梯度多孔载Ag羟基磷灰石陶瓷的制备和性能研究

本文采用添加造孔剂法制备孔隙呈现梯度分布的多孔载Ag羟基磷灰石(Ag-HA)陶瓷。研究了造孔剂分布、烧结温度和载Ag含量对梯度多孔Ag-HA陶瓷孔隙度的影响。分析了烧结产物的物相组成和微观形貌,测量了烧结后梯度多孔Ag-HA陶瓷的压缩性能和抗菌性能。研究结果表明:随着中间层造孔剂含量增加,梯度多孔Ag-HA陶瓷的孔隙度增大,抗压强度减小;随着烧结温度的增大,梯度多孔Ag-HA陶瓷的孔隙度减小,抗压强度增大;当造孔剂分布为20%-10%-20%(质量分数),压制压力为100 MPa,烧结温度为1 150 ℃,Ag含量为2.0%(摩尔分数)时,烧结后梯度多孔2.0Ag-HA陶瓷的孔隙度为24.7%,抗压强度为12.6 MPa。XRD分析表明烧结产物为掺杂Ag离子的HA相。SEM观察表明烧结样品的孔隙呈现梯度分布。梯度多孔Ag-HA陶瓷的抗菌实验表明:随载Ag含量和孔隙度的增大,梯度多孔Ag-HA陶瓷对于大肠杆菌和金黄色葡萄球菌的抑菌圈直径增加,表现出较强的抗菌性能,而纯HA陶瓷未表现出抗菌性能。     

Silica strengthened alumina ceramic cores prepared by 3D printing

Ceramic cores based on alumina and silica are important in the manufacturing of hollow blades. However, obtaining good properties and precision is still challenging. In this research, alumina-based ceramics cores were obtained by 3D printing technology, and the effects of silica contents on the mechanical properties of the as-obtained alumina ceramic cores were evaluated. The results showed significant improvements in flexural strengths of the ceramics from 13.3 MPa to 46.3 MPa at silica contents from 0 wt% to 30 wt% due to formation of mullite phase (Al₆Si₂O₁₃). By contrast, the flexural strengths declined as silica content further increased due to the generation of massive liquid phase. Also, porous structures and cracks were observed by scanning electron microscopy due to the removal of cured photosensitive resin and the mullitization reaction between alumina and silica, respectively. The manufacturing process of hollow blades required ceramic cores with flexural strengths greater than 20 MPa to resist the strike of metal liquid, as well as open porosity above 20 % to provide space for alkali liquor to dissolve the ceramic cores. As a result, 10 wt% silica was determined as the optimal value to yield ceramics with improved properties in terms of flexural strength (35.6 MPa) and open porosity (47.5 %), thereby satisfy the application requirement for the fabrication of ceramic cores.     

环氧树脂含量对激光选区烧结制备多孔煤系高岭土陶瓷性能的影响

目前,我国对煤系高岭土资源的整体深加工技术水平较低,导致了资源浪费和环境污染。本文分别以煅烧煤系高岭土和环氧树脂为原料和粘结剂,利用激光选区烧结工艺制备多孔煤系高岭土陶瓷,研究了环氧树脂含量对多孔煤系高岭土陶瓷性能的影响。研究表明,制备的多孔煤系高岭土陶瓷主要物相为莫来石和方石英,其孔隙分布均匀。随着环氧树脂质量分数从10%增大到25%,多孔煤系高岭土陶瓷素坯的抗弯强度由0.17 MPa增大到0.32 MPa,多孔煤系高岭土陶瓷的抗弯强度由2.81 MPa减小到0.82 MPa,其气孔率由50.37%增大到59.69%。以煤系高岭土为原料,采用激光选区烧结工艺制备多孔陶瓷对煤系高岭土资源的开发利用具有较为重要的意义。     

Complex mullite structures fabricated via digital light processing of a preceramic polysiloxane with active alumina fillers

By taking advantage of the multi-functional properties of preceramic polymers, their transformation into ceramic material at low sintering temperatures and the processing capabilities of polymer manufacturing processes, mullite components were fabricated by additive manufacturing. A photocurable silicone preceramic polymer resin containing alumina particles was shaped into complex structures via Digital Light Processing. Dense and crack-free, highly complex porous mullite ceramics were produced by firing a mixture of a commercially available photosensitive polysiloxane as the silica source, containing alumina powder as active filler, in air at a low sintering temperature (1300 °C). In particular, the developed formulations, coupled with the additive manufacturing approach, allow for precise control of the architecture of the porous ceramic components, providing better properties compared to parts with stochastic porosity.     

注凝成型微孔梯度陶瓷材料制备新工艺的研究(Ⅲ)

采用90年代初发明的注凝成型技术制备微孔梯度陶瓷材料。在研究了不同粒度的Al2O3和高温粘结剂混合物浆料的制备方法及固体含量、高温粘接剂、颗粒度对制品的烧成收缩率、气孔率、强度、孔径及其分布和渗透性等物理性能影响的基础上，进一步研究了微孔梯度陶瓷材料的制备方法及其性能。通过研究实现了孔梯度陶瓷材料一次烧成。坯体和烧结体的显微结构表明：不同粒度导的界面清晰，缺陷少，结合强度高；粒度、孔径在横向方向呈均匀分布，在纵向方向呈梯度分布，各层材料的收缩一致，确保了孔梯度陶瓷材料的稳定烧成。     

3D printed ceramic phosphor and the photoluminescence property under blue laser excitation

An Al₂O₃/YAG: Ce³⁺ ceramic phosphor was fabricated for high-flux laser lighting using the digital lighting process (DLP)-based 3D printing method for the first time. The photocurable ceramic suspension for 3D printing was prepared by blending well-treated Al₂O₃/YAG: Ce³⁺ composite powders with photosensitive resin monomers and photo-initiators. The printing parameters, debinding and sintering processes were designed delicately to fabricated the dense sub-millimeter-sized cylinder ceramic with high dimensional accuracy. The ceramic showed excellent luminescence property under blue laser excitation with a threshold of 20.7 W/mm², higher than that prepared via dry-pressing followed by vacuum sintering. The luminescence properties and the microstructures of both ceramics were further comparatively investigated to find the possible interpretations for improvement of laser flux for the 3D-printed ceramic. The present work indicated that the new developed 3D printing method was promising for preparing luminescent ceramics for high-flux laser lighting in a rapid, effective, low-cost and precision-controlled manner.     

Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration

Complex silicon carbide (SiC) ceramic components are difficult to fabricate due to their strong covalent bonds. Binder jetting (BJ) additive manufacturing has the outstanding advantages of high forming efficiency and no thermal deformation, especially suitable for printing complex structure SiC components. This study tried to obtain low silicon content silicon carbide ceramics by binder jetting followed by phenolic resin impregnation and pyrolysis (PRIP) and liquid silicon infiltration (LSI). BJ was used for the SiC green parts fabrication, and the highest compressive strength (7.7 ± 0.3 MPa) and lowest dimensional deviations (1.2–1.6 mm) were obtained with the printing layer thickness of 0.15 mm. Subsequently, PRIP treatments were introduced to increase the carbon content for the following LSI process. As the number of PRIP cycles increased, the carbon density of SiC/C preform increased and the porosity decreased. After the LSI treatment, the final Si-SiC composites processed with 2 PIRP cycles reached the highest flexural strength (257 ± 14.26 MPa) and the best wear resistance. This was attributed to the low residual silicon content (10.2 vol%) and almost no residual carbon. Furthermore, several complex structural components were fabricated using these methods. The preparation of complex components verifies the feasibility of BJ and LSI for manufacturing high-strength and high-precision SiC ceramics. Besides, this work hopes to provide technical guidance for the preparation of complex SiC composites in the future.     

Influence of number average molecular weight on the properties of 3D printed precursor ceramics

A deliberately selected end-capping agent was introduced into the precursor to form a low number average molecular weight precursor and meet the need for liquid crystal display (LCD) 3D printing. The influence of number average molecular weight on the photocuring properties of precursor and the physical properties of pyrolysis samples were studied in detail for the first time. The results proved that a relatively low number average molecular weight precursors had low ceramic yields after pyrolysis. As the number average molecular weight of the precursor decreased, the photocuring ability of the precursor photosensitive resin increased. With the decrease in the number average molecular weight of the precursor in the precursor photosensitive resin, the ceramic yield of 3D printed PDCs decreased from 58.4% to 30.2%, and the linear shrinkage increased from 27.2% to 40.3%. The bending strength of the LCD 3D printed specimen reached 61.5 ± 3.7 MPa. The low cost of precursor synthesis and equipment in this study points the way for the preparation of precursor non-oxide ceramic composites and can be conducive to the development and application of LCD 3D printing precursor ceramics.     

Preparation and performance of lightweight porous ceramics using metallurgical steel slag

In this paper, porous ceramics with high porosity and low bulk density were prepared by using steel slag and kaolin as main raw materials and polyurethane sponge as template. The effects of steel slag particle size, zirconia addition, the solid content of the slurry, and the addition of polycarboxylic acid water-reducing agent on the properties of ceramics were studied. In addition, by adding a surfactant (Sodium dodecyl sulfate) to form fine pores on the original framework of the three-dimensional network porous ceramic, the shortcomings of the single as well as the uncontrollable density and porosity of the porous ceramic, which are produced by the template method, are improved. When the grinding time of steel slag is 90 min, the content of zirconia is 3% wt, the solid content of ceramic slurry is 64% wt, and 0.6% wt polycarboxylic acid water-reducing agent and 0.4% of surfactant are added, the prepared porous ceramic skeleton is clear and good. The porous ceramic has a low bulk density (as low as 157.869 kg/m³), high porosity (about 94.05%) and high compressive strength (0.2 MPa). The crystalline phase of it is mainly composed of anorthite, gehlenite, forsterite and quartz. The addition of zirconia, water-reducing agent and surfactant only changes the macrostructure of porous ceramics, and does not change its crystal phase composition. The preparation of porous ceramics from steel slag not only solves the recycling problem of steel slag, but also provides a good substitute for main raw materials of porous ceramics.     

Dispersion and properties of zirconia suspensions for stereolithography

Stereolithography is an attractive technique for the fabrication of complex-shaped ceramic components with high dimensional accuracy. One of the challenges in this technology is the development of high solid loading, low viscosity photosensitive ceramic suspension. In this study, the dispersion of zirconia in photocurable resin and the slurry properties were intensively investigated. Rheological measurements showed that DISPERBYK-103 proved to be an effective dispersant. 42 vol% ZrO₂ suspension was successfully prepared using 3.5 wt% DISPERBYK-103 as the dispersant, with a suitable viscosity (4.88 Pa·s) below the maximum allowable viscosity value (5 Pa·s) for stereolithography applications. The adsorption behavior of DISPERBYK-103 on the surface of zirconia powders was characterized by TG and FT-IR, confirming the dispersion effect of dispersant. Contact angle measurements were also conducted to show that the adsorption of DISPERBYK-103 could help to improve the wettability between powder and photocurable resin. Results showed that DISPERBYK-103 was effective for the preparation of suitable slurries for the development of ZrO₂ ceramics through stereolithography.     

硅液相浸渍反应制备TiC/SiC和TiN/SiC复相陶瓷

以滤纸、酚醛树脂和氧化钛为原料,经过模压成型、固化、碳化及不同条件下渗硅制备了TiC/SiC和TiN/SiC复相陶瓷。通过X射线衍射和扫描电子显微镜研究了TiC/SiC和TiN/SiC复相陶瓷的微观结构和物相组成,测量了复相陶瓷的弯曲强度和断裂韧性。结果表明:真空条件下液态渗硅获得的TiC/SiC复相陶瓷具有多孔的微观结构,其弯曲强度和断裂韧性较小。氮气气氛下液态渗硅制备的TiN/SiC复相陶瓷结构致密,有较高的弯曲强度和断裂韧性。不同反应生成的TiC,TiN陶瓷颗粒对液态硅的润湿性不同,使得生成的复相陶瓷具有不同的微观结构。TiN/SiC复相陶瓷中TiN颗粒的引入,在基体与第二相颗粒间的界面上产生拉应力和压应力,使达到这一区域的裂纹偏转,从而获得增韧效果。     

A new Al2O3 porous ceramic prepared by addition of hollow spheres

A method for making porous ceramic prepared by adding hollow spheres was developed, and the resulting porous ceramic was named as hollow spheres ceramic. Water soluble epoxy resin was used as a gel former in the gelcasting process of the Al₂O₃ hollow sphere and Al₂O₃ powder, the porous ceramic porosity varies from 22.3 to 60.1 %. The influence of amount of Al₂O₃ hollow sphere and sintering temperature on the microstructure, compressive strength and thermal conductivity were investigated. With an increasing amount of hollow sphere in the matrix, the porosity increases, which leads to decreased bulk density, compressive strength and thermal conductivity. The compressive strength of the porous ceramics has a power law relation with the porosity, and the calculated power law index is 4.5. The equations of the relationship between porosity and thermal conductivity of porous ceramics are proposed. The thermal conductivity of samples with 60.1 % porosity is as low as 2.1 W/m k at room temperature.     

面向光固化3D打印陶瓷构件的光敏树脂体系研究

光敏树脂是光固化3D打印的材料基础,也是光固化3D打印陶瓷的成型媒介。光敏树脂体系影响光固化3D打印陶瓷构件成型过程的收缩率与脱脂过程的应力,本文设计了含环状结构的单官能度树脂、三官能度树脂及引入预聚物及稀释剂的多组分树脂三个树脂体系,测试了三个树脂体系的收缩率,研究表明引入预聚物及稀释剂的树脂体系具有最低的固化收缩率,有效缓解了因固化反应收缩造成的3D打印氧化铝陶瓷素坯开裂的问题。采用热失重分析和热处理实验研究了三个树脂体系的热分解行为,多组分树脂体系具有分阶段热解的特性,采用该树脂体系制备了光敏性氧化铝浆料,优化了光固化打印参数及脱脂气氛,3D打印厚壁实心(12 mm×12 mm×12 mm)样件与大尺寸(?80 mm×50 mm)的氧化铝陶瓷素坯脱脂后均无裂纹等缺陷。     

Novel Three‐Dimensional Extrusion of Multilayered Ceramic/Camphene Mixture for Gradient Porous Ceramics

This study proposes an innovative way of creating porous ceramics with a unique gradient porous structure using three‐dimensional extrusion of a multilayered ceramic/camphene feed rod, denoted as “3D‐Ex_m”. This 3D‐Ex_m technique utilizes the wall slip phenomenon during the extrusion process, which can create a gradient core/shell structure with a gradual change in the core/shell thickness ratio. In addition, the microstructure of ceramic filaments can be tuned through the use of the camphene as a pore‐forming agent. Porous alumina ceramics produced using a bilayered feed rod comprised of the alumina/camphene mixtures with the relatively high (?_H = 40 vol%) and low ceramic contents (?_L = 10 vol%) showed a gradual change in porosity in the intermediate region between the relatively dense (porosity = ~3 vol%) and highly porous regions (porosity = ~85 vol%).     

Microstructural comparison of porous oxide ceramics from the system Al2O3–ZrO2 prepared with starch as a pore-forming agent

In this paper we show examples of microstructures of porous oxide ceramics prepared by traditional slip casting (TSC) and starch consolidation casting (SCC) and present results obtained using different microstructural characterization techniques; Archimedes method (open and total porosity), shrinkage measurement, mercury intrusion porosimetry (pore size distribution) and microscopic methods – optical microscopy with microscopic image analysis (pore size distribution) and scanning electron microscopy (detailed investigation of the local microstructure). In particular, microstructures are compared for porous ceramics from the system Al₂O₃–ZrO₂ prepared with rice and corn starch. It is shown that maximum values of the total porosity of porous ceramics prepared with starch as a pore-forming agent were approx. 50%. A major finding by using SEM with respect to starch-produced porous ceramics is the existence of pore fillings in the form of small sintered ceramic shell inside the pores, as a result of starch granule shrinkage during the drying and burn-out steps.     

Enhancing thermal insulation and mechanical strength of porous ceramic through size-graded MA Hollow Spheres

In this study, a series of porous ceramics were prepared using different ratios of small and large size MA hollow ceramic spheres as pore-forming agents, and their thermal insulation properties were investigated. The results showed that increasing the proportion of small size hollow ceramic spheres could effectively decrease the thermal conductivity and improve the compressive strength of the porous ceramics. The optimal porous ceramic was prepared with a ratio of 10∼50 of small and large size hollow ceramic spheres, which had a thermal conductivity of 0.368 W/(m·K) at 800 °C and a compressive strength of 22.43 MPa. Microscopic analysis indicated that the enhanced thermal insulation and mechanical properties were due to the improved pore structure and the enhanced bonding strength between the ceramic spheres and the matrix. The findings provide valuable insights for the development of high-performance thermal insulation materials.     

Recent developments in gelcasting of ceramics

Gelcasting is a well-established colloidal processing method with a short forming time, high yields, high green capacity and low-cost machining, and has been used to prepare high-quality and complex-shaped dense/porous ceramic parts. In this article, we reviewed recent developments in gelcasting technology for ceramic preparation. For environmental pollution reduction during ceramic preparation by gelcasting, the development of low-toxic and nontoxic gelcasting systems is discussed. The occurrence and control of inner stress and surface-exfoliation in ceramic green bodies prepared by gelcasting are analyzed, and then some methods to control and eliminate the inner stress and surface-exfoliation in ceramic gelcast green bodies, especially for colloidal injection molding of ceramics (CIMC) are proposed. Finally, the applications of gelcasting for the fabrication of porous ceramics and complex-shaped ceramics (e.g., microbeads, rutile capacitor, thin-wall rutile tube, refractory nozzle) are summarized.     

新型陶瓷改性环氧树脂涂料的制备及性能表征

本文用甘氨酸改性环氧树脂,制备了水性环氧乳液。所制得的水性环氧乳液与陶瓷粉混合,在固化剂的作用下,得到了环氧树脂陶瓷涂料。通过正交实验确定了该涂料的最佳配方为:环氧树脂20g,甘氨酸3.3g,聚乙二醇(10000)1.6g,陶瓷粉6g,环氧固化剂4.5g。经性能测试,该涂料具有较好的涂膜性能,涂层可在室温下固化,使用方便。     

Preparation of three-dimensionally linked pore-like porous atomized ceramics with high oil and water absorption rates

Ceramic atomization cores are a new application of porous ceramics; however, the challenging regulation of the pore structures of porous ceramics has limited their application. To improve the low liquid absorption rates and low liquid storage capacity of porous ceramics in the field of atomization, this study used three substances, polymethyl methacrylate (PMMA), starch, and diatomaceous earth, to produce porous ceramics with a three-dimensional interconnected triple-porous structure by sacrificial templating. In the porous ceramics, large pores resulting from PMMA increase liquid storing capacity, medium pores resulting from the starch facilitate the transport of liquid, and small pores resulting from diatomaceous earth enhance capillary action, significantly increasing the rate of liquid absorption. By varying the PMMA contents and type of starch in the preform, water and oil storage capacities of up to 123% and 143%, respectively, can be achieved. We found that an optimized porous ceramic with dimensions of 15 mm × 15 mm × 15 mm absorbs water rapidly (reaching saturation in only 1.67 s), demonstrates good solid–liquid properties and shape stability, and is recyclable (requires drying before reuse). The proposed porous ceramics have promising atomization core and oil–water separation applications.     

硅藻土光固化成型浆料和多孔陶瓷的制备

本文成功开发了用于光固化成型的树脂基硅藻土浆料,系统探讨了分散剂种类、含量及固含量对硅藻土浆料流变特性的影响,并对其作用机理进行了分析,获得了用于光固化成型的高固含量、低黏度的硅藻土浆料,并采用3D陶瓷光固化设备制备了结构复杂的硅藻土多孔陶瓷。结果表明,BYK2009为硅藻土浆料的最佳分散剂,且当分散剂相对粉体质量为3%时,浆料黏度最低。成功制备出粉体体积分数为40%的硅藻土浆料,在剪切速率为30 s^-1时,硅藻土浆料黏度为17.30 Pa·s。在900 ℃烧结时得到显气孔率为51.30%、抗弯强度为(46.28±2.63) MPa的硅藻土多孔陶瓷。本研究为光固化成型具有复杂多级孔结构的硅藻土载体提供了参考。