Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied.The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated.Cloudi...Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied.The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated.Clouding occurred when the concentration of PEG was large enough in the betaine aqueous solution,and the concentration of PEG at cloud point decreased with the increase of PEG molecular weight for a constant betaine concentration.The bottom phase was the PEG-rich phase,and the upper phase was the betaine-rich phase.The volumetric ratio of PEG-rich phase to betaine-rich phase,at the same difference between the PEG concentration and the one at the cloud point,ΔC cp(0.1 g·ml-1),decreased as the PEG molecular weight increased and approached 1 for higher PEG molecular weight(about 20000),which was similar to the typical aqueous two-phase system.This volumetric ratio depended on the initial PEG concentration,but independent of PEG molecular weight.The concentration ratio of betaine to PEG in both phases depended on the ΔC cp,independent of PEG molecular weight.展开更多
In this study, the poly(L-lactide)/poly(D-lactide)(PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and p...In this study, the poly(L-lactide)/poly(D-lactide)(PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and phase separation behaviors of these blends are investigated. Results reveal that optical purity and molecular weight do not vary the crystal structure of PLA stereocomplex(sc) and homochiral crystallites(hc). As the optical purity increasing in the blends, the melting temperature of sc(Tsc) and the content of sc(ΔHsc) increased, while the melting temperature of hc(Thm) hardly changes, although the content of hc(ΔHhm) decreased gradually. The Tsc and ΔHsc are also enhanced as the molecular weight of PDLA reduces, and the ΔHhm reduces rapidly even though the Thm does not vary apparently. With lower optical purities of PLLA and higher molecular weights of PDLA, three types of crystals form in the blends, i.e., PLA sc, PLLA hc and PDLA hc. As molecular weight decreases and optical purity enhances, the crystal phase decreases to two(sc and PDLA hc), and one(sc) finally. This investigation indicates that the phase separation behavior between PLLA and PDLA in the PLLA/PDLA blends not only depends on molecular weights, but also relies on the optical purities of polymers.展开更多
By preparing homogenous blend samples with different degrees of chain entanglement, we report an anomalous contribution of chain entanglement to phase separation temperature and rate of poly(methyl methacrylate)/poly(...By preparing homogenous blend samples with different degrees of chain entanglement, we report an anomalous contribution of chain entanglement to phase separation temperature and rate of poly(methyl methacrylate)/poly(styrene-comaleic anhydride)(PMMA/SMA) blends presenting a typical lower critical solution temperature(LCST) behavior. The meltmixed PMMA/SMA blends with a higher chain entanglement density present a lower cloud point(Tc) and shorter delay time, but lower phase separation rate at the given temperature than solution-cast ones, suggesting that for the polymer blends with different condensed state structure, thermodynamically more facilitation to phase separation(lower Tc) is not necessarily equivalent to faster kinetics(decomposition rate). The experimental results indicate that the lower Tc of melt-mixed sample is ascribed to smaller concentration fluctuation wavelength(Λm) induced by higher entanglement degree, while higher entanglement degree in melt-mixed sample leads to a confined segmental dynamics and consequently a slower kinetics(decomposition rate) dominated by macromolecular diffusion at a comparable quench depth. These results reveal that the chain packing in polymer blends can remarkably influence the liquid-liquid phase separation behavior, which is a significant difference from decomposition of small molecular mixtures.展开更多
A series of hexagonal close-packed(HCP) Co-W thin films were deposited by sputtering on surface oxidized silicon substrates at 300℃.A linear dependency of saturation magnetization(Ms) on W content was found up to abo...A series of hexagonal close-packed(HCP) Co-W thin films were deposited by sputtering on surface oxidized silicon substrates at 300℃.A linear dependency of saturation magnetization(Ms) on W content was found up to about 9 at.pct W,and then it underwent an increased Ms vs.W content curve as compared to the initial linear dependency.The thermal magnetization technique was used to confirm that the increased Ms behaviour is correlated to the phase separation of the Co-W thin films.The phase separation behaviour was also found to be dependent on W content and the reason was discussed in detail.Finally an interesting composition range was suggested to be about 13 at.pct-17 at.pct W for the Co-W thin films,in which they exhibit much higher magnetic anisotropy energy than Co-Cr thin films and improved phase separation.展开更多
A series of mixed, random cylindrical brush copolymers bearing polystyrene(PS) and poly(ε-caprolactone)(PCL) side chains were synthesized via the combination of ring-opening polymerization(ROP) and atom transfer radi...A series of mixed, random cylindrical brush copolymers bearing polystyrene(PS) and poly(ε-caprolactone)(PCL) side chains were synthesized via the combination of ring-opening polymerization(ROP) and atom transfer radical polymerization(ATRP). These novel cylindrical brush copolymers have been characterized by means of nuclear magnetic resonance(NMR) spectroscopy, gel permeation chromatography(GPC) and differential scanning calorimetry(DSC). It was found that the mikto-armed cylindrical brush copolymers were microphase-separated in bulks and that the morphologies were dependent on the mass ratios of PS to PCL side chains. One of the cylindrical brush copolymers was employed to incorporate into epoxy thermoset to investigate effect of the mikto-armed cylindrical brush architecture on the reaction-induced microphase separation behavior. Depending on the concentration of the cylindrical brush in epoxy, the thermosets can display the morphologies with the spherical, worm-like and lamellar PS microdomains dispersing in continuous thermosetting matrices.展开更多
The effect of clay on the morphology and phase-separation behavior of poly(methyl methacrylate)/poly(styreneco-acrylonitrile)(PMMA/SAN) blends and the variation of clay dispersion have been investigated. With the evol...The effect of clay on the morphology and phase-separation behavior of poly(methyl methacrylate)/poly(styreneco-acrylonitrile)(PMMA/SAN) blends and the variation of clay dispersion have been investigated. With the evolution of phase separation in PMMA/SAN, most of the clays are first located at the boundaries between PMMA and SAN, and then gradually move to the PMMA-rich domain, owing to the affinity of clay to PMMA. The introduction of clay causes the increase of binodal and spinodal temperatures of PMMA/SAN and enlarges their metastable region, indicating the phase stabilizing effect of clay on the matrix. But the influence of clay on the cloud points obviously depends on the composition of PMMA/SAN. The selective adsorption of PMMA on the clay results in the difference between the composition of surface layer and that of polymer matrix. Hence, the clay plays the role of an agent changing the conditions of phase structure formation.展开更多
The effect of nanoclay on the phase-separation behavior of poly(methyl methacrylate)/poly(vinyl acetate)(PMMA/PVAc) blends has been mainly investigated by small-angle laser light scattering. It is found that the effec...The effect of nanoclay on the phase-separation behavior of poly(methyl methacrylate)/poly(vinyl acetate)(PMMA/PVAc) blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors.展开更多
基金Supported by the National Natural Science Foundation of China （20676069）.
文摘Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied.The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated.Clouding occurred when the concentration of PEG was large enough in the betaine aqueous solution,and the concentration of PEG at cloud point decreased with the increase of PEG molecular weight for a constant betaine concentration.The bottom phase was the PEG-rich phase,and the upper phase was the betaine-rich phase.The volumetric ratio of PEG-rich phase to betaine-rich phase,at the same difference between the PEG concentration and the one at the cloud point,ΔC cp(0.1 g·ml-1),decreased as the PEG molecular weight increased and approached 1 for higher PEG molecular weight(about 20000),which was similar to the typical aqueous two-phase system.This volumetric ratio depended on the initial PEG concentration,but independent of PEG molecular weight.The concentration ratio of betaine to PEG in both phases depended on the ΔC cp,independent of PEG molecular weight.
基金financially supported by the National Natural Science Foundation of China(Nos.5127319851373169+4 种基金510330035130317651321062 and 51403089)863 Program(No.2011AA02A202)from the Ministry of Science and Technology of ChinaInnovative Research Group(No.51321062)
文摘In this study, the poly(L-lactide)/poly(D-lactide)(PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and phase separation behaviors of these blends are investigated. Results reveal that optical purity and molecular weight do not vary the crystal structure of PLA stereocomplex(sc) and homochiral crystallites(hc). As the optical purity increasing in the blends, the melting temperature of sc(Tsc) and the content of sc(ΔHsc) increased, while the melting temperature of hc(Thm) hardly changes, although the content of hc(ΔHhm) decreased gradually. The Tsc and ΔHsc are also enhanced as the molecular weight of PDLA reduces, and the ΔHhm reduces rapidly even though the Thm does not vary apparently. With lower optical purities of PLLA and higher molecular weights of PDLA, three types of crystals form in the blends, i.e., PLA sc, PLLA hc and PDLA hc. As molecular weight decreases and optical purity enhances, the crystal phase decreases to two(sc and PDLA hc), and one(sc) finally. This investigation indicates that the phase separation behavior between PLLA and PDLA in the PLLA/PDLA blends not only depends on molecular weights, but also relies on the optical purities of polymers.
基金financially supported by the National Natural Science Foundation of China(No.51173165)the Fundamental Research Funds for the Central Universities(No.2013QNA4048)
文摘By preparing homogenous blend samples with different degrees of chain entanglement, we report an anomalous contribution of chain entanglement to phase separation temperature and rate of poly(methyl methacrylate)/poly(styrene-comaleic anhydride)(PMMA/SMA) blends presenting a typical lower critical solution temperature(LCST) behavior. The meltmixed PMMA/SMA blends with a higher chain entanglement density present a lower cloud point(Tc) and shorter delay time, but lower phase separation rate at the given temperature than solution-cast ones, suggesting that for the polymer blends with different condensed state structure, thermodynamically more facilitation to phase separation(lower Tc) is not necessarily equivalent to faster kinetics(decomposition rate). The experimental results indicate that the lower Tc of melt-mixed sample is ascribed to smaller concentration fluctuation wavelength(Λm) induced by higher entanglement degree, while higher entanglement degree in melt-mixed sample leads to a confined segmental dynamics and consequently a slower kinetics(decomposition rate) dominated by macromolecular diffusion at a comparable quench depth. These results reveal that the chain packing in polymer blends can remarkably influence the liquid-liquid phase separation behavior, which is a significant difference from decomposition of small molecular mixtures.
基金supported by the National Natural Science Foundation of China(No50671020)Ministry of Education of China (No108039)
文摘A series of hexagonal close-packed(HCP) Co-W thin films were deposited by sputtering on surface oxidized silicon substrates at 300℃.A linear dependency of saturation magnetization(Ms) on W content was found up to about 9 at.pct W,and then it underwent an increased Ms vs.W content curve as compared to the initial linear dependency.The thermal magnetization technique was used to confirm that the increased Ms behaviour is correlated to the phase separation of the Co-W thin films.The phase separation behaviour was also found to be dependent on W content and the reason was discussed in detail.Finally an interesting composition range was suggested to be about 13 at.pct-17 at.pct W for the Co-W thin films,in which they exhibit much higher magnetic anisotropy energy than Co-Cr thin films and improved phase separation.
基金financially supported by the National Natural Science Foundation of China(Nos.51133003,21274091 and 21774078)the Shanghai Synchrotron Radiation Facility under the projects(Nos.10sr0260 and 10sr0126)
文摘A series of mixed, random cylindrical brush copolymers bearing polystyrene(PS) and poly(ε-caprolactone)(PCL) side chains were synthesized via the combination of ring-opening polymerization(ROP) and atom transfer radical polymerization(ATRP). These novel cylindrical brush copolymers have been characterized by means of nuclear magnetic resonance(NMR) spectroscopy, gel permeation chromatography(GPC) and differential scanning calorimetry(DSC). It was found that the mikto-armed cylindrical brush copolymers were microphase-separated in bulks and that the morphologies were dependent on the mass ratios of PS to PCL side chains. One of the cylindrical brush copolymers was employed to incorporate into epoxy thermoset to investigate effect of the mikto-armed cylindrical brush architecture on the reaction-induced microphase separation behavior. Depending on the concentration of the cylindrical brush in epoxy, the thermosets can display the morphologies with the spherical, worm-like and lamellar PS microdomains dispersing in continuous thermosetting matrices.
基金financially supported by the National Natural Science Foundation of China(No.51003093)the Program for Zhejiang Provincial Innovative Research Teams(No.2009R50004)the Research Foundation of Education Bureau of Zhejiang Province(No.Y200908238)
文摘The effect of clay on the morphology and phase-separation behavior of poly(methyl methacrylate)/poly(styreneco-acrylonitrile)(PMMA/SAN) blends and the variation of clay dispersion have been investigated. With the evolution of phase separation in PMMA/SAN, most of the clays are first located at the boundaries between PMMA and SAN, and then gradually move to the PMMA-rich domain, owing to the affinity of clay to PMMA. The introduction of clay causes the increase of binodal and spinodal temperatures of PMMA/SAN and enlarges their metastable region, indicating the phase stabilizing effect of clay on the matrix. But the influence of clay on the cloud points obviously depends on the composition of PMMA/SAN. The selective adsorption of PMMA on the clay results in the difference between the composition of surface layer and that of polymer matrix. Hence, the clay plays the role of an agent changing the conditions of phase structure formation.
基金supported by the National Natural Science Foundation of China(Nos.51003093 and 51273173)the Program for Zhejiang Provincial Innovative Research Teams(No.2009R50004)the Research Foundation of Education Bureau of Zhejiang Province(No.Y200908238)
文摘The effect of nanoclay on the phase-separation behavior of poly(methyl methacrylate)/poly(vinyl acetate)(PMMA/PVAc) blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors.
