Yanzhao Li, Christina Pyromali, Flanco Zhuge, Charles-André Fustin, Jean-François Gohy, Dimitris Vlassopoulos, Evelyne van Ruymbeke
We study the linear viscoelastic properties of polymeric networks formed by poly(n-butyl acrylate) telechelic stars end-capped with 2,2:6,2″-terpyridine (Star-PnBA-tpy4) and two types of metal-ligand cross-links with different lifetimes. The influence of interactions, mediated by temperature, nature of metal ions, and ion content, on the linear viscoelastic behavior of both single and double dynamics transient networks is systematically investigated by small amplitude oscillatory shear and creep rheometry. The experimental results reveal that the dynamics of networks with two different metal-ligand cross-links is much faster than expected, characterized by the average sticker lifetime rather than a discrete contribution of each metal-ligand complex. We model the dynamics with the help of our modified tube-based time marching algorithm by accounting for both association/dissociation dynamics of metal-ligand coordination and the entanglement dynamics. Two parameters are defined in the model, namely, the proportion of dangling ends and the average time during which a sticker is free. This allows us to quantify the transient dynamics of the network and, in particular, to determine how the sticker dynamics depend on temperature and ion content.
{"title":"Dynamics of entangled metallosupramolecular polymer networks combining stickers with different lifetimes","authors":"Yanzhao Li, Christina Pyromali, Flanco Zhuge, Charles-André Fustin, Jean-François Gohy, Dimitris Vlassopoulos, Evelyne van Ruymbeke","doi":"10.1122/8.0000418","DOIUrl":"https://doi.org/10.1122/8.0000418","url":null,"abstract":"We study the linear viscoelastic properties of polymeric networks formed by poly(<i>n</i>-butyl acrylate) telechelic stars end-capped with 2,2:6,2″-terpyridine (Star-PnBA-tpy4) and two types of metal-ligand cross-links with different lifetimes. The influence of interactions, mediated by temperature, nature of metal ions, and ion content, on the linear viscoelastic behavior of both single and double dynamics transient networks is systematically investigated by small amplitude oscillatory shear and creep rheometry. The experimental results reveal that the dynamics of networks with two different metal-ligand cross-links is much faster than expected, characterized by the average sticker lifetime rather than a discrete contribution of each metal-ligand complex. We model the dynamics with the help of our modified tube-based time marching algorithm by accounting for both association/dissociation dynamics of metal-ligand coordination and the entanglement dynamics. Two parameters are defined in the model, namely, the proportion of dangling ends and the average time during which a sticker is free. This allows us to quantify the transient dynamics of the network and, in particular, to determine how the sticker dynamics depend on temperature and ion content.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":"193 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138542813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Clément Coutouly, Evelyne van Ruymbeke, Laurence Ramos, Philippe Dieudonné-George, Charles-André Fustin
This work focuses on the temperature-dependent structural and rheological characterization of polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymers (PS-b-PnBA-b-PS) in the melt and, in particular, on their ability to show a lower disorder-to-order temperature (LDOT). To this aim, copolymers of varying block lengths, but keeping the PnBA block as a major component, were synthesized. Small-angle x-ray scattering revealed that the copolymers with short PS blocks (∼10 kg/mol) approach an LDOT but do not cross it. At room temperature, these copolymers exhibit higher moduli compared to a PnBA homopolymer due to the reinforcing effect of the PS but are flowing at temperatures above the glass transition of the PS. Increasing the PS and PnBA block length, to keep the same PS fraction, induces more profound changes in the structural and viscoelastic behaviors. Such a copolymer crosses the LDOT, leading to a microphase-separated and ordered state at high temperature. Contrary to the copolymers with short PS blocks, the flow regime was not reached, even at temperatures well above the glass transition of the PS. Instead, a low-frequency plateau was observed in rheology, showing the increased lifetime of the microphase-separated PS domains. ABA triblock copolymers exhibiting an LDOT behavior could, thus, be of interest for the design of thermoplastic elastomers or pressure-sensitive adhesives that can resist the flow at high temperatures.
{"title":"Exploiting the lower disorder-to-order temperature in polystyrene-b-poly(n-butyl acrylate)-b-polystyrene triblock copolymers to increase their flow resistance at high temperature","authors":"Clément Coutouly, Evelyne van Ruymbeke, Laurence Ramos, Philippe Dieudonné-George, Charles-André Fustin","doi":"10.1122/8.0000506","DOIUrl":"https://doi.org/10.1122/8.0000506","url":null,"abstract":"This work focuses on the temperature-dependent structural and rheological characterization of polystyrene-<i>b</i>-poly(<i>n-</i>butyl acrylate)-<i>b</i>-polystyrene triblock copolymers (PS-<i>b</i>-P<i>n</i>BA-<i>b</i>-PS) in the melt and, in particular, on their ability to show a lower disorder-to-order temperature (LDOT). To this aim, copolymers of varying block lengths, but keeping the P<i>n</i>BA block as a major component, were synthesized. Small-angle x-ray scattering revealed that the copolymers with short PS blocks (∼10 kg/mol) approach an LDOT but do not cross it. At room temperature, these copolymers exhibit higher moduli compared to a P<i>n</i>BA homopolymer due to the reinforcing effect of the PS but are flowing at temperatures above the glass transition of the PS. Increasing the PS and P<i>nBA</i> block length, to keep the same PS fraction, induces more profound changes in the structural and viscoelastic behaviors. Such a copolymer crosses the LDOT, leading to a microphase-separated and ordered state at high temperature. Contrary to the copolymers with short PS blocks, the flow regime was not reached, even at temperatures well above the glass transition of the PS. Instead, a low-frequency plateau was observed in rheology, showing the increased lifetime of the microphase-separated PS domains. ABA triblock copolymers exhibiting an LDOT behavior could, thus, be of interest for the design of thermoplastic elastomers or pressure-sensitive adhesives that can resist the flow at high temperatures.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":"318 ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138519345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yanzhao Li, Christina Pyromali, Flanco Zhuge, C. Fustin, J. Gohy, D. Vlassopoulos, E. van Ruymbeke
We study the linear viscoelastic properties of polymeric networks formed by poly( n-butyl acrylate) telechelic stars end-capped with 2,2:6,2″-terpyridine (Star-PnBA-tpy4) and two types of metal-ligand cross-links with different lifetimes. The influence of interactions, mediated by temperature, nature of metal ions, and ion content, on the linear viscoelastic behavior of both single and double dynamics transient networks is systematically investigated by small amplitude oscillatory shear and creep rheometry. The experimental results reveal that the dynamics of networks with two different metal-ligand cross-links is much faster than expected, characterized by the average sticker lifetime rather than a discrete contribution of each metal-ligand complex. We model the dynamics with the help of our modified tube-based time marching algorithm by accounting for both association/dissociation dynamics of metal-ligand coordination and the entanglement dynamics. Two parameters are defined in the model, namely, the proportion of dangling ends and the average time during which a sticker is free. This allows us to quantify the transient dynamics of the network and, in particular, to determine how the sticker dynamics depend on temperature and ion content.
{"title":"Li et al.: Dynamics of entangled metallosupramolecular polymer networks combining stickers with different lifetimes","authors":"Yanzhao Li, Christina Pyromali, Flanco Zhuge, C. Fustin, J. Gohy, D. Vlassopoulos, E. van Ruymbeke","doi":"10.1122/8.0000568","DOIUrl":"https://doi.org/10.1122/8.0000568","url":null,"abstract":"We study the linear viscoelastic properties of polymeric networks formed by poly( n-butyl acrylate) telechelic stars end-capped with 2,2:6,2″-terpyridine (Star-PnBA-tpy4) and two types of metal-ligand cross-links with different lifetimes. The influence of interactions, mediated by temperature, nature of metal ions, and ion content, on the linear viscoelastic behavior of both single and double dynamics transient networks is systematically investigated by small amplitude oscillatory shear and creep rheometry. The experimental results reveal that the dynamics of networks with two different metal-ligand cross-links is much faster than expected, characterized by the average sticker lifetime rather than a discrete contribution of each metal-ligand complex. We model the dynamics with the help of our modified tube-based time marching algorithm by accounting for both association/dissociation dynamics of metal-ligand coordination and the entanglement dynamics. Two parameters are defined in the model, namely, the proportion of dangling ends and the average time during which a sticker is free. This allows us to quantify the transient dynamics of the network and, in particular, to determine how the sticker dynamics depend on temperature and ion content.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46966990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jake Song, Qiaochu Li, Pangkuan Chen, Bavand Keshavarz, Brian S. Chapman, Joseph B. Tracy, Gareth H. McKinley, Niels Holten-Andersen
We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low functionality (f) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high-f junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high-f junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high-f) and metal ion (low-f) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high-f networks.
{"title":"Dynamics of dual-junction-functionality associative polymer networks with ion and nanoparticle metal-coordinate cross-link junctions","authors":"Jake Song, Qiaochu Li, Pangkuan Chen, Bavand Keshavarz, Brian S. Chapman, Joseph B. Tracy, Gareth H. McKinley, Niels Holten-Andersen","doi":"10.1122/8.0000410","DOIUrl":"https://doi.org/10.1122/8.0000410","url":null,"abstract":"We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low <i>functionality</i> (<i>f</i>) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high-<i>f</i> junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high-<i>f</i> junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high-<i>f</i>) and metal ion (low-<i>f</i>) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high-<i>f</i> networks.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":"39 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138542529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Burak Tavsanli, Çiğdem Bilici, P. Sungur, S. İde, O. Okay
Recently, a simple strategy was developed for preparing interconnected interpenetrating polymer networks (IPNs) based on butyl rubber (IIR) and poly( n-octadecyl acrylate) (PC18A). Solvent-free UV polymerization of n-octadecyl acrylate (C18A) monomer in the melt of IIR at ambient temperature resulted in IPNs with self-healing and shape-memory functions. Here, we demonstrate that the use of IIR grafted with acrylic acid, methacrylic acid, and 10-undecenoic acid instead of unmodified IIR provides a significant improvement in the mechanical properties of IPNs. Differential scanning calorimetry, small-angle x-ray scattering, and wide-angle x-ray scattering analysis reveal side-by-side packing of C18 side chains of PC18A to form lamellar crystals with a melting temperature Tm between 46 and 52 °C. Transmission electron microscopy analysis indicates the existence of quasispherical nanoparticles composed of crystalline domains, which are dispersed in a continuous interpenetrating rubber-PC18A matrix. This microstructure provides them a complete self-recovery behavior induced by heating and an efficient shape-memory function. IPNs exhibit around tenfold higher chemical cross-link density as compared to those prepared from the native IIR, reflecting the effect of pendant vinyl groups on the extent of covalent interconnections between the IIR and PC18A components. The type of the grafted monomers significantly affects the mechanical performance of IPNs, which can be explained with the individual contributions of chemical and physical cross-links to the total cross-link density. The amount of the grafted rubbers in IPN could be further increased up to 80 wt. % by the incorporation of toluene into the reaction system, resulting in IPNs with a wide range of tunable thermal and mechanical properties.
{"title":"Tavsanli et al.: Butyl rubber as a macro-cross-linker in the preparation of a shape-memory and self-healing polymer","authors":"Burak Tavsanli, Çiğdem Bilici, P. Sungur, S. İde, O. Okay","doi":"10.1122/8.0000576","DOIUrl":"https://doi.org/10.1122/8.0000576","url":null,"abstract":"Recently, a simple strategy was developed for preparing interconnected interpenetrating polymer networks (IPNs) based on butyl rubber (IIR) and poly( n-octadecyl acrylate) (PC18A). Solvent-free UV polymerization of n-octadecyl acrylate (C18A) monomer in the melt of IIR at ambient temperature resulted in IPNs with self-healing and shape-memory functions. Here, we demonstrate that the use of IIR grafted with acrylic acid, methacrylic acid, and 10-undecenoic acid instead of unmodified IIR provides a significant improvement in the mechanical properties of IPNs. Differential scanning calorimetry, small-angle x-ray scattering, and wide-angle x-ray scattering analysis reveal side-by-side packing of C18 side chains of PC18A to form lamellar crystals with a melting temperature Tm between 46 and 52 °C. Transmission electron microscopy analysis indicates the existence of quasispherical nanoparticles composed of crystalline domains, which are dispersed in a continuous interpenetrating rubber-PC18A matrix. This microstructure provides them a complete self-recovery behavior induced by heating and an efficient shape-memory function. IPNs exhibit around tenfold higher chemical cross-link density as compared to those prepared from the native IIR, reflecting the effect of pendant vinyl groups on the extent of covalent interconnections between the IIR and PC18A components. The type of the grafted monomers significantly affects the mechanical performance of IPNs, which can be explained with the individual contributions of chemical and physical cross-links to the total cross-link density. The amount of the grafted rubbers in IPN could be further increased up to 80 wt. % by the incorporation of toluene into the reaction system, resulting in IPNs with a wide range of tunable thermal and mechanical properties.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47765389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Simone Sbrescia, T. Engels, E. van Ruymbeke, M. Seitz
The mechanical properties of multiblock copolymer thermoplastic elastomers (TPEs) are governed by the interplay of different reversible dynamics [e.g., hard block (HB) association and chain entanglements]. Understanding how these physical processes influence the high-temperature deformation behavior is relevant as many TPEs lose toughness with increasing temperature. Increasing molecular weight (Mw) improves their temperature resistance that is attributed to an increase in network connectivity. Indeed, longer chains are characterized by more HBs per chain and by a longer lifetime of the entanglements in the amorphous phase. Both the associating HB and disentanglement dynamics are temperature and rate dependent. To further understand the interconnected role of Mw, temperature and rate dependencies on the mechanical properties, we perform Temperature Scanning Stress Relaxation (TSSR) tests. The method consists of measuring the stress relaxation of the materials as the temperature monotonically increases, allowing us to probe the stress response as the HBs progressively disassociate due to the increase in temperature. The results show that increasing Mw improves the high-temperature relaxation behavior, allowing the material to retain more stress than its low Mw counterpart as the temperature increases. This distinction does not show itself when performing standard small strain dynamic mechanical thermal analyses. Depending on the deformation experienced before the TSSR is performed, different relaxation behaviors are observed illustrating the importance of the current microstructure in determining the mechanical properties. The TSSR approach is well-suited to benchmark the high-temperature stress-bearing properties of network-based polymers whose morphology and, hence, properties are strongly deformation dependent.
{"title":"Molecular weight effects on the stress-relaxation behavior of soft thermoplastic elastomer by means of temperature scanning stress relaxation (TSSR)","authors":"Simone Sbrescia, T. Engels, E. van Ruymbeke, M. Seitz","doi":"10.1122/8.0000444","DOIUrl":"https://doi.org/10.1122/8.0000444","url":null,"abstract":"The mechanical properties of multiblock copolymer thermoplastic elastomers (TPEs) are governed by the interplay of different reversible dynamics [e.g., hard block (HB) association and chain entanglements]. Understanding how these physical processes influence the high-temperature deformation behavior is relevant as many TPEs lose toughness with increasing temperature. Increasing molecular weight (Mw) improves their temperature resistance that is attributed to an increase in network connectivity. Indeed, longer chains are characterized by more HBs per chain and by a longer lifetime of the entanglements in the amorphous phase. Both the associating HB and disentanglement dynamics are temperature and rate dependent. To further understand the interconnected role of Mw, temperature and rate dependencies on the mechanical properties, we perform Temperature Scanning Stress Relaxation (TSSR) tests. The method consists of measuring the stress relaxation of the materials as the temperature monotonically increases, allowing us to probe the stress response as the HBs progressively disassociate due to the increase in temperature. The results show that increasing Mw improves the high-temperature relaxation behavior, allowing the material to retain more stress than its low Mw counterpart as the temperature increases. This distinction does not show itself when performing standard small strain dynamic mechanical thermal analyses. Depending on the deformation experienced before the TSSR is performed, different relaxation behaviors are observed illustrating the importance of the current microstructure in determining the mechanical properties. The TSSR approach is well-suited to benchmark the high-temperature stress-bearing properties of network-based polymers whose morphology and, hence, properties are strongly deformation dependent.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45530086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The dynamics of polymer chains in entangled semidilute solution have been of theoretical and experimental interest. Among a number of characteristic lengths and times of the polymer in solution, those of the correlation blob are the key to understand the applicability of the Rouse and Zimm models to rheology of the semidilute solution. Direct rheological measurements of Rouse and Zimm modes are limited as the corresponding time scale is out of the range of classical rheological techniques. We investigated the single chain dynamics of entangled poly(ethylene oxide) in semidilute aqueous solutions by high-frequency micro-rheology based on diffusing-wave spectroscopy compared to classical shear macro-rheology. Concentration dependence of the three characteristic times of the entangled polymer chains, reptation time, entanglement time, and correlation time, was studied with the help of the time-concentration superposition. At the low frequency range, dynamic moduli measured by macro-rheology and micro-rheology showed a good agreement without adjustable parameters. At the higher frequency range, we found the Rouse regime in the mean square displacement of the probe particles and in the magnitude of the complex specific viscosity of the solution. We propose a simple method to estimate the boundary of the Rouse regime. Finally, at the high frequency range, we demonstrate that the contribution of the solvent to the solution viscosity needs to be subtracted to observe the power-law behavior of the Zimm mode.
{"title":"Microrheological study of single chain dynamics in semidilute entangled flexible polymer solutions: Crossover from Rouse to Zimm modes","authors":"T. Indei, T. Narita","doi":"10.1122/8.0000402","DOIUrl":"https://doi.org/10.1122/8.0000402","url":null,"abstract":"The dynamics of polymer chains in entangled semidilute solution have been of theoretical and experimental interest. Among a number of characteristic lengths and times of the polymer in solution, those of the correlation blob are the key to understand the applicability of the Rouse and Zimm models to rheology of the semidilute solution. Direct rheological measurements of Rouse and Zimm modes are limited as the corresponding time scale is out of the range of classical rheological techniques. We investigated the single chain dynamics of entangled poly(ethylene oxide) in semidilute aqueous solutions by high-frequency micro-rheology based on diffusing-wave spectroscopy compared to classical shear macro-rheology. Concentration dependence of the three characteristic times of the entangled polymer chains, reptation time, entanglement time, and correlation time, was studied with the help of the time-concentration superposition. At the low frequency range, dynamic moduli measured by macro-rheology and micro-rheology showed a good agreement without adjustable parameters. At the higher frequency range, we found the Rouse regime in the mean square displacement of the probe particles and in the magnitude of the complex specific viscosity of the solution. We propose a simple method to estimate the boundary of the Rouse regime. Finally, at the high frequency range, we demonstrate that the contribution of the solvent to the solution viscosity needs to be subtracted to observe the power-law behavior of the Zimm mode.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41551564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Burak Tavsanli, Cigdem Bilici, Pelin Sungur, Semra Ide, Oguz Okay
Recently, a simple strategy was developed for preparing interconnected interpenetrating polymer networks (IPNs) based on butyl rubber (IIR) and poly(n-octadecyl acrylate) (PC18A). Solvent-free UV polymerization of n-octadecyl acrylate (C18A) monomer in the melt of IIR at ambient temperature resulted in IPNs with self-healing and shape-memory functions. Here, we demonstrate that the use of IIR grafted with acrylic acid, methacrylic acid, and 10-undecenoic acid instead of unmodified IIR provides a significant improvement in the mechanical properties of IPNs. Differential scanning calorimetry, small-angle x-ray scattering, and wide-angle x-ray scattering analysis reveal side-by-side packing of C18 side chains of PC18A to form lamellar crystals with a melting temperature Tm between 46 and 52 °C. Transmission electron microscopy analysis indicates the existence of quasispherical nanoparticles composed of crystalline domains, which are dispersed in a continuous interpenetrating rubber-PC18A matrix. This microstructure provides them a complete self-recovery behavior induced by heating and an efficient shape-memory function. IPNs exhibit around tenfold higher chemical cross-link density as compared to those prepared from the native IIR, reflecting the effect of pendant vinyl groups on the extent of covalent interconnections between the IIR and PC18A components. The type of the grafted monomers significantly affects the mechanical performance of IPNs, which can be explained with the individual contributions of chemical and physical cross-links to the total cross-link density. The amount of the grafted rubbers in IPN could be further increased up to 80 wt. % by the incorporation of toluene into the reaction system, resulting in IPNs with a wide range of tunable thermal and mechanical properties.
{"title":"Butyl rubber as a macro-cross-linker in the preparation of a shape-memory and self-healing polymer","authors":"Burak Tavsanli, Cigdem Bilici, Pelin Sungur, Semra Ide, Oguz Okay","doi":"10.1122/8.0000414","DOIUrl":"https://doi.org/10.1122/8.0000414","url":null,"abstract":"Recently, a simple strategy was developed for preparing interconnected interpenetrating polymer networks (IPNs) based on butyl rubber (IIR) and poly(<i>n</i>-octadecyl acrylate) (PC18A). Solvent-free UV polymerization of <i>n</i>-octadecyl acrylate (C18A) monomer in the melt of IIR at ambient temperature resulted in IPNs with self-healing and shape-memory functions. Here, we demonstrate that the use of IIR grafted with acrylic acid, methacrylic acid, and 10-undecenoic acid instead of unmodified IIR provides a significant improvement in the mechanical properties of IPNs. Differential scanning calorimetry, small-angle x-ray scattering, and wide-angle x-ray scattering analysis reveal side-by-side packing of C18 side chains of PC18A to form lamellar crystals with a melting temperature <i>T<sub>m</sub></i> between 46 and 52 °C. Transmission electron microscopy analysis indicates the existence of quasispherical nanoparticles composed of crystalline domains, which are dispersed in a continuous interpenetrating rubber-PC18A matrix. This microstructure provides them a complete self-recovery behavior induced by heating and an efficient shape-memory function. IPNs exhibit around tenfold higher chemical cross-link density as compared to those prepared from the native IIR, reflecting the effect of pendant vinyl groups on the extent of covalent interconnections between the IIR and PC18A components. The type of the grafted monomers significantly affects the mechanical performance of IPNs, which can be explained with the individual contributions of chemical and physical cross-links to the total cross-link density. The amount of the grafted rubbers in IPN could be further increased up to 80 wt. % by the incorporation of toluene into the reaction system, resulting in IPNs with a wide range of tunable thermal and mechanical properties.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138519344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Consiglia Carillo, S. Zoellner, E. van Ruymbeke, D. Vlassopoulos
We investigate the linear viscoelastic properties of industrial pressure sensitive adhesives comprising double networks with an entangled acrylate-based polymer and two types of intermolecular associations (crosslinking), permanent (epoxide) and reversible (metal-chelate), having different compositions. A combination of shear rheometry and an appropriately modified version of the Time Marching Algorithm (TMA) allows to probe and analyze the behavior of the different double dynamic networks, in particular, the effects of the type and amount of crosslinks on their linear viscoelastic spectra. To this end, the dynamics of the double networks are compared with the respective individual responses of the polymeric component without crosslinks and the single networks (possessing only physical or only chemical crosslinks), in order to quantify their contributions to the relaxation mechanisms, particularly the interplay between disentanglement and bond association/dissociation processes. With the help of the TMA model, we also examine the respective roles of the lifetime of stickers, polydispersity, and molar mass. Triggered by the good comparison between predictions and experimental data, we propose a framework to tune material parameters in order to obtain a desired viscoelastic behavior.
{"title":"Tailoring the linear viscoelastic response of industrial double dynamics networks through the interplay of associations","authors":"Consiglia Carillo, S. Zoellner, E. van Ruymbeke, D. Vlassopoulos","doi":"10.1122/8.0000406","DOIUrl":"https://doi.org/10.1122/8.0000406","url":null,"abstract":"We investigate the linear viscoelastic properties of industrial pressure sensitive adhesives comprising double networks with an entangled acrylate-based polymer and two types of intermolecular associations (crosslinking), permanent (epoxide) and reversible (metal-chelate), having different compositions. A combination of shear rheometry and an appropriately modified version of the Time Marching Algorithm (TMA) allows to probe and analyze the behavior of the different double dynamic networks, in particular, the effects of the type and amount of crosslinks on their linear viscoelastic spectra. To this end, the dynamics of the double networks are compared with the respective individual responses of the polymeric component without crosslinks and the single networks (possessing only physical or only chemical crosslinks), in order to quantify their contributions to the relaxation mechanisms, particularly the interplay between disentanglement and bond association/dissociation processes. With the help of the TMA model, we also examine the respective roles of the lifetime of stickers, polydispersity, and molar mass. Triggered by the good comparison between predictions and experimental data, we propose a framework to tune material parameters in order to obtain a desired viscoelastic behavior.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43323588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jake Song, Qiaochu Li, Pangkuan Chen, B. Keshavarz, Brian S. Chapman, J. B. Tracy, G. McKinley, Niels Holten-Andersen
We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low functionality ( f) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high- f junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high- f junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high- f) and metal ion (low- f) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high- f networks.
{"title":"Song et al.: Dynamics of dual-junction-functionality associative polymer networks with ion and nanoparticle metal-coordinate cross-link junctions","authors":"Jake Song, Qiaochu Li, Pangkuan Chen, B. Keshavarz, Brian S. Chapman, J. B. Tracy, G. McKinley, Niels Holten-Andersen","doi":"10.1122/8.0000575","DOIUrl":"https://doi.org/10.1122/8.0000575","url":null,"abstract":"We provide a canonical introduction to dual-junction-functionality associative polymer networks, which combine high and low functionality ( f) dynamic cross-link junctions to impart load-bearing, dissipation, and self-repairing ability to the network. This unique type of network configuration offers an alternative to traditional dual-junction networks consisting of covalent and reversible cross-links. The high- f junctions can provide load-bearing abilities similar to a covalent cross-link while retaining the ability to self-repair and concurrently confer stimuli-responsive properties arising from the high- f junction species. We demonstrate the mechanical properties of this design motif using metal-coordinating polymer hydrogel networks, which are dynamically cross-linked by different ratios of metal nanoparticle (high- f) and metal ion (low- f) cross-link junctions. We also demonstrate the spontaneous self-assembly of nanoparticle-cross-linked polymers into anisotropic sheets, which may be generalizable for designing dual-junction-functionality associative networks with low volume fraction percolated high- f networks.","PeriodicalId":16991,"journal":{"name":"Journal of Rheology","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2022-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47739993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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