CN108002843B - 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法 - Google Patents

一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法 Download PDF

Info

Publication number
CN108002843B
CN108002843B CN201711142473.5A CN201711142473A CN108002843B CN 108002843 B CN108002843 B CN 108002843B CN 201711142473 A CN201711142473 A CN 201711142473A CN 108002843 B CN108002843 B CN 108002843B
Authority
CN
China
Prior art keywords
paste
silicon nitride
porous silicon
oxide
complex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711142473.5A
Other languages
English (en)
Other versions
CN108002843A (zh
Inventor
史玉升
刘荣臻
吴甲民
陈双
陈鹏
陈安南
文世峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201711142473.5A priority Critical patent/CN108002843B/zh
Publication of CN108002843A publication Critical patent/CN108002843A/zh
Application granted granted Critical
Publication of CN108002843B publication Critical patent/CN108002843B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/591—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by reaction sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness
    • C04B2235/9638—Tolerance; Dimensional accuracy

Abstract

本发明属于材料成型技术领域，并公开了一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，将光固化工艺与碳热还原氮化工艺结合，以氧化硅、碳粉等为原料，采用基于陶瓷膏体的光固化成型工艺制备出复合复杂形状件后，通过碳热还原氮化工艺将其氮化为多孔氮化硅部件。本发明所提出的工艺方法采用陶瓷膏体为原料，所制备的坯体具有较高的尺寸精度，而后处理所用的碳热还原氮化方法也具有非常好的近净成型特性，适合成型高精度复杂形状多孔氮化硅件。本发明所提出的制备方法具有工艺流程短、近净尺寸成型性好等特点，是一种具有良好工业应用前景的复杂形状多孔氮化硅件制备方法。

Description

一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法
技术领域
本发明属于材料成型技术领域，更具体地，涉及一种多孔氮化硅复杂形状件制备方法。
背景技术
多孔氮化硅具有强度高、耐高温、耐腐蚀等优点，广泛应用于过滤器、催化剂载体和生物反应器等多个工业领域中。同时多孔氮化硅具有良好的介电性能是雷达天线罩的理想材料，但由于多孔氮化硅硬度高、脆性大、难加工，因此其复杂形状件特别是高精度复杂形状件的制备一直是制约陶瓷工程应用的难题之一。为此发展了诸如凝胶注模、注浆成型、挤出成型、直接凝固注模成型等多种氮化硅陶瓷复杂形状件的成型工艺，以解决这一难题(如邓健等，注浆成型结合真空发泡法制备梯度多孔氮化硅陶瓷，无机材料学报，2016，vol.31(8)：865-868以及余娟丽等，凝胶注模成型制备微多孔氮化硅陶瓷，稀有金属材料与工程，2009,vol.38(增刊2):340-343)。
虽然上述技术可制备复杂形状件，但仍然依赖于模具的制造(如成来飞等《一种制备复杂形状多孔氮化硅陶瓷制品的方法》，申请号：201510623703.4)，模具制造周期长、成本高，使得复杂形状多孔氮化硅的制造成本居高不下。除上述技术之外，多孔氮化硅陶瓷的增材制造技术在复杂形状件的制备上表现出很大的优势。这种技术基于离散-堆积原理，通过逐点、逐线或逐面的将原料进行叠加成型出复杂形状件，是解决陶瓷复杂形状件最有前景的技术方法之一。当前常用的陶瓷增材制造技术中可实现大尺寸陶瓷部件的技术包括间接选区激光烧结技术(indirect SLS)、熔融沉积造型技术(FDM)和光固化技术(SLA)等。特别是光固化技术，采用光敏树脂作为固化成分在紫外激光辐照下直接固化，具有成型精度高、表面质量好、能够制备复杂形状精密零件等优点，非常适于高精度复杂形状多孔氮化硅件的批量化定制生产。但目前光固化技术中往往直接以氮化硅陶瓷浆料为原料，经光固化成型坯体后再经过高温后处理以获得氮化硅复杂形状件。一方面，由于多采用浆料进行光固化成型，原料的固含量低、稳定性差，不利于陶瓷零件长时间的生产制造；另一方面，由于大量氮化硅粉体的应用使得成品成本难以降低。
因此为解决上述问题，实现大尺寸、高精度、复杂形状多孔氮化硅陶瓷的制造，本发明所提出方法先采用氧化硅、碳粉、光敏树脂等为原料先制备出相对成本较低、高固含量的陶瓷膏体，再利用光固化工艺对原料膏体进行复杂形状件成型，最后通过碳热还原氮化的方法将多孔氧化硅预制体转变为多孔氮化硅材料。首先使用高固含量膏体作为原料，改善了原料稳定性，还避免了粉料离散和堆积造成的表面粗糙度高、精度差等问题；其次碳热还原工艺的应用，一方面降低了高纯氮化硅的使用量，降低了原料成本；另一方面碳热还原具有近净成型特点，保障了成型制品的精度，使得本发明所提供的方法适宜于高精度、大尺寸复杂形状多孔氮化硅件的制备；再次，有效利用光敏树脂裂解形成的碳作为碳源，将脱脂排胶工艺与高温烧结工艺进行有机结合，大幅减少了工艺流程、缩短了光固化陶瓷件的制备工艺周期。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，适宜于高精度、大尺寸、复杂形状多孔氮化硅零部件的制备。
为实现上述目的，按照本发明，提供了一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，包括以下步骤：
1)按如下重量比例准备原料：氧化硅粉22份～46份，碳粉3.5份～13.5份，烧结助剂1.5份～3.5份，氮化硅晶种3份～7份，光敏树脂30份～70份；
2)将以上述原料混合制备出复合膏体；
3)通过光固化成型的方式预成型出复合坯体；
4)对复合坯体进行碳热还原氮化烧结，获得多孔氮化硅复杂形状件。
优选地，所述氧化硅粉的平均粒径为0.1μm～30μm，并且其杂质元素百分含量小于1wt.％。
优选地，所述碳粉的平均粒径为0.01μm～10μm，其杂质百分含量小于0.5wt.％
优选地，所述烧结助剂为氧化铁、氧化亚铁、氧化钇、氧化镧、氧化铝、氧化锆、氧化镁中的一种或多种，该烧结助剂的平均粒径为0.1μm～10μm且杂质百分含量小于0.5wt.％。
优选地，所述氮化硅晶种中β-Si3N4的含量不低于95％，平均粒径为0.01～10μm。
优选地，所述光敏树脂包括树脂、分散剂、光引发剂和溶剂，其中，所述树脂为丙烯酸酯树脂和/或环氧树脂，所述丙烯酸酯树脂为环氧丙烯酸酯和/或聚氨酯丙烯酸酯，所述环氧树脂为缩水甘油醚类环氧树脂和/或缩水甘油酯类环氧树脂，分散剂为柠檬酸铵、聚丙烯酸钠、四甲基氢氧化铵、二甲基甲酰胺、聚乙烯吡咯烷酮、六偏磷酸钠、油酸、硬脂酸中的一种或多种，光引发剂为自由基光引发剂和/或阳离子光引发剂，溶剂为去离子水、无水乙醇、丙三醇、丙酮中的一种或多种。
优选地，步骤2)中所述复合膏体的获取方法如下：将氧化硅粉、碳粉、分散剂、光敏树脂和烧结助剂采用机械球磨方式混合，球磨转速200r/min-400r/min，球磨时间为0.5h-12h，球磨后采用真空除气方法对膏体进行脱气，然后再使膏体内的部分溶剂挥发以调节膏体粘度到合3Pa·s-15Pa·s。
优选地，步骤3)中采用光固化成型的方式预成型出复合坯体的过程如下：在空气气氛下，将所述复合膏体放入进料缸中，采用激光辐照的方式对复合膏体进行固化成型，光固化成型完成后去除未固化的复合膏体，即得到复合坯体。
优选地，步骤4)中碳热还原氮化烧结的具体过程如下：复合合坯体干燥后放置在氮气气氛烧结炉中，在流动氮气气氛下，升温速率在0.5℃～20℃/min，氮气压力不低于0.1MPa，逐步升温至1750℃，保温1h-4h，烧结完成后即获得多孔氮化硅的复杂形状件。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：
1)本发明所提出方法采用氧化硅、碳粉、光敏树脂等为原料先制备出高固含量的陶瓷膏体，再利用光固化工艺对原料膏体进行复杂形状件成型，最后通过碳热还原氮化的方法将多孔氧化硅预制体转变为多孔氮化硅材料。由于使用高固含量膏体作为原料，原料稳定性得到提升，还避免了粉料离散和堆积造成的表面粗糙度高、精度差等问题，提高了所成型复杂形状多孔氮化硅件坯体的精度。
2)本发明所采用的多孔氮化硅复杂形状件制备工艺，以高固含量陶瓷膏体为原料，将碳热还原氮化工艺与光固化成型工艺结合，无需单独进行脱脂，直接以氧化硅为原料，利用光固化中光敏树脂裂解生成的碳用作碳热还原中的碳源进行碳热还原氮化，避免了大量高纯度的氮化硅粉料的使用；另一方面碳热还原具有近净成型特点，保障了成型制品的强度，使得本发明所提供的方法适宜于高精度复杂形状多孔氮化硅件的制备。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
一种复杂形状多孔氮化硅件的制备，包括下述步骤：
步骤一、原料准备：按重量比例准备0.1μm氧化硅粉22份，0.01μm碳粉3.5份，0.01μm氮化硅晶种3份，0.1μm氧化铁1.5份，光敏树脂70份，将上述材料分别称量后放入球磨罐中，进行机械球磨球磨速度为200转/min，球磨时间为4h后得到陶瓷膏体，对陶瓷复合膏体进行真空除气处理，并通过搅拌鼓风的方式将溶剂挥发，调节其粘度至3Pa·s；
步骤二、光固化成型：将上述复合膏体放入光固化成型设备所用进料缸中，按照所设计的模型信息，将膏体逐层铺料逐层固化，光固化成型完成后即获得陶瓷膏体制备的复合坯体；
步骤三、碳热还原氮化：将上述复合坯体放入氮气烧结炉中，将其放入氮气烧结炉中，通入流动氮气进行最终的反应烧结，1400℃以下时升温速率为0.5℃/min，大于1400℃时升温速率为10℃/min，氮气压力为0.3MPa，逐步升温至1750℃，保温1h，烧结完成后即获得多孔氮化硅的复杂形状件。
实施例2
一种复杂形状多孔氮化硅件的制备，包括下述步骤：
步骤一、原料准备：按重量比例准备30μm氧化硅粉36份，10μm碳粉7.5份，10μm氮化硅晶种7份，10μm氧化镧1份，10μm氧化亚铁2.5份，光敏树脂34份，将上述材料分别称量后放入球磨罐中，进行机械球磨球磨速度为200转/min，球磨时间为4h后得到陶瓷膏体，对陶瓷复合膏体进行真空除气处理，并通过搅拌鼓风的方式将溶剂挥发，调节其粘度至15Pa·s；
步骤二、光固化成型：将上述复合膏体放入光固化成型设备所用进料缸中，按照所设计的模型信息，将膏体逐层铺料逐层固化，光固化成型完成后即获得陶瓷膏体制备的复合坯体；
步骤三、碳热还原氮化：将上述复合坯体放入氮气烧结炉中，将其放入氮气烧结炉中，通入流动氮气进行最终的反应烧结，1400℃以下时升温速率为0.5℃/min，大于1400℃时升温速率为2℃/min，氮气压力为0.3MPa，逐步升温至1750℃，保温2h，烧结完成后即获得多孔氮化硅的复杂形状件。
实施例3
一种复杂形状多孔氮化硅件的制备，包括下述步骤：
步骤一、原料准备：按重量比例准备0.1μm氧化硅粉46份，0.01μm碳粉13.5份，0.01μm氮化硅晶种7份，10μm氧化锆2.5份，10μm氧化镁1份，光敏树脂30份，将上述材料分别称量后放入球磨罐中，进行机械球磨球磨速度为200转/min，球磨时间为6h后得到陶瓷膏体，对陶瓷复合膏体进行真空除气处理，并通过搅拌鼓风的方式将溶剂挥发，调节其粘度至12Pa·s；
步骤二、光固化成型：将上述复合膏体放入光固化成型设备所用进料缸中，按照所设计的模型信息，将膏体逐层铺料逐层固化，光固化成型完成后即获得陶瓷膏体制备的复合坯体；
步骤三、碳热还原氮化：将上述复合坯体放入氮气烧结炉中，将其放入氮气烧结炉中，通入流动氮气进行最终的反应烧结，1400℃以下时升温速率为0.5℃/min，大于1400℃时升温速率为20℃/min，氮气压力为0.3MPa，逐步升温至1750℃，保温3h，烧结完成后即获得多孔氮化硅的复杂形状件。
实施例4
一种复杂形状多孔氮化硅件的制备，包括下述步骤：
步骤一、原料准备：按重量比例准备3μm氧化硅粉22份，0.2μm碳粉3.5份，0.2μm氮化硅晶种7份，0.2μm氧化钇2份，0.2μm氧化铝1.5份，光敏树脂70份，将上述材料分别称量后放入球磨罐中，进行机械球磨球磨速度为400转/min，球磨时间为12h后得到陶瓷膏体，对陶瓷复合膏体进行真空除气处理，并通过搅拌鼓风的方式将溶剂挥发，调节其粘度至5Pa·s；
步骤二、光固化成型：将上述复合膏体放入光固化成型设备所用进料缸中，按照所设计的模型信息，将膏体逐层铺料逐层固化，光固化成型完成后即获得陶瓷膏体制备的复合坯体；
步骤三、碳热还原氮化：将上述复合坯体放入氮气烧结炉中，将其放入氮气烧结炉中，通入流动氮气进行最终的反应烧结，1400℃以下时升温速率为0.5℃/min，大于1400℃时升温速率为10℃/min，氮气压力为0.3MPa，逐步升温至1750℃，保温4h，烧结完成后即获得多孔氮化硅的复杂形状件。
实施例5
一种复杂形状多孔氮化硅件的制备，包括下述步骤：
步骤一、原料准备：按重量比例准备3μm氧化硅粉24份，0.2μm碳粉3.5份，0.2μm氮化硅晶种5份，0.2μm氧化钇0.5份，0.2μm氧化铝1.5份，光敏树脂70份，将上述材料分别称量后放入球磨罐中，进行机械球磨球磨速度为300转/min，球磨时间为8h后得到陶瓷膏体，对陶瓷复合膏体进行真空除气处理，并通过搅拌鼓风的方式将溶剂挥发，调节其粘度至7Pa·s；
步骤二、光固化成型：将上述复合膏体放入光固化成型设备所用进料缸中，按照所设计的模型信息，将膏体逐层铺料逐层固化，光固化成型完成后即获得陶瓷膏体制备的复合坯体；
步骤三、碳热还原氮化：将上述复合坯体放入氮气烧结炉中，将其放入氮气烧结炉中，通入流动氮气进行最终的反应烧结，1400℃以下时升温速率为0.5℃/min，大于1400℃时升温速率为10℃/min，氮气压力为0.3MPa，逐步升温至1750℃，保温4h，烧结完成后即获得多孔氮化硅的复杂形状件。
以上各实施例所制得的多孔氮化硅的复杂形状件的部分性能参数参见表1。
表1本发明实施例中多孔氮化硅的部分性能参数
Figure BDA0001471708370000081
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，包括以下步骤：
1)按如下重量比例准备原料：氧化硅粉22份～46份，碳粉3.5份～13.5份，烧结助剂1.5份～3.5份，氮化硅晶种3份～7份，光敏树脂30份～70份；
2)将以上述原料混合制备出复合膏体；步骤2)中所述复合膏体的获取方法如下：将氧化硅粉、碳粉、分散剂、光敏树脂和烧结助剂采用机械球磨方式混合为膏体，球磨转速200r/min-400r/min，球磨时间为0.5h-12h，球磨后采用真空除气方法对膏体进行脱气，然后再使膏体内的部分溶剂挥发以调节膏体粘度到合3Pa·s-15Pa·s；
3)通过光固化成型的方式预成型出复合坯体；步骤3)中采用光固化成型的方式预成型出复合坯体的过程如下：在空气气氛下，将所述复合膏体放入进料缸中，采用激光辐照的方式对复合膏体进行固化成型，光固化成型完成后去除未固化的复合膏体，即得到复合坯体；
4)对复合坯体进行碳热还原氮化烧结，获得多孔氮化硅复杂形状件；所述的碳热还原氮化烧结过程中无需单独进行脱脂，直接以氧化硅为原料，利用光固化中光敏树脂裂解生成的碳用作碳热还原中的碳源进行碳热还原氮化。
2.根据权利要求1所述的一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，所述氧化硅粉的平均粒径为0.1μm～30μm，并且其杂质元素百分含量小于1wt.％。
3.根据权利要求1所述的一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，所述碳粉的平均粒径为0.01μm～10μm，其杂质百分含量小于0.5wt.％。
4.根据权利要求1所述的一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，所述烧结助剂为氧化铁、氧化亚铁、氧化钇、氧化镧、氧化铝、氧化锆、氧化镁中的一种或多种，该烧结助剂的平均粒径为0.1μm～10μm且杂质百分含量小于0.5wt.％。
5.根据权利要求1所述的一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，所述氮化硅晶种中β-Si3N4的含量不低于95％，平均粒径为0.01～10μm。
6.如权利要求1所述的一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，所述光敏树脂包括树脂、分散剂、光引发剂和溶剂，其中，所述树脂为丙烯酸酯树脂和/或环氧树脂，所述丙烯酸酯树脂为环氧丙烯酸酯和/或聚氨酯丙烯酸酯，所述环氧树脂为缩水甘油醚类环氧树脂和/或缩水甘油酯类环氧树脂，分散剂为柠檬酸铵、聚丙烯酸钠、四甲基氢氧化铵、二甲基甲酰胺、聚乙烯吡咯烷酮、六偏磷酸钠、油酸、硬脂酸中的一种或多种，光引发剂为自由基光引发剂和/或阳离子光引发剂，溶剂为去离子水、无水乙醇、丙三醇、丙酮中的一种或多种。
7.如权利要求1所述一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法，其特征在于，步骤4)中碳热还原氮化烧结的具体过程如下：复合合坯体干燥后放置在氮气气氛烧结炉中，在流动氮气气氛下，升温速率在0.5℃～20℃/min，氮气压力不低于0.1MPa，逐步升温至1750℃，保温1h-4h，烧结完成后即获得多孔氮化硅的复杂形状件。
CN201711142473.5A 2017-11-17 2017-11-17 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法 Active CN108002843B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711142473.5A CN108002843B (zh) 2017-11-17 2017-11-17 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711142473.5A CN108002843B (zh) 2017-11-17 2017-11-17 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法

Publications (2)

Publication Number Publication Date
CN108002843A CN108002843A (zh) 2018-05-08
CN108002843B true CN108002843B (zh) 2020-07-10

Family

ID=62052743

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711142473.5A Active CN108002843B (zh) 2017-11-17 2017-11-17 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法

Country Status (1)

Country Link
CN (1) CN108002843B (zh)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108675796B (zh) * 2018-06-05 2021-05-11 广东工业大学 一种氮化硅陶瓷浆料、氮化硅陶瓷及其制备方法和应用
JP2021536381A (ja) 2018-08-31 2021-12-27 スリーエム イノベイティブ プロパティズ カンパニー 非酸化物セラミック物品を製造するための積層造形方法、並びにエアロゲル、キセロゲル、及び多孔質セラミック物品
CN112721339B (zh) * 2020-12-31 2023-04-28 福建闽华建材科技发展有限公司 一种环保的高分子复合防水卷材及其制备方法
CN113024227A (zh) * 2021-04-07 2021-06-25 麻建华 一种耐高低温的防滑瓷砖及其制备方法
CN113563087A (zh) * 2021-07-05 2021-10-29 淄博国创中心先进车用材料技术创新中心 氮化硅陶瓷零件及其制造方法
CN113563088B (zh) * 2021-07-30 2023-06-13 淄博国创中心先进车用材料技术创新中心 多孔氮化硅陶瓷零件及其制造方法
CN116813354A (zh) * 2023-06-06 2023-09-29 东莞理工学院 一种原位制备氮化硅陶瓷的方法、制得的氮化硅陶瓷及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60226452A (ja) * 1984-04-23 1985-11-11 四季ロ−ル株式会社 管状または棒状のセラミツク製造方法
CN105315006A (zh) * 2015-12-03 2016-02-10 盐城工学院 一种梯度多孔氮化硅陶瓷的制备方法
CN106699191A (zh) * 2017-01-20 2017-05-24 广东工业大学 一种基于光固化成型的3d打印制备氮化硅陶瓷的方法
CN107158474A (zh) * 2017-05-26 2017-09-15 山东工业陶瓷研究设计院有限公司 光固化3d打印牙科种植体用浆料及其制备方法和应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1007724B (zh) * 1985-06-24 1990-04-25 川崎制铁株式会社 制造α-氮气化硅粉末的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60226452A (ja) * 1984-04-23 1985-11-11 四季ロ−ル株式会社 管状または棒状のセラミツク製造方法
CN105315006A (zh) * 2015-12-03 2016-02-10 盐城工学院 一种梯度多孔氮化硅陶瓷的制备方法
CN106699191A (zh) * 2017-01-20 2017-05-24 广东工业大学 一种基于光固化成型的3d打印制备氮化硅陶瓷的方法
CN107158474A (zh) * 2017-05-26 2017-09-15 山东工业陶瓷研究设计院有限公司 光固化3d打印牙科种植体用浆料及其制备方法和应用

Also Published As

Publication number Publication date
CN108002843A (zh) 2018-05-08

Similar Documents

Publication Publication Date Title
CN108002843B (zh) 一种基于膏体的高精度多孔氮化硅复杂形状件的制备方法
CN106966709B (zh) 一种基于光固化成型的3d打印制备透明氧化铝陶瓷的方法
CN107021771B (zh) 一种基于3d打印技术的氧化钙基陶瓷铸型制造方法
CN101456737B (zh) 一种碳化硼基复合陶瓷及其制备方法
CN103553632B (zh) 一种致密化氮化硅陶瓷材料的制备方法
CN110028324B (zh) 一种氮化物陶瓷的制备方法
CN110590388A (zh) 一种低成本、高效氧化铝纤维增强氧化铝复合材料制备方法
CN108002842B (zh) 一种复杂形状多孔氮化硅件的制备方法
CN102875132B (zh) 一种大尺寸高纯氧化铝陶瓷材料的制备方法
CN104909765A (zh) 一种低成本、快速制备高性能Si3N4陶瓷球的方法
CN102808100B (zh) 定向孔陶瓷增强金属基复合材料的制备方法
CN104326766A (zh) 一种具有球形孔结构的多孔氮化硅陶瓷材料的制备方法
CN104308155A (zh) 一种粉末微注射成形制造微阵列的方法
CN107935628B (zh) 一种泡沫碳化硅陶瓷及其制备方法
CN113105252A (zh) 一种制备氮化硅陶瓷的烧结助剂及其应用、氮化硅陶瓷的制备方法
CN101734920B (zh) 一种氮化钛多孔陶瓷及其制备方法
CN103102172B (zh) 一种碳酸氢铵发泡法制备多孔氮化硅陶瓷的方法
CN112390641B (zh) 一种基于3d凝胶打印技术的yag透明陶瓷光纤制备方法
CN113999032A (zh) 一种硅硼氮纤维增强石英陶瓷材料及其制备方法
CN111499386A (zh) 一种复合陶瓷材料及其制备方法
CN107619282B (zh) 一种高韧性钛碳化硅-碳化硅复相陶瓷异形件的制备方法
CN112341164B (zh) 一种用于玻璃热弯成型的陶瓷模具及其制备方法
CN112759399B (zh) 铝基碳化硅封装部件材料及其碳化硅预置坯体制备方法
CN112457047B (zh) 一种低介电低密度石英质陶瓷材料制备方法
CN107573076B (zh) 一种高韧性钛碳化硅-碳化硅复相陶瓷异形件

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant