基于疏水作用的陶瓷浆料自发凝固成型研究进展

doi:10.15541/jim20220014

摘要/Abstract

摘要：

自发凝固成型是一种新型的陶瓷浆料原位固化成型方法, 通过吸附在陶瓷颗粒表面的分子链间弱作用(氢键, 疏水作用)实现浆料的固化, 具有普适性和适于常温大气环境操作的特点, 已成为先进陶瓷制备领域的研究热点。本文简述发现兼具分散和凝固功能的阴离子型高分子分散剂的历程, 以及自发凝固成型与其它原位固化成型的异同。在此基础上, 基于疏水作用设计合成了系列自发凝固成型剂, 进而满足以不同尺寸颗粒为原料的致密陶瓷和泡沫陶瓷的自发凝固成型。综述了面向实际应用所开发的陶瓷无界面连接、晶粒定向构造、干燥脱水等关键技术, 以及致密陶瓷和泡沫陶瓷制备等研发进展, 展望了未来自发凝固成型的发展方向。

关键词: 自发凝固成型, 注凝成型, 陶瓷浆料, 疏水作用, 氧化铝, 致密陶瓷, 泡沫陶瓷, 综述

Abstract:

Spontaneous coagulation casting (SCC) is a novel in-situ ceramic forming method, not only universal for various ceramics but also working well at room temperature in air. Here presents the finding of SCC, involving an anion dispersant which acts as both dispersing and coagulating agent. Then, the difference between SCC and other in-situ coagulation methods in principle was elucidated. In SCC, particles participate in the formation of organic network which originates from hydrophobic interaction and hydrogen bonding among the dispersant molecular chains. The ceramic gel formed by SCC is a physical gel and possesses low density which is conducive to water transportation and stress relaxation during drying. In contrast, the one by conventional gelcasting is a chemical gel in which particles are fixed by a dense organic network. Based on the hydrophobic interaction, this review focuses on the design and synthesis of a series of SCC agents to meet the demand of forming dense and porous ceramics from particles with different sizes. That is, an anion dispersant is hydrophobically modified by a surfactant with a short or long chain. The obtained two agents are used for preparation of dense and porous ceramics, respectively. Progress of key technologies in this area including ceramic joining without interface, construction of grain orientation, drying, preparation of dense ceramics and porous ceramics, by SCC is summarized. Typically, alumina disc with a diameter up to 1010 nm and alumina parts with complicated shape such as dome and guide are shown. Future development of SCC is also proposed to enable SCC is a more universal forming technology for advanced ceramics with a large and/or complicated dimension.

Key words: spontaneous coagulation casting, gelcasting, ceramic slurry, hydrophobic interaction, alumina, dense ceramics, porous ceramics, review

中图分类号:

TQ174

王士维. 基于疏水作用的陶瓷浆料自发凝固成型研究进展[J]. 无机材料学报, 2022, 37(8): 809-820.

WANG Shiwei. Progress of Spontaneous Coagulation Casting of Ceramic Slurries Based on Hydrophobic Interaction[J]. Journal of Inorganic Materials, 2022, 37(8): 809-820.

图/表 16

图1 三维有机网络固化陶瓷颗粒示意图(a)和半透明Al2O3薄板照片(100 mm×100 mm×1 mm) (b)

Fig. 1 Schematic diagram of ceramic particles solidified by three-dimensional organic network (a) and photo of translucent Al2O3 sheet (100 mm × 100 mm × 1 mm) (b)

图2 PIBM分子结构简式(a)以及自发凝固(b)和注凝(c)所制备坯体中颗粒间低密度和高密度有机网络示意图

Fig. 2 Simplified structure of PIBM molecule (a) and schematic diagrams of organic network with low and high density by spontaneous coagulation casting (b) and gelcasting (c), respectively

图3 TMAH含量对氧化铝浆料流变性的影响(a)以及浆料固含量对陶瓷坯体干燥及烧结收缩率的影响(b)[43]

Fig. 3 Effect of TMAH content on the rheology of alumina slurry (a), and effect of slurry solid content on drying and sintering shrinkage (b)[43]

图4 疏水基团对自发凝固成型的影响

Fig. 4 Effect of hydrophobic groups on spontaneous coagulation (a) Hydrophobic modification reaction; (b) Schematic diagram of ceramic particle dispersion and hydrophobic association curing mechanism

表1 不同疏水链改性后Isobam 600 AF的溶解情况

Table 1 Dissolution of Isobam 600 AF after different hydrophobic chain modification

Organic ammonium salt	Molecular weight	Solubility of Isobam after hydrophobic modification
TMAC (Tetramethyl ammonium chloride)	109.6	Soluble
TEAC (Tetraethylammonium chloride)	165.7	Soluble
MTAC (Methyltributylammonium chloride)	235.8	Soluble
OTAC (Octyltrimethylammonium chloride)	207.8	Insoluble
DTAC (Dodecyltrimethylammonium chloride)	263.0	Insoluble

图5 引入不同疏水链制备的氧化铝浆料的Zeta电位(a)、粘度(b)和储能模量(c)[47]

Fig. 5 Zeta potential (a), viscosity (b), and storage modulus (c) of alumina slurry prepared by introducing different hydrophobic chains[47]

图6 TMAC对添加PAA和CE-64所配制氧化铝浆料粘度(a)和储能模量(b)的影响[47]

Fig. 6 Effect of TMAC on viscosity (a) and storage modulus (b) of alumina slurry prepared by adding PAA and CE-64[47]

图7 疏水化的陶瓷颗粒稳定泡沫示意图(a)及其局部放大图(展示颗粒表面疏水修饰的分散剂) (b)

Fig. 7 Schematic diagram of stabilized foam with hydrophobized ceramic particles (a) and corresponding magnification part (showing a modified dispersant on a particle) (b)

图8 氧化铝陶瓷坯体无界面连接前(a)后(b)的照片和脱水收缩时间对陶瓷烧结后(1600 ℃×2 h)抗弯强度的影响(c)[54]

Fig. 8 Pictures of wet green bodies before (a) and after (b) joining, and effect of syneresis time on flexural strength of sintered samples (1600 ℃×2 h) derived from wet green bodies (c) [54]

图9 氧化铝陶瓷凝胶和压滤后样品干燥的线性收缩率(a)和干燥后素坯的密度分布(b)[55]

Fig. 9 Linear shrinkage (a) and bulk density distribution (b) of the gelled and pressure-filtrated samples after drying[55]

图10 不同分散体系制备的陶瓷素坯的密度差(a)和烧结后样品 (280 mm×130 mm×20 mm)的照片(b)[56]

Fig. 10 Density difference of ceramic green bodies prepared by different dispersion systems (a) and photos of sintered samples (280 mm×130 mm×20 mm)(b)[56]

图11 不同压力下湿坯的干燥曲线(a)和制备的陶瓷直线透过率(样品厚 1mm)(b)[57]

Fig. 11 Drying curves of wet bodies under different pressures (a) and in-line transmittance of corresponding ceramics (1 mm thick) (b)[57]

图12 片晶在剪切流下定向排布的示意图(a)、添加片晶所制备的素坯表面(b)、素坯经不同温度烧结后的XRD图谱(c)以及片晶含量和种类对陶瓷直线透过率的影响(样品厚1 mm)(d)[61]

Fig. 12 Schematic diagram of orientation of the platelet under shear flow (a), surface of the green body with platelet (b), XRD patterns of the green bodies sintered at different temperatures (c), and the influence of the content and type of the platelet on the linear transmittance of the ceramic (1 mm thick) (d)[61]

图13 由疏水化的陶瓷颗粒稳定泡沫所制备的闭孔氧化铝泡沫陶瓷

Fig. 13 Closed-cell alumina foam ceramics prepared by hydrophobized ceramic particles (a) Coarse-grained[65]; (b) Fine-grained[67]

图14 直径1010 mm 氧化铝圆盘照片

Fig. 14 Photo of alumina disc with a diameter of ϕ 1010 mm

图15 自发凝固成型制备复杂形状氧化铝半球状部件(a), 氧化铝导轨(b)以及氮化铝部件(c)

Fig. 15 Pictures of alumina dome (a) and guide (b), and AlN ceramic hat sink (c) prepared by spontaneous coagulation casting

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