JP2023046932A - Manufacturing method of composite ceramic - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 98
- 239000000919 ceramic Substances 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 44
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 41
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000010304 firing Methods 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009760 electrical discharge machining Methods 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000003754 machining Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005325 percolation Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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Abstract
Description
本発明は、複合セラミックス及びその製造方法に関する。 TECHNICAL FIELD The present invention relates to composite ceramics and a method for producing the same.
炭化ホウ素は、ダイヤモンド及び立方晶窒化ホウ素に次ぐ極めて高い硬度を示すセラミックスである。さらに、炭化ホウ素は、そのかさ比重（密度）が、代表的なセラミックスの一種であるアルミナの約２／３以下であるため、軽量で機械的特性に優れた製品を構成する材料として有用である。炭化ホウ素は、従来、線引きダイスやブラストノズル等の耐摩耗材の他、高い衝撃破壊抵抗性が要求される部品等の構成材料として用いられている。また、炭化ホウ素は高い弾性率を示すことから、そのかさ比重とのパラメータである比剛性（単位質量当たりの変形の程度）が炭素系の複合材料と比較しても高い。このため、半導体製造設備に用いられているステッパーや光学反射ミラー等の高速可動する部材の構成材料としての有用性が認められている。 Boron carbide is a ceramic that exhibits extremely high hardness next to diamond and cubic boron nitride. Furthermore, boron carbide has a bulk specific gravity (density) of about two-thirds or less that of alumina, a typical ceramic, and is therefore useful as a material for constructing products that are lightweight and have excellent mechanical properties. . Boron carbide is conventionally used as a constituent material for parts that require high resistance to impact fracture, as well as for wear-resistant materials such as wire drawing dies and blast nozzles. Moreover, since boron carbide exhibits a high elastic modulus, its specific rigidity (degree of deformation per unit mass), which is a parameter of its bulk specific gravity, is high compared to carbon-based composite materials. For this reason, it is recognized as useful as a constituent material for members that move at high speed, such as steppers and optical reflecting mirrors used in semiconductor manufacturing equipment.
しかし、炭化ホウ素は、難焼結性及び難加工性といった課題を有する材料である。炭化ホウ素は、共有結合性に富んだ結合を有することから、焼結性に著しく劣る。このため、高品質な炭化ホウ素を簡易かつ経済的に製造することは困難であった。さらに、炭化ホウ素は、高硬度であることから形状加工が困難である。 However, boron carbide is a material that has problems such as difficulty in sintering and difficulty in processing. Boron carbide has extremely poor sinterability due to its highly covalent bonds. Therefore, it has been difficult to easily and economically produce high-quality boron carbide. Furthermore, boron carbide is difficult to shape due to its high hardness.
このような状況の下、炭化ホウ素粉末、二酸化チタン粉末、及び炭素粉末の混合物を加圧焼結することで、放電加工可能な炭化ホウ素－二ホウ化チタン焼結体を製造する方法が提案されている（特許文献１及び２）。放電加工は、電極と被加工物の間で短い周期で繰り返し発生させるアーク放電によって被加工物の一部を除去する機械加工技術の一種である。放電加工によれば、従来の機械加工技術では困難であった高硬度の材料を加工することができる。但し、放電加工によって加工する被加工物は、導電性を有する必要がある。炭化ホウ素は導電性に乏しいため、特許文献１及び２で提案された方法においては、電気抵抗率が低い二ホウ化チタンを含ませることで導電性を付与し、放電加工に適した材料としている。 Under these circumstances, a method has been proposed for producing a boron carbide-titanium diboride sintered body capable of electrical discharge machining by pressure sintering a mixture of boron carbide powder, titanium dioxide powder, and carbon powder. (Patent Documents 1 and 2). Electrical discharge machining is a type of machining technology that removes a portion of a workpiece by arc discharge that is repeatedly generated at short intervals between an electrode and the workpiece. Electrical discharge machining makes it possible to machine materials with high hardness that are difficult to machine with conventional machining techniques. However, the workpiece to be machined by electrical discharge machining must have electrical conductivity. Since boron carbide has poor conductivity, in the methods proposed in Patent Documents 1 and 2, titanium diboride, which has low electrical resistivity, is added to impart conductivity, making it a material suitable for electrical discharge machining. .
しかし、特許文献１及び２で提案された方法は、加圧条件下で焼成して炭化ホウ素－二ホウ化チタンを製造する方法であるため、加圧するための特別な製造設備が必要であるとともに製造コストもかかり、簡易かつ経済的な方法であるとは言えなかった。このように、加圧焼結によって炭化ホウ素系の焼結体を製造するには、設備面での制約が多く、産業上幅広く応用されている常圧焼結で培われてきた技術をそのまま適用できないという課題があった。 However, the methods proposed in Patent Documents 1 and 2 are methods of producing boron carbide-titanium diboride by sintering under pressurized conditions, so special production equipment for pressurizing is required. The manufacturing cost is high, and it cannot be said to be a simple and economical method. In this way, the production of boron carbide-based sintered bodies by pressure sintering is subject to many restrictions in terms of equipment, and the technology cultivated in pressureless sintering, which is widely applied in industry, is applied as it is. I had a problem that I couldn't do it.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、高比剛性及び高硬度であるとともに、電気抵抗率が低く、放電加工により所望の形状に加工することが可能な、炭化ホウ素及び二ホウ化チタンを含む緻密質な複合セラミックスを提供することにある。また、本発明の課題とするところは、上記の複合セラミックスを加圧せずとも常圧下で焼成して得ることが可能な複合セラミックスの製造方法を提供することにある。 The present invention has been made in view of the problems of the prior art, and its object is to provide a high specific rigidity and high hardness, a low electrical resistivity, and a desired property by electric discharge machining. An object of the present invention is to provide a dense composite ceramic containing boron carbide and titanium diboride, which can be processed into a shape. Another object of the present invention is to provide a method for producing a composite ceramic that can be obtained by sintering the composite ceramic under normal pressure without applying pressure.
すなわち、本発明によれば、以下に示す複合セラミックスが提供される。
［１］炭化ホウ素（Ｂ４Ｃ）及び二ホウ化チタン（ＴｉＢ２）を含む緻密質な複合セラミックスであって、前記炭化ホウ素と前記二ホウ化チタンの合計を基準とする、前記炭化ホウ素の含有量が５０～７５質量％であるとともに、前記二ホウ化チタンの含有量が２５～５０質量％であり、前記二ホウ化チタンが、そのアスペクト比が１．５以上の粒子であり、相対密度が８９％以上である複合セラミックス。
［２］比剛性が１４０ＧＰａ／（ｇ／ｃｍ３）以上であり、電気抵抗率が９．５×１０－３Ω・ｃｍ以下であり、ビッカース硬度が２，０００Ｈｖ以上である前記［１］に記載の複合セラミックス。
［３］光学反射ミラーの構成材料として用いられる前記［１］又は［２］に記載の複合セラミックス。
That is, according to the present invention, composite ceramics shown below are provided.
[1] A dense composite ceramic containing boron carbide (B 4 C) and titanium diboride (TiB 2 ), wherein the amount of boron carbide is based on the sum of the boron carbide and the titanium diboride The content is 50 to 75% by mass, the content of the titanium diboride is 25 to 50% by mass, the titanium diboride is particles having an aspect ratio of 1.5 or more, and the relative Composite ceramics having a density of 89% or more.
[2] The above [1], which has a specific rigidity of 140 GPa/(g/cm 3 ) or more, an electrical resistivity of 9.5×10 −3 Ω·cm or less, and a Vickers hardness of 2,000 Hv or more. Composite ceramics as described.
[3] The composite ceramics according to [1] or [2], which is used as a constituent material of an optical reflection mirror.
また、本発明によれば、以下に示す複合セラミックスの製造方法が提供される。
［４］前記［１］～［３］のいずれかに記載の複合セラミックスの製造方法であって、炭化ホウ素（Ｂ４Ｃ）粉末及び二ホウ化チタン（ＴｉＢ２）粉末を含有する平均粒子径１．７μｍ以下の混合粉末を成形して成形体を得る工程と、前記成形体を２，０００～２，２１５℃で常圧焼成して前記複合セラミックスを得る工程と、を有する複合セラミックスの製造方法。
［５］前記混合粉末が、アルミニウム（Ａｌ）成分をさらに含有し、前記混合粉末中の前記アルミニウム（Ａｌ）成分の含有量が、前記炭化ホウ素（Ｂ４Ｃ）粉末及び前記二ホウ化チタン（ＴｉＢ２）粉末の合計１００質量部に対して、Ａｌ換算で１～５質量部である前記［４］に記載の複合セラミックスの製造方法。
［６］前記成形体をアルミニウム（Ａｌ）源の共存下で常圧焼成する前記［４］又は［５］に記載の複合セラミックスの製造方法。
Further, according to the present invention, there is provided a method for producing composite ceramics as described below.
[4] The method for producing a composite ceramic according to any one of [1] to [3] above, wherein the average particle size of the boron carbide (B 4 C) powder and the titanium diboride (TiB 2 ) powder is contained. Manufacture of composite ceramics comprising the steps of molding a mixed powder of 1.7 μm or less to obtain a compact, and firing the compact at normal pressure at 2,000 to 2,215° C. to obtain the composite ceramic. Method.
[5] The mixed powder further contains an aluminum (Al) component, and the content of the aluminum (Al) component in the mixed powder is equal to the boron carbide (B 4 C) powder and the titanium diboride ( The method for producing composite ceramics according to [4] above, wherein the TiB 2 ) powder is 1 to 5 parts by mass in terms of Al with respect to a total of 100 parts by mass of the powder.
[6] The method for producing composite ceramics according to [4] or [5], wherein the compact is fired under normal pressure in the presence of an aluminum (Al) source.
本発明によれば、高比剛性及び高硬度であるとともに、電気抵抗率が低く、放電加工により所望の形状に加工することが可能な、炭化ホウ素及び二ホウ化チタンを含む緻密質な複合セラミックスを提供することができる。また、本発明によれば、上記の複合セラミックスを加圧せずとも常圧下で焼成して得ることが可能な複合セラミックスの製造方法を提供することができる。 According to the present invention, dense composite ceramics containing boron carbide and titanium diboride that have high specific rigidity and high hardness, low electrical resistivity, and can be processed into a desired shape by electrical discharge machining. can be provided. Further, according to the present invention, it is possible to provide a method for producing a composite ceramic that can be obtained by firing the composite ceramic under normal pressure without applying pressure.
＜複合セラミックス＞
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明の一実施形態である複合セラミックスは、炭化ホウ素（Ｂ４Ｃ）及び二ホウ化チタン（ＴｉＢ２）を含む緻密質な複合セラミックスであり、炭化ホウ素と二ホウ化チタンの合計を基準とする、炭化ホウ素の含有量が５０～７５質量％であるとともに、二ホウ化チタンの含有量が２５～５０質量％である。そして、二ホウ化チタンが、そのアスペクト比が１．５以上の粒子であり、相対密度が８９％以上の緻密な複合セラミックスである。以下、本実施形態の複合セラミックスの詳細について説明する。
<Composite ceramics>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. A composite ceramic, which is one embodiment of the present invention, is a dense composite ceramic containing boron carbide (B 4 C) and titanium diboride (TiB 2 ). The content of boron carbide is 50 to 75% by mass, and the content of titanium diboride is 25 to 50% by mass. Titanium diboride is particles with an aspect ratio of 1.5 or more, and dense composite ceramics with a relative density of 89% or more. Details of the composite ceramics of this embodiment will be described below.
従来、炭化ホウ素の含有量の多い炭化ホウ素－二ホウ化チタン複合セラミックスを常圧下での焼結によって製造することは困難であった。本発明者らは、より経済性に優れているとともに、簡易な方法によって上記の複合セラミックスを製造する方法について鋭意検討した。その結果、原料の組成及び粒径、並びに焼成温度を適切に制御することで、これまで困難とされていた常圧焼成によって、高比剛性及び高硬度であるとともに、放電加工により所望の形状に加工することが可能な複合セラミックスが得られることを見出し、本発明に至った。 Conventionally, it has been difficult to produce boron carbide-titanium diboride composite ceramics containing a large amount of boron carbide by sintering under normal pressure. The present inventors have made intensive studies on a method for manufacturing the above-described composite ceramics by a more economical and simpler method. As a result, by appropriately controlling the composition and particle size of the raw material, as well as the firing temperature, it is possible to achieve high specific rigidity and high hardness by normal pressure firing, which has been considered difficult until now, and to obtain the desired shape by electrical discharge machining. The inventors have found that a composite ceramic that can be processed can be obtained, leading to the present invention.
高比剛性及び高硬度であるとともに、放電加工により所望の形状に加工しうる程度に電気抵抗率が低い炭化ホウ素及び二ホウ化チタンを含む緻密質な複合セラミックスとするには、第一に、炭化ホウ素と二ホウ化チタンの合計を基準とする、炭化ホウ素の含有量を５０～７５質量％、好ましくは６０～７０質量％とし、二ホウ化チタンの含有量を２５～５０質量％、好ましくは３０～４０質量％とすることが重要である。第二に、複合セラミックス中の二ホウ化チタンは、そのアスペクト比が１．５以上の粒子であることが重要である。 In order to obtain a dense composite ceramic containing boron carbide and titanium diboride, which has a high specific rigidity and a high hardness and has a low electrical resistivity to the extent that it can be processed into a desired shape by electric discharge machining, first, Based on the sum of boron carbide and titanium diboride, the content of boron carbide is 50 to 75% by mass, preferably 60 to 70% by mass, and the content of titanium diboride is 25 to 50% by mass, preferably is important to be 30 to 40% by mass. Second, it is important that the titanium diboride in the composite ceramics is particles with an aspect ratio of 1.5 or more.
上記の要件をいずれも満たす本実施形態の複合セラミックスは、例えば、比剛性が１４０ＧＰａ／（ｇ／ｃｍ３）以上、好ましくは１４５～１５２ＧＰａ／（ｇ／ｃｍ３）である。また、本実施形態の複合セラミックスは、例えば、電気抵抗率が９．５×１０－３Ω・ｃｍ以下である。さらに、本実施形態の複合セラミックスは、例えば、ビッカース硬度が２，０００Ｈｖ以上、好ましくは３，０００Ｈｖ以上である。このため、本実施形態の複合セラミックスは、その特性を生かし、例えば、高速駆動するとともに高い位置精度が要求される光学反射ミラーの他、半導体搬送装置、摺動部材、ノズル、切削工具、及び防弾板等の構成材料として有用である。 The composite ceramic of the present embodiment, which satisfies all of the above requirements, has a specific rigidity of, for example, 140 GPa/(g/cm 3 ) or more, preferably 145 to 152 GPa/(g/cm 3 ). In addition, the composite ceramics of this embodiment has an electric resistivity of, for example, 9.5×10 −3 Ω·cm or less. Furthermore, the composite ceramics of this embodiment has a Vickers hardness of, for example, 2,000 Hv or more, preferably 3,000 Hv or more. For this reason, the composite ceramics of the present embodiment can make use of its characteristics, for example, in addition to optical reflection mirrors that are driven at high speed and require high positional accuracy, semiconductor conveying devices, sliding members, nozzles, cutting tools, and bulletproof devices. It is useful as a constituent material for plates and the like.
本明細書における「アスペクト比」は、試料となる複合セラミックスの表面を走査型電子顕微鏡で観察及び撮影して得た写真を使用し、画像解析ソフト（ＷｉｎＲＯＯＦ）を用いて測定した任意の３０個以上の粒子の短径に対する長径の比（長径／短径）の値の平均値である。 The "aspect ratio" in this specification is any 30 pieces measured using image analysis software (WinROOF) using a photograph obtained by observing and photographing the surface of a composite ceramic sample with a scanning electron microscope. It is the average value of the ratio of the long diameter to the short diameter (long diameter/short diameter) of the above particles.
本明細書における「ビッカース硬度」は、ＪＩＳ Ｒ１６１０：２００３に準拠して測定される値であり、市販のビッカース硬度計を使用し、室温下、荷重３～１０ｋｇｆ、保持時間１０秒の条件にて測定される値である。なお、ビッカース硬度は、例えば「１０２（無単位）≒１ＧＰａ」と換算することができる。 "Vickers hardness" in the present specification is a value measured in accordance with JIS R1610: 2003, using a commercially available Vickers hardness tester, at room temperature, under the conditions of a load of 3 to 10 kgf and a holding time of 10 seconds. It is the measured value. The Vickers hardness can be converted to, for example, "102 (no unit)≈1 GPa".
複合セラミックスの相対密度は８９％以上であり、好ましくは９３％以上である。複合セラミックスの相対密度が８９％未満であると、複合セラミックス中に気孔（いわゆる欠陥）が多く存在することになるため、耐久性が低下する。なお、複合セラミックスの相対密度は、例えば、焼成温度や焼成時間を調整することによって制御することができる。 The composite ceramic has a relative density of 89% or more, preferably 93% or more. When the relative density of the composite ceramics is less than 89%, many pores (so-called defects) are present in the composite ceramics, resulting in deterioration of durability. The relative density of composite ceramics can be controlled by adjusting the firing temperature and firing time, for example.
本実施形態の複合セラミックスは、具体的には、炭化ホウ素からなるマトリックス中に、電気抵抗率が低い二ホウ化チタンが粒子状に分散した組織構造を有する。一般に、複合材料の電気抵抗率と材料比率の関係は、パーコレーション理論で説明されている。パーコレーション理論とは、対象とする材料が複合材料内でどのように繋がっているか、その繋がり方の特徴が複合材料の特性にどの様な影響を与えるかを対象とする理論である。対象材料が繋がってできた塊はクラスターと呼ばれ、ある特定濃度（閾値）以上でクラスターが生成され、複合材料全体の特性が大きく変化する。パーコレーション理論では、アスペクト比が１より大きなフレーク状及び繊維状などの導電性材料を添加した複合材料では導電性材料同士が繋がりやすく、アスペクト比が１に近い球状粒子が複合化された場合よりも低い添加比率で導電性パスが形成されることが報告されている。本発明の場合、二ホウ化チタン量と複合セラミックスの電気抵抗率の関係がパーコレーション理論で説明できると考えられる。すなわち、粒子状の二ホウ化チタンのアスペクト比を大きくすることにより、より少量の二ホウ化チタンで電気抵抗率を下げることができる。そして、二ホウ化チタンの粒子のアスペクト比を１．５以上としたことで特有の導電パスが形成され、電気抵抗率が低いといった特性を示す。 Specifically, the composite ceramic of the present embodiment has a texture structure in which titanium diboride having a low electrical resistivity is dispersed in the form of particles in a matrix made of boron carbide. In general, the relationship between electrical resistivity and material ratio of composite materials is explained by percolation theory. Percolation theory is a theory that deals with how target materials are connected in a composite material and how the characteristics of the connection affect the properties of the composite material. A mass formed by connecting target materials is called a cluster, and clusters are generated at a specific concentration (threshold value) or higher, and the properties of the entire composite material change significantly. According to percolation theory, in a composite material to which conductive materials such as flakes and fibrous materials with an aspect ratio greater than 1 are added, the conductive materials are more likely to connect with each other, and spherical particles with an aspect ratio close to 1 are combined. It has been reported that a conductive path is formed at a low addition ratio. In the case of the present invention, it is considered that the relationship between the amount of titanium diboride and the electrical resistivity of the composite ceramics can be explained by percolation theory. That is, by increasing the aspect ratio of particulate titanium diboride, the electrical resistivity can be lowered with a smaller amount of titanium diboride. By setting the aspect ratio of the particles of titanium diboride to 1.5 or more, a unique conductive path is formed, and characteristics such as low electrical resistivity are exhibited.
焼結助剤として遊離炭素を含有させてもよいが、複合セラミックス中の遊離炭素の含有量は、好ましくは３質量％以下であり、さらに好ましくは２質量％以下である。遊離炭素の含有量を３質量％以下とすることで、複合セラミックスの焼結性を向上させることができる。その際、平均粒子径０．０５μｍ以上２．０μｍ以下の原料粉末を用いることが好ましい。 Although free carbon may be contained as a sintering aid, the content of free carbon in the composite ceramics is preferably 3% by mass or less, more preferably 2% by mass or less. By setting the content of free carbon to 3% by mass or less, the sinterability of the composite ceramics can be improved. At that time, it is preferable to use a raw material powder having an average particle size of 0.05 μm or more and 2.0 μm or less.
遊離炭素とは、金属炭化物等を構成する炭素成分を除く、遊離した炭素（Ｃ）を意味する。複合セラミックス中の遊離炭素の含有量は、以下の方法によって測定することができる。まず、試料となる複合セラミックスを微粉砕した後、融剤を添加し、高周波誘導加熱等により短時間で高温まで加熱して試料を分解し、二酸化炭素を発生させる。赤外分光法により、発生した二酸化炭素の量から総炭素量を算出する。また、ホウ素（Ｂ）及びチタン（Ｔｉ）の含有量については、それぞれ別の方法によって定量する。その後、Ｘ線回折等により結晶相を同定し、特定された化学式から、ホウ素と炭素の比率、及びチタンと炭素の比率をそれぞれ算出し、これらの差から遊離炭素の含有量を求めることができる。 Free carbon means free carbon (C) excluding carbon components constituting metal carbides and the like. The content of free carbon in composite ceramics can be measured by the following method. First, after pulverizing composite ceramics as a sample, a flux is added, and the sample is heated to a high temperature in a short time by high-frequency induction heating or the like to decompose the sample and generate carbon dioxide. The total carbon content is calculated from the amount of carbon dioxide generated by infrared spectroscopy. Also, the contents of boron (B) and titanium (Ti) are quantified by different methods. After that, the crystal phase is identified by X-ray diffraction or the like, and from the specified chemical formula, the ratio of boron to carbon and the ratio of titanium to carbon are calculated, respectively, and the content of free carbon can be obtained from the difference between them. .
＜複合セラミックスの製造方法＞
本実施形態の複合セラミックスは、以下に示す方法によって製造することができる。すなわち、本発明の複合セラミックスの製造方法の一実施形態は、上述の複合セラミックスを製造する方法であり、炭化ホウ素（Ｂ４Ｃ）粉末及び二ホウ化チタン（ＴｉＢ２）粉末を含有する平均粒子径１．７μｍ以下の混合粉末を成形して成形体を得る工程（成形工程）と、この成形体を２，０００～２，２１５℃で常圧焼成して複合セラミックスを得る工程（焼成工程）と、を有する。
<Method for producing composite ceramics>
The composite ceramics of this embodiment can be manufactured by the method shown below. That is, one embodiment of the method for producing composite ceramics of the present invention is a method for producing the composite ceramics described above, wherein average particles containing boron carbide (B 4 C) powder and titanium diboride (TiB 2 ) powder A step of molding a mixed powder having a diameter of 1.7 μm or less to obtain a compact (molding step), and a step of firing the compact at normal pressure at 2,000 to 2,215° C. to obtain a composite ceramic (firing step). and have
成形工程では、例えば、炭化ホウ素粉末及び二ホウ化チタン粉末を含有する平均粒子径１．７μｍ以下、好ましくは１．５μｍ以下の混合粉末を、非加熱条件下、２０ＭＰａ以下の圧力条件で加圧成形して、所望とする形状の成形体を得る。得られる複合セラミックス中に遊離炭素（Ｃ）を含有させる場合には、その平均粒子径が０．０５μｍ以上１．７μｍ以下の炭素（Ｃ）粉末を混合粉末に含有させればよい。また、得られる複合セラミックス中に遊離炭素を含有させる場合には、混合粉末の平均粒子径を０．５μｍ以上とすることが好ましい。本明細書における平均粒子径とは、体積基準の累積５０％粒子径（メジアン径（Ｄ５０））を意味する。 In the molding step, for example, a mixed powder containing boron carbide powder and titanium diboride powder and having an average particle size of 1.7 μm or less, preferably 1.5 μm or less, is pressed under a pressure condition of 20 MPa or less under non-heated conditions. Molding is performed to obtain a molded body having a desired shape. When free carbon (C) is contained in the obtained composite ceramics, carbon (C) powder having an average particle size of 0.05 μm or more and 1.7 μm or less may be contained in the mixed powder. Moreover, when free carbon is contained in the resulting composite ceramics, the average particle size of the mixed powder is preferably 0.5 μm or more. The average particle size as used herein means a volume-based cumulative 50% particle size (median size (D50)).
混合粉末には、アルミニウム（Ａｌ）成分をさらに含有させることが好ましい。アルミニウム成分としては、アルミニウムや、酸化アルミニウム、窒化アルミニウムなどのアルミニウムを含む化合物（アルミニウム化合物）を用いることができる。アルミニウム成分を、例えば、炭化ホウ素（Ｂ４Ｃ）粉末及び二ホウ化チタン（ＴｉＢ２）粉末の合計１００質量部に対して、Ａｌ換算で１～５質量部含有する混合粉末を用いることで、アルミニウム成分を含有しない混合粉末を用いる場合に比して、１００～２００℃低い焼成温度によって、同等の特性を有する複合セラミックスを得ることができる。 The mixed powder preferably further contains an aluminum (Al) component. As the aluminum component, aluminum or a compound containing aluminum (aluminum compound) such as aluminum oxide or aluminum nitride can be used. By using a mixed powder containing an aluminum component, for example, 1 to 5 parts by mass in terms of Al with respect to a total of 100 parts by mass of boron carbide (B 4 C) powder and titanium diboride (TiB 2 ) powder, Composite ceramics having similar characteristics can be obtained at a firing temperature lower by 100 to 200° C. than when a mixed powder containing no aluminum component is used.
焼成工程では、成形体を２，０００～２，２１５℃、好ましくは２，１００～２，２００℃で常圧焼成する。これにより、所望とする本実施形態の複合セラミックスを得ることができる。加圧することなく常圧で焼成するため、特殊な加圧設備等が不要であり、容易かつ安価に複合セラミックスを製造することができる。また、炭化ホウ素セラミックスの一般的な焼成温度よりも低い温度で焼成することで、エネルギー面で有利であるとともに、電気抵抗率の局所的なバラつきを抑制し、ワイヤー放電加工等による加工性に優れた複合セラミックスとすることができる。 In the firing step, the compact is fired at 2,000 to 2,215°C, preferably at 2,100 to 2,200°C under normal pressure. Thereby, the desired composite ceramics of the present embodiment can be obtained. Since sintering is performed at normal pressure without applying pressure, special pressurization equipment is not required, and composite ceramics can be produced easily and inexpensively. In addition, by firing at a temperature lower than the general firing temperature of boron carbide ceramics, it is advantageous in terms of energy, suppresses local variations in electrical resistivity, and has excellent workability by wire electric discharge machining, etc. composite ceramics.
焼成工程では、アルミニウム（Ａｌ）源の共存下で成形体を常圧焼成することが好ましい。すなわち、アルミニウムを含有する蒸気が存在する雰囲気中で焼成することで、より緻密化することができるとともに、電気抵抗率をさらに低下させることが可能であり、同等以上の特性を有する複合セラミックスを得ることができる。 In the firing step, the compact is preferably fired under normal pressure in the presence of an aluminum (Al) source. That is, by sintering in an atmosphere in which steam containing aluminum is present, it is possible to make it more dense, and it is possible to further reduce the electrical resistivity, and obtain composite ceramics having properties equal to or higher than those of the ceramics. be able to.
アルミニウム源の共存下で成形体を常圧焼成するには、例えば、アルミニウムを含有する粉末、成形体、及び焼成体等を炉内に配置すればよい。アルミニウムとしては、好ましくは純度９０％以上、さらに好ましくは純度９５％以上のものを用いる。アルミニウムの粉末を用いる場合には、アルミニウムの粉末を収容したルツボを炉内に配置すればよい。アルミニウムの成形体や焼結体としては、任意の形状のものを用いることができる。金属アルミニウム、アルミニウム炭化物、及びアルミニウム窒化物を用いると、所望する複合セラミックスをより安定的に得ることができるために好ましい。 In order to sinter the compact under normal pressure in the coexistence of an aluminum source, for example, a powder containing aluminum, a compact, a sintered compact, and the like may be placed in a furnace. Aluminum having a purity of 90% or higher, more preferably 95% or higher, is used as the aluminum. When aluminum powder is used, a crucible containing aluminum powder may be placed in the furnace. Any shape can be used as the aluminum molded body or sintered body. The use of metallic aluminum, aluminum carbide, and aluminum nitride is preferable because the desired composite ceramics can be obtained more stably.
例えば、アルミニウムの粉末を収容したルツボを炉内に配置して焼成する場合、ほぼすべてのアルミニウムが複合セラミックス中へと移行する。すなわち、得られる複合セラミックス中のアルミニウムの含有量を任意に設計することができる。 For example, when a crucible containing aluminum powder is placed in a furnace and fired, almost all of the aluminum migrates into the composite ceramics. That is, the content of aluminum in the obtained composite ceramics can be arbitrarily designed.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。 EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.
＜複合セラミックスの製造＞
（実施例１）
炭化ホウ素粉末（平均粒子径０．８μｍ、純度９９．５％（酸素含有量１．２％及び窒素含有量０．２％を除く））６８．４部、及びホウ化チタン粉末（平均粒子径１．７μｍ、純度９９％）３１．６部を混合した。さらに、遊離炭素の含有量が２％となる量の樹脂（焼成後の残留炭素量３０％）を添加した後、粉砕メディアとしてＳｉＣボール（直径５ｍｍφ）を含むエタノール中でアトライターを使用して混合及び粉砕し、スラリーを得た。得られたスラリーをスプレードライヤーにより乾燥造粒して、平均粒子径１．３３μｍ、ＢＥＴ比表面積１１．５ｍ２／ｇの混合粉末を得た。得られた混合粉末を直径２５ｍｍの金型に充填し、１０ＭＰａにて一軸加圧成形後、２００ＭＰａにて静水圧成形し、成形体を得た。得られた成形体を２，２１５℃で４時間、アルミニウム粉末を配置したルツボ内で常圧焼成して、複合セラミックスを得た。
<Production of composite ceramics>
(Example 1)
Boron carbide powder (average particle size 0.8 μm, purity 99.5% (excluding oxygen content 1.2% and nitrogen content 0.2%)) 68.4 parts, and titanium boride powder (average particle size 1.7 μm, 99% purity) were mixed. Furthermore, after adding an amount of resin that makes the content of free carbon 2% (30% residual carbon after firing), an attritor is used in ethanol containing SiC balls (5 mm in diameter) as grinding media. Mixed and pulverized to obtain slurry. The obtained slurry was dried and granulated with a spray dryer to obtain a mixed powder having an average particle size of 1.33 μm and a BET specific surface area of 11.5 m 2 /g. The obtained mixed powder was filled in a mold having a diameter of 25 mm, and after uniaxial pressure molding at 10 MPa, it was hydrostatically molded at 200 MPa to obtain a compact. The resulting compact was sintered at 2,215° C. for 4 hours under normal pressure in a crucible containing aluminum powder to obtain composite ceramics.
（実施例２～２１、比較例１～８）
表１に示す組成及び物性の混合粉末を得るとともに、表１に示す焼成条件で焼成したこと以外は、前述の実施例１と同様にして、複合セラミックスを得た。なお、比較例１及び７については焼成により溶融してしまい、目的とする複合セラミックスを得ることができなかった。実施例１３の複合セラミックスの電子顕微鏡写真（２，０００倍）、及びその二値化像を図１及び２に示す。また、比較例５の複合セラミックスの電子顕微鏡写真（２，０００倍）、及びその二値化像を図３及び４に示す。図１～４中、明色部が二ホウ化チタン粒子を示し、「ａ」が二ホウ化チタン粒子の短径、「ｂ」が二ホウ化チタン粒子の長径をそれぞれ示す。
(Examples 2 to 21, Comparative Examples 1 to 8)
A mixed powder having the composition and physical properties shown in Table 1 was obtained, and composite ceramics were obtained in the same manner as in Example 1 described above, except that the mixed powder was fired under the firing conditions shown in Table 1. In Comparative Examples 1 and 7, the composite ceramics were melted during firing, and the intended composite ceramics could not be obtained. An electron micrograph (2,000 times) of the composite ceramic of Example 13 and its binarized image are shown in FIGS. 3 and 4 show an electron micrograph (2,000 times) of the composite ceramic of Comparative Example 5 and its binarized image. In FIGS. 1 to 4, light-colored portions indicate titanium diboride particles, "a" indicates the short diameter of the titanium diboride particles, and "b" indicates the long diameter of the titanium diboride particles.
＜評価＞
（相対密度）
炭化ホウ素の理論密度は２．５２ｇ／ｃｍ３であり、二ホウ化チタンの理論密度は４．５１ｇ／ｃｍ３である。このことから、炭化ホウ素と二ホウ化チタンの質量比率に応じて理論密度を算出し、複合セラミックスのかさ密度（実測値）を理論密度で除して得た値を複合セラミックスの相対密度とした。結果を表２に示す。
<Evaluation>
(relative density)
The theoretical density of boron carbide is 2.52 g/cm 3 and that of titanium diboride is 4.51 g/cm 3 . From this, the theoretical density was calculated according to the mass ratio of boron carbide and titanium diboride, and the value obtained by dividing the bulk density (measured value) of the composite ceramic by the theoretical density was taken as the relative density of the composite ceramic. . Table 2 shows the results.
（弾性率、かさ密度、及び比剛性）
ＪＩＳ Ｒ １６０２：１９９５に準拠した方法により、複合セラミックスの弾性率を測定した。また、ＪＩＳ Ｒ １６２８：１９９７に準拠した方法により、複合セラミックスのかさ密度を測定した。そして、測定した弾性率及びかさ密度から、複合セラミックスの比剛性（＝弾性率／かさ密度）を算出した。結果を表２に示す。
(elastic modulus, bulk density, and specific stiffness)
The modulus of elasticity of the composite ceramics was measured according to JIS R 1602:1995. Also, the bulk density of the composite ceramics was measured by a method based on JIS R 1628:1997. Then, from the measured elastic modulus and bulk density, the specific rigidity (=elastic modulus/bulk density) of the composite ceramics was calculated. Table 2 shows the results.
（電気抵抗率）
ＪＩＳ Ｒ １６５０－２：２００２に準拠した方法により、複合セラミックスの電気抵抗率を測定した。結果を表２に示す。
(Electrical resistivity)
The electrical resistivity of the composite ceramics was measured by a method conforming to JIS R 1650-2:2002. Table 2 shows the results.
（ビッカース硬度）
ＪＩＳ Ｒ １６１０：２００３に準拠した方法により、複合セラミックスのビッカース硬度を測定した。結果を表２に示す。
(Vickers hardness)
The Vickers hardness of the composite ceramics was measured by a method based on JIS R 1610:2003. Table 2 shows the results.
（二ホウ化チタンの（ＴｉＢ２）粒子のアスペクト比）
電子顕微鏡を使用して複合セラミックスの断面を観察し、二ホウ化チタン（ＴｉＢ２）粒子のアスペクト比を測定及び算出した。結果を表２に示す。
(Aspect ratio of (TiB 2 ) particles of titanium diboride)
A cross-section of the composite ceramics was observed using an electron microscope, and the aspect ratio of titanium diboride (TiB 2 ) particles was measured and calculated. Table 2 shows the results.
本発明の複合セラミックスは、高速駆動するとともに高い位置精度が要求される光学反射ミラーの他、半導体搬送装置、摺動部材、ノズル、切削工具、及び防弾板等の構成材料として有用である。 INDUSTRIAL APPLICABILITY The composite ceramics of the present invention are useful as constituent materials for optical reflecting mirrors that are driven at high speed and require high positional accuracy, as well as semiconductor transfer devices, sliding members, nozzles, cutting tools, bulletproof plates, and the like.
（実施例２～１４、１６、１７、１９～２１、参考例１５、１８、比較例１～８）
表１に示す組成及び物性の混合粉末を得るとともに、表１に示す焼成条件で焼成したこと以外は、前述の実施例１と同様にして、複合セラミックスを得た。なお、比較例１及び７については焼成により溶融してしまい、目的とする複合セラミックスを得ることができなかった。実施例１３の複合セラミックスの電子顕微鏡写真（２，０００倍）、及びその二値化像を図１及び２に示す。また、比較例５の複合セラミックスの電子顕微鏡写真（２，０００倍）、及びその二値化像を図３及び４に示す。図１～４中、明色部が二ホウ化チタン粒子を示し、「ａ」が二ホウ化チタン粒子の短径、「ｂ」が二ホウ化チタン粒子の長径をそれぞれ示す。
(Examples 2 to 14, 16, 17, 19 to 21, Reference Examples 15 and 18, Comparative Examples 1 to 8)
A mixed powder having the composition and physical properties shown in Table 1 was obtained, and composite ceramics were obtained in the same manner as in Example 1 described above, except that the mixed powder was fired under the firing conditions shown in Table 1. In Comparative Examples 1 and 7, the composite ceramics were melted during firing, and the intended composite ceramics could not be obtained. An electron micrograph (2,000 times) of the composite ceramic of Example 13 and its binarized image are shown in FIGS. 3 and 4 show an electron micrograph (2,000 times) of the composite ceramic of Comparative Example 5 and its binarized image. In FIGS. 1 to 4, light-colored portions indicate titanium diboride particles, "a" indicates the short diameter of the titanium diboride particles, and "b" indicates the long diameter of the titanium diboride particles.
Claims (6)
前記炭化ホウ素と前記二ホウ化チタンの合計を基準とする、前記炭化ホウ素の含有量が５０～７５質量％であるとともに、前記二ホウ化チタンの含有量が２５～５０質量％であり、
前記二ホウ化チタンが、そのアスペクト比が１．５以上の粒子であり、
相対密度が８９％以上である複合セラミックス。 A dense composite ceramic containing boron carbide (B 4 C) and titanium diboride (TiB 2 ),
Based on the total of the boron carbide and the titanium diboride, the content of the boron carbide is 50 to 75% by mass, and the content of the titanium diboride is 25 to 50% by mass,
The titanium diboride is particles having an aspect ratio of 1.5 or more,
Composite ceramics having a relative density of 89% or more.
炭化ホウ素（Ｂ４Ｃ）粉末及び二ホウ化チタン（ＴｉＢ２）粉末を含有する平均粒子径１．７μｍ以下の混合粉末を成形して成形体を得る工程と、
前記成形体を２,０００～２,２１５℃で常圧焼成して前記複合セラミックスを得る工程と、を有する複合セラミックスの製造方法。 A method for producing a composite ceramic according to any one of claims 1 to 3,
a step of molding a mixed powder containing boron carbide (B 4 C) powder and titanium diboride (TiB 2 ) powder and having an average particle size of 1.7 μm or less to obtain a compact;
and sintering the compact at 2,000 to 2,215° C. under normal pressure to obtain the composite ceramic.
前記混合粉末中の前記アルミニウム（Ａｌ）成分の含有量が、前記炭化ホウ素（Ｂ４Ｃ）粉末及び前記二ホウ化チタン（ＴｉＢ２）粉末の合計１００質量部に対して、Ａｌ換算で１～５質量部である請求項４に記載の複合セラミックスの製造方法。 The mixed powder further contains an aluminum (Al) component,
The content of the aluminum (Al) component in the mixed powder is 1 to 1 in terms of Al with respect to a total of 100 parts by mass of the boron carbide (B 4 C) powder and the titanium diboride (TiB 2 ) powder. 5. The method for producing composite ceramics according to claim 4, wherein the content is 5 parts by mass.
6. The method for producing composite ceramics according to claim 4 or 5, wherein the compact is fired under normal pressure in the coexistence of an aluminum (Al) source.
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