The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(...The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(100 ﹣ x)SiO<sub>2</sub> (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li<sub>2</sub>O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates I<sub>st</sub> of lithium disilicate crystals in the 23.4Li<sub>2</sub>O·76.6SiO<sub>2</sub>, 26Li<sub>2</sub>O·74SiO<sub>2</sub> and 29.1Li<sub>2</sub>O·70.9SiO<sub>2</sub> glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates I<sub>st</sub> for the glass of the stoichiometric lithium disilicate composition 33.51Li<sub>2</sub>O·66.5SiO<sub>2</sub>. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li<sub>2</sub>O-SiO<sub>2</sub> system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.展开更多
Molecular dynamics computer simulation based on the Born-Mayer-Huggins potential function has been carried out to study the effects of cluster size and temperature on the nucleation rate of sodium chloride clusters in...Molecular dynamics computer simulation based on the Born-Mayer-Huggins potential function has been carried out to study the effects of cluster size and temperature on the nucleation rate of sodium chloride clusters in the temperature range of 580 K to 630 K. Clusters with 256 and 500 NaCl molecules have been studied and the results have been compared with those obtained from 108 molecule clusters. The melting point (MP) of the clusters were observed to increase with the size of the clusters and can be well described by a linear equation MP=1107(37)-1229(23)N -1/3 (N is the number of molecules in the cluster). The nucleation rate was found to decrease with increasing the cluster size or temperature. Various nucleation theories have been used to interpret the nucleation rates obtained from this molecular dynamics simulation. It is possible to use a constant diffuse interface thickness to interpret the nucleation rate from the diffuse interface theory in the temperature range of this study. However,the interfacial free energy estimated from classical nucleation theory and diffuse interface theory increases too fast with increasing the temperature while that from Gran-Gunton theory does not change with changing temperatures. The sizes of critical nuclei estimated from all the theories are smaller than those estimated from our simulations.展开更多
Since the separation of crystal of KCl saturated aqueous is similar to the crystallization of liquid metals, the melts nucleation can be simulated by the experiment of the crystal of salt aqueous solution. In this exp...Since the separation of crystal of KCl saturated aqueous is similar to the crystallization of liquid metals, the melts nucleation can be simulated by the experiment of the crystal of salt aqueous solution. In this experiment pulsation treatment was imposed on KCl saturated aqueous in order to study the effect of pulsation treatment on crystallization in the salt solution, and the influence of different pulsation treating time, super-heating and bine of prescription were investigated. The results show that it is possible to modify the crystallization over satured solution temperature and the degree of under-cooling for salt crystal separation was reduced by applying pulse treating on KCl saturated aqueous solution. In addition, this technology may generate embryos for nucleation even at the temperature over melting point or satured solubility.展开更多
Molecular dynamics （MD） computer simulations have been carried out to study the structures, properties and crystal nucleation of nanoparticles with 453 Cu atoms. Structure information was analyzed from the MD simula...Molecular dynamics （MD） computer simulations have been carried out to study the structures, properties and crystal nucleation of nanoparticles with 453 Cu atoms. Structure information was analyzed from the MD simulations, while properties of nanoparticles of Cu453, such as melting point, freezing temperature, heat capacity and mo- lar volumes, have been estimated. The face center cubic （FCC） phase and icosahedron （Ih） phase were observed during the quenching process, and nucleation rates of crystallization to FCC crystal of Cu453 at temperatures of 650, 700, 750, and 800 K were analyzed. Both classical nucleation theory （CNT） and diffuse interface theory （DIT） were used to interpret our observed nucleation rates. The free energy and diffuse interface thickness between the liquid and the FCC crystal phases were estimated by the CNT and DIT respectively, and the results show that the DIT does not work properly to the system.展开更多
In this paper, poly(butylene-terephthalate)-layered silicate of clay nanocomposites (NPBT) are reported. Their thermal properties, heat distortion temperature (HDT) and crystallization nucleation are investigated. NPB...In this paper, poly(butylene-terephthalate)-layered silicate of clay nanocomposites (NPBT) are reported. Their thermal properties, heat distortion temperature (HDT) and crystallization nucleation are investigated. NPBT samples have apparent viscosity over 0.85, HDT of 30℃ to 50℃ higher than that of poly (butylene-terephthalate) (PBT) for clay load from 1.0% to 10.0% (by mass), and higher capability to accommodate clay than other polymers. The nonisothermal crystallization experiments indicate that the better thermal degradation behavior and crystallization rate of NPBT are 50% higher than PBT, and its injection mould processing temperature is lowered from 110℃ to 55℃. NPBT samples are characterized by several techniques. X-ray shows an original clay interlayer distance enlarged from 1.0 nm to 2.5 nm, while both TBM and AFM indicate an average size from 30nm to lOOnm of exfoliated clay layers, and 3%(by mass) of particle agglomeration being phase separated from PBT matrix, which are factors on some mechanical properties decrease of NPBT. The disappearance of spherulitic morphology in NPBT resulted from layers nucleation is detected. Improving NPBT properties by treating clay with long chain organic reagent and controlling the way to load it is suggested.展开更多
Differential fast scanning calorimetry（DFSC） was employed on the study of self-nucleation behavior of poly（butylene succinate）（PBS）.The ultra-fast cooling ability of DFSC allows investigating the effect of self-...Differential fast scanning calorimetry（DFSC） was employed on the study of self-nucleation behavior of poly（butylene succinate）（PBS）.The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.展开更多
Zinc aluminosilicate glasses containing Li2 O, ZnO , Al2O3 and SiO2 were prepared by conventional melting and quenching technique, and subsequently converted to transparent glass-ceramics by controlled nucleation and...Zinc aluminosilicate glasses containing Li2 O, ZnO , Al2O3 and SiO2 were prepared by conventional melting and quenching technique, and subsequently converted to transparent glass-ceramics by controlled nucleation and crystallization. The glass was melted in a platinum crucible at 1 600 ℃ for 2 h and then two-step heat treated for the nucleation and the crystal growth. The nucleation and crystallization temperatures were determined by differential thermal analysis. Specimens heat-treated on different schedules were analyzed by the X-ray diffraction to determine crystalline phases. Scanning electron microscopy was used to study the glass-ceramics morphology, the grain size and distribution in the residual glass matrix. The reorganization of the amorphous solid was confirmed by FT-IR spectroscopy. The transmittance was measured by a UV-Vis-NIR scanning spectrophotometer .展开更多
We present simulations of the mechanism of secondary nucleation of polymer crystallization,based on a new model accounting for the microscopic kinetics of attaching and detaching.As the key feature of the model,we int...We present simulations of the mechanism of secondary nucleation of polymer crystallization,based on a new model accounting for the microscopic kinetics of attaching and detaching.As the key feature of the model,we introduced multibody-interaction parameters that establish correlations between the attaching and detaching rate constants and the resulting thickness and width of the crystalline lamella.Using MATLAB and Monte Carlo method,we followed the evolution of the secondary nuclei as a function of various multibody-interaction parameters.We identified three different growth progressions of the crystal：（i） Widening,（ii） thickening and（iii） simultaneously thickening and widening of lamellar crystals,controlled by the corresponding kinetic parameters.展开更多
ZSM-22 （TON） zeolite crystal morphology was successfully controlled using a microwave-assisted solvothermal fabrication method. Different co-solvents, including ethanol, 2-propanol, glycerol, and ethylene glycol, we...ZSM-22 （TON） zeolite crystal morphology was successfully controlled using a microwave-assisted solvothermal fabrication method. Different co-solvents, including ethanol, 2-propanol, glycerol, and ethylene glycol, were also applied in the synthesis mixture. The effects of various parameters such as the aging time, the type and amount of co-solvent on the ZSM-22 crystal aspect ratio were investigated. When employing this microwave irradiation synthesis, a long aging time was crucial to obtain smaller and more uniform crystal sizes. The addition of co-solvent resulted in elongated ZSM-22 crystals, regard- less of the actual co-solvent used, although ZSM-22 zeolite crystallinity was sensitive to the co-solvent type. In general, the use of a co-solvent stimulated the appearance of ZSM-5 zeolite as an impurity and the amount of this impurity was proportional to the concentration of co-solvent in the synthesis mixture.展开更多
A series of ternary blends of polypropylene/ethylene-propylene random copolymer/ethylene-propylene segmented copolymer（HPP/EPR/Eb P） whose microstructures are similar to those of impact polypropylene copolymer（IPC...A series of ternary blends of polypropylene/ethylene-propylene random copolymer/ethylene-propylene segmented copolymer（HPP/EPR/Eb P） whose microstructures are similar to those of impact polypropylene copolymer（IPC） were prepared in order to systematically investigate the effects of composition on microstructure and crystallization behavior of IPC. The observation of primary phase morphology reveals that the dispersed phase with core-shell structure could be rebuilt in certain composition and excessive EPR leads to a bicontinuous phase structure in ternary blends. After undergoing same quiescent crystallization including isothermal and non-isothermal crystallization, these blend samples exhibit special composition-dependent melting behavior, i.e., the melting point increases markedly with the increase of EPR content until it turns down at a critical content（about 30 wt%）. The crystallization behavior is mainly ascribed to the different nucleation abilities. It is suggested that although the compatibility between EPR and HPP components becomes worse with the increase of EPR content due to the increased interfacial area and the decreased concentration of Eb P, higher EPR content in the blend facilitates to heterogeneous nucleation except for the appearance of obvious bicontinuous phase structure.展开更多
Crystallization of flexible polymer chains reveals distinct characters compared to small molecules, which provides a platform to study molecular self-assembly and morphogenesis. In this review, some examples, e.g., tw...Crystallization of flexible polymer chains reveals distinct characters compared to small molecules, which provides a platform to study molecular self-assembly and morphogenesis. In this review, some examples, e.g., twisting chirality of polymer lamellar crystals, recognition of different chain units and competitive nucleation of different polymorphs and different lamellar thicknesses are briefly discussed. It is shown that the polymer crystallization process far from equilibrium is in practically minimization of the system free energy in local space and finite time, leading to formation of twisted crystals, metastable polymorphism and lamellar crystals with finite thickness. Though each molecule is blind to others, the peculiar ordered configurations with stronger long-range interactions are chosen from the enormous random trials. At the end, we list some remaining questions and outlook the perspectives.展开更多
Poly（L-lactide）（PLLA）/pristine vermiculite nanocomposites were prepared by melt blending in a twin-screw extruder, and the detailed information of vermiculite dispersion state and effect of vermiculite on thermal ...Poly（L-lactide）（PLLA）/pristine vermiculite nanocomposites were prepared by melt blending in a twin-screw extruder, and the detailed information of vermiculite dispersion state and effect of vermiculite on thermal and mechanical properties were systematically studied. The results show that the dispersion of vermiculite in the matrix is quite well when the loading content does not exceed 3 wt%. Pristine vermiculite can obviously improve the melt-crystallization temperature during the nonisothermal crystallization. Both crystallization time span and spherulitic size of PLLA decrease with the increasing amount of vermiculite under isothermal crystallization condition by enhancing the primary nucleation of PLLA. And the adding vermiculite can also improve the tensile modulus and Izod impact strength of PLLA. The intrinsic mechanism for the nucleating effect of vermiculite on PLLA is proposed to be the epitaxial crystallization and specific interaction between vermiculite and PLLA.展开更多
文摘The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(100 ﹣ x)SiO<sub>2</sub> (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li<sub>2</sub>O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates I<sub>st</sub> of lithium disilicate crystals in the 23.4Li<sub>2</sub>O·76.6SiO<sub>2</sub>, 26Li<sub>2</sub>O·74SiO<sub>2</sub> and 29.1Li<sub>2</sub>O·70.9SiO<sub>2</sub> glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates I<sub>st</sub> for the glass of the stoichiometric lithium disilicate composition 33.51Li<sub>2</sub>O·66.5SiO<sub>2</sub>. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li<sub>2</sub>O-SiO<sub>2</sub> system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.
文摘Molecular dynamics computer simulation based on the Born-Mayer-Huggins potential function has been carried out to study the effects of cluster size and temperature on the nucleation rate of sodium chloride clusters in the temperature range of 580 K to 630 K. Clusters with 256 and 500 NaCl molecules have been studied and the results have been compared with those obtained from 108 molecule clusters. The melting point (MP) of the clusters were observed to increase with the size of the clusters and can be well described by a linear equation MP=1107(37)-1229(23)N -1/3 (N is the number of molecules in the cluster). The nucleation rate was found to decrease with increasing the cluster size or temperature. Various nucleation theories have been used to interpret the nucleation rates obtained from this molecular dynamics simulation. It is possible to use a constant diffuse interface thickness to interpret the nucleation rate from the diffuse interface theory in the temperature range of this study. However,the interfacial free energy estimated from classical nucleation theory and diffuse interface theory increases too fast with increasing the temperature while that from Gran-Gunton theory does not change with changing temperatures. The sizes of critical nuclei estimated from all the theories are smaller than those estimated from our simulations.
文摘Since the separation of crystal of KCl saturated aqueous is similar to the crystallization of liquid metals, the melts nucleation can be simulated by the experiment of the crystal of salt aqueous solution. In this experiment pulsation treatment was imposed on KCl saturated aqueous in order to study the effect of pulsation treatment on crystallization in the salt solution, and the influence of different pulsation treating time, super-heating and bine of prescription were investigated. The results show that it is possible to modify the crystallization over satured solution temperature and the degree of under-cooling for salt crystal separation was reduced by applying pulse treating on KCl saturated aqueous solution. In addition, this technology may generate embryos for nucleation even at the temperature over melting point or satured solubility.
文摘Molecular dynamics （MD） computer simulations have been carried out to study the structures, properties and crystal nucleation of nanoparticles with 453 Cu atoms. Structure information was analyzed from the MD simulations, while properties of nanoparticles of Cu453, such as melting point, freezing temperature, heat capacity and mo- lar volumes, have been estimated. The face center cubic （FCC） phase and icosahedron （Ih） phase were observed during the quenching process, and nucleation rates of crystallization to FCC crystal of Cu453 at temperatures of 650, 700, 750, and 800 K were analyzed. Both classical nucleation theory （CNT） and diffuse interface theory （DIT） were used to interpret our observed nucleation rates. The free energy and diffuse interface thickness between the liquid and the FCC crystal phases were estimated by the CNT and DIT respectively, and the results show that the DIT does not work properly to the system.
基金Supported by China National Petroleum Corporation Innovation Foundation(No.J02060)and Subsidized by Special Funds for Major State Basic Research Projects(No.G1999064800)
文摘In this paper, poly(butylene-terephthalate)-layered silicate of clay nanocomposites (NPBT) are reported. Their thermal properties, heat distortion temperature (HDT) and crystallization nucleation are investigated. NPBT samples have apparent viscosity over 0.85, HDT of 30℃ to 50℃ higher than that of poly (butylene-terephthalate) (PBT) for clay load from 1.0% to 10.0% (by mass), and higher capability to accommodate clay than other polymers. The nonisothermal crystallization experiments indicate that the better thermal degradation behavior and crystallization rate of NPBT are 50% higher than PBT, and its injection mould processing temperature is lowered from 110℃ to 55℃. NPBT samples are characterized by several techniques. X-ray shows an original clay interlayer distance enlarged from 1.0 nm to 2.5 nm, while both TBM and AFM indicate an average size from 30nm to lOOnm of exfoliated clay layers, and 3%(by mass) of particle agglomeration being phase separated from PBT matrix, which are factors on some mechanical properties decrease of NPBT. The disappearance of spherulitic morphology in NPBT resulted from layers nucleation is detected. Improving NPBT properties by treating clay with long chain organic reagent and controlling the way to load it is suggested.
基金financially supported by the National Natural Science Foundation of China(Nos.21474049,51673094 and 21404055)the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20160531151102203 and JCYJ20160608140827794)Tianshan Scholars Program by Yili Normal University
文摘Differential fast scanning calorimetry（DFSC） was employed on the study of self-nucleation behavior of poly（butylene succinate）（PBS）.The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.
基金Funded bythe Chinese Education Ministry(No.KB20026)
文摘Zinc aluminosilicate glasses containing Li2 O, ZnO , Al2O3 and SiO2 were prepared by conventional melting and quenching technique, and subsequently converted to transparent glass-ceramics by controlled nucleation and crystallization. The glass was melted in a platinum crucible at 1 600 ℃ for 2 h and then two-step heat treated for the nucleation and the crystal growth. The nucleation and crystallization temperatures were determined by differential thermal analysis. Specimens heat-treated on different schedules were analyzed by the X-ray diffraction to determine crystalline phases. Scanning electron microscopy was used to study the glass-ceramics morphology, the grain size and distribution in the residual glass matrix. The reorganization of the amorphous solid was confirmed by FT-IR spectroscopy. The transmittance was measured by a UV-Vis-NIR scanning spectrophotometer .
基金financially supported by the National Natural Science Foundation of China(No.21374054)the Sino-German Center for Research Promotion
文摘We present simulations of the mechanism of secondary nucleation of polymer crystallization,based on a new model accounting for the microscopic kinetics of attaching and detaching.As the key feature of the model,we introduced multibody-interaction parameters that establish correlations between the attaching and detaching rate constants and the resulting thickness and width of the crystalline lamella.Using MATLAB and Monte Carlo method,we followed the evolution of the secondary nuclei as a function of various multibody-interaction parameters.We identified three different growth progressions of the crystal：（i） Widening,（ii） thickening and（iii） simultaneously thickening and widening of lamellar crystals,controlled by the corresponding kinetic parameters.
文摘ZSM-22 （TON） zeolite crystal morphology was successfully controlled using a microwave-assisted solvothermal fabrication method. Different co-solvents, including ethanol, 2-propanol, glycerol, and ethylene glycol, were also applied in the synthesis mixture. The effects of various parameters such as the aging time, the type and amount of co-solvent on the ZSM-22 crystal aspect ratio were investigated. When employing this microwave irradiation synthesis, a long aging time was crucial to obtain smaller and more uniform crystal sizes. The addition of co-solvent resulted in elongated ZSM-22 crystals, regard- less of the actual co-solvent used, although ZSM-22 zeolite crystallinity was sensitive to the co-solvent type. In general, the use of a co-solvent stimulated the appearance of ZSM-5 zeolite as an impurity and the amount of this impurity was proportional to the concentration of co-solvent in the synthesis mixture.
基金financially supported by the National Natural Science Foundation of China(Nos.51173157 and 51173165)the Fundamental Research Funds for the Central Universities(No.2013QNA4048)Nature Science Foundation of Zhejiang Province(No.Y4100314)
文摘A series of ternary blends of polypropylene/ethylene-propylene random copolymer/ethylene-propylene segmented copolymer（HPP/EPR/Eb P） whose microstructures are similar to those of impact polypropylene copolymer（IPC） were prepared in order to systematically investigate the effects of composition on microstructure and crystallization behavior of IPC. The observation of primary phase morphology reveals that the dispersed phase with core-shell structure could be rebuilt in certain composition and excessive EPR leads to a bicontinuous phase structure in ternary blends. After undergoing same quiescent crystallization including isothermal and non-isothermal crystallization, these blend samples exhibit special composition-dependent melting behavior, i.e., the melting point increases markedly with the increase of EPR content until it turns down at a critical content（about 30 wt%）. The crystallization behavior is mainly ascribed to the different nucleation abilities. It is suggested that although the compatibility between EPR and HPP components becomes worse with the increase of EPR content due to the increased interfacial area and the decreased concentration of Eb P, higher EPR content in the blend facilitates to heterogeneous nucleation except for the appearance of obvious bicontinuous phase structure.
基金the National Natural Science Foundation of China (No. 21374054)Fund of Key Laboratory of Advanced Materials of Ministry of Education (No. 2017AML07) for financial support
文摘Crystallization of flexible polymer chains reveals distinct characters compared to small molecules, which provides a platform to study molecular self-assembly and morphogenesis. In this review, some examples, e.g., twisting chirality of polymer lamellar crystals, recognition of different chain units and competitive nucleation of different polymorphs and different lamellar thicknesses are briefly discussed. It is shown that the polymer crystallization process far from equilibrium is in practically minimization of the system free energy in local space and finite time, leading to formation of twisted crystals, metastable polymorphism and lamellar crystals with finite thickness. Though each molecule is blind to others, the peculiar ordered configurations with stronger long-range interactions are chosen from the enormous random trials. At the end, we list some remaining questions and outlook the perspectives.
基金financially supported by the National Natural Science Foundation of China(No.21304108)the Science Foundation of China University of Petroleum-Beijing(No.YJRC-2013-142462013BJRC001)
文摘Poly（L-lactide）（PLLA）/pristine vermiculite nanocomposites were prepared by melt blending in a twin-screw extruder, and the detailed information of vermiculite dispersion state and effect of vermiculite on thermal and mechanical properties were systematically studied. The results show that the dispersion of vermiculite in the matrix is quite well when the loading content does not exceed 3 wt%. Pristine vermiculite can obviously improve the melt-crystallization temperature during the nonisothermal crystallization. Both crystallization time span and spherulitic size of PLLA decrease with the increasing amount of vermiculite under isothermal crystallization condition by enhancing the primary nucleation of PLLA. And the adding vermiculite can also improve the tensile modulus and Izod impact strength of PLLA. The intrinsic mechanism for the nucleating effect of vermiculite on PLLA is proposed to be the epitaxial crystallization and specific interaction between vermiculite and PLLA.
