Cracking during freeze-drying in dense freeze cast ceramics: Role of drying rate

Cracks can form during the freeze-drying of freeze cast ceramic suspensions while attempting to produce dense ceramics. The suspensions contain alumina particles dispersed in cyclohexane. The rate of drying is controlled by the pressure and temperature during drying (slow drying at atmospheric pressure and −15°C and fast drying under vacuum while the temperature slowly increases from −80°C to room temperature). X-Ray micro-computed tomography was used to characterize internal crack formation. Cracks were found to occur during freeze-drying rather than during freezing. Both slow and fast drying produced cracks, although two different morphologies were observed. Mechanistic models are proposed for the formation of both types of cracks. The rate of freezing was found to influence the formation of cracks. Slow freezing tended to reduce the formation of drying cracks because the slower freezing produced a more heterogeneous distribution of particles and porous regions, which tends to allow stress to be relieved by opening up existing pores rather than forming cracks in the more homogeneous fast frozen bodies.     

Producing Large Complex‐Shaped Ceramic Particle Stabilized Foams

Highly porous ceramic foams can be produced by combining particle stabilized foams and gelcasting concepts. Sulfonate‐type surfactants are selected to weakly hydrophobize the alumina surface and stabilize air bubbles in suspensions containing gelcasting additives, polyvinyl alcohol (PVA), and 2,5‐dimethoxy‐2,5‐dihydrofurane (DHF). The aim of this work was to prepare large complex‐shaped ceramic foam objects with homogeneous microstructure and high porosity. A key to avoiding drying cracks is to strengthen the wet green body via gelcasting. The influence of the amount of gelcasting additives on the mechanical strength of the ceramic foam green bodies is investigated as well as the effect of using cross‐linking agent versus the addition of just a binder. The presence of a cross‐linked polymeric network within the green body increases its mechanical strength and minimizes crack formation during drying.     

高浓度尿素废水泠冻浓缩极限

冷冻浓缩技术是处理尿素厂废水和尿液等高浓度尿素废水的有效方法之一,浓缩极限的确定则是预测和评价该工艺最高水回收率和工作效率的必要条件.以尿素溶液为研究对象,采用差示扫描量热技术分析了溶液在冷冻过程中的相态变化规律,通过冷冻试验确定了溶液发生尿素共晶析出时的浓度;以尿液为对象,研究了确定高浓度尿素废水冷冻浓缩极限的方法.研究结果表明：尿素废水在达到浓缩极限之前,当尿素浓度高于26.3%时,继冰晶析出之后会共晶析出尿素;尿素废水在浓缩极限处呈玻璃态,由差示扫描量热分析可确定废水玻璃化转变温度、推算冷冻浓缩工艺最高水回收率;尿液的玻璃化转变温度为-108.33 ℃,相应的溶液浓度为57.92%,冷冻浓缩可达到的最高水回收率为97.75%.     

Protection of fish oil from oxidation by microencapsulation using freeze‐drying techniques

(N‐3)‐Polyunsaturated fatty acids (PUFAs) reduce the risk of coronary heart disease. Cold sea water plankton and plankton‐consuming fish are known sources of (n‐3)‐PUFAs. Enriching normal food components with fish oil is a tool for increasing the intake of (n‐3)‐PUFAs. Due to the high sensitivity of fish oil with respect to oxidation, it has to be protected from oxygen and light. The investigations presented demonstrate the microencapsulation of fish oil using freeze‐drying techniques. Emulsions containing 10% fish oil, 10% sodium caseinate, 10% carbohydrate and 70% water were frozen using different freezing techniques and subsequently freeze‐dried. Several parameters regarding formulation and process (addition of antioxidants to the fish oil, use of carbohydrates, homogenisation and freezing conditions, initial freeze‐drying temperature, grinding) were varied to evaluate their influence on the oxidative stability of dried microencapsulated fish oil. The shelf life of the produced samples was determined by measuring the development of volatile oxidation products vs. storage time. It could be shown that the addition of antioxidants to fish oil was necessary to produce dried microencapsulated fish oil with an adequate shelf life. The best shelf life was achieved for the dried product which was frozen with a slow freezing rate.     

Fabrication of porous three‐dimensional fibroin structures through a freezing process

Silk fibroin has been investigated for various biomedical applications. In this research, through a green process, without using freeze‐drying, which is energy consuming during a single step process that is completely aqueous‐based, without using any additional materials during or after structure formation, water‐insoluble silk fibroin sponges have been obtained; these achieved only through keeping fibroin solutions frozen at a suitable temperature for a sufficient time. The effect of solution concentration and freezing conditions on the pore morphology and size, microstructure, and mechanical properties was investigated. A discussion has been proposed for the formation of structures. The average measured pore sizes were approximately from 4 to 77 μm. Elastic modules of the investigated structures varied from about 100 to 900 kPa. Cyclic mechanical tests were performed; the remaining strain of the structures reached to about 1%. A less considered issue which can be considered as the possible significant change of the mechanical behavior of as‐prepared samples after one or more times of loading and unloading should be noted. The used method in this study as a cost effective and convenient procedure could have the potential for application in the production of porous structures for biomedical applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46537.     

An analysis of capillary water behavior in poly‐p‐phenylenebenzobisoxazole fiber

This study concerns with analysis of water inside a poly‐p‐phenylenebenzobisoxazole (PBO) fiber. It is important to analyze the state of water attached to polymer, because it may affect properties of fibers as the increase of drying speed of water from the fiber. To carry out such observation, differential scanning calorimetry and nuclear magnetic resonance spectroscopy were applied. They reveal the large freezing point depression and the state of water inside wet PBO fiber. It shows extraordinary low crystallization temperature. The reason may be that the water is packed into capillary voids whose diameter is around 2–3 nm. Proton NMR analysis also suggests the above result. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1030–1036, 2001     

Preparation and characterization of biocompatible spongy cryogels of poly(vinyl alcohol)–gelatin and study of water sorption behaviour

Porous biocompatible spongy hydrogels of poly(vinyl alcohol) (PVA)–gelatin were prepared by the freezing–thawing method and characterized by infrared and differential scanning calorimetry. The prepared so‐called ‘cryogels’ were evaluated for their water‐uptake potential and the influence of various factors, such as the chemical architecture of the spongy hydrogels, pH and the temperature of the swelling bath, on the degree of water sorption by the cryogels was investigated. It was found that the water sorption capacity constantly decreased with increasing concentration of PVA while initially an increase and thereafter a decrease in swelling was obtained with increasing amounts of gelatin in the cryogel. The water sorption capacity decreased with an increase in the number of freeze–thaw cycles. The hydrogels were also swollen in salt solutions and various simulated biological fluids and a fall in swelling ratio was noticed. The effect of the drying temperature of the cryogel on its water sorption capacity was also investigated, and a decrease in swelling was obtained with increasing temperature of drying. The biocompatibility of the prepared materials was assessed by in vitro methods of blood‐clot formation, platelet adhesion, and per cent haemolysis. It was noticed that with increasing concentration of PVA and gelatin the biocompatibility increased, while a reduced biocompatibility was noted with an increasing number of freeze–thaw cycles. Copyright © 2005 Society of Chemical Industry     

EXERGY ANALYSIS FOR THE FREEZING STAGE OF THE FREEZE DRYING PROCESS

The mathematical expressions for exergy and the exergy analysis of the freezing stage of the freeze drying process are presented. The exergy analysis indicates that very substantial reductions in the magnitudes of the total exergy loss and of the exergy input due to the heat that must be removed during the freezing stage, can be obtained when the freezing stage is operated through the use of a rational distribution in the magnitude of the temperature of the cooling source. The rational distribution in the magnitude of the temperature of the cooling source should provide significant savings in the utilization of energy during the freezing stage of the freeze drying process as well as satisfactory freezing rates that form ice crystals that are continuous and highly connected and their shape and size are such that the pores of the porous matrix of the dried layer generated by sublimation during the primary drying stage, have a pore size distribution, pore shape, and pore connectivity that are appropriate to allow high rates for mass and heat transfer during the primary and secondary drying stages of the lyophilization process.     

预冻在冻干过程中的作用简

预冻环节中降温速度、冻结温度、冻结时间都是重要的工艺参数,它们互相作用,影响着冻结体的结晶情况,最终会对冻干过程形成决定性的影响。本文通过实例,介绍了预冻过程中冻结速率对冻干结果的影响。说明适当的预冻参数可大大提高冻干效率和产品质量。     

Highly porous Y2SiO5 ceramic with extremely low thermal conductivity prepared by foam‐gelcasting‐freeze drying method

Foam‐gelcasting‐freeze drying method is developed to fabricate porous Y₂SiO₅ ceramic with ultrahigh porosity of 92.2%‐95.8% and isotropous multiple pore structures. As prepared porous samples have quite low shrinkages of 0.8%‐1.9% during demolding and drying processes, lightweights of 0.19‐0.35 g/cm³, and extremely low thermal conductivities of 0.054‐0.089 W·(m·K)^?1. Our approach combines the merits of foam‐gelcasting method and freeze drying method. It is a simple and effective method to fabricate porous ceramics with very high porosity and extremely low thermal conductivity through low shrinkage of green body and near net complex shape forming.     

Water absorption by acrylic‐based latex blend films and its effect on their properties

The absorption of moisture, from liquid as well as gaseous states of water, is known to strongly influence the properties of many polymeric materials. In this article, we examine the unusually high affinity for water of acrylic‐based latex blend films, which lose their transparency and turn white upon water absorption. Composed of rubbery and glassy phases at room temperature, these blends absorb significant amounts of water, which results in only a minor plasticization of the glassy component. When redried at elevated temperatures, the blend films return to their original transparent state but remain white and opaque when freeze‐dried at −70°C. Scanning electron micrographs of the freeze‐fractured surfaces of wet samples exhibit micron‐sized holes that suggest clusters of water inside the bulk of the films. A qualitative model associates these water clusters to residual surfactant inside the samples that is left behind after the drying of original latices. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1407–1419, 1999     

Freeze casting for near‐net‐shaping of dense zirconium diboride ceramics

Zirconium diboride (ZrB₂) was formed into dense complex shapes using freeze casting as a near‐net‐shaping technique. Aqueous‐based formulations were compared with nonaqueous (cyclohexane) based formulations in terms of rheological behavior, particle packing in the green body, sintered density, macroscale porosity, and cracking. The influence of particle solids concentration and freezing rate was investigated. The aqueous formulations were found to be deficient in that they produced macroscale porosity that could not be eliminated during sintering resulting in low density and large pores in the final shaped objects. The nonaqueous‐based system was able to produce complex shaped objects with significantly reduced macroscale porosity. The higher concentration of solids in the nonaqueous‐based formulations was primarily responsible for the reduced macroscale porosity and enabled higher sintered densities (up to 90%‐91.5% of theoretical density for fast freezing). The microstructure of the ZrB₂ formed at fast freezing rates and high solids content typically had isolated pores in the order of 5‐10 μm in size, mainly found along grain boundaries (grain sizes between 20 and 50 μm). Although this rapid freezing produced denser components, it tended to produce objects with internal cracks. When slower freezing rates were used, intricate complex shaped objects could be produced without cracks but their density was only between 65% and 80% of theoretical density.     

Controlled freezing and freeze drying: a versatile route for porous and micro‐/nano‐structured materials

Freeze drying is a process whereby solutions are frozen in a cold bath and then the frozen solvents are removed via sublimation under vacuum, leading to formation of porous structures. Pore size, pore volume and pore morphology are dependent on variables such as freeze temperature, solution concentration, nature of solvent and solute, and the control of the freeze direction. Aqueous solutions, organic solutions, colloidal suspensions, and supercritical CO₂ solutions have been investigated to produce a wide range of porous and particulate structures. Emulsions have recently been employed in the freeze drying process, which can exert a systematic control on pore morphology and pore volume and can also lead to the preparation of organic micro‐ and nano‐particles. Spray freezing and directional freezing have been developed to form porous particles and aligned porous materials. This review describes the principles, latest progress and applications of materials prepared by controlled freezing and freeze drying. First of all the basics of freeze drying and the theory of freezing are discussed. Then the materials fabricated by controlled freezing and freeze drying are reviewed based on their morphologies: porous structures, microwires and nanowires, and microparticles and nanoparticles. The review concludes with new developments in this area and a brief look into the future. Copyright © 2010 Society of Chemical Industry     

冷冻干燥法制备层状多孔羟基磷灰石支架过程中的溶剂升华行为

采用水基羟基磷灰石(hydroxyapatite,HA)浆料,经冷冻干燥和烧结工艺(1 250℃烧结3 h)制备了层状多孔HA支架.研究了冷冻温度、干燥压力和干燥温度对水基HA浆料中溶剂升华行为的影响.结果表明:随着冷冻温度的降低,多孔HA支架的层间距逐渐减小,支架的升华时间增加;由于样品的干燥过程同时受到传热和传质的...     

A study on the fabrication of porous chitosan/gelatin network scaffold for tissue engineering

A novel porous chitosan/gelatin scaffold for tissue engineering was prepared via polyelectrolyte complex formation, freeze drying and post‐crosslinking with glutaraldehyde. The porosity and mean pore diameters could be controlled within 30∼100 µm by varying the original water content and the freezing conditions. Dipping the scaffolds in poly(lactic acid) provided good mechanical properties making it a promising candidate towards tissue engineering. © 2000 Society of Chemical Industry     

Drying Behavior of a Slip Cast Body Using a Microwave Heating

To reduce the drying period a significant enhancement of manufacturing speed and improvement of productivity of ceramic fabrication were needed. The evaporation and transport of water were the keys to drying and controlling the kinetics of drying, which subsequently affects the properties of green bodies. This research was conducted to investigate the effects of rapid drying of ZnO slip cast bodies by microwave drying and compared with those dried by conventional drying techniques. From these results, the extent of warpage of a dried body was smaller in microwave drying than in other conventional drying methods. Furthermore, the number and size of pores were smaller for this drying technique than for other drying methods after sintering. Microwave heating was tentatively considered as a small difference in the water content between the inside and the outside of the green body, because the free and bound waters with NH₄⁺ salt of polyacrylic acid in a green body were selectively heated compared with ZnO powder, and evaporation and diffusion of water was done efficiently from the inside of the green body under microwave drying. Microwave drying has merits in terms of both the rapid drying and structural uniformity of dried bodies. It not only reduces drying period, but also improves the characteristics of green and sintered bodies.     

Reduced Cracking in Oxide Fiber‐Reinforced Oxide Composites via Freeze‐Dry Processing

Porous oxide matrix composites typically develop significant numbers of matrix cracks during processing. Eliminating such cracks will lead to improved matrix‐dominated properties and will also provide a significant step toward producing a dense oxide matrix composite. However, attaining a crack‐free oxide matrix composite has been elusive due to the large shrinkages of the matrix in drying and sintering in the presence of the constraints to macro shrinkage imposed by fiber reinforcement, and to direct effects of drying. By utilizing a camphene based freeze‐drying process combined with a nonshrinking matrix, the shrinkage cracks in an oxide fiber‐reinforced composite can be essentially eliminated. This concept was validated for 2D fabric‐reinforced composites.     

抗冻岩石膨化硝铵炸药的实验研究

介绍了通过降低复合油相的凝固点来制备抗冻型岩石膨化硝铵炸药的方法，对多种抗冻剂的抗冻性能进行了测试和分析，并得出最佳的抗冻复合油相配方及其炸药。实验结果表明，该炸药在经过低温（－18℃）贮存后仍具有优良的物理性能和爆炸性能。     

Optimal Control of the Secondary Drying Stage of Freeze Drying of Solutions in Vials Using Variational Calculus

Abstract:

The problem of operating freeze drying of pharmaceutical products in vials loaded on trays of freeze dryer to obtain a desired final bound water content in minimum time is formulated as an optimal control problem. Two different types of freeze dryer designs were considered. In the type I freeze dryer design, upper and lower plate temperatures were controlled together, while in the type II freeze dryer design, upper and lower plate temperatures were controlled independently. The heat input to the material being dried and the drying chamber pressure were considered as control variables. Only the scorch temperature was considered as a constraint on the system state variables during the secondary drying stage, because all the free water content (frozen water) is removed from the solid matrix during the primary drying stage of freeze drying. Necessary conditions of optimality for the secondary drying stage of freeze drying process in vials were derived and presented by using rigorous multidimensional unsteady-state mathematical models. The theoretical approach presented in this work was applied in the freeze drying of skim milk. Significant reductions in drying times of the secondary drying stage of the freeze drying process in vials were observed and more uniform bound water and temperature distributions in the material being dried were obtained compared to the conventional operational policies.     

Thermal conductivity of ceramic green bodies during drying

The thermal conductivity of alumina and kaolin green bodies has been studied as a function of the water loss during drying. Experimental measurements show strong variations with 3 distinct regimes. In the first regime, thermal conductivity increases during shrinkage. When shrinkage stops, a decrease in thermal conductivity with water loss is observed which becomes even stronger during the last phase of drying. This can be explained by the variations in the volume fractions of each phase and the effective thermal contacts between grains. Using analytical relations, the thermal resistance of an equivalent plane of small area grain-grain contacts is shown to increase strongly at the end of drying due to the removal of water. Finally, in certain drying conditions, if a portion of the heat required for drying, is supplied by conduction through the green body, then the rate of water evaporation increases with higher thermal conductivity.