TBA-based freeze/gel casting of porous hydroxyapatite scaffolds

Porous ceramic scaffolds with a controlled “designer” pore structure have been prepared by the freeze/gel casting route using a TBA-based hydroxyapatite slurry system with 20–40 wt.% solid content. The products were characterized in terms of sintered microstructure, together with physical and mechanical properties. After sintering at 1050–1250 °C, the advantages of freeze casting and gel casting appeared in the pore structure and compressive strength of the ceramics, i.e., unidirectional aligned macro-pore channels developed by controlling the solidification direction of the TBA solvent used in the freeze casting together with small diameter (micron sized) isolated pores formed in the dense outer walls of the pore channels when processed by gel casting. The sintered porosity and pore size generally resulted in a high solid loading giving low porosity and small pore size, this leading to higher compressive strengths. The scaffolds obtained exhibited an average porosity and compressive strength in the range 41.9–79.3% and 35.1–2.7 MPa, respectively, depending on the processing conditions used.     

凝胶注模法制备多孔羟基磷灰石陶瓷

采用凝胶注模法制备了多孔羟基磷灰石陶瓷,探讨了制备工艺对陶瓷显微结构和力学性能的影响。结果表明,以柠檬酸三铵C6H17O7N3为分散剂,最佳加入量(以粉料质量计算)为2%,最佳的球磨时间为5 h,球磨时最佳的水/粉料的质量比为1.5∶1,球磨时的最佳pH值为10,在1 200℃下烧成了HA多孔陶瓷。单体浓度10%的样品在1 200℃下2 h烧成的陶瓷,开孔率为39.87%,抗压强度为83.60 MPa,抗折强度为0.059 2 MPa;单体浓度15%的样品在1 200℃下3 h烧成的陶瓷,开孔率为39.59%,抗压强度为83.92 MPa,抗折强度为0.062 6 MPa。     

Microstructure and mechanical properties of hydroxyapatite obtained by gel-casting process

In the present work, well-shaped HAp green bodies were obtained by the gel-casting process with 50 vol.% slurry. After drying, the microstructure and pore distribution of the green body were investigated. The density, compressive strength and flexural strength of the green body were 1.621 g/cm³, 32.6 ± 3.2 MPa and 13.8 ± 1.0 MPa, respectively. After pressureless sintering at the range of 1100–1300 °C for 2 h, the relative density of the final product ranges from 71.8 to 97.1% th. The maximum value of flexural strength, elastic modulus, hardness and fracture toughness were 84.6 ± 12.6 MPa, 138 ± 7 GPa, 4.45 ± 0.18 GPa and 0.95 ± 0.13 MPa m^1/2, respectively. SEM images show a compact and uniform microstructure; the average grain size was found by using the linear intercept method. XRD and FTIR determined the phase and the radical preserved after sintering.     

Preparation of mesoporous carbon by freeze drying

Resorcinol–formaldehyde (RF) cryogels were synthesized by sol-gel polycondensation of resorcinol with formaldehyde and freeze drying with t-butanol. The cryogels were characterized by nitrogen adsorption and density measurements. Their porous properties were compared with those of RF aerogels prepared by supercritical drying with carbon dioxide. RF cryogels were mesoporous materials with large mesopore volumes >0.58 cm³/g. Although surface areas and mesopore volumes of the cryogels were smaller than those of the aerogels, the cryogels were useful precursors of mesoporous carbons. Carbon cryogels were obtained by pyrolyzing RF cryogels in an inert atmosphere. Carbon cryogels were mesoporous materials with high surface areas >800 m²/g and large mesopore volumes >0.55 cm³/g. When pyrolyzed, micropores are formed inside the cryogels more easily than inside the aerogels.     

Chitosan scaffolds formation by a supercritical freeze extraction process

A crucial step of Tissue Engineering (TE) approach is the fabrication of 3-D biodegradable scaffolds. It has been achieved using various techniques, such as gas foaming, fiber bonding, solvent casting/particulate leaching, phase separation and 3D-printing. Each technique presents specific advantages and disadvantages; but, all of them share the difficulty to obtain simultaneously the macro, micro and nanostructure. In this work, a Supercritical Freeze Extraction Process (SFEP) is proposed for the formation of chitosan structures suitable for TE applications. We showed that it is possible to produce chitosan scaffolds characterized by a micrometric cellular structure, nanofibrous sub-structure and porous surfaces. The low process temperature allows to obtain 3-D solids, whose structure is preserved during supercritical drying. Preliminary results on cell cultivation confirmed that the generated chitosan scaffolds are characterized by a morphology that is potentially suitable for TE applications. A good cell adhesion was obtained and a large percentage of living cells was observed. This result can depend on the micrometric morphology of the scaffolds, that assures a good nutrient diffusion, and on the nanometric sub-structure that allows an adequate cells adhesion.     

Evaluating the suitability of fast sintering techniques for the consolidation of calcium phosphate scaffolds produced by DLP

Porous scaffolds were fabricated via Digital Light Processing (DLP) from β-TCP powder and sintered by conventional sintering in air (CSA), rapid sintering in air (RSA) and pressure-less spark plasma sintering in vacuum (pl-SPS), at four different temperatures: 1200, 1300, 1400 and 1500 ºC. Each sintering strategy resulted in scaffolds with different phase composition, microstructure and mechanical properties. Long dwell times or high temperatures were required to achieve a complete β→α transformation, and rapid cooling rates avoided the reverse transformation. The presence of graphite in the sintering chamber played a crucial role in stabilising the α-TCP phase, phase prevailing in SPS-treated scaffolds, hindered their densification and avoided the generation of transformation-induced cracks. All scaffolds exhibited compressive strengths within the range of cancellous bone, with the highest average value of 22 ± 4 MPa achieved by the RSA scaffolds sintered at 1300 ºC, thanks to their greater densification and fine microstructure.     

药品真空冷冻干燥一般工艺初探

简述了药品真空冷冻干燥的基本要求、一般工艺及其过程的控制。     

Cellular PVA hydrogels produced by freeze/thawing

Cellular poly(vinyl alcohol) (PVA) hydrogels that exhibit enhanced swelling kinetics from an initial dry state were prepared by freezing and thawing techniques in the presence of NaCl. Gels that were dried immediately after preparation demonstrated a dual‐sorption effect upon swelling. Gels that were exposed to a 10‐day washing period to remove NaCl and excess PVA chains before drying showed an increased initial rate of swelling and overall water content. Freeze/thawed, cellular PVA gels showed overall enhanced swelling with increased mechanical strength over traditional gels prepared by chemical or irradiative crosslinking techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2075–2079, 2000     

Near net shape fabrication of porous cordierite by combination of foam gel-casting and freeze-drying

Near net shape fabrication of porous cordierite was successfully achieved through a combination of foam gel-casting, freeze-drying, and in situ synthesis. Environment friendly gelation was used as gel system, and the gelatin concentration influenced the drying shrinkage vastly. Combined with the volume expansion coming from phase transition and solid reaction during in situ synthesis of cordierite, the total linear shrinkage could be controlled around zero (−1.87% to 0.45%) by adjusting the gelation concentration and solid content in the slurry, meanwhile the prepared porous cordierite ceramics showed both high porosity (85.9%–91.1%) and high compressive strength (0.58–3.37 MPa). The sample with 0.05 g/ml gelatin concentration and 20 vol% solid content possessed excellent performance: total porosity of 89.1%, compressive strength of 1.36 MPa, and specific strength of 4.9 MPa/(g/cm³), showing the potential usage of filter carrier.     

喷雾冷冻干燥对颗粒产品形态的影响

喷雾冷冻干燥作为一种新型颗粒制备技术,产品具有尺寸可控、多孔、速溶、流动性好等优点。鉴于该技术在医药、食品、化工等行业生产独特产品的优势,本文综述了国内外喷雾冷冻干燥过程中有关颗粒形成及其形态变化的影响因素,具体介绍了其冻结过程对蛋白质颗粒形态、脂质体颗粒稳定性、疫苗颗粒、无机材料形态等产品的影响。同时还指出了喷雾冷冻干燥技术存在过程不连续、规模化程度不高、低温液体处理不便等问题需要解决,表明合理优化喷雾冷冻干燥工艺及强化干燥过程将是该技术未来研究的重点。     

Porous asymmetric microfiltration membranes shaped by combined alumina freeze and tape casting

An assembled asymmetric alumina microfiltration membrane with high performance was prepared by combining freeze and tape casting techniques followed by two sintering steps. Freeze casting was used for manufacturing of the porous support layer with a highly interconnected pore network. Tape casting was applied on the top layer to form a pre-membrane with smaller pore size and controlled thickness, which was set on the sintered support. Morphology influences were investigated for different solid loadings, additives content and the assembled layer membrane structures. No delamination among the layers was observed. The assembled ceramic membrane had an average pore size between 30 and 50 μm together with a top surface layer around 0.35 μm, which is suitable to the microfiltration separation process. Porosity in the range of 26–50 % and water flux of 11–32 m³ m^?2 h^?1 bar^?1 were reached for samples prepared with two sintering steps at 1600 and 1300 °C for 2 h.     

真空冷冻干燥过程中几个影响因素的探讨

以某混合培养基使用 VIRTIS真空冷冻干燥机为例 ,探讨预冻温度、水汽凝结器温度、真空度、制品的温度控制四因素对真空冷冻干燥的影响。     

Pore-forming agent induced microstructure evolution of freeze casted hydroxyapatite

There were interconnected small lamellar pores, big spherical pores and ceramic walls in the hydroxyapatite (HAP) ceramics fabricated by a freeze casting/pore-former method. As keeping the content of polymethyl methacrylate (PMMA) constant and decreasing the size of PMMA, the size of spherical pores and length of ceramic wall both decreased, and the compressive strength increased. As keeping the size of PMMA and decreasing the content of PMMA, the open porosity decreased and compressive strength increased. The shapes of pores caused by ice crystals were reticular, lamellar and treelike, in turn. The HAP ceramics with the spherical pores of 150-250 μm, open porosity of 62.13% and compressive strength of 7.01 MPa are prospective to have biomedical application.     

真空冷冻干燥法制备CuO-ZnO-ZrO2甲醇合成催化剂

采用真空冷冻干燥法制备了一系列CuO-ZnO-ZrO2甲醇合成催化剂,在微型固定床反应器上考察了其对CO2加氢合成甲醇的催化性能及影响,并用XRD、H2-TPR、CO2-TPD、TEM、EDAX、BET等手段进行了表征。研究结果表明,采用真空冷冻干燥法能够制备出高比表面积、高活性、高选择性的甲醇合成催化剂CuO-ZnO-ZrO2。     

Morphology of alumina granules obtained by spray freeze drying with twin-fluid atomization

This study presents the results of the morphological dependence of alumina granules obtained by spray freeze drying (SFD) with twin-fluid atomization. It is shown that the introduction of 1-, 2- and 4-wt.% polyvinyl alcohol (PVA) as a binder in an alumina suspension leads to the formation of irregular granules. Depending on atomization conditions, spherical, “tadpole-like,” granule-satellite and granule aggregates may form during SFD. Increasing the flight time of droplets before the fixing of their shape when they come in contact with liquid nitrogen effectively contributes to the spheroidization of alumina granules. Compacting PVA-free SFD granules leads to the formation of diagonal flaws in a green-body structure. Adding PVA prevents the abovementioned defects by increasing the strength of alumina granules. Increasing the amount of PVA leads to an increase in “tadpole-like” granule content and, consequently, a decrease in a green-body density.     

The drying strategy of atmospheric freeze drying apple cubes based on glass transition

Freeze drying (FD) yields the best quality of dried apple cubes but at the cost of long drying time and also the overall cost. To achieve economical freeze drying along with a high quality product an atmospheric freeze drying (AFD) technique was developed to dry apple cubes. The effect of different air temperature loading scheme on product quality and drying process was studied during AFD. According to the glass transition temperature of apple, a step-up temperature loading strategy for AFD process was developed to reduce the drying time by almost half and provided a similar good product quality.     

Porous silicate cement membranes generated by the novel method combining freeze casting and heat-dry curing

Porous silicate cement membranes (PSCMs) fabricated by the freeze casting method show great potential to be utilized in seawater pretreatment, fermentation broth separation, and industrial wastewater treatment due to its merit of high-temperature resistance, low-cost, and hierarchically ordered porous structures, while the freeze casting method is complex and time-consuming. In this work, a combination of freeze casting and heat-dry curing was initially applied to generate PSCMs. The preparation periods of PSCMs could be shortened by simplifying preparation processes and reducing curing time. The resulting membranes presented double-layer structures, containing a nucleation zone (N-zone) with dense structures and a stability zone (S-zone) with lamellar pore structures. The X-ray diffraction pattern of membranes displayed the mixed hexagonal and rhombohedral structures. This novel method could save more than half of energy consumption compared with the traditional preparation technology of silicate cement samples. The membranes with a mesopore size of 3.794 nm showed high permeation performance with pure water flux reaching 207.23 L m⁻² h⁻¹ under 0.15 MPa and room temperature. The separation efficiency of oil-water was 78.05% under operating pressure of 0.05 MPa. Molecular dynamics simulation was applied to narrate the microscopic process of transformation during heat-dry curing, and obtained a good similarity of consequences between the computational method simulation and experimental operation.     

Comparison of freeze drying and spray drying to obtain porous nanostructured granules from nanosized suspensions

This work studies the spray drying and freeze drying of different nanosized ceramic materials and the physicochemical characteristics of the obtained granules. Colloidal suspensions of alumina, titania, and a 87/13 mixture were studied. The influence of temperature, pressure, nozzle diameter, and solids loading on the morphology and characteristics of dried granules were evaluated. It was demonstrated that these processing parameters have practically no influence, and the only parameter determining the granules characteristics is the solids content of the suspensions, in both processes. Spray drying leads to a monomodal distribution with higher granule size, while freeze drying produces more porous granules, with a bimodal intragranular distribution. The flowability of spray-dried powder is better than that of the freeze-dried powder and suit better the requirements of a feedstock targeted to obtain coatings by plasma thermal spraying whereas freeze drying can produce high porosity, softer granules.     

冻干技术及其在药品生产中的应用

对冻干技术的工作原理进行介绍 ,详细分析在初级干燥阶段和辅助干燥阶段物料的干燥过程及特性 ,物料温度在冻干过程中的变化及其参考性 ,以及影响冻干产品质量的若干问题和相应的解决措施