JP2500012B2 - Method for manufacturing ceramics sintered body having composite coating layer - Google Patents
Method for manufacturing ceramics sintered body having composite coating layerInfo
- Publication number
- JP2500012B2 JP2500012B2 JP3119243A JP11924391A JP2500012B2 JP 2500012 B2 JP2500012 B2 JP 2500012B2 JP 3119243 A JP3119243 A JP 3119243A JP 11924391 A JP11924391 A JP 11924391A JP 2500012 B2 JP2500012 B2 JP 2500012B2
- Authority
- JP
- Japan
- Prior art keywords
- coating layer
- sintered body
- layer
- silicon nitride
- composite coating
- 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.)
- Expired - Fee Related
Links
- 239000011247 coating layer Substances 0.000 title claims description 77
- 239000002131 composite material Substances 0.000 title claims description 32
- 239000000919 ceramic Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 17
- 239000010410 layer Substances 0.000 claims description 73
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 67
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 66
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 50
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005049 silicon tetrachloride Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱基材上に化学気相
成長法例えばＣＶＤ法により窒化珪素および炭化珪素か
らなる複合被覆層を層状に形成した複合被覆セラミック
ス焼結体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite-coated ceramic sintered body in which a composite coating layer made of silicon nitride and silicon carbide is formed in layers on a heat-resistant substrate by a chemical vapor deposition method such as a CVD method. .
【０００２】[0002]
【従来の技術】窒化珪素および炭化珪素焼結体は高温高
強度であり、耐熱衝撃性に優れているため、ガスタービ
ン部品等の高温構造材料に使用されている。また、窒化
珪素および炭化珪素焼結体は耐腐食性、耐薬品性に優れ
ているため、半導体部品製造に用いるサセプター、炉心
管、治具等の部品に用いられている。窒化珪素焼結体の
耐酸化性を向上させるため、ＣＶＤ法により耐酸化性の
優れた窒化珪素を被覆した窒化珪素焼結体が特公昭６１
−４０６３０号公報および特開昭６０−１６１３８３号
公報に開示されている。また、高温においては窒化珪素
焼結体の粒界相成分と窒化珪素被覆層との反応が生じて
十分な効果を得ることが難しいため、粒界相を結晶化さ
せた窒化珪素焼結体およびＣＶＤ法による炭化珪素を被
覆した窒化珪素焼結体が特開昭６１−８７５７３号公報
および特開平２−２８９４７６号公報に開示されてい
る。しかし、窒化珪素焼結体にＣＶＤ法による窒化珪素
を被覆した場合には、窒化珪素被覆層と窒化珪素焼結体
の粒界相成分との反応を完全に防ぐことはできず、ＣＶ
Ｄ法による炭化珪素を被覆した場合には、反応は防止で
きるが被覆層と基材との熱膨張差が大きく十分な密着性
を得ることが困難となる。また、窒化珪素または炭化珪
素の何れを被覆した場合においても、被覆により窒化珪
素焼結体の強度が低下する問題があった。2. Description of the Related Art Sintered silicon nitride and silicon carbide have high temperature and high strength and are excellent in thermal shock resistance, so that they are used for high temperature structural materials such as gas turbine parts. In addition, since silicon nitride and silicon carbide sintered bodies have excellent corrosion resistance and chemical resistance, they are used for parts such as susceptors, core tubes, jigs, etc. used for manufacturing semiconductor parts. In order to improve the oxidation resistance of a silicon nitride sintered body, a silicon nitride sintered body coated with silicon nitride having excellent oxidation resistance by a CVD method is disclosed in JP-B-61.
-40630 and JP-A-60-161383. Further, at a high temperature, a reaction between the grain boundary phase component of the silicon nitride sintered body and the silicon nitride coating layer occurs, and it is difficult to obtain a sufficient effect. Therefore, it is difficult to obtain a sufficient effect. A silicon nitride sintered body coated with silicon carbide by the CVD method is disclosed in JP-A-61-87573 and JP-A-2-289476. However, when the silicon nitride sintered body is coated with silicon nitride by the CVD method, the reaction between the silicon nitride coating layer and the grain boundary phase component of the silicon nitride sintered body cannot be completely prevented, and the CV
When silicon carbide is coated by the method D, the reaction can be prevented, but the thermal expansion difference between the coating layer and the substrate is large, and it becomes difficult to obtain sufficient adhesion. In addition, regardless of whether silicon nitride or silicon carbide is coated, there is a problem that the strength of the silicon nitride sintered body decreases due to the coating.
【０００３】一方、炭化珪素焼結体を半導体部品製造に
用いるサセプター、炉心管、治具等の部品に用いる場
合、焼結体に気孔が多く、気孔中に残存する不純物によ
って半導体を汚染する問題があるため、ＣＶＤ法による
高純度な炭化珪素での被覆が行なわれている。また、焼
結体の気孔をＣＶＤ法による炭化珪素で埋めることによ
り、強度の改善が行なわれている。しかし、炭化珪素被
覆層の厚みが増すと粒成長が著しく、十分な強度、耐食
性を得ることが困難であるという問題があった。On the other hand, when the silicon carbide sintered body is used for parts such as a susceptor, a core tube, and a jig used for manufacturing semiconductor parts, the sintered body has many pores and the semiconductor is contaminated by impurities remaining in the pores. Therefore, coating with high-purity silicon carbide is performed by the CVD method. Further, the strength is improved by filling the pores of the sintered body with silicon carbide by the CVD method. However, when the thickness of the silicon carbide coating layer is increased, there is a problem that grain growth is remarkable and it is difficult to obtain sufficient strength and corrosion resistance.
【０００４】これらの問題を解決するため、ＣＶＤ法に
よる窒化珪素および炭化珪素との積層物からなる複合被
覆層を形成した窒化珪素焼結体および炭化珪素焼結体が
特公昭６０−４５１５４号公報に開示されている。この
ように窒化珪素と炭化珪素とを積層することで、基材と
の熱膨張差の制御、基材との反応の抑制、高強度化が達
成できると考えられる。In order to solve these problems, a silicon nitride sintered body and a silicon carbide sintered body formed with a composite coating layer made of a laminate of silicon nitride and silicon carbide by the CVD method are disclosed in Japanese Patent Publication No. 60-154154. Is disclosed in. By stacking silicon nitride and silicon carbide in this way, it is considered that the difference in thermal expansion from the base material can be controlled, the reaction with the base material can be suppressed, and the strength can be increased.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
ＣＶＤ法により窒化珪素と炭化珪素との複合被覆層を合
成する方法は、原料ガスのうち窒素源と炭素源とを交互
に瞬時に切替えて反応炉に導入することにより複合被覆
層を合成するので、原料ガスの切替え時に反応炉中に不
必要なガスが残存し、基材に形成される複合被覆層がこ
の残留ガスにより多孔質になりやすい。このため、複合
被覆層が低強度となり、また、基材を高温空気、燃焼ガ
ス、薬品等の外気から十分に保護できないという問題が
ある。本発明はこのような問題点を解決するためになさ
れたもので、窒化珪素あるいは炭化珪素焼結体等のセラ
ミックス基材上に緻密で密着性の良好な複合被覆層を形
成するセラミックス焼結体の製造方法を提供することを
目的とする。However, in the conventional method of synthesizing the composite coating layer of silicon nitride and silicon carbide by the CVD method, the nitrogen source and the carbon source in the raw material gas are alternately switched to react with each other. Since the composite coating layer is synthesized by introducing it into the furnace, unnecessary gas remains in the reaction furnace when the source gas is switched, and the composite coating layer formed on the substrate is likely to become porous due to this residual gas. . Therefore, there is a problem that the composite coating layer has low strength and the base material cannot be sufficiently protected from the outside air such as high temperature air, combustion gas, chemicals and the like. The present invention has been made to solve such a problem, and is a ceramics sintered body for forming a dense and good composite coating layer on a ceramics substrate such as a silicon nitride or silicon carbide sintered body. It aims at providing the manufacturing method of.
【０００６】[0006]
【課題を解決するための手段】前記課題を解決するため
の本発明の第１発明による複合被覆層を有するセラミッ
ク焼結体の製造方法は、窒化珪素または炭化珪素焼結体
等のセラミックスまたは炭素基材の表面に化学気相成長
法により窒化珪素層および炭化珪素層の複合被覆層を層
状に形成する方法であって、各被覆層を形成するために
反応炉に流す反応ガスの切替え時、反応炉内に水素ガス
を流通させ、この反応炉内に導入する水素ガス量を室温
大気圧下で反応炉内の容積よりも少なくとも３．４倍以
上の容積のガス量に設定したことを特徴とする。第２発
明による複合被覆層を有するセラミックス焼結体の製造
方法は、前記化学気相成長法が減圧熱ＣＶＤ法であるこ
とを特徴とする。第３発明による複合被覆層を有するセ
ラミックス焼結体の製造方法は、前記化学気相成長法に
よる窒化珪素の層状被覆層を形成する原料ガスとして、
四塩化珪素およびアンモニアを用い、炭化珪素の層状被
覆層を形成する原料ガスとして、四塩化珪素およびメタ
ンを用いることを特徴とする。第４発明による複合被覆
層を有するセラミックス焼結体の製造方法は、窒化珪素
と炭化珪素の各被覆層の厚みを傾斜させたことを特徴と
する。第５発明による複合被覆層を有するセラミックス
焼結体の製造方法は、基材が窒化珪素または炭化珪素焼
結体であることを特徴とする。A method for producing a ceramic sintered body having a composite coating layer according to the first aspect of the present invention for solving the above-mentioned problems is a ceramic such as silicon nitride or a silicon carbide sintered body or carbon. A method of forming a composite coating layer of a silicon nitride layer and a silicon carbide layer in layers on the surface of a substrate by chemical vapor deposition, when switching the reaction gas flowing to the reaction furnace to form each coating layer, Hydrogen gas is circulated in the reaction furnace, and the amount of hydrogen gas introduced into the reaction furnace is set to be at least 3.4 times the volume of the hydrogen gas in the reaction furnace at room temperature and atmospheric pressure. And The method for producing a ceramics sintered body having a composite coating layer according to the second aspect of the invention is characterized in that the chemical vapor deposition method is a low pressure thermal CVD method. The method for producing a ceramics sintered body having a composite coating layer according to the third aspect of the present invention uses as a raw material gas for forming the layered coating layer of silicon nitride by the chemical vapor deposition method,
Silicon tetrachloride and ammonia are used, and silicon tetrachloride and methane are used as a raw material gas for forming a layered coating layer of silicon carbide. A method of manufacturing a ceramic sintered body having a composite coating layer according to the fourth aspect of the present invention is characterized in that the thickness of each coating layer of silicon nitride and silicon carbide is inclined. The method for producing a ceramics sintered body having a composite coating layer according to the fifth aspect of the invention is characterized in that the base material is a silicon nitride or silicon carbide sintered body.
【０００７】本発明における基材には、セラミックス焼
結体または炭素等の耐熱材料の使用が可能であり、特に
窒化珪素および炭化珪素焼結体は、窒化珪素あるいは炭
化珪素原料と種々の添加物を含み、常圧あるいは加圧焼
結、ホットプレス、ＨＩＰ等の通常の方法により得られ
る焼結体の適用が可能である。また、焼結体の形状およ
び寸法等についても特に制限されるものではない。A ceramic sintered body or a heat-resistant material such as carbon can be used as the base material in the present invention. In particular, silicon nitride and silicon carbide sintered bodies include silicon nitride or silicon carbide raw materials and various additives. It is possible to apply a sintered body obtained by a normal method including normal pressure or pressure sintering, hot pressing, HIP and the like. Further, the shape and size of the sintered body are not particularly limited.
【０００８】化学気相成長（ＣＶＤ）法としては、減圧
熱ＣＶＤ法を用いることが望ましい。この場合、緻密な
窒化珪素あるいは炭化珪素被覆層を形成するために原料
ガスの組成、反応温度、反応圧力等が適当に制御され
る。窒化珪素と炭化珪素が積層した構造の複合被覆層を
合成する場合、原料ガスとして、窒化珪素の合成に珪素
源と窒素源、炭化珪素の合成に珪素源と炭素源を用い
る。特に高温構造材料等に適用する場合においては、四
塩化珪素（SiCl4 ）、アンモニア（NH3 ）、メタン（CH
3 ）等の入手しやすい原料を用いて減圧熱ＣＶＤ法によ
り製造すると結晶性の良好な複合被覆層を高速で安価に
製造できる。さらに、積層する窒化珪素および炭化珪素
の厚みを段階的に増減させあるいは一方を厚くして他方
を薄くするという方法により、被覆層の熱膨張を傾斜さ
せることおよび全体の熱膨張を制御して基材の焼結体の
熱膨張に合わせることが可能である。例えば、窒化珪素
層が厚く、炭化珪素層が薄い場合には熱膨張を窒化珪素
単独の熱膨張に近づけることが可能となる。As the chemical vapor deposition (CVD) method, it is desirable to use a low pressure thermal CVD method. In this case, the composition of the raw material gas, the reaction temperature, the reaction pressure and the like are appropriately controlled in order to form a dense silicon nitride or silicon carbide coating layer. When synthesizing a composite coating layer having a structure in which silicon nitride and silicon carbide are laminated, as a source gas, a silicon source and a nitrogen source are used for synthesizing silicon nitride, and a silicon source and a carbon source are used for synthesizing silicon carbide. Especially when applied to high temperature structural materials, etc., silicon tetrachloride (SiCl 4 ), ammonia (NH 3 ), methane (CH 3
When a low pressure thermal CVD method is used to manufacture easily available raw materials such as 3 ), a composite coating layer with good crystallinity can be manufactured at high speed and at low cost. Further, by gradually increasing or decreasing the thickness of silicon nitride and silicon carbide to be laminated, or thickening one of them and thinning the other, the thermal expansion of the coating layer is graded and the thermal expansion of the entire layer is controlled to control the thermal expansion. It is possible to match the thermal expansion of the sintered body of the material. For example, when the silicon nitride layer is thick and the silicon carbide layer is thin, it is possible to bring the thermal expansion close to that of silicon nitride alone.
【０００９】反応炉内に導入する水素ガスを室温大気圧
下で反応炉内の容積よりも少なくとも３．４倍以上の容
積のガス量に設定した理由は、水素ガスがこの容積値未
満であると、層状被覆層が多孔質になるからである。す
なわち、反応炉内の容積の３．４倍以上の容積の水素ガ
ス量を反応炉に流通させることにより、反応ガスの切替
え時に残留している原料ガスを被覆層形成に影響しない
程度まで除去し、各被覆層を合成する前に反応炉内が十
分に清浄されるからである。ここで、反応炉の容積と
は、実質的に原料ガスが導入される部分の容積をいい、
外部加熱式の反応炉等においては加熱部を除いて原料ガ
スの導入される反応管部分のみの容積をいう。The reason why the hydrogen gas introduced into the reaction furnace is set to have a volume of gas which is at least 3.4 times the volume in the reaction furnace at room temperature and atmospheric pressure is that the hydrogen gas is less than this volume value. This is because the layered coating layer becomes porous. That is, by flowing a hydrogen gas amount of 3.4 times or more the volume in the reaction furnace into the reaction furnace, the raw material gas remaining at the time of switching the reaction gas is removed to the extent that it does not affect the coating layer formation. This is because the inside of the reaction furnace is thoroughly cleaned before synthesizing each coating layer. Here, the volume of the reaction furnace means the volume of the portion into which the raw material gas is substantially introduced,
In an external heating type reaction furnace or the like, it refers to the volume of only the reaction tube portion into which the raw material gas is introduced, excluding the heating portion.
【００１０】[0010]
【作用】本発明による複合被覆層を有するセラミックス
焼結体の製造方法は、窒化珪素あるいは炭化珪素等のセ
ラミックス表面に化学気相成長（ＣＶＤ）法により窒化
珪素層と炭化珪素層とが積層した構造の複合被覆層を形
成するに当たり、セラミックス表面に窒化珪素あるいは
炭化珪素の第１層を形成した後、反応炉の容積の少なく
とも３．４倍以上の水素ガスを反応炉中に流通させ、窒
化珪素あるいは炭化珪素の第２層を形成する。そして、
第３層以降の被覆層を合成する前にも同様に水素ガスを
流通させる。これにより、複合被覆層が多孔質となるこ
とを防止し、緻密で基材を十分に保護できる複合被覆層
の合成ができる。また、被覆層が緻密なため、合成時間
の調節により各被覆層の厚みを制御でき、被覆層の熱膨
張を制御できる。さらに窒化珪素焼結体に被覆した場
合、窒化珪素と炭化珪素との積層により、窒化珪素焼結
体の粒界相成分と被覆層との反応を十分に抑制すること
ができる。また、積層構造であるため、被覆層の結晶粒
の成長を抑制し、微細結晶からなる高強度の被覆層を形
成することができる。In the method of manufacturing a ceramics sintered body having a composite coating layer according to the present invention, a silicon nitride layer and a silicon carbide layer are laminated on the surface of a ceramic such as silicon nitride or silicon carbide by a chemical vapor deposition (CVD) method. In forming a composite coating layer having a structure, after forming a first layer of silicon nitride or silicon carbide on the surface of ceramics, hydrogen gas of at least 3.4 times the volume of the reaction furnace is passed through the reaction furnace to form a nitride film. A second layer of silicon or silicon carbide is formed. And
Hydrogen gas is also circulated in the same manner before synthesizing the third and subsequent coating layers. As a result, it is possible to prevent the composite coating layer from becoming porous, and to synthesize a composite coating layer that is dense and can sufficiently protect the substrate. Further, since the coating layer is dense, the thickness of each coating layer can be controlled by adjusting the synthesis time, and the thermal expansion of the coating layer can be controlled. Further, when the silicon nitride sintered body is coated, the reaction between the grain boundary phase component of the silicon nitride sintered body and the coating layer can be sufficiently suppressed by stacking silicon nitride and silicon carbide. Further, since it has a laminated structure, it is possible to suppress the growth of crystal grains of the coating layer and form a high-strength coating layer made of fine crystals.
【００１１】[0011]
【実施例】以下、本発明の実施例を説明する。実施例１〜実施例８ 実施例１〜実施例８は、常圧焼結窒化珪素焼結体を基材
とし、この基材表面に減圧熱ＣＶＤ装置を用いてＳｉ3
Ｎ4 およびＳｉＣの層状被覆層を次に示すように形成し
た。まず、容積１１４５１ｃｍ3 の反応管内に基材を挿
入し、この基材を所定の合成温度に加熱した状態でＳｉ
Ｃｌ4 とＮＨ3 の混合ガスを所定時間流し、基材表面上
にＳｉ3 Ｎ4 層を形成する。次いで反応管内に表１に示
す条件でＨ2 ガスを導入し、次にＳｉＣｌ4 とＣＨ4 の
混合ガスを反応管内に所定時間流す。するとＳｉＣ層が
形成される。さらにＳｉＣ層上にＳｉ3 Ｎ4 層を形成す
る場合は、表１に示す条件でＨ2 ガスを再び反応管内に
流した後、ＳｉＣｌ4 とＮＨ3 の混合ガスを所定時間反
応管内に流す。このようにして基材の表面にＳｉ3 Ｎ4
層とＳｉＣ層とを交互に層状に形成した。表１に実施例
１〜実施例８の積層数を示す。Embodiments of the present invention will be described below. Example 1 to Example 8 In Example 1 to Example 8, a pressureless sintered silicon nitride sintered body is used as a base material, and a Si 3
A layered coating of N 4 and SiC was formed as follows. First, a base material was inserted into a reaction tube having a volume of 11451 cm 3 , and the base material was heated to a predetermined synthesis temperature to obtain Si.
A mixed gas of Cl 4 and NH 3 is flown for a predetermined time to form a Si 3 N 4 layer on the surface of the base material. Then, H 2 gas is introduced into the reaction tube under the conditions shown in Table 1, and then a mixed gas of SiCl 4 and CH 4 is flown in the reaction tube for a predetermined time. Then, a SiC layer is formed. Further, when forming a Si 3 N 4 layer on the SiC layer, H 2 gas is again flown into the reaction tube under the conditions shown in Table 1, and then a mixed gas of SiCl 4 and NH 3 is flown into the reaction tube for a predetermined time. Thus, the Si 3 N 4
The layers and the SiC layers were formed alternately in layers. Table 1 shows the number of stacked layers of Examples 1 to 8.
【００１２】[0012]
【表１】 [Table 1]
【００１３】Ｓｉ3 Ｎ4 層およびＳｉＣ層の合成温度
は、実施例１および実施例３〜実施例８については１４
５０℃とし、実施例２については１４３０℃とした。ま
た、Ｓｉ3 Ｎ4 層およびＳｉＣ層の合成時間は、実施例
１および実施例３〜実施例８の場合、Ｓｉ3 Ｎ4 層およ
びＳｉＣ層ともに一層につき５分とし、実施例２につい
ては、最下層から上層にいくに従い順にＳｉ3 Ｎ4 層２
分、ＳｉＣ層５分、Ｓｉ 3 Ｎ4 層４分、ＳｉＣ層５分、
Ｓｉ3 Ｎ4 層５分とした。Si3 NFour Temperature of layer and SiC layer
Is 14 for Example 1 and Examples 3-8.
The temperature was 50 ° C., and in Example 2 it was 1430 ° C. Ma
Si3 NFour The synthesis time of the layer and the SiC layer is the same as that of the example.
In the case of 1 and Examples 3 to 8, Si3 NFour Layers and
5 minutes per layer for both the SiC and SiC layers
In order, from the bottom layer to the top layer, Si3 NFour Layer 2
Min, SiC layer 5 min, Si 3 NFour Layer 4 minutes, SiC layer 5 minutes,
Si3 NFour Layer 5 minutes.
【００１４】実施例９および実施例１０ 実施例９および実施例１０は、常圧焼結炭化珪素焼結体
を基材とし、この基材表面に実施例１〜実施例８と同様
な方法によりＳｉ3 Ｎ4 層およびＳｉＣ層の層状被覆層
を形成した。この場合、実施例９および実施例１０の被
覆層の積層数および反応管への導入Ｈ2 ガスの条件は、
表１に示すように設定した。Ｓｉ3 Ｎ4 層およびＳｉＣ
層の合成温度は、実施例９および実施例１０ともに１４
５０℃とし、Ｓｉ3 Ｎ4 層およびＳｉＣ層の合成時間
は、実施例９および実施例１０ともに一層につき５分と
した。 Example 9 and Example 10 In Example 9 and Example 10, an atmospheric pressure sintered silicon carbide sintered body was used as a base material, and the surface of this base material was processed in the same manner as in Examples 1 to 8. Layered coating layers of Si 3 N 4 layer and SiC layer were formed. In this case, the number of layers of the coating layers of Examples 9 and 10 and the conditions of H 2 gas introduced into the reaction tube were as follows:
The settings were made as shown in Table 1. Si 3 N 4 layer and SiC
The synthesis temperature of the layer was 14 in both Example 9 and Example 10.
The temperature was 50 ° C., and the synthesis time of the Si 3 N 4 layer and the SiC layer was 5 minutes for each layer in both Example 9 and Example 10.
【００１５】比較例１〜比較例５ 比較例１〜比較例５は、常圧焼結窒化珪素焼結体を基材
とし、この基材表面に減圧熱ＣＶＤ装置を用いてＳｉ3
Ｎ4 およびＳｉＣの層状被覆層を次に示すように形成し
た。まず、容積１１４５１ｃｍ3 の反応管内に基材を挿
入し、この基材を所定の合成温度に加熱した状態でＳｉ
Ｃｌ4 とＮＨ3 の混合ガスを所定時間流し、基材表面上
にＳｉ3 Ｎ4 層を形成する（比較例１）。次いでＳｉＣ
ｌ4とＣＨ4 の混合ガスを反応管内に所定時間流す。す
るとＳｉＣ層が形成される（比較例２〜比較例５）。さ
らにＳｉＣ層上にＳｉ3 Ｎ4 層を形成する場合は、表１
に示す条件でＨ2 ガスを再び反応管内に流した後、Ｓｉ
Ｃｌ4 とＮＨ3 の混合ガスを所定時間反応管内に流す。
このようにして基材の表面にＳｉ3 Ｎ4層とＳｉＣ層と
を交互に層状に形成する。表１に比較例１〜比較例５の
積層数を示す。Ｓｉ3 Ｎ4 層およびＳｉＣ層の合成温度
は、比較例１〜比較例５ともに１４５０℃とし、Ｓｉ3
Ｎ4 層およびＳｉＣ層の合成時間は、比較例１〜比較例
５ともに一層につき５分とした。 Comparative Examples 1 to 5 In Comparative Examples 1 to 5, a pressureless sintered silicon nitride sintered body is used as a base material, and a Si 3
A layered coating of N 4 and SiC was formed as follows. First, a base material was inserted into a reaction tube having a volume of 11451 cm 3 , and the base material was heated to a predetermined synthesis temperature to obtain Si.
A mixed gas of Cl 4 and NH 3 is allowed to flow for a predetermined time to form a Si 3 N 4 layer on the surface of the base material (Comparative Example 1). Then SiC
A mixed gas of l 4 and CH 4 is caused to flow in the reaction tube for a predetermined time. Then, a SiC layer is formed (Comparative Examples 2 to 5). Further, when forming a Si 3 N 4 layer on the SiC layer, Table 1
After flowing H 2 gas again into the reaction tube under the conditions shown in
A mixed gas of Cl 4 and NH 3 is flown into the reaction tube for a predetermined time.
In this way, Si 3 N 4 layers and SiC layers are alternately formed in layers on the surface of the base material. Table 1 shows the number of laminated layers of Comparative Examples 1 to 5. The synthesis temperature of the Si 3 N 4 layer and the SiC layer was 1450 ° C. in Comparative Examples 1 to 5, and Si 3
The synthesis time of the N 4 layer and the SiC layer was set to 5 minutes for each of Comparative Examples 1 to 5.
【００１６】比較例６ 比較例６は、常圧焼結窒化珪素焼結体を基材とし、基材
表面に被覆層を形成しなかった。 Comparative Example 6 In Comparative Example 6, a pressureless sintered silicon nitride sintered body was used as the base material, and no coating layer was formed on the surface of the base material.
【００１７】比較例７〜比較例９ 比較例７〜比較例９は、常圧焼結炭化珪素焼結体を基材
とし、この基材表面に比較例１〜比較例５と同様な方法
によりＳｉ3 Ｎ4 およびＳｉＣの層状被覆層を形成し
た。この場合、比較例７〜比較例９の積層数および導入
Ｈ2 ガスの条件は、表１に示すように設定した。Ｓｉ3
Ｎ4 層およびＳｉＣ層の合成温度は、比較例７〜比較例
９ともに１４５０℃とし、Ｓｉ3 Ｎ4 層およびＳｉＣ層
の合成時間は、比較例７〜比較例９ともに一層につき５
分とした。 Comparative Examples 7 to 9 In Comparative Examples 7 to 9, a pressureless sintered silicon carbide sintered body is used as a base material, and the surface of the base material is processed in the same manner as in Comparative Examples 1 to 5. A layered coating of Si 3 N 4 and SiC was formed. In this case, the number of layers and the conditions of the introduced H 2 gas in Comparative Examples 7 to 9 were set as shown in Table 1. Si 3
The synthesis temperature of the N 4 layer and the SiC layer was 1450 ° C. in all of Comparative Examples 7 to 9, and the synthesis time of the Si 3 N 4 layer and the SiC layer was 5 in each of Comparative Examples 7 to 9.
Minutes
【００１８】次に、実施例１〜実施例１０および比較例
１〜比較例９について、被覆層全体の厚さおよび被覆層
の気孔率について調査し、さらに室温４点曲げ強度試験
および耐酸化性試験を行なった。４点曲げ強度試験は、
ＪＩＳ Ｒ−１６０１ファインセラミックスの曲げ強さ
試験法に準じて行ない、耐酸化性試験は、大気圧下、１
３００℃、１００時間の条件下、ＪＩＳ Ｒ−１６０６
非酸化物系ファインセラミックス耐酸化性試験法に準じ
て行なった。また、気孔率は画像解析による気孔面積率
より求めた。結果を表２に示す。Next, with respect to Examples 1 to 10 and Comparative Examples 1 to 9, the thickness of the entire coating layer and the porosity of the coating layer were investigated, and further, room temperature 4-point bending strength test and oxidation resistance were conducted. The test was conducted. The 4-point bending strength test
The bending resistance test method of JIS R-1601 fine ceramics was carried out.
JIS R-1606 under conditions of 300 ° C and 100 hours
The test was performed according to the non-oxide fine ceramics oxidation resistance test method. The porosity was obtained from the porosity area ratio by image analysis. Table 2 shows the results.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２に示すように、実施例１〜実施例１０
および比較例１〜比較例９は、Ｓｉ3 Ｎ4 層またはＳｉ
Ｃ層の合成時間に応じた層厚の被覆層が形成されてい
る。被覆層の積層状態は、例えば実施例１によると、層
厚９μｍのＳｉ3 Ｎ4 と層厚４μｍのＳｉＣの層厚が交
互に積層され被覆層全体の層厚が３５μｍであった。ま
た、実施例２によると、Ｓｉ3 Ｎ4 およびＳｉＣが交互
に層厚５μｍ、４μｍ、３μｍ、８μｍ、１０μｍで積
層され被覆層全体の層厚が３１μｍであった。被覆層の
気孔率を比較すると、実施例１〜実施例１０は、被覆層
の気孔率が小さいのに対し、比較例１〜比較例９は、被
覆層を形成していないもの（比較例７）および被覆層が
単層のもの（比較例１および比較例７）を除き、被覆層
の気孔率が１０％以上と大きくなっている。また、実施
例１〜実施例１０は、室温４点曲げ強度および耐酸化性
ともに優れた値を示し、破断面の外観も良好であった。
これにに対し、比較例１〜比較例９は、室温４点曲げ強
度および耐酸化性のうち少なくとも一方が小さく、破断
面の外観が多孔質になっていた。As shown in Table 2, Examples 1 to 10
And Comparative Examples 1 to 9 are Si 3 N 4 layer or Si.
A coating layer having a layer thickness corresponding to the synthesis time of the C layer is formed. As for the laminated state of the coating layer, according to Example 1, for example, the layer thickness of Si 3 N 4 having a layer thickness of 9 μm and the layer thickness of SiC having a layer thickness of 4 μm were alternately laminated, and the layer thickness of the entire coating layer was 35 μm. Further, according to Example 2, Si 3 N 4 and SiC were alternately laminated to have a layer thickness of 5 μm, 4 μm, 3 μm, 8 μm, and 10 μm, and the layer thickness of the entire coating layer was 31 μm. Comparing the porosities of the coating layers, the porosities of the coating layers in Examples 1 to 10 are small, whereas in Comparative Examples 1 to 9, the coating layers are not formed (Comparative Example 7). ) And a coating layer having a single layer (Comparative Example 1 and Comparative Example 7), the porosity of the coating layer is as large as 10% or more. In addition, in Examples 1 to 10, the room temperature 4-point bending strength and the oxidation resistance were excellent, and the appearance of the fracture surface was also good.
On the other hand, in Comparative Examples 1 to 9, at least one of room temperature 4-point bending strength and oxidation resistance was small, and the appearance of the fracture surface was porous.
【００２１】前記実施例１〜実施例１０により得られた
Ｓｉ3 Ｎ4 −ＳｉＣ積層構造をもつ被覆層の破断面およ
びその研磨面は、例えば図１および図３のようになる。
図１および図３から明らかなように被覆層は層状に緻密
に形成される。これに対し前記比較例１〜比較例９の場
合の被覆層の破断面およびその研磨面は、例えば図２お
よび図４のようになる。図２および図４から明らかなよ
うに、被覆層は多孔質である。The fracture surface and the polished surface of the coating layer having the Si 3 N 4 --SiC laminated structure obtained in Examples 1 to 10 are as shown in FIGS. 1 and 3, for example.
As is clear from FIGS. 1 and 3, the coating layer is densely formed in layers. On the other hand, the fracture surface and the polished surface of the coating layer in Comparative Examples 1 to 9 are as shown in FIGS. 2 and 4, for example. As is clear from FIGS. 2 and 4, the coating layer is porous.
【００２２】[0022]
【発明の効果】以上説明したように、本発明の複合被覆
層を有するセラミックス焼結体の製造方法によれば、原
料ガスの切替え時に反応炉の容積よりも少なくとも３．
４倍以上の容積のH2ガスを反応室中に流すことによっ
て、セラミックス焼結体表面に緻密で密着性の良好な窒
化珪素と炭化珪素とが積層した構造の複合被覆層が形成
できる。また、各被覆層の厚みの制御により、任意の熱
膨張を有するセラミックス基材に複合被覆層の形成が可
能となる。このため、窒化珪素焼結体については高温で
の被覆層と窒化珪素焼結体の粒界層との反応が防止さ
れ、耐酸化性が良好で高強度の複合被覆窒化珪素焼結体
が得られる。また、炭化珪素焼結体においては高強度で
耐蝕性に優れた複合被覆炭化珪素焼結体が得られる。As described above, according to the method for producing a ceramics sintered body having a composite coating layer of the present invention, at least 3.
By flowing H 2 gas having a volume of 4 times or more into the reaction chamber, it is possible to form a composite coating layer having a structure in which silicon nitride and silicon carbide which are dense and have good adhesion are laminated on the surface of the ceramic sintered body. Further, by controlling the thickness of each coating layer, it becomes possible to form a composite coating layer on a ceramic substrate having an arbitrary thermal expansion. Therefore, for the silicon nitride sintered body, the reaction between the coating layer and the grain boundary layer of the silicon nitride sintered body at high temperature is prevented, and a high-strength composite coated silicon nitride sintered body having good oxidation resistance is obtained. To be Further, in the silicon carbide sintered body, a composite-coated silicon carbide sintered body having high strength and excellent corrosion resistance can be obtained.
【図１】本発明の実施例１による被覆層の破断面を示す
電子顕微鏡写真である。FIG. 1 is an electron micrograph showing a fracture surface of a coating layer according to Example 1 of the present invention.
【図２】従来の比較例１による被覆層の破断面を示す電
子顕微鏡写真である。FIG. 2 is an electron micrograph showing a fracture surface of a coating layer according to a conventional comparative example 1.
【図３】本発明の実施例１による被覆層の研磨面を示す
光学顕微鏡写真である。FIG. 3 is an optical micrograph showing a polished surface of a coating layer according to Example 1 of the present invention.
【図４】従来の比較例１による被覆層の研磨面を示す光
学顕微鏡写真である。FIG. 4 is an optical micrograph showing a polished surface of a coating layer according to Comparative Example 1 of the related art.
Claims (5)
長法により窒化珪素層および炭化珪素層の複合被覆層を
層状に形成する方法であって、各被覆層を形成するため
に反応炉に流す反応ガスの切替え時、反応炉内に水素ガ
スを流通させ、この反応炉内に導入する水素ガス量を室
温大気圧下で反応炉内の容積よりも少なくとも３．４倍
以上の容積のガス量に設定したことを特徴とする複合被
覆層を有するセラミックス焼結体の製造方法。1. A method of forming a composite coating layer of a silicon nitride layer and a silicon carbide layer in layers on the surface of a base material such as ceramics by a chemical vapor deposition method, wherein a reactor is used to form each coating layer. At the time of switching the reaction gas flowing through the reactor, hydrogen gas is circulated in the reactor, and the amount of hydrogen gas introduced into the reactor is at least 3.4 times the volume in the reactor at room temperature and atmospheric pressure. A method for producing a ceramics sintered body having a composite coating layer, wherein the amount of gas is set.
ることを特徴とする請求項１に記載の複合被覆層を有す
るセラミックス焼結体の製造方法。2. The method for producing a ceramics sintered body having a composite coating layer according to claim 1, wherein the chemical vapor deposition method is a low pressure thermal CVD method.
被覆層を形成する原料ガスとして、四塩化珪素およびア
ンモニアを用い、炭化珪素の層状被覆層を形成する原料
ガスとして、四塩化珪素およびメタンを用いることを特
徴とする請求項１または請求項２に記載の複合被覆層を
有するセラミックス焼結体の製造方法。3. Silicon tetrachloride and ammonia are used as a raw material gas for forming the layered coating layer of silicon nitride by the chemical vapor deposition method, and silicon tetrachloride and ammonia are used as a source gas for forming the layered coating layer of silicon carbide. Methane is used, The manufacturing method of the ceramics sintered compact which has the composite coating layer of Claim 1 or Claim 2 characterized by the above-mentioned.
斜させたことを特徴とする請求項１または請求項２に記
載の複合被覆層を有するセラミックス焼結体の製造方
法。4. The method for producing a ceramics sintered body having a composite coating layer according to claim 1, wherein the thickness of each coating layer of silicon nitride and silicon carbide is graded.
る請求項１、２、３または４に記載の複合被覆層を有す
るセラミックス焼結体の製造方法。5. The method for producing a ceramics sintered body having a composite coating layer according to claim 1, 2, 3 or 4, wherein the base material is a silicon nitride or silicon carbide sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3119243A JP2500012B2 (en) | 1991-04-22 | 1991-04-22 | Method for manufacturing ceramics sintered body having composite coating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3119243A JP2500012B2 (en) | 1991-04-22 | 1991-04-22 | Method for manufacturing ceramics sintered body having composite coating layer |
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| Publication Number | Publication Date |
|---|---|
| JPH04321578A JPH04321578A (en) | 1992-11-11 |
| JP2500012B2 true JP2500012B2 (en) | 1996-05-29 |
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| JP3119243A Expired - Fee Related JP2500012B2 (en) | 1991-04-22 | 1991-04-22 | Method for manufacturing ceramics sintered body having composite coating layer |
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