate groups was synthesized and further vulcanized to prepare the model compound V-PIP-P.Through analyzing the test results,it was found that these phosphate groups formed polar aggregates in non-polar polyisoprene rubber matrix,serving as an additional dynamic cross-linking sites,which increases the cross-linking density and improves mechanical properties.The influence of the phosphate groups on the strain-induced crystallization(SIC)was further investigated via synchrotron wide-angle X-ray diffraction(WAXD)experiment.These phosphate group aggregates not only reduced the onset strain of SIC,but also slowed down the molecular chain mobility,which hinder the crystal lateral growth.The above results help us to gain a deeper understanding for the function of phosphate groups in the formation of"naturally occurring network"and guide the molecular design of next generation polyisoprene rubber.