CN110357634B - 一种碳化硼陶瓷作为压敏陶瓷材料的应用 - Google Patents

一种碳化硼陶瓷作为压敏陶瓷材料的应用 Download PDF

Info

Publication number
CN110357634B
CN110357634B CN201910620167.0A CN201910620167A CN110357634B CN 110357634 B CN110357634 B CN 110357634B CN 201910620167 A CN201910620167 A CN 201910620167A CN 110357634 B CN110357634 B CN 110357634B
Authority
CN
China
Prior art keywords
boron carbide
carbide ceramic
sintering
ceramic
pressure
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
CN201910620167.0A
Other languages
English (en)
Other versions
CN110357634A (zh
Inventor
陈健
祝明
黄政仁
朱云洲
陈忠明
刘学建
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.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
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 Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201910620167.0A priority Critical patent/CN110357634B/zh
Publication of CN110357634A publication Critical patent/CN110357634A/zh
Application granted granted Critical
Publication of CN110357634B publication Critical patent/CN110357634B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/563—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 carbides or oxycarbides based on boron carbide
    • 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
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/118—Carbide, e.g. SiC type
    • 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
    • C04B2235/60—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
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/782—Grain size distributions
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, 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
    • C04B2235/70—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ceramic Products (AREA)

Abstract

本发明涉及一种碳化硼陶瓷作为压敏陶瓷材料的应用，所述碳化硼陶瓷具有压敏特性，所述碳化硼陶瓷的密度为1.82～2.52g•cm‑3，所述碳化硼陶瓷在电流密度为10 mA·cm‑2下的压敏电压U 10mA·cm‑2 ≥0.3V•mm‑1，非线性系数≥1.1。

Description

一种碳化硼陶瓷作为压敏陶瓷材料的应用
技术领域
本发明涉及一种碳化硼陶瓷作为压敏陶瓷材料的应用，属于压敏陶瓷领域。
背景技术
碳化硼在19世纪作为金属硼化物研究的副产品被发现，直到1930年才被科学地研究。作为化学性质最稳定的化合物之一，碳化硼具有优良的耐腐蚀性能和抗高温氧化性能。在常温下不与酸、碱和大多数无机化合物反应，仅在氢氟酸-硫酸、氢氟酸-硝酸混合物中有缓慢的腐蚀。碳化硼是硬度仅次于金刚石和立方氮化硼的高硬材料，具有低密度、高模量和优良的高温性能，因此碳化硼粉体主要用作磨料，致密碳化硼陶瓷则主要由于优良的力学性能而作机械部件。碳化硼的中子吸收能力很强，其中子吸收截面高达347×10-24cm2，仅次于Gd、Sm、Cd等少数几种元素，吸收能谱宽，吸收后没有强的γ射线二次福射，原料丰富，废料易处理。碳化硼中子吸收能力还可以通过添加B元素进一步改善。碳化硼熔点高达2450℃，沸点为3500℃，热膨胀系数为5.71×10-6/K(28-1770℃)，其Seebeek系数较大，热导率较低，高温电导率较高和热稳定性好，尤其热电性能随温度升高而提高。碳化硼中C含量可以在一定范围内变化，通过调整B和C的比例，可使碳化硼获得较高的热电性，热电系数Z超过性能最好的p型半导体Si、Ge。碳化硼(B4C)陶瓷由于具有低密度、超硬度、高熔点、耐化学腐蚀和良好的中子吸收性能等，在航天航空、军工、机械、化工、核工业和能源等行业具有广泛的用途和极大的应用潜力。
碳化硼陶瓷常以半导体作为电学器件被使用，碳化硼的禁带宽度约为2.1eV，由于禁带宽度较小，当有杂质缺陷的时候容易变成导体，电阻在102量级，被认为具有线性电阻特性。
压敏电阻陶瓷材料是指在一定温度下和某一特定电压范围内具有非线性伏安特性、其电阻随电压的增加而急剧减小的一种半导体陶瓷材料。根据压敏电阻陶瓷材料的非线性伏安特性，可以用这种半导体陶瓷材料制成非线性电阻器，即压敏电阻器。压敏电阻是一种限压型保护器件。利用压敏电阻的非线性特性，当过电压出现在压敏电阻的两极间，压敏电阻可以将电压钳位到一个相对固定的电压值，从而实现对后级电路的保护。压敏电阻器的应用很广，可以用来灭火花、过电压保护、制备避雷针和电压稳定化等。
发明内容
在本发明中，首次发现碳化硼陶瓷具有压敏特性，并利用调节烧结温度实现碳化硼陶瓷的压敏特性的调控。
一方面，本发明提供了一种碳化硼陶瓷作为压敏陶瓷材料的应用，所述碳化硼陶瓷具有压敏特性，所述碳化硼陶瓷的密度为1.82～2.52g·cm-3，所述碳化硼陶瓷在电流密度10mA·cm-2下的压敏电压
Figure BDA0002125234700000021
非线性系数≥1.1。
较佳的，所述碳化硼陶瓷的制备方法包括：放电等离子烧结法或热压烧结法；
所述放电等离子烧结法包括：
(1)将碳化硼粉体用氢氟酸清洗，得到洗净后的碳化硼粉体；
(2)将洗净后的碳化硼粉体置于石墨模具内，在40～60MPa压力、1600～2500℃下放电等离子烧结5～15分钟，得到所述碳化硼陶瓷；
所述热压烧结法包括：
(1)将碳化硼粉体用氢氟酸清洗，得到洗净后的碳化硼粉体；
(2)将洗净后的碳化硼粉体、烧结助剂和溶剂混合，得到混合浆料；
(3)将所得混合浆料直接烘干或进行喷雾造粒，得到碳化硼陶瓷粉体；
(4)将所得碳化硼陶瓷粉体放入石墨模具中，在20～60MPa压力、1800～2300℃下热压烧结0.5～2小时，得到所述碳化硼陶瓷。
较佳的，所述碳化硼粉体的粒径为0.2～2μm。
较佳的，所述放电等离子烧结的气氛为真空，优选真空度为1mbar下；所述热压烧结的气氛为真空或氩气气氛，优选真空度为1mbar下或氩气。
较佳的，所述烧结助剂为B-C体系的烧结助剂(碳化物-硼化物)，Al、Si、Ti、V、Cr中的至少一种，加入量为洗净后的碳化硼粉体质量的0～3wt％。
较佳的，所述放电等离子烧结的升温速率为80～120℃/分钟；所述热压烧结的升温速率为10～20℃/分钟。
较佳的，采用热压烧结法得到的碳化硼陶瓷在电流密度10mA·cm-2下的压敏电压
Figure BDA0002125234700000022
非线性系数≥1.6。
另一方面，本发明提供了一种调控碳化硼陶瓷压敏特性的方法，选用氢氟酸清洗后的碳化硼粉体作为原料放电等离子烧结制备碳化硼陶瓷，通过控制放电等离子烧结的温度1600～2500℃以调节碳化硼陶瓷的压敏特性以使其压敏电压在电流密度为10mA·cm-2下的压敏电压
Figure BDA0002125234700000023
非线性系数≥1.1。
本发明采用SPS法(如图1所示)制备了碳化硼陶瓷。其中，SPS是在模具或样品中直接施加大的脉冲电流，通过热效应和其他场效应，使实验材料烧结的一种全新的材料制备技术。SPS法具有升温速度快、烧结温度低、烧结时间短的特点，可以烧结出显微结构细小均匀致密度高的材料。本发明通过控制放电等离子烧结的温度1600～2500℃，使得碳化硼陶瓷的显微结构细小均匀，且致密度变高，最终实现其压敏特性的可控性。
再一方面，本发明提供了一种调控碳化硼陶瓷压敏特性的方法，选用氢氟酸清洗后的碳化硼粉体作为原料，选用B-C体系的烧结助剂、Al、Si、Ti、V、Cr中的至少一种作为烧结助剂热压烧结制备碳化硼陶瓷，通过控制热压烧结的温度1800～2300℃以调节碳化硼陶瓷的压敏特性以使其压敏电压
Figure BDA0002125234700000031
非线性系数≥1.6。
HP法是一种机械加压的烧结方法。这种方法是把材料的粉末装在模具内，然后将材料加热到一定温度并采用加压的方式补充驱动力，从而在较短时间内得到较为致密晶粒细小均匀的块体材料。粉末材料中的原子、分子动能不断增加，当有部分原子、分子的动能大到不能维持原来的有序排列状态时，固态粉末软化，其力学性能明显下降，流动性显著增加，这时施加一定的压力，可使材料的孔隙度不断减少，致密度增加。本发明通过控制热压烧结的温度1800～2300℃，使得碳化硼陶瓷的孔隙度不断减少，致密度增加，最终实现期压敏特性的可控性。
附图说明
图1为本发明制备碳化硼压敏陶瓷的SPS示意图；
图2为本发明制备碳化硼压敏陶瓷的HP示意图；
图3为实施例3中通过SPS法获得的碳化硼压敏陶瓷微观结构照片；
图4为实施例4中通过HP法获得的碳化硼压敏陶瓷微观结构照片；
图5为实施例1-3中不同温度下用SPS法制备的碳化硼压敏陶瓷的伏安特性曲线；
图6为实施例4中用HP法制备的碳化硼压敏陶瓷的伏安特性曲线。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
在本公开中，碳化硼陶瓷具有压敏特性，且密度可为1.82～2.52g/cm3，在电流密度为10mA·cm-2下的压敏电压
Figure BDA0002125234700000032
非线性系数≥1.1。
在本发明以实施方式中，通过SPS方法和HP方法制备高致密高纯碳化硼陶瓷(或称碳化硼压敏陶瓷)。
以下示例性地说明本发明提供的SPS法制备碳化硼压敏陶瓷的方法。
碳化硼粉体用氢氟酸洗净，得到洗净后的碳化硼粉体。碳化硼粉体的平均粒径可为0.2-2μm。其中，洗净的步骤包括：将碳化硼粉体和氢氟酸(1-5wt％)混合，静置1-2小时，后用去离子水清洗并烘干处理，得到洗净后的碳化硼粉体。
称取一定量的洗净后的碳化硼粉体置于石墨模具内，并使用软碳毡包裹，置于放电等离子烧结设备中(参见图1)。具体烧结参数如下：烧结压力控制在40-60MPa，控制升温阶段升温速率为80～120℃/min(例如，100℃/min)，在温度达到1600～2500℃时进行保温，保温时间5-15分钟(例如，5～10min)。烧结过程始终保持真空条件下进行。上述烧结过程中的真空度优选为1mbar及以下。
以下示例性地说明本发明提供的热压烧结法制备碳化硼压敏陶瓷的方法。
碳化硼粉体用氢氟酸洗净，得到洗净后的碳化硼粉体。碳化硼粉体的平均粒径可为0.2-2μm。其中洗净的步骤包括：将碳化硼粉体和氢氟酸(1-5wt％)混合，静置1-2小时，后用去离子水清洗并烘干处理，得到洗净后的碳化硼粉体。
以用氢氟酸洗净的碳化硼粉体为原料，再加入烧结助剂和溶剂后球磨混合均匀得到固含量为40-50wt％(优选为40-45wt％)的混合浆料。上述烧结助剂可为B-C体系的烧结助剂，也可为Al、Si、Ti、V、Cr等烧结助剂。热压烧结法的溶剂可为水或无水乙醇。
将混合浆料直接烘干或进行喷雾造粒，得到混合均匀的碳化硼陶瓷粉体(简称混合粉体)。
将碳化硼陶瓷粉体放入模具中，并在热压烧结设备(参见图2)中进行热压烧结，具体的烧结参数如下：控制升温阶段升温速率为10-20℃/min，烧结温度在1800-2300℃，保温时间为30min-2h，控制压力为20-60Mpa，得到碳化硼陶瓷。上述烧结过程在真空或氩气气氛保护下进行。上述HP烧结所得碳化硼压敏陶瓷在电流密度为10mA·cm-2下的压敏电压
Figure BDA0002125234700000041
非线性系数≥1.6。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。下述实施例中，若无特殊说，其中洗净的步骤包括：将碳化硼粉体和氢氟酸(1wt％)混合，静置2小时，后用去离子水清洗并烘干处理，得到洗净后的碳化硼粉体。
实施例1
将碳化硼粉体用氢氟酸洗净，并称取一定量的洗净后的碳化硼粉体置于石墨模具内，并使用软碳毡包裹，置于放电等离子烧结设备中。烧结压力控制在40MPa，控制升温阶段升温速率为100℃/min，在温度达到1700℃时进行保温，保温时间10min。烧结过程始终保持真空条件下进行，真空度为1mbar，得到碳化硼陶瓷，所述碳化硼陶瓷的致密度为72％，密度为1.82g/cm3，其晶粒尺寸大小为1-2μm。将获得的碳化硼陶瓷加工成Φ10mm、厚度2mm的圆片，并将其两端磨平，在其两端均匀的涂覆上银浆电极，然后将其在马弗炉中750℃保温30min，获得的碳化硼陶瓷圆片经Keithley2450多通道测试系统测试的伏安特性曲线(如图5所示)，其压敏电压
Figure BDA0002125234700000051
非线性系数α＝1.38。
实施例2
将碳化硼粉体用氢氟酸洗净，称取一定量的洗净后的碳化硼粉体置于石墨模具内，并使用软碳毡包裹，置于放电等离子烧结设备中。烧结压力控制在40MPa，控制升温阶段升温速率为100℃/min，在温度达到1800℃时进行保温，保温时间10min。烧结过程始终保持真空条件下进行，真空度为1mbar，得到碳化硼陶瓷，所述碳化硼陶瓷的致密度为73％，密度为1.84g/cm3，其晶粒尺寸大小为1-2μm，将获得的碳化硼陶瓷加工成Φ10mm、厚度2mm的圆片，并将其两端磨平，在其两端均匀的涂覆上银浆电极，然后将其在马弗炉中750℃保温30min，获得的碳化硼陶瓷圆片经Keithley2450多通道测试系统测试的伏安特性曲线(如图5所示)，其压敏电压
Figure BDA0002125234700000052
非线性系数α＝1.44。
实施例3
将碳化硼粉体用氢氟酸洗净，称取一定量的洗净后的碳化硼粉体置于石墨模具内，并使用软碳毡包裹，置于放电等离子烧结设备中。烧结压力控制在40MPa，控制升温阶段升温速率为100℃/min，在温度达到1900℃时进行保温，保温时间10min。烧结过程始终保持真空条件下进行，真空度为1mbar，得到碳化硼陶瓷，所述碳化硼陶瓷的致密度为85％，密度为2.15g/cm3，其微观结构如图3所示，从图3中可知碳化硼陶瓷的晶粒尺寸大小为1-2μm。将获得的碳化硼陶瓷加工成Φ10mm、厚度2mm的圆片，并将其两端磨平，在其两端均匀的涂覆上银浆电极，然后将其在马弗炉中750℃保温30min，获得的碳化硼陶瓷圆片经Keithley2450多通道测试系统测试的伏安特性曲线(如图5所示)，其压敏电压
Figure BDA0002125234700000053
Figure BDA0002125234700000054
非线性系数α＝1.12。
实施例4
本发明以用氢氟酸洗净的碳化硼粉体为原料，再加入烧结助剂(注：具体组分是Al粉和Si粉，加入量分别为洗净的碳化硼粉体的0.5wt％和0.1wt％)后球磨混合均匀得到固含量为45wt％的浆料。将固含量为45wt％的混合浆料直接烘干或进行喷雾造粒，得到混合均匀的碳化硼陶瓷粉体。将所得碳化硼陶瓷粉体放入模具中进行热压烧结，具体的烧结参数如下：控制升温阶段升温速率为15℃/min，烧结温度在2000℃，保温时间为1h，控制压力为60Mpa，在真空或氩气气氛保护下进行，得到碳化硼陶瓷。所述碳化硼陶瓷的致密度为99％，密度为2.51g/cm3，其微观结构如图4所示，从图中可知碳化硼陶瓷的晶粒尺寸大小为0.5-1μm。将获得的碳化硼陶瓷加工成Φ10mm、厚度2mm的圆片，并将其两端磨平，在其两端均匀的涂覆上银浆电极，然后将其在马弗炉中750℃保温30min，获得的碳化硼陶瓷圆片经Keithley2450多通道测试系统测试的伏安特性曲线(如图6所示)，其压敏电压
Figure BDA0002125234700000061
非线性系数α＝1.63。

Claims (8)

1.一种碳化硼陶瓷作为压敏陶瓷材料的应用，其特征在于，所述碳化硼陶瓷具有压敏特性，所述碳化硼陶瓷的密度为1.82～2.52g•cm-3，所述碳化硼陶瓷在电流密度为10 mA·cm-2下的压敏电压U 10mA·cm-2 ≥0.3V•mm-1，非线性系数≥1.1；
所述碳化硼陶瓷的制备方法包括：放电等离子烧结法或热压烧结法；
所述放电等离子烧结法包括：
（1）将碳化硼粉体用氢氟酸清洗，得到洗净后的碳化硼粉体；
（2）将洗净后的碳化硼粉体置于石墨模具内，在40～60MPa压力、1600～2500℃下放电等离子烧结5～15分钟，得到所述碳化硼陶瓷；
所述热压烧结法包括：
（1）将碳化硼粉体用氢氟酸清洗，得到洗净后的碳化硼粉体；
（2）将洗净后的碳化硼粉体、烧结助剂和溶剂混合，得到混合浆料；
（3）将所得混合浆料直接烘干或进行喷雾造粒，得到碳化硼陶瓷粉体；
（4）将所得碳化硼陶瓷粉体放入石墨模具中，在20～60MPa压力、1800～2300℃下热压烧结0.5～2小时，得到所述碳化硼陶瓷。
2.根据权利要求1所述的应用，其特征在于，所述碳化硼粉体的粒径为0.2～2μm。
3.根据权利要求1所述的应用，其特征在于，所述放电等离子烧结的气氛为真空；所述热压烧结的气氛为真空或氩气气氛。
4.根据权利要求3所述的应用，其特征在于，所述放电等离子烧结的真空度为1mbar及以下；所述热压烧结的真空度为1mbar。
5.根据权利要求1所述的应用，其特征在于，所述烧结助剂为B-C体系的烧结助剂，Al、Si、Ti、V、Cr中的至少一种，加入量为洗净后的碳化硼粉体质量的0～3 wt%。
6.根据权利要求1-3中任选一项所述的应用，其特征在于，所述放电等离子烧结的升温速率为80～120℃/分钟；所述热压烧结的升温速率为10～20℃/分钟。
7.一种调控碳化硼陶瓷压敏特性的方法，其特征在于，选用氢氟酸清洗后的碳化硼粉体作为原料放电等离子烧结制备碳化硼陶瓷，通过控制放电等离子烧结的温度为1600～2500℃以调节碳化硼陶瓷的压敏特性以使其压敏电压U 10mA·cm-2 ≥0.3 V•mm-1，非线性系数≥1.1。
8.一种调控碳化硼陶瓷压敏特性的方法，其特征在于，选用氢氟酸清洗后的碳化硼粉体作为原料，通过控制热压烧结的温度为1800～2300℃以调节碳化硼陶瓷的压敏特性以使其压敏电压 U 10mA·cm-2 ≥1.2 V•mm-1，非线性系数≥1.6。
CN201910620167.0A 2019-07-10 2019-07-10 一种碳化硼陶瓷作为压敏陶瓷材料的应用 Active CN110357634B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910620167.0A CN110357634B (zh) 2019-07-10 2019-07-10 一种碳化硼陶瓷作为压敏陶瓷材料的应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910620167.0A CN110357634B (zh) 2019-07-10 2019-07-10 一种碳化硼陶瓷作为压敏陶瓷材料的应用

Publications (2)

Publication Number Publication Date
CN110357634A CN110357634A (zh) 2019-10-22
CN110357634B true CN110357634B (zh) 2021-08-31

Family

ID=68218574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910620167.0A Active CN110357634B (zh) 2019-07-10 2019-07-10 一种碳化硼陶瓷作为压敏陶瓷材料的应用

Country Status (1)

Country Link
CN (1) CN110357634B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111233479B (zh) * 2020-01-25 2022-05-06 大连正兴磨料有限公司 一种高纯度、高致密度、大尺寸碳化硼陶瓷的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1030842A (zh) * 1987-07-16 1989-02-01 Eos科技有限公司 电过载保护材料及工艺
US5068634A (en) * 1988-01-11 1991-11-26 Electromer Corporation Overvoltage protection device and material
PL178133B1 (pl) * 1995-10-24 2000-03-31 Os Bad Rozwojowy Mikroelektron Sposób wykonania rezystora
CN101269967A (zh) * 2008-05-13 2008-09-24 武汉理工大学 一种制备碳化硼陶瓷的方法
CN103113108A (zh) * 2013-04-03 2013-05-22 常熟华融太阳能新型材料科技有限公司 一种碳化硼陶瓷的制备方法
CN104402441A (zh) * 2014-10-28 2015-03-11 东华大学 一种低温快速烧结制备碳化硼陶瓷材料的方法
CN105565813A (zh) * 2015-12-22 2016-05-11 中国科学院上海硅酸盐研究所 一种碳化硅低压压敏陶瓷及其固相烧结制备方法
CN107746270A (zh) * 2017-10-23 2018-03-02 佛山市瑞生通科技有限公司 一种压敏电阻陶瓷材料及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8446245B2 (en) * 2011-09-19 2013-05-21 Polytronics Technology Corp. Over-current protection device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1030842A (zh) * 1987-07-16 1989-02-01 Eos科技有限公司 电过载保护材料及工艺
US5068634A (en) * 1988-01-11 1991-11-26 Electromer Corporation Overvoltage protection device and material
PL178133B1 (pl) * 1995-10-24 2000-03-31 Os Bad Rozwojowy Mikroelektron Sposób wykonania rezystora
CN101269967A (zh) * 2008-05-13 2008-09-24 武汉理工大学 一种制备碳化硼陶瓷的方法
CN103113108A (zh) * 2013-04-03 2013-05-22 常熟华融太阳能新型材料科技有限公司 一种碳化硼陶瓷的制备方法
CN104402441A (zh) * 2014-10-28 2015-03-11 东华大学 一种低温快速烧结制备碳化硼陶瓷材料的方法
CN105565813A (zh) * 2015-12-22 2016-05-11 中国科学院上海硅酸盐研究所 一种碳化硅低压压敏陶瓷及其固相烧结制备方法
CN107746270A (zh) * 2017-10-23 2018-03-02 佛山市瑞生通科技有限公司 一种压敏电阻陶瓷材料及其制备方法

Also Published As

Publication number Publication date
CN110357634A (zh) 2019-10-22

Similar Documents

Publication Publication Date Title
CN112159233B (zh) 一种高耐电场强度碳化硅基复相陶瓷材料及其制备方法
CN106673660B (zh) 一种液相烧结SiC非线性电阻陶瓷及其制备方法
CN105565813B (zh) 一种碳化硅低压压敏陶瓷及其固相烧结制备方法
CN106083058B (zh) 一种碳化硅基复相压敏陶瓷材料及其制备方法
CN106796910B (zh) 陶瓷结构体、基板保持装置用部件及陶瓷结构体的制法
JP2001516142A (ja) 機械グラインディングによって形成したナノ結晶子粉末ベースのバリスタ
JP2001163672A (ja) 窒化アルミニウム焼結体および半導体製造用部材
KR102657287B1 (ko) 세라믹 구조체, 그 제법 및 반도체 제조 장치용 부재
JP7248653B2 (ja) 複合焼結体、半導体製造装置部材および複合焼結体の製造方法
CN110357634B (zh) 一种碳化硼陶瓷作为压敏陶瓷材料的应用
Takahashi et al. Fabrication and electrical properties of Bi4Ti3O12 ceramics by spark plasma sintering
Nahm Nonlinear behavior of Tb4O7-modified ZnO-Pr6O11-based ceramics with high breakdown field
JP2010208871A (ja) 酸化アルミニウム焼結体、その製法及び半導体製造装置部材
CN107500773B (zh) 一种碳化硅基复相高温热敏陶瓷材料
CN106083057B (zh) 一种碳化硅基复相陶瓷材料及其制备方法
CN112723891A (zh) 一种镧钙复合六硼化物多晶阴极材料及其制备方法
CN108358643B (zh) 一种红外光源材料及其制备方法
CN111410537B (zh) 一种具有线性导电特性的碳化硼基复相陶瓷材料及其制备方法
CN108727031B (zh) 一种碳化硅基复相压敏陶瓷及其液相烧结制备方法
Gao et al. Influence of MoSi2 content on the microstructure and properties of MoSi2–RSiC composites
CN114149261B (zh) 一种铪酸铅反铁电陶瓷材料及其制备方法
CN107540377B (zh) 一种碳化硅基复相陶瓷材料在高温电阻元件中的应用
KR101483016B1 (ko) 전도성 탄화규소 벌크소재 및 그 조성물
CN114591087A (zh) 一种以max相-钛碳化铝为助剂的复相碳化硅导电陶瓷及其制备方法
CN107235729B (zh) 一种高纯SiC压敏陶瓷

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