Microbatch macromolecular crystallization on a thermal gradient

We can exploit the temperature dependence of protein solubility in a blind search for optimal crystallization conditions by conducting experiments on thermal gradients. A microbatch technique coupled with a specially constructed thermal gradient allows us to conduct polythermal experiments over the range 6–30°C using as little as 7 μl of solution. The crystallization vessel is a micropipette commonly used in blood testing labs. As many as 150 simultaneous experiments can be conducted on a gradient machined out of a 200×250×25 mm aluminium plate.     

Protein crystallization in low gravity by step gradient diffusion method.

Two-step crystallization experiments were conducted in low gravity employing a liquid-liquid diffusion method in an effort to eliminate problems associated with protein crystal growth under the supersaturating conditions required for nucleation. Experiments were performed in diffusion cells formed by the sliding of blocks on orbit. Step gradient diffusion experiments consisted of first exposing protein solutions in diffusion half-wells for brief periods to initiating buffer solutions of high precipitant concentrations to induce nucleation followed by expoure of the same protein solutions to solutions of lower precepitant concentration to promote growth of induced nuclei into crystals. To avoid convective disturbances that occur when solutions of discrepant densities are interfaced at normal gravity, crystallization of hen egg-white lysozyme and rabbit skeletal muscle aldolase by step gradient diffusion was investigated in low gravity on four NASA space shuttle flights. In general, the largest ctystals of both proteins formed at the highest initiating precipitant concentration used, which is consistent with nuclei formation upon brief exposure to high precipitant concentration, and that these nuclei are competent for sustained growth at lower precipitant concentration. The two-step approach dissociates nucleation events from crystal growth allowing parameters affecting nucleation kinetics such as time, precipitant concentration and temperature of nucleation to be varied separately from conditions used for post-nucleation growth.     

Electric twinning in quartz by temperature gradient

This paper presents a new method for obtaining electric twins in quartz crystal: thermal treatment in a temperature gradient at about 500 °C, that means under phase transition point. + 5X quartz crystal plates for resonators were used; a temperature gradient of 15–25 °C was applied for 4–5 hours along the Y axis (the place length). For + 5X resonators, the diminution of the resonant frequency and the increase of the inductance were plotted as a function of the level of twinning.     

The migration of gas-filled brine inclusions in rock salt under a temperature gradient

In natural halite crystals two sorts of inclusions will move if there exists a temperature gradient. The direction of moving brine inclusions is orientated towards the heat source. Brine inclusions which additionally contain more than 10% gas move towards the cold end of a specimen. This model is well known but detailed information about the migration mechanism of these so-called SORBY inclusions have been lacking in literature so far. In this paper it will be demonstrated that SORBY inclusions having a diameter of up to 20 micrometers can move undisturbed through the crystal. SORBY inclusions with a diameter of more than 20 micrometers are fixed and form droplets with their tips directed towards the cold side of the specimen. Later when the tips have grown the inclusions will emit a new daughter inclusion which can move through the crystal. The velocity of migration depends on the generation of daughters. Extended kinds of SORBY inclusions are stable for a long time. However, these can decay into many individuals which will move through the crystal like the others.     

Synthesis of chalcogenide and pnictide crystals in salt melts using a steady-state temperature gradient

Some examples of growing crystals of metals, alloys, chalcogenides, and pnictides in melts of halides of alkali metals and aluminum at a steady-state temperature gradient are described. Transport media are chosen to be salt melts of eutectic composition with the participation of LiCl, NaCl, KCl, RbCl, CsCl, AlCl₃, AlBr₃, KBr, and KI in a temperature range of 850–150°C. Some crystals have been synthesized only using a conducting contour. This technique of crystal growth is similar to the electrochemical method. In some cases, to exclude mutual influence, some elements have been isolated and forced to migrate to the crystal growth region through independent channels. As a result, crystals of desired quality have been obtained using no special equipment and with sizes sufficient for study under laboratory conditions.     

Effect of crystallization behavior on the oxidation resistance of a Zr–Al–Cu metallic glass below the crystallization temperature

The crystallization behavior of Zr_65.0Al_7.5Cu_27.5 (at.%) metallic glass with 753 and 1053 K annealing treatment and its effect on oxidation resistance around the supercooled liquid region at 623 and 663 K was studied. The crystalline phase of bct-Zr₂Cu precipitates for the specimen annealed at 753 K was observed, while duplex structures of bct-Zr₂Cu and Zr₂Al formed in the specimen annealed at 1053 K. The oxidation resistance of the specimen depended on the amount of crystalline precipitates. Regardless of the exposure temperature, the annealed specimens showed higher oxidation resistance than the melt-spun one, especially for the specimen annealed at 1053 K. The formation of numerous crystalline phases of bct-Zr₂Cu and Zr₂Al from the matrix was responsible for improving the oxidation resistance due to their higher oxidation resistance and promotion of the development of Al₂O₃ and oxides of copper. The oxide constituents of the amorphous alloy after long exposure depended on the temperature. The oxide was composed of a large amount of CuO, some tetragonal and monoclinic-ZrO₂ and a minor amount of Cu₂O as well as a slight amount of Al₂O₃ for the melt-spun specimen during exposure at 623 K. Under the 663 K exposure, however, the oxide state of Cu³⁺ in the scale was also detected.     

Controlling the axial temperature gradient in inductively heated Czochralski systems

A heating system is described that allows to increase the temperature gradients in rf‐heated Czochralski setups during the growth. This system applies an active afterheater, operated by a separate induction coil parallel to that heating the crucible. By changing the inductivity of an additional coil located outside the growth chamber, the ratio of the rf currents flowing through the crucible and afterheater and, consequently, the geometry of the heat input to the setup can be altered. The efficiency of the heating systems has been demonstrated in various experiments.     

Effect of temperature gradient on the lamellar structure formation

The detailed definition of interplay between interface curvature and concentration field is presented. It explains an effect of horizontal component of temperature gradient on the lamellar structure formation during the steady-state eutectic growth. This definition is composed of two competitive terms connected with the heat and matter transfers, respectively. The above competition is interpreted by using the thermodynamics of irreversible processes. Finally, it is shown that the lamellar spacing depends on both the growth rate and temperature gradient for a given regular eutectic solidifying under stationary conditions. The proposed analysis is the fourth part of model developing in “Crystal Research and Technology” which is mentioned in the References.     

Morphology of sic epitaxial layers grown by temperature gradient zone melting (I). Dependence of the crystallization boundary smoothness on the epitaxial layers growth conditions

The dependence of the smoothness of the crystallization boundary on the temperature gradient zone melting conditions is investigated. The observed depth of the crystallization boundary is compared with the depth, calculated by the method proposed by D. E. TEMKIN.     

The melt temperature change influence on the crystallization rate in czochralski growth system

This paper opens a series of publications about growth system parameters change influence on the crystallization rate. The influence of crucible melt temperature fluctuations and mechanical instability will be investigated. In approximation of one-dimensional heat transfer the behaviour of crystallization rate in case of crucible melt temperature small change is investigated in this paper. As an example characteristic time values and system sensitivity are given for fluorite and silicon crystals.     

The influence of heat-dissipation and temperature fluctuations on SbSI crystallization in thin layers

Single crystal films of SbSI 5 to 100 μ in thickness have been obtained by crystallization from melts in a close spacing. The films crystallized under conditions under conditions of direct heat -dissipation and periodical fluctuations of temperature near the melting point. The phase transition in the films was revealed by means of capacity measurements at temperatures of ∼ 20 °C.     

Prediction of maximum homogeneous nucleation temperature for crystallization of metallic glasses

A graphical method is used to find out the viscosity at any temperature between the melting temperature and glass transition temperature, which in turn is used to predict the temperature corresponding to the maximum in homogeneous nucleation rate. The present approach does not need any critical experimental data and the model predictions are very close to those experimentally measured in known metallic glasses. This model can be applied for both pure metals and glass forming alloys.     

Re-examination of effects of nucleation temperature and time on glass crystallization

The effects of nucleation temperature and time on the kinetics of non-isothermal glass crystallization have been re-examined to demonstrate the limitations of some approximate solutions used to extract kinetic parameters from differential thermal analysis (DTA) experiments. Those features were analyzed by numerical solutions of equations describing the dependence of fraction crystallized on the rates of nucleation and growth, and the corresponding transient time, reported for lithium disilicate. It was shown that the temperature of maximum nucleation rate varies on changing the nucleation time. Some guidelines were established to assist the selection of suitable conditions to perform crystallization studies by DTA, and to extract the values of activation energy and dimensionality of growth from the dependences of crystallization peak temperature on heating rate, and nucleation time. The main limitations of these methods were identified and discussed.     

General principles of the synthesis of chalcogenides and pnictides in salt melts using a steady-state temperature gradient

The possibilities of growing crystals of metals, alloys, chalcogenides, and pnictides in halide melts using a steady-state temperature gradient are analyzed. Halides of alkali metals and aluminum can be used as transport media. The choice is determined by the melting temperature of salt mixtures. A conducting contour can also be applied to increase transport efficiency. This technique of crystal growth is similar to the electrochemical method. To eliminate interference during migration, some elements can be isolated and forced to migrate through independent channels to the crystal formation region. The technique considered here makes it possible to grow crystals of necessary quality without special equipment; the small crystal sizes are sufficient for laboratory study.     

Effect of Ni-addition on the crystallization behavior and the oxidation resistance of Zr-based metallic glasses below the crystallization temperature

The crystallization behavior of Zr_65.0Al_7.5Ni_10.0Cu_17.5 metallic glasses by addition of Ni with 753 K annealing treatment and its effect on the oxidation resistance around the supercooled liquid region at 663 K were studied. By annealing at 753 K, the nanocrystalline phase of bct-Zr₂Cu precipitates was observed in the Zr_65.0Al_7.5Cu_27.5 specimen, while microstructures consisting of finer nanocrystalline bct-Zr₂Cu, fcc-Zr₂Ni and Zr₆Al₂Ni formed in the Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen. The oxidation resistance of the melt-spun Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen was improved by addition of Ni, which is evidenced by less mass gain and thin oxide scale. The microstructural refinement by the formation of numerous nanocrystalline phases of bct-Zr₂Cu, fcc-Zr₂Ni and Zr₆Al₂Ni from the matrix resulted in an improvement of the oxidation resistance, whereas a relative coarse nanocrystalline phase consisting of bct-Zr₂Cu exhibited fast oxidation along grain boundaries. Although the oxide species for both specimens were composed of a large amount of CuO/Cu₂O, some tetragonal and monoclinic-ZrO₂ as well as a minor amount of the oxide state of Cu³⁺, the amount of oxides especially for ZrO₂ in the Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen was lower, which was probably due to suppressed oxygen diffusion in ZrO₂.     

The effect of mass transfer on the temperature gradient of a crystal growing from melt

The change in the temperature gradient on the crystal side while the rate of crystal growth from melt is varied has long been debated. Abe and Takahashi have recently reported an unambiguous experimental demonstration that the temperature gradient is a decreasing function of the growth rate, which is different from previous theories, experimental results, and widely held notion of other researchers. The present paper provides a theoretical basis for this seemingly peculiar effect of the growth rate on the temperature gradient. The essential matter is the effect of mass transfer, the role of which had been commonly disregarded in old studies. Although the rate of mass transfer is not large compared to that of heat conduction, it is proven that the temperature gradient is subjected to the mass transfer in a definite manner. Our analysis shows that the effect becomes significant when the crystal diameter is large, which is consistent with the experimental observation. Another effect of the mass transfer is the change in the shape of melt/crystal interface. In old studies, the temperature gradient was determined by Stefan's equation; however, this treatment confuses the cause and effect. The temperature gradient should be determined by the fundamental equation of heat conduction. When the gradient is determined in this way, the shape of the melt/crystal interface spontaneously adjusts to satisfy Stefan's equation.     

Simulation of mass transfer in a kinetic experiment based on migration of flat layers of a solution in a melt in a temperature gradient field

Mass transfer upon migration of flat liquid layers of a solution in a melt under conditions of slow change in the average temperature at a constant rate has been analyzed for the dislocation and nucleation mechanisms of interface processes. It is shown that the experimental data on the dependence of the migration rate of flat layers on their thickness can be adequately described within the theory developed for strictly steady thermal conditions. A technique is proposed for determining the overall limitations on the mass transfer at interfaces and the migration rate in the diffusion mode from the experimental results obtained in a mixed migration mode.

     

Study of deformation fields as a function of the temperature gradient in the mirror block of an interferometer

The formation of moiré fringes in an X-ray interferometer is studied. It is shown experimentally that the well-known expression for calculating the period of moiré pattern cannot be always used to calculate the period of moire patterns obtained in an X-ray interferometer. The change in the moiré period caused by the temperature gradient in the crystal block of an interferometer is calculated.     

Growth of p-type InP single crystals by the temperature gradient method

P-type InP single crystals doped with zinc or cadmium have been prepared from a solution using indium as a solvent in which a temperature gradient was maintained for the transport of the InP solute. The average growth rate was between 1.1 and 3.0 mm/week. The room temperature hole concentration of the crystals obtained was in a range of 10¹⁷ to 10¹⁸ cm^-3. The distribution coefficients of zinc and cadmium were 0.8 and 0.004, respectively. The temperature gradient method makes it possible to dope the crystals with volatile impurities in a controlled manner.     

Batch crystallization of soluble proteins: effect of precipitant, temperature and additive

Although techniques used for protein crystallization have been progressing greatly, successful crystallization is still largely empirical and operatordependent. The crystallization of biological macromolecules is a pretty complicated process involving numerous parameters, thus the detailed understanding of the effect of crystallization conditions on macromolecule crystallization is advantageous. In this study, we have investigated the effect of precipitant, temperature, and additive on the crystallization of lysozyme and chymotrypsinogen A. As the precipitant, sodium chloride is more effective to the crystallization of lysozyme, and ammonium sulfate is more suitable to the crystallization of chymotrypsinogen A. Temperature is found to have no effect on the crystal habit of chymotrypsinogen A, while lysozyme crystallization displays highly sensitive temperature dependence, gradually varied temperature can result in better crystal habit and quality of lysozyme crystals. Furthermore, non-electrolytic additives dimethyl sulfoxide (DMSO) and glycerol are found to not only to increase the protein's solubility, but also decrease the critical supersaturation S_c for explosive nucleation of highly supersaturated protein solution. It is suggested that these additives can affect the interactions between protein molecules, thermodynamic equilibrium, surface energy of the crystal, and nucleation process of protein crystallization.