冷冻干燥中升华过程界面的微CT观察及气固相变分析

采用微CT扫描成像、图像重构及灰度值分析技术对冷冻干燥中升华过程界面及气固相变进行实验观察与分析。采用高斯误差函数拟合,计算得到冰的平均灰度值为154。在后续灰度值比价分析中,固体物料苹果本身的灰度值高于冰的灰度值,从而可以分析冰晶的移动特性。从直接扫描图像和重构图像,均可看到升华界面的移动是一个立体的移动,由它所包裹的冻结区逐渐向物料几何中心收缩。对比冻结物料和冻干物料的灰度值曲线,可见刚开始灰度值较低的冰区,在冻干结束后变成灰度值相对较高的孔疏区。     

粒状物料常压吸附流化床冷冻干燥的传热研究

以粒状马铃薯为研究对象,在常压吸附流化床冷冻干燥的实验基础上,建立了吸附流化床内对流边界条件下的球坐标冻干模型,并采用变时间步长的有限差分法,求解了物料内部温度分布及升华界面的移动速率,与实验结果吻合较好,分析了有关因素对于冻干过程中传热及干燥过程的影响。     

Influence of Position on the Microstructure of Carbon Black/Polyvinyl Alcohol Composite Obtained by the Directional Freeze-drying Process

Carbon black (CB)/polyvinyl alcohol (PVA) composites with porous structure were obtained by a directional freeze-drying process of their solution in water. The microstructures of this composite at different positions through the thickness were investigated. The study shows that the composite formed a lamellar structure at the lower surface of the specimen because of the basic crystallographic and crystal growth characteristics of ice. The composite near the top surface of the specimen showed an alignment direction of the ice vertical to the container's wall and the direction of solution lowering into the liquid nitrogen. The alignment direction deflects gradually and finally converges with the aligned direction grown from the bottom position near the middle part of the CB/PVA composite. The ice crystals grow very fast along the direction of temperature gradients, which results in that a small fraction of PVA solute was entrapped within the ice crystals, leading to the formation of trans-bridge lamellar structure near the top surface of the specimen. This result shows that the position in the sample has a great influence on the structure of the porous CB/PVA composite obtained by the directional freeze-drying process.     

Substrate dependent sublimation kinetics of mesoscopic ice films

We have measured the sublimation kinetics of 2–30 nm thick ice layers deposited in ultra high vacuum at 100 K, on different surfaces; Pt(111) and graphite (0001) surfaces with and without various pre-adsorbed monolayers. The results reveal (i) a much more complex sublimation kinetics than expected for a simple molecular solid, and (ii) a strong influence of the underlying substrate on the kinetics. These features, which are reproduced by computer simulations, are due to (i) a phase transition from amorphous to crystalline ice during sublimation, and (ii) substrate dependent nucleation and growth of the ice layers, respectively. The results are correlated with the hydrophobicity-hydrophilicity of the surfaces, and suggest a new method to characterize the wetting properties of solid surfaces. It can be easily performed with state-of-the-art surface cleanliness control, contrary to conventional wetting methods. Applied to the present results, and those of Smith et al. in the preceding paper [Surf. Sci. 367 (1996) L13], this gives, in order of decreasing wetting of water; clean Pt(111)>cleanRu(001)>Cs covered graphite>clean graphite>octane covered Pt(111)⩾clean Au(111).     

冻干过程中升华界面温度测量方法的研究

压力测温技术是基于在平衡状态下,冰晶温度与其饱和蒸汽压为单值函数这一基本规律,在升华干燥过程中,突然中断从冻干室流向冷阱的水蒸汽流,通过测量冻干室内压力回升情况去推算升华界面温度的一种非接触式测温方法。与热电偶或热敏电阻测温相比,压力测温技术即不破坏冻干样品的结构,又能够较为准确地反应出移动升华界面的温度,并能判断升华干燥过程终点。文中分析了升华界面温度测量的意义与困难,建立了压力测温技术的数学模型与分析方法,并通过实验研究了压力测温技术。     

Formation of nanocarbon films on the SiC surface through sublimation in vacuum

The possibility of forming nanocarbon films on the SiC surface with the use of the technology employed in sublimation epitaxy of silicon carbide has been demonstrated. The temperature range in which nanocarbon films four to five lattice-cells thick form is found. The presence in films of two-dimensional graphite crystals is revealed.     

Study of multigraphene films prepared by sublimation on the sic surface

Graphene films were prepared by sublimation epitaxy of SiC under vacuum. The films were studied by Auger electron spectroscopy, reflection high-energy electron diffraction, atomic force microscopy, and Raman spectroscopy. It is concluded that the films prepared are polycrystalline and consist of graphene single crystals about 50 nm in size.     

基于微元法的冻干过程模拟计算

为准确预测一次干燥时间,降低能耗,应用准稳态传热传质理论,在考虑干燥层传质能力对干燥速率影响的情况下,建立了基于微元法的传质控制模型。利用循环计算的方法,对模型进行了求解。计算结果表明:所建立的模型能准确地预测冻干过程,模拟值与实验值吻合良好。若对模型进一步完善和修正,对实际应用有一定的指导意义。     

在不同条件下冻干猪主动脉的过程及结果的分析

本实验将猪主动脉血管的冷冻干燥与微CT扫描相结合,对不同一次干燥和二次干燥温度下的猪主动脉血管进行非侵入的扫描.通过计算样品的失水率,比较出快冻与慢冻对样品的影响,及不同一次干燥和二次干燥温度下对冻干的猪主动脉血管造成的差异,并比较这些差异,得出冻干的最优条件.同时,也对不同冻干条件下样品表面折皱的照片和CT扫描的图像...     

Effect of Crucibles on Qualities of Self-Seeded Aluminium Nitride Crystals Grown by Sublimation

Self-seeded aluminium nitride （AlN） crystals are grown in tungsten and hot pressed boron nitride （HPBN） crucibles with different shapes by a sublimation method. The qualities of the AlN crystals are characterized by high-resolution transmission electronic microscopy （HRTEM）, scanning electron microscopy （SEM） and Micro-Rarnan spectroscopy. The results indicate that the better quality crystals can be collected in conical tungsten crucible.     

Propagation of ballistic phonons in crystals and their detection with a detachable bolometer

Ballistic phonons were generated in single-crystalline sapphire samples by scanning the crystal surface with the electron beam in a scanning electron microscope equipped with a low-temperature stage. The phonons were detected using a superconducting thin film (granular Al) bolometer configuration which could be detached from the sample crystal (allowing repeated use). We have applied these experimental techniques for obtaining phonon images of laser-drilled holes in the sample crystals, achieving a spatial resolution of better than 10 m.     

Morphology study of freeze-drying mononuclear cells of human cord blood

The research on haematopoietic stem cells of human cord blood has become more important recently. At present, cord blood is mainly preserved at ultra-low temperatures. In the former study, we compared the effects of preserving mononuclear cells (MNC) and whole human cord blood by freeze-drying. This time, a further study was conducted on freeze-drying mononuclear cells. Samples in the presence of PVP, sucrose, mannitol and FBS were firstly frozen to -38 degrees C. Afterwards, they were vacuum-dried at a selected shelf temperature of -30 degrees C for the main drying stage, and then vacuum-dried at 15 degrees C for the second drying stage. The entire time of freeze-drying process was 41 hours. Samples were stored at room temperature for 7 days prior to evaluation. Subsequently, the dried samples were resuspended in an isotonic phosphate-buffered saline solution. The residual moisture content was 6.5 +/- 0.87%. The recovery of the cells was tested by a haemacytometer, and the numerical cell count recovery of rehydrated MNC increased by 8%. Morphology of the fresh and rehydrated MNC was analyzed respectively using standard light microscopy, scanning electron microscope and transmission electron microscope. The results showed that karyons changed and cytoplasm decreased after rehydration, but it is still unknown that whether these changes will influence the proliferative ability of the stem cells.     

The microscopic visualisation of the sonocrystallisation of ice using a novel ultrasonic cold stage

This work reports dynamic video images of the influence of ultrasonic cavitation on the sonocrystallisation of ice at a microscopic level. This has been achieved through the construction of a unique ultrasonic system for an optical microscope. The system consists of (1). an ultrasonic cold stage, (2). a temperature control system, and (3). a microscope and imaging setup. This allows the temperature of a sample to be systematically controlled while it is subjected to simultaneous excitation with alternating pressures in the ultrasonic frequency range. Both the amplitude of excitation and the frequency can be varied. Experiments on ice crystals in pure water and sucrose solutions were conducted. Three distinct phenomena were observed. Firstly, there is a tendency for cavitation bubbles to form at the grain boundaries between ice crystals. Secondly, there is a progressive melting of ice by cavitation bubbles which appear to eat their way into the ice phase. Thirdly, the dendritic ice structures may fragment under the influence of ultrasound, thus increasing the number of nuclei which may subsequently grow (secondary nucleation). These observations form the basis of a significantly enhanced understanding and exploitation of the sonocrystallisation of ice.     

升华能随温度和压强的变化

从克拉珀龙方程出发讨论了金属的升华能随温度和压强的变化规律.研究表明,升华能随温度或压强的增大而近似线性地减小.     

Industrial challenges for numerical simulation of crystal growth

Numerical simulation of industrial crystal growth is difficult due to its multidisciplinary nature and the complex geometry of the real-life growth equipment. An attempt is made to itemize physical phenomena dominant in the different methods for growth of bulk crystals from the melt and the vapor phase as well as to review corresponding numerical approaches. Academic research and industrial applications are compared. Development of a computational engine and a graphic user interface of the industry-oriented codes is discussed. A simulator for the entire growth process of bulk crystals by sublimation method is described.     

Effect of magnetic field on self-assembling of colloidal Co magnetic nanoparticles

In this paper the formation of 3-D structures composed of Co nanoparticles (NPs) is reported. Structures were obtained by drying a droplet of a colloidal solution of NPs in a magnetic field perpendicular to the substrate. The Co nanoparticles were prepared by thermolysis of Co₂(CO)₈. The 3-D NP structures were characterized by scanning electron microscopy (SEM) and atomic and magnetic force microscopy (AFM/MFM). It has been found that at the border of the droplet, NPs assemble into hexagonally ordered 3-D columns or they form a labyrinthine structure. The formation of the 3-D structures can be explained by the outflow of NPs to the border of the droplet during the drying process. Within this model the pattern formation is dependent on the concentration of the NPs and the degree of alignment of the magnetic moments of NPs in the 3-D columns.     

A study on the primary and secondary nucleation of ice by power ultrasound

Several different investigations have been carried out to study the primary and secondary nucleation of ice by sonocrystallisation. Firstly, the primary nucleation of discrete ice crystals in a supercooled sucrose solution has been observed. For increasing concentrations of sucrose solutions from 0 to 45 wt%, the nucleation temperature consistently occurs at a higher nucleation temperature in the presence of ultrasound. The nucleation temperature also increases as the power output and duty cycle of a commercial ultrasonic horn are increased. Snap shot images of the bubble clouds obtained from the ultrasonic horn also show that the number of bubbles appears to increase as the ultrasonic output is increased. This suggests that the nucleation of ice is related to the power output and number of cavitation bubbles. The effect of a single bubble on the sonocrystallisation of ice is discussed. High-speed movies (1120 fps) have shown that the crystallisation appears to occur in the immediate vicinity of the single bubble. In most cases, many crystals are observed and it is not known whether a single ice crystal is being fragmented by the bubble or whether many crystals are being initiated. The bubble appears to undergo a dancing regime, frequently splitting and rejoining and also emitting some small microbubbles. A study on the secondary nucleation of ice in sucrose solutions has been carried out using a unique ultrasonic cold stage device. Images taken using a microscope system show that the pre-existing ice dendrite crystals can be broken up into smaller fragments by an ultrasonic field. Cavitation bubbles appear to be important during the fragmentation process, possibly melting any ice crystals in their path. Flow patterns around cavitation bubbles have also been observed, and these may be responsible for the fragmentation of ice crystals.     

Defect reduction in sublimation grown SiC bulk crystals

For several years the major focus of material issues in SiC substrates was laid on the reduction of macroscopic defects like polytype inclusions, low angle grain boundaries and micropipes. Although significant improvements have been achieved, there are still shortcomings in material quality that have to be overcome. Since it is clear that dislocations are the main reason for degradation in power devices the prevailing attention has shifted to that field of material research. The aim of our work was to investigate the mechanisms that affect the generation of macroscopic and microscopic defects during sublimation growth. Intense studies were utilized on dislocation and stacking fault formation. For this reason we systematically varied parameters of the growth process and applied several methods for the characterization to evaluate material properties most precisely, e.g. KOH-defect-etching, X-ray-diffraction, electron microscopy and optical microscopy. The investigations were accompanied by failure analysis of devices of the Schottky type. We found out that for the improvement of substrate quality emphasis has to be laid on the reduction of thermoelastic stress in the growing crystal. From results of numerical calculations we were able to derive moderate growth conditions with reduced temperature gradients prevailing during the growth process. As a consequence we succeeded in decreasing the defect concentration. The best value so far achieved for the sum of both BPD and TED was 7×10³ cm⁻².     

Optical properties of InBr single crystals

Single crystals of orthorhombic InBr were grown by the sublimation technique. Two of the three principal refractive indices were determined by measuring interference due to multiple reflection. The absorption curve near the band edge was measured at 295,80 and 10°K for different polarisation vectors of the incident light. At low temperatures large exciton absorptions could be seen which enabled us to determine accurate values of the band gap energy.     

Mechanical properties of kaolinite ‘macro-crystals’

The mechanical properties of a rare sample of kaolinite macroscopic crystals were evaluated using instrumented indentation. The crystals were also characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and Fourier transform infrared spectroscopy before and after heat treatment at 1100°C. The results are explained in terms of the fracture process occurring in the layered structure of kaolinite, and of the effect of roughness on the hardness and elastic modulus. Data analysis using One-way ANOVA (p?<?0.05) showed that the values of hardness and elastic modulus obtained are statistically homogeneous. Before heat treatment, the sample was composed essentially of kaolinite, with hardness of 42?MPa and elastic modulus equal to 1.3?GPa. After calcination at 1100°C, the sample keeps its layered habit and consists of amorphous metakaolinite. The hardness increases to 360?MPa and the elastic modulus increases to 6.9?GPa.