JPS63274679A - Method for joining ceramics and metallic film - Google Patents
Method for joining ceramics and metallic filmInfo
- Publication number
- JPS63274679A JPS63274679A JP10959187A JP10959187A JPS63274679A JP S63274679 A JPS63274679 A JP S63274679A JP 10959187 A JP10959187 A JP 10959187A JP 10959187 A JP10959187 A JP 10959187A JP S63274679 A JPS63274679 A JP S63274679A
- Authority
- JP
- Japan
- Prior art keywords
- oxide layer
- metal film
- metallic film
- oxide
- ceramics
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000919 ceramic Substances 0.000 title abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 229910052575 non-oxide ceramic Inorganic materials 0.000 claims abstract description 30
- 239000011225 non-oxide ceramic Substances 0.000 claims abstract description 30
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000010301 surface-oxidation reaction Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000004544 sputter deposition Methods 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 238000001771 vacuum deposition Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Pressure Welding/Diffusion-Bonding (AREA)
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、窒化珪素等の非酸化物系セラミックスと金属
膜とを強固に、しかも簡易に接合する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for firmly and easily bonding a non-oxide ceramic such as silicon nitride and a metal film.
近年、セラミックス材料が有する優れた緒特性が注目さ
れている。このためセラミックス材料が工業技術の様々
な分野゛で利用されている。中でも種々の特性が良好な
窒化珪素（Ｓ ＩＳ Ｎ４ ） 、炭化珪素（ＳｉＣ）
等の非酸化物系セラミックスが多く用いられる傾向にあ
る。In recent years, the excellent properties of ceramic materials have attracted attention. For this reason, ceramic materials are used in various fields of industrial technology. Among them, silicon nitride (SIS N4) and silicon carbide (SiC) have good various properties.
There is a tendency for non-oxide ceramics such as
実際に、これらのセラミックスを利用する際にはセラミ
ックスとそれ以外の物質との間で高強度の接合が必要と
なる事が多い、しかし、非酸化物系セラミックスと金属
との接合では、各々の物質内の原子間での結合機構が異
なるために、高強度の接合は容易ではない。In fact, when using these ceramics, a high-strength bond is often required between the ceramic and other materials, but when bonding non-oxide ceramics and metals, each High-strength bonding is difficult because the bonding mechanisms between atoms within a material are different.
このため、非酸化物系セラミックスと金属膜又は金属部
材との接合強度を向上させる方法が幾つか提案されてい
る。For this reason, several methods have been proposed to improve the bonding strength between non-oxide ceramics and metal films or metal members.
例えば、特開昭６０−２００８８４では、Ｓｉ２Ｎ４及
びＳｉＣに対してその表面をアルカリ水溶液でエツチン
グして変質せしめ、然る後に金属めっきを行い、これを
熱処理する事により、変質層を介してセラミックスと金
属膜とを接合せしめている。しかし、この方法は、変質
層の形成及び金属膜形成に湿式法を用いたものであるた
め１反応物質の取り扱いとその後処理、さらには形成物
の水洗いや乾燥等も必要となり、工程が繁雑である。For example, in JP-A No. 60-200884, the surfaces of Si2N4 and SiC are etched with an alkaline aqueous solution to alter their properties, and then metal plating is performed, which is then heat-treated to form ceramics through the altered layer. It is bonded to a metal film. However, since this method uses a wet method to form the altered layer and metal film, it requires handling and subsequent treatment of one reactant, as well as washing and drying the formed material, making the process complicated. be.
また、特開昭６１−９１０７２では、５ｉｓＮ４及びＳ
ｉＣの表面に酸化珪素（Ｓｉｎ、）と酸化マグネシウム
（ＭｇＯ）とバインダー等からなる表面改質剤を塗布、
焼成し、金属部材とのろう付性を向上している。しかし
ながら、これらの酸化物は粉末を用いており、ｖＬ成に
より十分な接合強度を得るためには１粒度をある程度以
下に揃えなくてはならない。In addition, in JP-A-61-91072, 5isN4 and S
A surface modifier consisting of silicon oxide (Sin), magnesium oxide (MgO), binder, etc. is applied to the surface of iC,
Sintered to improve brazing properties with metal parts. However, these oxides use powders, and in order to obtain sufficient bonding strength through VL formation, the grain size must be adjusted to a certain level or less.
さらに、この表面改質剤の塗布量など、制御すべき変数
が数多く、その接合法が簡易性に欠ける。Furthermore, there are many variables to be controlled, such as the amount of surface modifier applied, and the bonding method lacks simplicity.
さらに、特開昭６０−２４６２７８では、５ｉｘＮａの
表面を、ｌＸｌ０−エＴｏｒｒ以上の真空度で、かつ１
２００°Ｃ以上の高温下において珪素（Ｓｉ）と窒素（
Ｎ）とに解離させ、同時に金属部材を圧着させている。Furthermore, in JP-A No. 60-246278, the surface of 5ixNa was exposed to a vacuum degree of 1X10-Torr or more and
Silicon (Si) and nitrogen (
N), and at the same time, the metal member is crimped.
しかし、この方法においても、真空と高温と部材の圧着
という３つの条件を同時に満たす必要があり、多機能を
有する装置の使用が前提条件となっている。However, even in this method, it is necessary to simultaneously satisfy three conditions: vacuum, high temperature, and pressure bonding of the members, and the use of a multifunctional device is a prerequisite.
本発明は、上記従来技術に鑑み、非酸化物系セラミック
スと金属膜とを強固にしかも簡易に接合できる方法を提
供しようとするものである。In view of the above-mentioned prior art, the present invention aims to provide a method for strongly and easily bonding non-oxide ceramics and metal films.
本発明は、窒化珪素等の非酸化物系セラミックスの表面
を酸化して酸化層を形成する工程と。The present invention includes a step of oxidizing the surface of a non-oxide ceramic such as silicon nitride to form an oxide layer.
該酸化層表面に接合すべき金属膜を堆積させる工程と。Depositing a metal film to be bonded to the surface of the oxide layer.
該酸化層と金属膜とを相互拡散させて接合する工程とよ
りなることを特徴とする非酸化物系セラミックスと金属
膜との接合方法にある。A method of bonding a non-oxide ceramic and a metal film, comprising a step of bonding the oxide layer and the metal film by mutual diffusion.
本発明において、非酸化物系セラミックスとしては、Ｓ
ｉ、Ｎｎ、ＳｉＣ等が挙げられる。In the present invention, the non-oxide ceramics include S
i, Nn, SiC, etc.
また、これと接合する金属膜としては、ニッケル（Ｎ
ｉ ） 、チタン（”Ｔ”ｉ）、鉄（Ｆ ｅ） 、ジル
コニウム（Ｚｒ）、タンタル（Ｔａ）等の活性金属、又
はこれら活性金属のうち少なくとも１つを含む合金を用
いる。In addition, the metal film bonded to this is nickel (N
i), titanium ("T"i), iron (Fe), zirconium (Zr), tantalum (Ta), or an alloy containing at least one of these active metals.
非酸化物系セラミックスの表面を酸化して酸化層を形成
する方法としては、非酸化物系セラミックスを酸化性雰
囲気中で加熱する方法がある。この加熱は、９００’Ｃ
以上において行うことが好ましい、酸化性雰囲気として
は、大気中、高酸素濃度ガスなどがある。大気中加熱の
場合は、１０００゛Ｃ以上、１時間の加熱で、約１０ｐ
程度の酸化層を形成することができる。ｆＩＩ化層の厚
みは５１Ｉｍ以上形成することが好ましく、これより薄
い場合は金属膜との接合強度が低くなるおそれがある。As a method of oxidizing the surface of non-oxide ceramics to form an oxide layer, there is a method of heating non-oxide ceramics in an oxidizing atmosphere. This heating is 900'C
The oxidizing atmosphere that is preferably carried out in the above includes air, high oxygen concentration gas, and the like. In the case of heating in the atmosphere, heating at 1000°C or higher for 1 hour will reduce the temperature by about 10p.
It is possible to form an oxidized layer of approximately It is preferable that the fII layer has a thickness of 51 Im or more; if it is thinner than this, the bonding strength with the metal film may be lowered.
なお、上記酸化層の形成は、非酸化物系セラミックスが
５ｉｓＮａである場合には、ＳｉｚＮｍ中のＮを酸素（
０）によって置換することにより行うものである。Note that when the non-oxide ceramic is 5isNa, the formation of the oxide layer is performed by replacing N in SizNm with oxygen (
0).
上記酸化層の上に接合すべき金属膜の形成（堆積）は、
前記した金属を真空蒸着、スパッタリング、イオンブレ
ーティング等の物理的蒸着などにより行う、このうち、
スパッタリング、イオンブレーティング法は、金属膜の
より強い密着性をもたらし、好ましい方法である。金属
膜の厚みは。The formation (deposition) of the metal film to be bonded on the oxide layer is as follows:
The above-mentioned metal is applied by physical vapor deposition such as vacuum evaporation, sputtering, ion blating, etc.
Sputtering and ion blasting methods provide stronger adhesion of the metal film and are preferred methods. What is the thickness of the metal film?
後の相互拡散において拡散に必要とされる盪であれば良
いが、少なくとも１μｍが必要である。また、膜応力に
よる膜の剥離を抑えるためには３μｍ以下とすることが
好ましい。It may be as long as the thickness required for diffusion in later interdiffusion, but it is required to be at least 1 μm. Further, in order to suppress peeling of the film due to film stress, the thickness is preferably 3 μm or less.
次に、上記酸化層と金属膜との相互拡散は、高温に加熱
すること、により行う、この際の温度は約ａ ｏ ｏ
’ｃ以上１時間は１時間以上とするのが好ましい、また
、加熱雰囲気は大気中、あるいは窒素。Next, the interdiffusion between the oxide layer and the metal film is performed by heating to a high temperature, at a temperature of about a o o
The heating time is preferably 1 hour or more, and the heating atmosphere is air or nitrogen.
アルゴン等の非酸化雰囲気など、特に限定するものでは
ない、この相互拡散処理によって、非酸化物系セラミッ
クス上の前記酸化層と上記金属膜とが互いに拡散し合っ
て、金属膜が非酸化物系セラミックス上に強固に接合さ
れることとなるのである。Through this mutual diffusion treatment, which is not particularly limited to a non-oxidizing atmosphere such as argon, the oxide layer and the metal film on the non-oxide ceramics diffuse into each other, and the metal film becomes a non-oxide-based ceramic. This results in a strong bond to the ceramic.
（作用及び効果）
本発明においては、非酸化物系セラミックスと金属膜と
の間に非酸化物系セラミックスの酸化層を形成し、また
該酸化層は金属膜と相互拡散させている。(Functions and Effects) In the present invention, an oxidized layer of non-oxide ceramic is formed between the non-oxide ceramic and the metal film, and the oxide layer is interdiffused with the metal film.
そのため、非酸化物系セラミックスの内部と金属膜の外
部表面との間は、非酸化物系セラミックス、その酸化層
、金属膜が相互に拡散し合って連続的に変化した状態の
層が形成されており、そのため、これら王者間は強固に
結合している（実施例及び図参照）、シたがって１本発
明によれば非酸化物系セラミックスと金属膜とを強固に
接合できるのである。Therefore, between the inside of the non-oxide ceramic and the outer surface of the metal film, a layer is formed in which the non-oxide ceramic, its oxide layer, and the metal film are mutually diffused and continuously changed. Therefore, these two types of bonding are strongly bonded (see examples and figures). Therefore, according to the present invention, it is possible to firmly bond non-oxide ceramics and metal films.
また１本発明は、前記従来技術で示したエツチング処理
等を行う湿式法、また表面改質剤やその塗布、焼成を行
う方法、更には５ｉｚＮ−の表面を高真空下、高温下で
ＳｉとＮとに解離させる方法のごとく、繁雑な処理法、
圧着機構付の真空焼鈍炉などの複雑な装置を必要とせず
、部品な方法である。In addition, the present invention provides a wet method of performing etching treatment etc. as shown in the above-mentioned prior art, a method of applying a surface modifier, applying it, and baking, and furthermore, a method of etching the surface of 5izN- with Si under high vacuum and high temperature. Complicated processing methods, such as the method of dissociating N,
It is a simple method that does not require complicated equipment such as a vacuum annealing furnace with a crimping mechanism.
また６本発明の方法により得られた非酸化物系セラミッ
クスと金属膜とからなる材料は、非酸化物系セラミック
スの特性を有する各種の機能材料。Further, the material made of non-oxide ceramics and metal film obtained by the method of the present invention is various functional materials having the characteristics of non-oxide ceramics.
構造材料として使用することができる。Can be used as a structural material.
例えば、ターボロータは、窒化珪素によって作製するこ
とがあるが、使用中に粒子の衝突によりロータ翼が損傷
するおそれがある。そこで、その表面に前記金属膜を接
合することにより、この金属膜が粒子衝突時の緩衝膜と
して、また窒化珪素の補強膜として有効に作用し、ター
ボロータの強度を向上させることができる。For example, turbo rotors are sometimes made from silicon nitride, but during use, particle bombardment can damage the rotor blades. Therefore, by bonding the metal film to the surface, this metal film effectively acts as a buffer film during particle collisions and as a reinforcing film for silicon nitride, thereby improving the strength of the turbo rotor.
また、非酸化物系セラミックスの表面に形成した金属膜
に対して、ろう付け、溶接等によって更に金属部材を接
合することもでき１両者からなる複合材や両者の結合製
品も製造することができる。Additionally, metal members can be further joined to the metal film formed on the surface of non-oxide ceramics by brazing, welding, etc., making it possible to manufacture composite materials made of both or products combining the two. .
たとえば、上記の窒化珪素製ターボロータと金属製シャ
フトとを強固に接合することができる。For example, the above silicon nitride turbo rotor and metal shaft can be firmly joined.
実施例１
３Ｘ４Ｘ２０−のＳ ｉ ３ Ｎｇ焼結体を、加熱炉内
において、大気中、１１００℃で１時間加熱した。これ
により、Ｓｉ、Ｎａの表面のＮを０に置換して、５ｉｘ
Ｎａの表面に酸化層を形成した。Example 1 A 3×4×20-S i 3 Ng sintered body was heated in a heating furnace at 1100° C. in the atmosphere for 1 hour. As a result, N on the surfaces of Si and Na is replaced with 0, and 5ix
An oxide layer was formed on the surface of Na.
次いで、この焼結体の表面の酸化層上に二極スパッタ装
置を用いて、Ａｒガス圧２ｍ１’ｏｒｒ、高周波人力３
００Ｗの条件により、Ｎｉの金属膜を１．８μｍ堆積さ
せた。更に、窒素中、９５０°Ｃにて１時間加熱し、Ｎ
ｉ１ｌｉと酸化層間の相互拡散処理を行い、５ｉｚＮａ
とＮｉ金属膜とが強固に結合した複合材料を得た。Next, the oxide layer on the surface of this sintered body was coated with Ar gas pressure of 2 m1'orr and high frequency manual power of 3.
A 1.8 μm thick Ni metal film was deposited under the conditions of 00W. Furthermore, it was heated at 950°C for 1 hour in nitrogen, and
Perform interdiffusion treatment between i1li and oxide layer, and 5izNa
A composite material was obtained in which the Ni metal film and the Ni metal film were firmly bonded.
次に、この複合材料について１種々の測定を行った。Next, various measurements were performed on this composite material.
まず、この複合材料を引っ掻き試験による密着性評価に
供した。この試験はダイヤモンド圧子先端径０，２Ｍ、
圧子移動速度５０■／分、圧子荷重５００ｇで行った。First, this composite material was subjected to an adhesion evaluation using a scratch test. This test was conducted using a diamond indenter with a tip diameter of 0.2M.
The indenter movement speed was 50 μ/min and the indenter load was 500 g.
圧子痕を走査型電子顕微鏡で観察し、引っ掻き痕周囲で
のＮｉ１Ｊの剥離の有無により密着性を評価した。その
結果、上記Ｎｉ膜の’ＪＪＩＭは何ら見られず、優れた
密着性を示していた。The indenter marks were observed with a scanning electron microscope, and the adhesion was evaluated based on the presence or absence of peeling of Ni1J around the scratch marks. As a result, no 'JJIM' was observed in the Ni film, indicating excellent adhesion.
次に、上記複合材料を、Ｎ＋膜１Ｍ化層に対して垂直に
破断し、上記顕＠鏡で観察したところ。Next, the composite material was cut perpendicularly to the 1M N+ film layer and observed using the microscope.
Ｎ１膜と酸化層、酸化層と５ｉｚＮｎの各界面とも不明
瞭で、その境界位置の特定は不可能であった。即ち、こ
れらの界面は互いに相互拡散しているのである。The interfaces between the N1 film and the oxide layer, and between the oxide layer and the 5izNn were unclear, and it was impossible to identify their boundary positions. That is, these interfaces are interdiffusing with each other.
そこで、この点を更に追求すべく、上記Ｎｉ膜から５ｉ
ｚＮｎの内部に向けて、ＥＰＭＡによる線分析を行った
。その結果を図に示す、同図より明らかなように、最表
面にあるＮｉ膜（符号Ｎｉ）は内部に入るに従ってその
量が減少し、これに変わって酸化層、の酸素（符号Ｏ）
が増加し、更に内部に入るに従って減少している。また
、５ｉ３Ｎｄ中の珪素（符号Ｓｔ）、窒素（符号Ｎ）は
。Therefore, in order to further pursue this point, 5i
EPMA line analysis was performed toward the inside of zNn. The results are shown in the figure. As is clear from the figure, the amount of the Ni film on the outermost surface (coded Ni) decreases as it goes inside, and the amount of oxygen in the oxide layer (coded O) decreases as it goes inside.
increases, and decreases as one goes further inside. In addition, silicon (symbol St) and nitrogen (symbol N) in 5i3Nd are.
表面には殆ど存在しないが、上記Ｎｉ更に酸化層の酸素
の減少と共に増加し、約３０ＩＩｍの深さ以降は５ｉｚ
Ｎ４のみであることが分かる。Although it hardly exists on the surface, it increases with the decrease of Ni and oxygen in the oxide layer, and after a depth of about 30 II m, the Ni
It can be seen that it is only N4.
上記の点に関し、今少し詳説すれば、前記接合後の複合
材料の組成は、その表面より内部に向かってＮｉ、Ｎｉ
Ｏｘ、５ｉＯｙＮｚ、Ｓｉ、Ｎａの順で主成分が変化し
、しかもその変化が連続的である。ここにＸ、Ｙ、ｌは
、各々０≦ｘ＜１゜０≦ｙ≦２．０≦２≦４／３であり
、また表面側から内部側へ入るに従ってＸ、Ｚは増加し
、ｙは減少する。Regarding the above point, to explain in more detail, the composition of the composite material after bonding increases from the surface to the inside: Ni, Ni.
The main components change in the order of Ox, 5iOyNz, Si, and Na, and the changes are continuous. Here, X, Y, and l are each 0≦x<1゜0≦y≦2.0≦2≦4/3, and X and Z increase as you go from the surface side to the inside, and y is Decrease.
実施例２
相互拡散工程における雰囲気を大気中とした他は、実施
例１と同様にして、５ｉｓＮａとＮ１との接合を行った
。Example 2 5isNa and N1 were bonded in the same manner as in Example 1, except that the atmosphere in the interdiffusion step was air.
得られた材料について、実施例１と同様の測定を行った
ところ、５ＩｘＮａとＮｉ膜とは実施例１と同様に優れ
た密着性を示していた。When the obtained material was measured in the same manner as in Example 1, it was found that the 5IxNa and Ni films exhibited excellent adhesion as in Example 1.
実施例３
ＳｉｓＮａ焼結体の表面に実施例１と同様にして酸化層
を形成し、その上にスパッタリング装置を用いて、Ａｒ
ガス圧３ｍＴｏ ｒ ｒ、高周波人力３００Ｗの条件下
で、モリブデン（Ｍｏ）−２０原子％チタン（Ｔｉ）合
金を、２０００人（オングストローム）の厚さに成膜し
た。Example 3 An oxide layer was formed on the surface of the SisNa sintered body in the same manner as in Example 1, and Ar was applied thereon using a sputtering device.
A molybdenum (Mo)-20 atomic % titanium (Ti) alloy was formed into a film with a thickness of 2000 angstroms under the conditions of a gas pressure of 3 mTorr and a high-frequency manual power of 300 W.
次に、このものを窒素雰囲気中で、８００″０゜１時間
加熱して、相互拡散処理を行った。Next, this material was heated in a nitrogen atmosphere to 800"0.degree. for 1 hour to perform interdiffusion treatment.
得られた材料につき、実施例１と同様の測定を行ったと
ころ、引っ掻き痕周辺におけるＭｏ−Ｔｉ金属膜の剥離
は何ら見られず、優れた密着性を示していた。また、オ
ージェ分析により表面から内部への組成分析を行ったと
ころ、Ｍｏ−Ｔｉ合金膜と５ｉｘＮ４焼結体との間にＴ
ｉと０とＮとからなる拡散層が見られた。When the obtained material was measured in the same manner as in Example 1, no peeling of the Mo-Ti metal film was observed around the scratch marks, indicating excellent adhesion. In addition, when we analyzed the composition from the surface to the inside using Auger analysis, we found that T was present between the Mo-Ti alloy film and the 5ixN4 sintered body.
A diffusion layer consisting of i, 0, and N was observed.
実施例４
上記実施例１において得た材料に対して、これと同寸法
のＮｉ部材を準備し１両者の３×４−の面を向い合せ、
上記材料のＮ（膜面と該Ｎｉ部材の両者をはんだ付けし
た。はんだ付けは、５ｎ６０％−Ｐｂ４０％組成のはん
だを大気中で約２００℃に加熱する条件により行った。Example 4 For the material obtained in Example 1 above, prepare a Ni member with the same dimensions as this, and place the 3 x 4- faces of the two members facing each other,
Both the N (film surface) of the above material and the Ni member were soldered. Soldering was performed under the condition that a solder having a composition of 5N60%-Pb40% was heated to about 200°C in the atmosphere.
次に１前接合部の曲げ強度を測定したところ。Next, we measured the bending strength of the first joint.
はんだ付けした部分において、７Ｘ１０’Ｐａの応力で
破断し、Ｎｉ膜と５ｉｓＮ４との接合部は異常がなかっ
た。これにより、ＮｉｐとＳｉ、Ｎ４との接合部の曲げ
強度は７Ｘ１０’Ｐａ以上の付着力を有していることが
分かる。The soldered part broke under a stress of 7×10'Pa, and there was no abnormality in the joint between the Ni film and 5isN4. This shows that the bending strength of the joint between Nip, Si, and N4 has an adhesion force of 7×10'Pa or more.
比較例１
Ｓｔ、Ｎ、焼結体における表面の酸化層形成を行わなか
った以外は実施例１と同様の方法で、Ｎ１膜と５ｔｓＮ
、との接合を行った。Comparative Example 1 A N1 film and a 5tsN
, was joined with.
その結果、引っ掻き試験においては、引っ掻き痕周辺で
Ｎｉ膜の多大の剥離が見られ、密着性はかなり劣ってい
ることが判明した。As a result, in the scratch test, it was found that a large amount of the Ni film was peeled off around the scratch marks, and the adhesion was found to be quite poor.
比較例２ ３Ｘ４Ｘ２０鵬の５ＩｘＮ−焼結体の表面に。Comparative example 2 3X4X20 on the surface of 5IxN-sintered body.
下記の表面改質剤を塗布し、室温下で脱水乾燥し。Apply the following surface modifier and dehydrate and dry at room temperature.
更に１２５０″Ｃで６０分間加熱し、改質層を形成した
。上記表面改質剤としては、３２５メツシユ以下の５１
０□粉末４０重量％、１００メツシュ以下のＭｇＯ粉末
６０重量％からなる混合物にポリビニルアルコールを加
えて混練したものを用いた。The surface modifier was further heated at 1250"C for 60 minutes to form a modified layer.
A mixture of 40% by weight of 0□ powder and 60% by weight of MgO powder with a mesh size of 100 or less was mixed with polyvinyl alcohol and kneaded.
次いで、上記と同寸法のＮｉ部材を準備し、これと改質
層を形成した上記Ｓｉ、Ｎ、焼結体とを３×４−の面に
おいて、はんだ付けした。はんだ付けは、実施例４と同
様の条件とした。得られた材料について実施例４と同様
の破断試験を行った。Next, a Ni member having the same dimensions as above was prepared, and this and the Si, N, sintered body on which the modified layer was formed were soldered on a 3×4- surface. Soldering was carried out under the same conditions as in Example 4. The obtained material was subjected to the same breaking test as in Example 4.
その結果、上記はんだ付は部分ではなく Ｓ ｉ ２Ｎ
４焼結体と改質層との界面において、５Ｘ１０’Ｐａの
応力で破断した。As a result, the above soldering is not a partial but a S i 2N
4. At the interface between the sintered body and the modified layer, the sintered body fractured under a stress of 5×10'Pa.
図は１本発明の実施例１における。５ｉｓＮ−焼結体と
Ｎｉ１ｌとの接合部のＥＰＭＡ分析の結果を示す線図で
ある。The figure shows Embodiment 1 of the present invention. 5 is a diagram showing the results of EPMA analysis of the joint between the 5isN-sintered body and Ni1l. FIG.
Claims (4)
化して酸化層を形成する工程と、 該酸化層表面に接合すべき金属膜を堆積させる工程と、 該酸化層と金属膜とを相互拡散させて接合する工程とよ
りなることを特徴とする非酸化物系セラミックスと金属
膜との接合方法。(1) A step of oxidizing the surface of a non-oxide ceramic such as silicon nitride to form an oxide layer, a step of depositing a metal film to be bonded to the surface of the oxide layer, and a step of combining the oxide layer and the metal film. A method for joining non-oxide ceramics and a metal film, characterized by comprising a step of joining by mutual diffusion.
１０００℃以上において加熱することにより行うことを
特徴とする特許請求の範囲第１項に記載の非酸化物系セ
ラミックスと金属膜との接合方法。(2) Surface oxidation of the non-oxide ceramic is performed by heating at 1000° C. or higher in the atmosphere, Joining method.
おいて加熱することにより行うことを特徴とする特許請
求の範囲第１項に記載の非酸化物系セラミックスと金属
膜との接合方法。(3) A method for joining a non-oxide ceramic and a metal film according to claim 1, wherein the mutual diffusion between the oxide layer and the metal film is performed by heating at 800° C. or higher. .
特徴とする特許請求の範囲第１項に記載の非酸化物系セ
ラミックスと金属膜との接合方法。(4) The method for joining a non-oxide ceramic and a metal film according to claim 1, wherein the non-oxide ceramic is silicon nitride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10959187A JPS63274679A (en) | 1987-05-02 | 1987-05-02 | Method for joining ceramics and metallic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10959187A JPS63274679A (en) | 1987-05-02 | 1987-05-02 | Method for joining ceramics and metallic film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63274679A true JPS63274679A (en) | 1988-11-11 |
Family
ID=14514146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10959187A Pending JPS63274679A (en) | 1987-05-02 | 1987-05-02 | Method for joining ceramics and metallic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63274679A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6170734B1 (en) * | 1998-07-24 | 2001-01-09 | Korea Research Institute Of Chemical Technology | Method of joining silicon nitride to carbon steel |
-
1987
- 1987-05-02 JP JP10959187A patent/JPS63274679A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6170734B1 (en) * | 1998-07-24 | 2001-01-09 | Korea Research Institute Of Chemical Technology | Method of joining silicon nitride to carbon steel |
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