Organic molecules that exhibit long persistent luminescence (LPL) are rapidly gaining attention for a variety of applications. In this study, organic molecules with simple structures were selected and organic long per...Organic molecules that exhibit long persistent luminescence (LPL) are rapidly gaining attention for a variety of applications. In this study, organic molecules with simple structures were selected and organic long persistent luminescence (OLPL) crystals were prepared. The crystal structure of the prepared OLPL crystal was elucidated and the guideline for the design of OLPL crystal was clarified. LPL was observed in OLPL crystals prepared with TMB as the guest molecule and 1,2-bis(diphenylphosphino)ethane as the host molecule. XRD measurements of the OLPL crystals suggest that the guest molecule is a solid solution substituted in the stable crystal structure of the host molecule in a lattice-shrinking direction.展开更多
The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR ...The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.展开更多
In this paper a porous media seepage model was applied to analyze the permeability and study the seepage process of crystal pillar formed in the preparation of electronic grade phosphoric acid(EGPA).By inspecting the ...In this paper a porous media seepage model was applied to analyze the permeability and study the seepage process of crystal pillar formed in the preparation of electronic grade phosphoric acid(EGPA).By inspecting the seeping process,the structure parameter of crystal pillar could be obtained.Two basic ideal models(perfectly separated model and perfectly connected model)were presented and a characterized factorφwas introduced to modify the model.A good simulation result was obtained which met the experiment result well.The relationship betweenφand permeability were also discussed.The characterized factorφshowed potential application on optimizing process.展开更多
Increasing production effeciency and lowering costs are some of the many advantages melt crystallization technology offers over the conventional methodology of tabletting. A normal tablet consists of a pure shell or a...Increasing production effeciency and lowering costs are some of the many advantages melt crystallization technology offers over the conventional methodology of tabletting. A normal tablet consists of a pure shell or a coat and a separate core constituting the pharmaceutical active ingredient. Great emphasis is put on the purity of the shell since its purpose is to solely protect and deliver the active ingredient to its target. Melt crystallization is a purification (separation) process. It is discussed here for its ability to produce coated tablets, by separating the "coating" material from the "to be coated" material coming from one molten mixture. Molten drops of lutrol-ibuprofen mixture are produced using the drop forming technique. The subsequent analysis involves proving and quantifying the phase separation (coat purity). The mechanism of a crystallizing drop is shown as direct evidence of the ongoing process. Moreover, solidified tablet batches are analyzed for the purity of their coating by measuring the ibuprofen concentration. This optimization process is carried out through multiple stages of development and condition enhancements in order to produce the most pure tablet coating. As a result, a trial showing an almost purely coated tablet is presented here.展开更多
Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorph...Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.展开更多
Lunar anorthosite is a major rock of the lunar highlands,which formed as a result of plagioclasefloatation in the lunar magma ocean(LMO).Constraints on the sufficient conditions that resulted in the formation of a t...Lunar anorthosite is a major rock of the lunar highlands,which formed as a result of plagioclasefloatation in the lunar magma ocean(LMO).Constraints on the sufficient conditions that resulted in the formation of a thick pure anorthosite(mode of plagioclase 〉95 vol.%) is a key to reveal the early magmatic evolution of the terrestrial planets.To form the pure lunar anorthosite,plagioclase should have separated from the magma ocean with low crystal fraction.Crystal networks of plagioclase and mafic minerals develop when the crystal fraction in the magma(φ) is higher than ca.40-60 vol.%,which inhibit the formation of pure anorthosite.In contrast,when φ is small,the magma ocean is highly turbulent,and plagioclase is likely to become entrained in the turbulent magma rather than separated from the melt.To determine the necessary conditions in which anorthosite forms from the LMO,this study adopted the energy criterion formulated by Solomatov.The composition of melt,temperature,and pressure when plagioclase crystallizes are constrained by using MELTS/pMELTS to calculate the density and viscosity of the melt.When plagioclase starts to crystallize,the Mg~# of melt becomes 0.59 at 1291 C.The density of the melt is smaller than that of plagioclase for P 〉 2.1 kbar(ca.50 km deep),and the critical diameter of plagioclase to separate from the melt becomes larger than the typical crystal diameter of plagioclase(1.8-3 cm).This suggests that plagioclase is likely entrained in the LMO just after the plagioclase starts to crystallize.When the Mg~# of melt becomes 0.54 at 1263 C,the density of melt becomes larger than that of plagioclase even for 0 kbar.When the Mg~# of melt decreases down to 0.46 at 1218 C,the critical diameter of plagioclase to separate from the melt becomes 1.5-2.5 cm,which is nearly equal to the typical plagioclase of the lunar anorthosite.This suggests that plagioclase could separate from the melt.One of the differences between the Earth and the Moon is the presence of water.If the terrestrial magma ocean was saturated with H_2O,plagioclase could not crystallize,and anorthosite could not form.展开更多
2,6-Diisopropylnaphthalene (2,6-DIPN), as the precursor of important monomer 2,6-naphthalene dicarboxylic acid, could be produced by the shape-selective isopropylation of naphthalene with propene resulting in an iso...2,6-Diisopropylnaphthalene (2,6-DIPN), as the precursor of important monomer 2,6-naphthalene dicarboxylic acid, could be produced by the shape-selective isopropylation of naphthalene with propene resulting in an isomeric mixture having different alkylation levels. Since the boiling points of DIPNs were very close and the differences of melting points in-between isomers were quite distinctive, the static melt crystallization was applied to separate and purify 2,6-DIPN from its isomers. 2,6-DIPN with purity ≥99% was produced through a process of three stages: crystallization→sweating→melting. The phase diagram of 2,6-DIPN-2,7-DIPN binary system was plotted to opti- mize the temperature control of crystallization. By repeated crystallization of melts with different concentration levels, the yield of pure 2,6-DIPN could be enhanced to 87%. No solvent was necessary. Keywords 2,6-diisopropylnaphthalene, static melt crystallization, crystallization rate, sweating rate, eutectic temperature展开更多
2,6-Diisopropylnaphthalene(2,6-DIPN),as the precursor of important monomer 2,6-naphthalene dicarboxylic acid,was prepared by hydroisopropylation of refined naphthalene with propene over shape-selective catalyst.Naph...2,6-Diisopropylnaphthalene(2,6-DIPN),as the precursor of important monomer 2,6-naphthalene dicarboxylic acid,was prepared by hydroisopropylation of refined naphthalene with propene over shape-selective catalyst.Naphthalene conversion of 92% and 2,6-DIPN selectivity of 64% were obtained.Static melt crystallization was applied to separate and purify 2,6-DIPN from its isomers,resulted in a product purity of≥99%.The other isomers were converted into monoisopropylnaphthalene,which also reacted with propene to form 2,6-DIPN.A recycled process including hydroisopropylation,separation and transalkylation was established,the yield of 2,6-DIPN based on naphthalene could be doubled by one cycle operation.展开更多
In order to constrain temperature during subduction and subsequent exhumation of fel- sic continental crust, we carried out a Ti-in-zircon thermometer coupled with zircon internal structure and U-Pb age on migmatitic ...In order to constrain temperature during subduction and subsequent exhumation of fel- sic continental crust, we carried out a Ti-in-zircon thermometer coupled with zircon internal structure and U-Pb age on migmatitic gneisses from the Weihai region in the Sulu ultra-high pres- sure (UHP) metamorphic terrane, eastern China. The Weihai migmatitic gneisses are composed of in- tercalated compositional layers of melanosome and plagioclase (Pl)-rich lencosome and K-feldspar (Kfs)-rich pegmatite veins. Four stages of zircon growth were recognized in the Weihai migmatitic gneisses. They successively recorded informations of protolith, prograde metamorphism, decompres- sional partial melting during early stage exhumation and subsequent fractional crystallization of pri- mary melt during later stage cooling exhumation. The inherited cores in zircon from the melanosome and the Pl-rich leucosome suggest that the pro- tolith of the migmatitic gneiss is Mid- Neoproterozoic (-780 Ma) magmatic rock. Metamorphic zircons with concordant ages ranging from 243 to 256 Ma occur as over- growth mantles on the protolith magmatic zir- con cores. The estimated growth temperatures (625-717 "C) of the metamorphic zircons have a negative correlation with their ages, indicating a progressive metamorphism in HP eciogite-facies condition during subduction. Zircon recrystal- lized rims (228-2 Ma) in the PI-rich ieucosome layers provide the lower limit of the decompress-sional partial melting time during exhumation. The ages from 228^-2 to 219~2 Ma recorded in the Pl-rich leucosome and the Kfs-rich pegmatite vein, respectively, suggest the duration of the fractional crystallization of primary melt during exhumation. The calculated growth temperatures of the zircon rims from the Pl-rich leucosome range from 858 to 739 , and the temperatures of new growth zircon grains (219±2 Ma) in Kfs-rich vein are between 769 and 529 . The estimated temperatures have a positive correlation with ages from the Pl-rich leucosome to the Kfs-rich pegmatite vein, strongly indi- cating that a process of fractional crystallization of the partial melt during exhumation.展开更多
In this study, a series of monodispersed poly(L-lactide)(PLLA) were synthesized by the ring-opening polymerization with Schiff base aluminum catalyst, and the effects of the number-average molecular weight(Mn) o...In this study, a series of monodispersed poly(L-lactide)(PLLA) were synthesized by the ring-opening polymerization with Schiff base aluminum catalyst, and the effects of the number-average molecular weight(Mn) on the crystallization and melting behaviors of PLLA were investigated by differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The total crystallization rate of PLLA was Mn-dependent, which reached the maximum value for PLLA with Mn of 18.6 kg/mol. In addition, when Mn of PLLA was 18.6 kg/mol, the melting enthalpy(ΔHm) showed a maximum value(87.1 J/g), which was the highest reported value till now. The critical temperature for change of crystal formation from ?-form to ?-form crystals increased in the isothermal crystallization process with Mn increasing. In the reheating procedure, high-Mn PLLA demonstrated a small exothermal peak prior to the dominant melting peak, corresponding to crystal transition from ?- to ?-form, but low-Mn PLLA didn't show the peak of crystal transition. These different crystallization and melting behaviors were attributed to the different chain mobility of PLLA with different Mn.展开更多
In integrated circuit-grade single silicon Czochralski growth, the position and material of heat shield are main parameters affecting the heat exchange and crystal growth condition. By optimizing the above parameters,...In integrated circuit-grade single silicon Czochralski growth, the position and material of heat shield are main parameters affecting the heat exchange and crystal growth condition. By optimizing the above parameters, we attempted to increase the growth rate and crystal quality. Numerical simulation proved to verify the results before and after optimization. Through analyses of the temperature and microdefect distribution, it is found that the optimized heat shield can further increase the pulling rate and decrease the melt/crystal interface deflection, increase the average velocity of argon flow from ~2 to ~5 m·s-1, which is in favor of the transportation of SiO, and obtain the low defects concentration crystal and that the average temperature along the melt-free surface is 8 °C higher than before avoiding supercooled melt effectively. ? The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2012.展开更多
Numerical results show that an external magnetic field may influence significantly the flow pattern in the molten semiconductor of Czochralski crystal growth. The melt flow could be pronouncedly damped by a magnet. ic...Numerical results show that an external magnetic field may influence significantly the flow pattern in the molten semiconductor of Czochralski crystal growth. The melt flow could be pronouncedly damped by a magnet. ic field with the intensity of several thousands Gauss, while the temperature field is affected only in a less extent by the magnetic field.展开更多
A Nd3+:(Sr0.7Ca0.3)3Y(BO3)3 crystal with dimensions of Ф17×23 mm3 has been grown by the Czochralski method. The spectroscopic characterization of Nd3+:(Sr0.7Cao.3)aY(BO3)3 crystal was investigated. T...A Nd3+:(Sr0.7Ca0.3)3Y(BO3)3 crystal with dimensions of Ф17×23 mm3 has been grown by the Czochralski method. The spectroscopic characterization of Nd3+:(Sr0.7Cao.3)aY(BO3)3 crystal was investigated. The polarized absorption cross-sections of Nda+:(Sr0.7Ca0.3)aY(BO3)3 crystal are 2.81×10-20 cm2 with full width at half maximum (FWHM) of 14 nrn at 808 nm for σ-polarization and 2.04×10-20 cm2 with FWHM of 19 nm at 807 nm for 7r-polarization, respectively. The polarized emission cross-sections of Nd3+(Sr0.7Ca0.3)3Y(BO3)3 crystal are 12.2× 10.20 cm2 at 1062 nm for the π-polarization and 13.6×10-20 crn2 at 1061 nm for the a-polarization, respectively. After the Ca2+ ion partly substitutes for Sr2+ ion in the Sr3Y(BO3)3 crystal to form the (Sr0.7Ca0.3)3Y(BO3)3 solid solution, it can improve the quantum efficiency η of Nd3+:(Sr0.7TCa0.3)3Y(BO3)3 crystal. The quantum efficiency is 31.7%. These results may be regarded Nd3+:(Sr0.7Ca0.3)3Y(BO3)3 crystal as a potential solid-state laser material.展开更多
The quality of substrate crystals is critical to the performance of devices used in electronic and optoelectronic applications.These bulk crystals are mostly grown from the melt or solution,with a well controlled soli...The quality of substrate crystals is critical to the performance of devices used in electronic and optoelectronic applications.These bulk crystals are mostly grown from the melt or solution,with a well controlled solidification or supersaturation,which is affected significantly by the heat and mass flows.Particularly,in the melt growth,the interface kinetics is so fast that the growth is mainly controlled by the transport processes.Hence,the intricate coupling of heat and mass transfer and melt flow strongly influences the grown crystal quality,but its analysis and control is not a trivial task.For most materials,such as semiconductors and oxides,a detailed analysis of the transport processes through experiments is extremely difficult due to the long growth period at high temperature.Therefore,numerical simulation is inevitable.For the past ten years,crystal growth modeling has become one of the most active research fields in materials processing.Indeed,as long as the melt crystal growth of semiconductors remains a mainstay of the microelectronics industry,its modeling continues to be important.In this talk,the role of transport phenomena in bulk crystal growth and their detailed nonlinear analysis are illustrated through our research work over the years.Particular interests will be paid to the zone melting and Bridgman crystal growth.The control of convection and interface shape through external forces,such as rotation,magnetic fields,and vibration will be discussed.Interface instability leading to“pit formation”and interface breakdown due to thermal and solutal flows will also be illustrated.展开更多
The morphology and lateral growth rate of isotactic polybutene-1(it-PB1)have been investigated for crystallization from the melt over a wide range of crystallization temperatures from 50 to 110℃.The morphology of it-...The morphology and lateral growth rate of isotactic polybutene-1(it-PB1)have been investigated for crystallization from the melt over a wide range of crystallization temperatures from 50 to 110℃.The morphology of it-PB1 crystals is a rounded shape at crystallization temperatures lower than 85℃,while lamellarsingle crystals possess faceted morphology at higher crystallization temperatures.The kinetic roughening transi-tion occurs around 85℃.The nucleation and growth mechanism for crystallization does not work below 85℃,since the growth face is rough.However,the growth rate shows the supercooling dependence derived from the nucleation and growth mechanism.The nucleation theory seems still to work even for rough surface growth.Possible mechanisms for the crystal growth of this polymer are discussed.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
The crystallization behavior of syndiotactic polystyrene(s PS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory. O...The crystallization behavior of syndiotactic polystyrene(s PS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering(SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes: lamellae stable region(25-90 °C), melt-recrystallization region(90-185 °C) and pre-phase transition region(185-195 °C). As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the s PS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting(phase transition) temperatures were determined at around 390 and 220 °C on the basis of the thermodynamic phase diagram of the s PS γ form.展开更多
The absorption spectra, excitation spectra, and emission spectra of Tb3+/Eu3+ ions in LiYF4 single crystals synthesized by an improved Bridgman method are measured. The emission spectra of several bands, mainly loca...The absorption spectra, excitation spectra, and emission spectra of Tb3+/Eu3+ ions in LiYF4 single crystals synthesized by an improved Bridgman method are measured. The emission spectra of several bands, mainly located at blue^487 nm (Tb:5D4→7F6), yellowish green ~542 nm (Tb:SD4→ 7F5), and red ~611 nm (Eu:SD0 → 7F2) wavelengths, are observed under excitation by UV light. An ideal white light emission as a result of simultaneous combination of these emissions can be obtained from 1.11 mol%Tb3+ and 0.9 mol% Eu3+ co-doped LiYF4 single crystals with chromaticity coordinates of x = 0.3242, y = 0.3389, color temperature Tc = 5878 K, color rendering index Ra = 77, and color quality scale Qa = 75 under excitation of 384 nm light. The chromaticity coordinate, color rendering index, and color quality scale can be modified by the change of the concentration of rare-earth dopants and the excitation wavelength.展开更多
A Galerkin finite element method, together with the boundary conformal mapping tech-nique, is used to investigate the change of melt/crystal interface under low gravity during the growth of LICAF system. Results have ...A Galerkin finite element method, together with the boundary conformal mapping tech-nique, is used to investigate the change of melt/crystal interface under low gravity during the growth of LICAF system. Results have shown that strong convection can cause a deeply concave interface to-ward the crystal, and significantly increase radial thermal gradients nearthe interface. The flow intensi-ty and the change of the gravity have a linear relationship under low gravity ( g0 = 10 -2-10-6). At small Ma number, the maximum acceleration for keeping a planar growth interface is gmax = 1 x 10-3g under our given conditions. in addition, the growth velocity may have some influence on the growth interface shape even at vg gravity level, indicating that the growth velocity cannot be too fast even when convection is very weak.展开更多
The Yb:YAG and Yb:YAP crystals have been grown by Czochralski method. The absorption spectra and the fluorescence spectra of Yb:YAG and Yb:YAP crystals have been investigated. It is shown that the Yb:YAG crystal ...The Yb:YAG and Yb:YAP crystals have been grown by Czochralski method. The absorption spectra and the fluorescence spectra of Yb:YAG and Yb:YAP crystals have been investigated. It is shown that the Yb:YAG crystal has better laser properties and smaller threshold power than Yb:YAP crystal. In addition, the absorption cross-section of the Yb:YAP crystal is 2.16 times of that of the Yb:YAG crystal, so laser diode pumped Yb:YAG lasing can be easily realized. Because YAP single crystal is anisotropic, it is provided with polarization characteristics.展开更多
文摘Organic molecules that exhibit long persistent luminescence (LPL) are rapidly gaining attention for a variety of applications. In this study, organic molecules with simple structures were selected and organic long persistent luminescence (OLPL) crystals were prepared. The crystal structure of the prepared OLPL crystal was elucidated and the guideline for the design of OLPL crystal was clarified. LPL was observed in OLPL crystals prepared with TMB as the guest molecule and 1,2-bis(diphenylphosphino)ethane as the host molecule. XRD measurements of the OLPL crystals suggest that the guest molecule is a solid solution substituted in the stable crystal structure of the host molecule in a lattice-shrinking direction.
文摘The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.
文摘In this paper a porous media seepage model was applied to analyze the permeability and study the seepage process of crystal pillar formed in the preparation of electronic grade phosphoric acid(EGPA).By inspecting the seeping process,the structure parameter of crystal pillar could be obtained.Two basic ideal models(perfectly separated model and perfectly connected model)were presented and a characterized factorφwas introduced to modify the model.A good simulation result was obtained which met the experiment result well.The relationship betweenφand permeability were also discussed.The characterized factorφshowed potential application on optimizing process.
文摘Increasing production effeciency and lowering costs are some of the many advantages melt crystallization technology offers over the conventional methodology of tabletting. A normal tablet consists of a pure shell or a coat and a separate core constituting the pharmaceutical active ingredient. Great emphasis is put on the purity of the shell since its purpose is to solely protect and deliver the active ingredient to its target. Melt crystallization is a purification (separation) process. It is discussed here for its ability to produce coated tablets, by separating the "coating" material from the "to be coated" material coming from one molten mixture. Molten drops of lutrol-ibuprofen mixture are produced using the drop forming technique. The subsequent analysis involves proving and quantifying the phase separation (coat purity). The mechanism of a crystallizing drop is shown as direct evidence of the ongoing process. Moreover, solidified tablet batches are analyzed for the purity of their coating by measuring the ibuprofen concentration. This optimization process is carried out through multiple stages of development and condition enhancements in order to produce the most pure tablet coating. As a result, a trial showing an almost purely coated tablet is presented here.
基金This work was supported by the National Natural Science Foundation of China(No.2002541420374003).
文摘Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.
基金supported by a grant from the Ministry of Education,Culture,Sports,Science,and Technology of Japan,Grant-in-Aid for Scientific Research on Innovative Areas(Grant Number 26106002)
文摘Lunar anorthosite is a major rock of the lunar highlands,which formed as a result of plagioclasefloatation in the lunar magma ocean(LMO).Constraints on the sufficient conditions that resulted in the formation of a thick pure anorthosite(mode of plagioclase 〉95 vol.%) is a key to reveal the early magmatic evolution of the terrestrial planets.To form the pure lunar anorthosite,plagioclase should have separated from the magma ocean with low crystal fraction.Crystal networks of plagioclase and mafic minerals develop when the crystal fraction in the magma(φ) is higher than ca.40-60 vol.%,which inhibit the formation of pure anorthosite.In contrast,when φ is small,the magma ocean is highly turbulent,and plagioclase is likely to become entrained in the turbulent magma rather than separated from the melt.To determine the necessary conditions in which anorthosite forms from the LMO,this study adopted the energy criterion formulated by Solomatov.The composition of melt,temperature,and pressure when plagioclase crystallizes are constrained by using MELTS/pMELTS to calculate the density and viscosity of the melt.When plagioclase starts to crystallize,the Mg~# of melt becomes 0.59 at 1291 C.The density of the melt is smaller than that of plagioclase for P 〉 2.1 kbar(ca.50 km deep),and the critical diameter of plagioclase to separate from the melt becomes larger than the typical crystal diameter of plagioclase(1.8-3 cm).This suggests that plagioclase is likely entrained in the LMO just after the plagioclase starts to crystallize.When the Mg~# of melt becomes 0.54 at 1263 C,the density of melt becomes larger than that of plagioclase even for 0 kbar.When the Mg~# of melt decreases down to 0.46 at 1218 C,the critical diameter of plagioclase to separate from the melt becomes 1.5-2.5 cm,which is nearly equal to the typical plagioclase of the lunar anorthosite.This suggests that plagioclase could separate from the melt.One of the differences between the Earth and the Moon is the presence of water.If the terrestrial magma ocean was saturated with H_2O,plagioclase could not crystallize,and anorthosite could not form.
文摘2,6-Diisopropylnaphthalene (2,6-DIPN), as the precursor of important monomer 2,6-naphthalene dicarboxylic acid, could be produced by the shape-selective isopropylation of naphthalene with propene resulting in an isomeric mixture having different alkylation levels. Since the boiling points of DIPNs were very close and the differences of melting points in-between isomers were quite distinctive, the static melt crystallization was applied to separate and purify 2,6-DIPN from its isomers. 2,6-DIPN with purity ≥99% was produced through a process of three stages: crystallization→sweating→melting. The phase diagram of 2,6-DIPN-2,7-DIPN binary system was plotted to opti- mize the temperature control of crystallization. By repeated crystallization of melts with different concentration levels, the yield of pure 2,6-DIPN could be enhanced to 87%. No solvent was necessary. Keywords 2,6-diisopropylnaphthalene, static melt crystallization, crystallization rate, sweating rate, eutectic temperature
文摘2,6-Diisopropylnaphthalene(2,6-DIPN),as the precursor of important monomer 2,6-naphthalene dicarboxylic acid,was prepared by hydroisopropylation of refined naphthalene with propene over shape-selective catalyst.Naphthalene conversion of 92% and 2,6-DIPN selectivity of 64% were obtained.Static melt crystallization was applied to separate and purify 2,6-DIPN from its isomers,resulted in a product purity of≥99%.The other isomers were converted into monoisopropylnaphthalene,which also reacted with propene to form 2,6-DIPN.A recycled process including hydroisopropylation,separation and transalkylation was established,the yield of 2,6-DIPN based on naphthalene could be doubled by one cycle operation.
基金supported by the National Key Basic Research Program of China (No.2009CB825001)the National Natural Science Foundation of China (Nos.40603002,41072046,and 41090371)the Fundamental Research Funds for the Central Universities,China University of Geosciences,Wuhan (No.CUG120121)
文摘In order to constrain temperature during subduction and subsequent exhumation of fel- sic continental crust, we carried out a Ti-in-zircon thermometer coupled with zircon internal structure and U-Pb age on migmatitic gneisses from the Weihai region in the Sulu ultra-high pres- sure (UHP) metamorphic terrane, eastern China. The Weihai migmatitic gneisses are composed of in- tercalated compositional layers of melanosome and plagioclase (Pl)-rich lencosome and K-feldspar (Kfs)-rich pegmatite veins. Four stages of zircon growth were recognized in the Weihai migmatitic gneisses. They successively recorded informations of protolith, prograde metamorphism, decompres- sional partial melting during early stage exhumation and subsequent fractional crystallization of pri- mary melt during later stage cooling exhumation. The inherited cores in zircon from the melanosome and the Pl-rich leucosome suggest that the pro- tolith of the migmatitic gneiss is Mid- Neoproterozoic (-780 Ma) magmatic rock. Metamorphic zircons with concordant ages ranging from 243 to 256 Ma occur as over- growth mantles on the protolith magmatic zir- con cores. The estimated growth temperatures (625-717 "C) of the metamorphic zircons have a negative correlation with their ages, indicating a progressive metamorphism in HP eciogite-facies condition during subduction. Zircon recrystal- lized rims (228-2 Ma) in the PI-rich ieucosome layers provide the lower limit of the decompress-sional partial melting time during exhumation. The ages from 228^-2 to 219~2 Ma recorded in the Pl-rich leucosome and the Kfs-rich pegmatite vein, respectively, suggest the duration of the fractional crystallization of primary melt during exhumation. The calculated growth temperatures of the zircon rims from the Pl-rich leucosome range from 858 to 739 , and the temperatures of new growth zircon grains (219±2 Ma) in Kfs-rich vein are between 769 and 529 . The estimated temperatures have a positive correlation with ages from the Pl-rich leucosome to the Kfs-rich pegmatite vein, strongly indi- cating that a process of fractional crystallization of the partial melt during exhumation.
基金financially supported by the National Natural Science Foundation of China(Nos.5130317651373169+3 种基金5103300351473166 and 51403089)Innovative Research Group(No.51321062)The National High-tech R&D Program of China(863 program)(No.2011AA02A202)
文摘In this study, a series of monodispersed poly(L-lactide)(PLLA) were synthesized by the ring-opening polymerization with Schiff base aluminum catalyst, and the effects of the number-average molecular weight(Mn) on the crystallization and melting behaviors of PLLA were investigated by differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The total crystallization rate of PLLA was Mn-dependent, which reached the maximum value for PLLA with Mn of 18.6 kg/mol. In addition, when Mn of PLLA was 18.6 kg/mol, the melting enthalpy(ΔHm) showed a maximum value(87.1 J/g), which was the highest reported value till now. The critical temperature for change of crystal formation from ?-form to ?-form crystals increased in the isothermal crystallization process with Mn increasing. In the reheating procedure, high-Mn PLLA demonstrated a small exothermal peak prior to the dominant melting peak, corresponding to crystal transition from ?- to ?-form, but low-Mn PLLA didn't show the peak of crystal transition. These different crystallization and melting behaviors were attributed to the different chain mobility of PLLA with different Mn.
基金supported by the Major National Science & Technology Program of China(No.2009ZX02011)
文摘In integrated circuit-grade single silicon Czochralski growth, the position and material of heat shield are main parameters affecting the heat exchange and crystal growth condition. By optimizing the above parameters, we attempted to increase the growth rate and crystal quality. Numerical simulation proved to verify the results before and after optimization. Through analyses of the temperature and microdefect distribution, it is found that the optimized heat shield can further increase the pulling rate and decrease the melt/crystal interface deflection, increase the average velocity of argon flow from ~2 to ~5 m·s-1, which is in favor of the transportation of SiO, and obtain the low defects concentration crystal and that the average temperature along the melt-free surface is 8 °C higher than before avoiding supercooled melt effectively. ? The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2012.
基金supported by the National Natural Foundation of China
文摘Numerical results show that an external magnetic field may influence significantly the flow pattern in the molten semiconductor of Czochralski crystal growth. The melt flow could be pronouncedly damped by a magnet. ic field with the intensity of several thousands Gauss, while the temperature field is affected only in a less extent by the magnetic field.
基金Supported by the NNSFC(No.61108054)the NSF of Fujian Province(No.2011J01376)
文摘A Nd3+:(Sr0.7Ca0.3)3Y(BO3)3 crystal with dimensions of Ф17×23 mm3 has been grown by the Czochralski method. The spectroscopic characterization of Nd3+:(Sr0.7Cao.3)aY(BO3)3 crystal was investigated. The polarized absorption cross-sections of Nda+:(Sr0.7Ca0.3)aY(BO3)3 crystal are 2.81×10-20 cm2 with full width at half maximum (FWHM) of 14 nrn at 808 nm for σ-polarization and 2.04×10-20 cm2 with FWHM of 19 nm at 807 nm for 7r-polarization, respectively. The polarized emission cross-sections of Nd3+(Sr0.7Ca0.3)3Y(BO3)3 crystal are 12.2× 10.20 cm2 at 1062 nm for the π-polarization and 13.6×10-20 crn2 at 1061 nm for the a-polarization, respectively. After the Ca2+ ion partly substitutes for Sr2+ ion in the Sr3Y(BO3)3 crystal to form the (Sr0.7Ca0.3)3Y(BO3)3 solid solution, it can improve the quantum efficiency η of Nd3+:(Sr0.7TCa0.3)3Y(BO3)3 crystal. The quantum efficiency is 31.7%. These results may be regarded Nd3+:(Sr0.7Ca0.3)3Y(BO3)3 crystal as a potential solid-state laser material.
文摘The quality of substrate crystals is critical to the performance of devices used in electronic and optoelectronic applications.These bulk crystals are mostly grown from the melt or solution,with a well controlled solidification or supersaturation,which is affected significantly by the heat and mass flows.Particularly,in the melt growth,the interface kinetics is so fast that the growth is mainly controlled by the transport processes.Hence,the intricate coupling of heat and mass transfer and melt flow strongly influences the grown crystal quality,but its analysis and control is not a trivial task.For most materials,such as semiconductors and oxides,a detailed analysis of the transport processes through experiments is extremely difficult due to the long growth period at high temperature.Therefore,numerical simulation is inevitable.For the past ten years,crystal growth modeling has become one of the most active research fields in materials processing.Indeed,as long as the melt crystal growth of semiconductors remains a mainstay of the microelectronics industry,its modeling continues to be important.In this talk,the role of transport phenomena in bulk crystal growth and their detailed nonlinear analysis are illustrated through our research work over the years.Particular interests will be paid to the zone melting and Bridgman crystal growth.The control of convection and interface shape through external forces,such as rotation,magnetic fields,and vibration will be discussed.Interface instability leading to“pit formation”and interface breakdown due to thermal and solutal flows will also be illustrated.
文摘The morphology and lateral growth rate of isotactic polybutene-1(it-PB1)have been investigated for crystallization from the melt over a wide range of crystallization temperatures from 50 to 110℃.The morphology of it-PB1 crystals is a rounded shape at crystallization temperatures lower than 85℃,while lamellarsingle crystals possess faceted morphology at higher crystallization temperatures.The kinetic roughening transi-tion occurs around 85℃.The nucleation and growth mechanism for crystallization does not work below 85℃,since the growth face is rough.However,the growth rate shows the supercooling dependence derived from the nucleation and growth mechanism.The nucleation theory seems still to work even for rough surface growth.Possible mechanisms for the crystal growth of this polymer are discussed.
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financially supported by the National Natural Science Foundation of China (Nos. 51525305, 21134006 and 21704101)
文摘The crystallization behavior of syndiotactic polystyrene(s PS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering(SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes: lamellae stable region(25-90 °C), melt-recrystallization region(90-185 °C) and pre-phase transition region(185-195 °C). As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the s PS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting(phase transition) temperatures were determined at around 390 and 220 °C on the basis of the thermodynamic phase diagram of the s PS γ form.
基金supported in part by the National Natural Science Foundation of China(Nos.51472125 and 51272109)the K.C.Wong Magna Fund in Ningbo University
文摘The absorption spectra, excitation spectra, and emission spectra of Tb3+/Eu3+ ions in LiYF4 single crystals synthesized by an improved Bridgman method are measured. The emission spectra of several bands, mainly located at blue^487 nm (Tb:5D4→7F6), yellowish green ~542 nm (Tb:SD4→ 7F5), and red ~611 nm (Eu:SD0 → 7F2) wavelengths, are observed under excitation by UV light. An ideal white light emission as a result of simultaneous combination of these emissions can be obtained from 1.11 mol%Tb3+ and 0.9 mol% Eu3+ co-doped LiYF4 single crystals with chromaticity coordinates of x = 0.3242, y = 0.3389, color temperature Tc = 5878 K, color rendering index Ra = 77, and color quality scale Qa = 75 under excitation of 384 nm light. The chromaticity coordinate, color rendering index, and color quality scale can be modified by the change of the concentration of rare-earth dopants and the excitation wavelength.
文摘A Galerkin finite element method, together with the boundary conformal mapping tech-nique, is used to investigate the change of melt/crystal interface under low gravity during the growth of LICAF system. Results have shown that strong convection can cause a deeply concave interface to-ward the crystal, and significantly increase radial thermal gradients nearthe interface. The flow intensi-ty and the change of the gravity have a linear relationship under low gravity ( g0 = 10 -2-10-6). At small Ma number, the maximum acceleration for keeping a planar growth interface is gmax = 1 x 10-3g under our given conditions. in addition, the growth velocity may have some influence on the growth interface shape even at vg gravity level, indicating that the growth velocity cannot be too fast even when convection is very weak.
文摘The Yb:YAG and Yb:YAP crystals have been grown by Czochralski method. The absorption spectra and the fluorescence spectra of Yb:YAG and Yb:YAP crystals have been investigated. It is shown that the Yb:YAG crystal has better laser properties and smaller threshold power than Yb:YAP crystal. In addition, the absorption cross-section of the Yb:YAP crystal is 2.16 times of that of the Yb:YAG crystal, so laser diode pumped Yb:YAG lasing can be easily realized. Because YAP single crystal is anisotropic, it is provided with polarization characteristics.