JPS6140871A - Solderable si3n4 ceramic composite composition and manufacture - Google Patents
Solderable si3n4 ceramic composite composition and manufactureInfo
- Publication number
- JPS6140871A JPS6140871A JP59156174A JP15617484A JPS6140871A JP S6140871 A JPS6140871 A JP S6140871A JP 59156174 A JP59156174 A JP 59156174A JP 15617484 A JP15617484 A JP 15617484A JP S6140871 A JPS6140871 A JP S6140871A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- ceramic composite
- composite composition
- surface layer
- 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.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims description 84
- 239000000203 mixture Substances 0.000 title claims description 33
- 239000002131 composite material Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 229910052715 tantalum Inorganic materials 0.000 claims description 21
- 229910052758 niobium Inorganic materials 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 10
- 150000001875 compounds Chemical group 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000002344 surface layer Substances 0.000 description 53
- 238000007731 hot pressing Methods 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 238000005219 brazing Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 229910000679 solder Inorganic materials 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052574 oxide ceramic Inorganic materials 0.000 description 4
- 239000011224 oxide ceramic Substances 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 borides Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は鑞付けが可能な表面層を有する５１ｇＮａを主
成分とするセラミックス複合組成物及びその製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a ceramic composite composition containing 51 g Na as a main component and having a brazable surface layer, and a method for producing the same.
（従来技術）
セラミックスと金属を鑞接する際には一般にセラミック
スと金属鑞の濡れ性を上げるためにセラミックス表面を
金属化（メタライズ）処理した後鑞付けが行われている
。(Prior Art) When ceramics and metals are soldered together, brazing is generally performed after the surface of the ceramics is metallized in order to increase the wettability between the ceramics and the metal solder.
従来からＡＩ！２０ｇセラミックスなどの酸化物セラミ
ックスをメタライズする方法としてＭｏ、Ｗなどの高融
点金属とＭｎの混合粉末を用いて加湿Ｈ２中で処理を行
うテレフンケン法（高融点金属法）が知られている。母
材セラミックスがＡ／２０３の場合にはＭｏ、Ｗの一部
とＭｎの大部分が酸化されてＭ２Ｏ３及びＡＩ！２０ｓ
セラミックスに含まれているガラス成分と反応し液相を
形成してメタライズ層中の空隙部分を埋め接着強度が向
上する。Traditionally AI! As a method for metallizing oxide ceramics such as 20g ceramics, the Telefunken method (high melting point metal method) is known, in which a mixed powder of a high melting point metal such as Mo or W and Mn is treated in humidified H2. When the base ceramic is A/203, some of Mo and W and most of Mn are oxidized to form M2O3 and AI! 20s
It reacts with the glass component contained in the ceramic to form a liquid phase, filling the voids in the metallized layer and improving adhesive strength.
しかしながら母材がＳ ｉ ３Ｎ４を主成分とするセラ
ミックスである場合には上記の様な液相が形成されない
ため母材ＳｉｘＮ４セラミツクスとメタライズ層の接着
強度は非常に低く構造材料としての使用に耐え得るもの
ではない。However, when the base material is a ceramic whose main component is Si 3N4, the above liquid phase is not formed, so the adhesive strength between the base material SixN4 ceramics and the metallized layer is very low, making it unsuitable for use as a structural material. It's not a thing.
酸化物セラミックスをメタライズするもう１つの方法と
して酸化物セラミックスとＣｕ板をはり合わせ、大気中
で加熱してＣｕを酸化させながら酸化物セラミックスと
反応させる方法が報告されているが、母材がＳ ｉ ３
Ｎ４を主成分とするセラミックスの場合大気中１０００
℃付近で加熱を行うと、母材５ ｉ ３Ｎ４セラミツク
スが酸化し、性能が著しく低下することがわかった。Another method of metallizing oxide ceramics has been reported, in which oxide ceramics and Cu plates are bonded together and heated in the atmosphere to oxidize Cu while reacting with oxide ceramics. i 3
1000 in the atmosphere for ceramics containing N4 as the main component
It was found that heating at around 0.degree. C. oxidizes the base material 5 i 3N4 ceramics, resulting in a significant decrease in performance.
またＴｉ 、 Ｚ弄などの活性な金属と、これと低融点
？
の合金を作るＮｉ 、 Ｃｕ 、 Ａｇとを共晶組成に
した金属ンルダーを用い、真空中で加熱してセラミック
スと金属を接合する方法も知られているが、１０−５Ｔ
ｏｒｒ前後の高真空が必要であり工業的な方法とは言え
ない。Also, active metals such as Ti and Z and low melting point? There is also a known method of joining ceramics and metal by heating in vacuum using a metal binder with a eutectic composition of Ni, Cu, and Ag, which forms an alloy of 10-5T.
It cannot be said to be an industrial method as it requires a high vacuum around orr.
（発明が解決しようとする問題点）
以上述べた様に従来からあるメタライズ方法では鑞付け
が可能なＳｉｘＮ４セラミツクスを作製することは不可
能であった。本発明者らはこの問題を解決し、Ｓ ｉ
３Ｎ４セラミツクスの鑞付けを可能にするべく研究を重
ねた結果、本発明に到ったものである。(Problems to be Solved by the Invention) As described above, it has been impossible to produce brazable SixN4 ceramics using conventional metallization methods. The inventors solved this problem and S i
The present invention was developed as a result of repeated research to enable brazing of 3N4 ceramics.
（問題点を解決するための手段）
本発明が従来のメタライズ方法と最も大きく異なる点は
５１ｇＮ４セラミツクスの焼結体にメタライズ処理を施
すのではなく焼結前の成形体上にＭｏ 。(Means for Solving Problems) The biggest difference between the present invention and the conventional metallization method is that Mo is applied to the molded body before sintering, instead of metallizing the sintered body of 51 g N4 ceramics.
Ｎｂ、Ｔａ、Ｔｉ、Ｗの粉末、あるいはＭｏ 、 Ｎｂ
、 Ｔａ 、 Ｔｉ 。Nb, Ta, Ti, W powder, or Mo, Nb
, Ta, Ti.
Ｗの粉末とＳｉｘＮ４を主成分とする粉末の混合粉末よ
りなる層を形成し、しかる後にＳｉ３Ｎ４セラミツクス
母材と表面層を同時に焼結して鑞付は可能な面を形成す
るところにある。この時金属粉末と混合するＳ ｉ ３
Ｎ＜を主成分とする粉末にはＡ／２０！ 、 ＭｇＯ。A layer made of a mixed powder of W powder and powder mainly composed of SixN4 is formed, and then the Si3N4 ceramic base material and the surface layer are simultaneously sintered to form a surface that can be brazed. At this time, S i 3 mixed with metal powder
A/20 for powders whose main component is N<! , MgO.
周期律表■λ族元素の酸化物の１種又は２種以上が含ま
れている。Contains one or more oxides of group ■λ elements of the periodic table.
（作用）
このため焼結後のＳｉ３Ｎ４セラミックス母材と表面層
の界面においては母材セラミックスの結晶粒子と表面層
の結晶粒子が複雑に入り組んだ構造になっており、原子
拡散による接合以外に機械的にも界面の接着強度が向上
する。(Function) For this reason, at the interface between the Si3N4 ceramic base material and the surface layer after sintering, the crystal grains of the base ceramic material and the crystal grains of the surface layer have a complex structure. Also, the adhesive strength at the interface is improved.
さらに表面層がＭｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗの金属単体
及び／又はその炭化物、硼化物、窒化物とＳｉ６Ｎ４を
主成分とするセラミックスの複雑に入り組んだ組織とな
り、しかも表面層中のＳｉ３Ｎ４を主成分とするセラミ
ックス母材ＳｉａＮａセラミツクスが結合しているため
に母材セラミックスと表面層の接着強度が大巾に向上し
た。Furthermore, the surface layer has a complex structure of ceramics whose main components are Mo, Nb, Ta, Ti, and W, and/or their carbides, borides, and nitrides, and Si6N4. Since the ceramic base material SiaNa ceramic, which is the main component, is bonded, the adhesive strength between the base ceramic material and the surface layer has been greatly improved.
ここで表面層中のＭｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗの金属単
体及び／又はその炭化物、硼化物、窒化物とＳ ｉ ３
Ｎ４の組成比は金属と鑞付けする際に高い鑞付は強度を
維持するため次の通りであるヵ
母材Ｓｉ口Ｎ＜セラミックスと表面層の接着強度を上げ
るためには表面層中のＳ ｉ ＭＮ４を主成分とするセ
ラミックス粉末の割合を大きくすればよいが、反面Ｓ
ｉ ３Ｎ４が体積で６０％以上になると金属鑞と表面層
との接着強度が急激に低下するために表面層中のＳｉ
３Ｎ４の割合は６０体積チ以下に抑えなければならない
。これは表面層中に含まれている金属単体及び／または
化合物を全て原子に換算してＭｏ 、 Ｎｂ 、 Ｔａ
、 Ｔｉ 、 Ｗの１種又は２種以上とＳｉのモル比
が１以上であることにほぼ対応している。Here, elemental metals such as Mo, Nb, Ta, Ti, and W in the surface layer and/or their carbides, borides, and nitrides and S i 3
The composition ratio of N4 is as follows because high brazing strength is maintained when brazing with metal. i It is possible to increase the proportion of ceramic powder whose main component is MN4, but on the other hand,
i When the 3N4 content exceeds 60% by volume, the adhesive strength between the metal solder and the surface layer decreases rapidly.
The proportion of 3N4 must be kept below 60 vol. This means that all metal elements and/or compounds contained in the surface layer are converted into atoms such as Mo, Nb, and Ta.
, Ti, and W and the molar ratio of Si to at least 1.
表面層と母材５１ｇＮａセラミックスの熱膨張係数に差
があるため焼結後の冷却途中で熱応力が発生し母材セラ
ミックスを破壊する恐れがあり表面層の厚みはできるだ
け薄く抑えた方が良い。表面層と母材ＳｉｘＮａセラミ
ツクスとの熱膨張係数の差が４Ｘ１０−６以内であれば
焼結後の表面層の厚さを１鴫以内に抑えた場合には焼結
後の冷却途中で母材５１ｇＮａを破壊するほどの熱応力
は発生せず問題なく使用できた。これに対して表面層と
母材Ｓｉ３Ｎ４セラミツクスとの熱膨張係数の差が４Ｘ
１０’以内であっても表面層の厚さが１ｍｍを越えるよ
うな場合には焼結後の冷却中に母材ＳｉａＮ４セラミッ
クス内部の表面層との界面近傍に発生する熱応力によっ
て母材５１ｇＮ４セラミツクス中に亀裂が発生する場合
があった。また表面層と母材Ｓｉ３Ｎ４セラミックスと
の熱膨張係数の差が４Ｘ１０−６以上の場合でも表面層
の厚さをさらに薄くすることによって母材Ｓｉ’ｘＮ４
中に亀裂が発生するのを抑えることができた。Since there is a difference in thermal expansion coefficient between the surface layer and the base material 51 g Na ceramics, thermal stress may occur during cooling after sintering and destroy the base material ceramics, so it is better to keep the thickness of the surface layer as thin as possible. If the difference in thermal expansion coefficient between the surface layer and the base material SixNa ceramics is within 4X10-6, if the thickness of the surface layer after sintering is kept within 1 layer, the base material will be removed during cooling after sintering. No thermal stress was generated that would destroy 51 g Na, and it could be used without any problems. On the other hand, the difference in thermal expansion coefficient between the surface layer and the base material Si3N4 ceramics is 4X.
If the thickness of the surface layer exceeds 1mm even if it is within 10', the thickness of the base material 51gN4 ceramics will be reduced due to thermal stress generated near the interface with the surface layer inside the base material SiaN4 ceramics during cooling after sintering. Cracks may occur inside. Furthermore, even if the difference in thermal expansion coefficient between the surface layer and the base material Si3N4 ceramics is 4X10-6 or more, the base material Si'xN4 can be
We were able to prevent cracks from forming inside.
（実施例） 以下本発明を詳細な実施例によって説明する。(Example) The present invention will be explained below with reference to detailed examples.
実施例１゜
平均粒径０．１μｍのＳｉｘＮ４粉末９５体積チと平均
粒径０．０５μｍのＭｇＯ粉末粉末５係積係なる粉末を
ボールミルを用いてエチルアルコール中で３日間湿式混
合した。この混合粉末を金型プレスを用いて成形し、こ
の成形体上面にＷと上記の５１ｇＮａ−５体積％ＭｇＯ
混合粉末を第１表に示す割合で混合した粉末を散布した
後、更に軽く圧縮し表面層と母材Ｓｉ３Ｎ４セラミツク
スを密着させた。この複合体をＮ２１気圧中１７００℃
で圧力を掛けずに焼結した。焼結後の表面層の厚さは０
、３ ｗｎであった。この表面層と鋼の間に銀鑞をはさ
み、Ｈ２気流中６５０℃で鑞付けを行った。Example 1 95 volumes of SixN4 powder with an average particle size of 0.1 μm and 5 volumes of MgO powder with an average particle size of 0.05 μm were wet mixed in ethyl alcohol for 3 days using a ball mill. This mixed powder was molded using a mold press, and the upper surface of this molded body was covered with W and the above 51 g Na-5 volume % MgO.
After scattering the mixed powder in the ratio shown in Table 1, it was further lightly compressed to bring the surface layer and the base material Si3N4 ceramics into close contact. This composite was heated to 1700℃ in N21 atm.
Sintered without applying pressure. The thickness of the surface layer after sintering is 0
, 3 wn. Silver solder was sandwiched between this surface layer and the steel, and brazing was performed at 650° C. in an H2 gas flow.
これらのＳ ｉ ３Ｎ＜セラミックスと鋼の接合体の剪
断試験の結果を第１表に示す。Table 1 shows the results of shear tests of these S i 3N < ceramic and steel joints.
表面層中（こ６０体積チ以下のＳｉａＮ４を含む試料で
はＳｉ３Ｎ４セラミツクスと鋼の接合強度が大きく剪断
強度が１０Ｋｇ／Ｗ１１２を越す試料があった。Among the samples containing SiaN4 in the surface layer (less than 60 vol. Ti), the bonding strength between the Si3N4 ceramics and the steel was high, and the shear strength exceeded 10 Kg/W112 in some samples.
この時表面層中のＳｉ３Ｎ４の含有量によって破断する
部分が異なり表面層中に３０体積チ以下のＳｉａＮ４を
含む試料では剪断試験でＳ ｉ ３Ｎａセラミックス母
材と表面層の界面で剥離しＳｉ６Ｎ４が３０〜６０体積
チ含まれる試料では表面層中或は銀鑞中で破断した。表
面層中の５１ｇＮａ量が６０体積チを越す試料では銀鑞
と表面層の接着強度が低下するために剪断試験を行うと
銀鑞と表面層の界面で破断し強度が小さかった。At this time, the part that breaks depends on the content of Si3N4 in the surface layer, and in the case of a sample containing 30 volume Ti or less of SiaN4 in the surface layer, it peels off at the interface between the Si3Na ceramic base material and the surface layer in a shear test, and the Si6N4 breaks down by 30 volume. In the sample containing ~60 volumes, the fracture occurred in the surface layer or in the silver solder. In a sample in which the amount of 51 g Na in the surface layer exceeded 60 volumes, the adhesive strength between the silver solder and the surface layer decreased, so when a shear test was performed, the adhesive broke at the interface between the silver solder and the surface layer, and the strength was low.
第 １ 表
実施例２゜
実施例１．と同様の方法にて作製したＳｉ３Ｎａセラミ
ツクスの成形体の上面に６０体積チのＭｏ 。Table 1 Example 2゜Example 1. A 60 volume layer of Mo was placed on the top surface of a molded body of Si3Na ceramics prepared in the same manner as above.
Ｎｂ 、 Ｔａ 、 Ｔｉ 、Ｗの各金属粉末と４０体
積チの母材Ｓｉ６Ｎ＋セラミツクスと同一組成の粉末の
混合物の成形体を重ねＮｚ ｊ ａｔｍ中、２００ Ｋ
９／ｃｍ２の加圧下１７００℃でホットプレスした。A molded body of a mixture of Nb, Ta, Ti, and W metal powders, 40 volumes of base material Si6N+ceramics, and powders with the same composition was stacked and heated at 200 K in Nzj atm.
Hot pressing was carried out at 1700° C. under a pressure of 9/cm 2 .
ホットプレス後の表面層の厚さは全て０．４ ｒｔｖｎ
前後になる様に調整した。この表面層上にＮｉめつきを
施し、Ｈ２気流中９００℃でＮｉを拡散処理した後Ｈ２
気流中６５０℃で鋼に銀鑞付けした。これらのＳ ｉ
３Ｎａセラミックスと鋼の接合体の剪断試験の結果を第
２表に示す。The thickness of the surface layer after hot pressing is all 0.4 rtvn
I adjusted it so that it was around. After applying Ni plating on this surface layer and performing Ni diffusion treatment at 900°C in an H2 air flow, H2
The steel was silver-brazed at 650°C in an air stream. These S i
Table 2 shows the results of the shear test of the 3Na ceramic and steel joint.
ホットプレス後表面層のＸ線回折を行うと第２表に示す
ように金属単体以外に炭化物、珪化物、硼珪化物などの
生成が認められた。炭化物はホットプレスの際に炭素型
の中がＮ２とωの混合ガス雰囲気になるため表面層中の
金属が炭化して出来た可能性が大きい。珪化物の生成に
関しては表面層中のＳｉａＮａ及び母材５１ｇＮ４と金
属が反応して生成したものと考えられる。さらｉｃｓｉ
ｇＮ４と金属並びにホットプレスの際に炭素型とセラミ
ックス成形体の間に離型剤として介在させたＢＮの３者
が反応して硼珪化物が生成したものと考えられる。When the surface layer was subjected to X-ray diffraction after hot pressing, as shown in Table 2, the formation of carbides, silicides, borosilicides, etc. in addition to simple metals was observed. There is a high possibility that the carbide is formed by carbonizing the metal in the surface layer because the inside of the carbon mold becomes a mixed gas atmosphere of N2 and ω during hot pressing. The formation of silicide is thought to be caused by the reaction of SiaNa in the surface layer and the base material 51gN4 with the metal. Sara icsi
It is thought that the borosilicide was produced by the reaction of gN4, metal, and BN, which was interposed as a mold release agent between the carbon mold and the ceramic molded body during hot pressing.
実施例３゜
実施例１．と同様の方法にて作製したＳ ｉ ３Ｎ４セ
ラミツクスの成形体の上面に５０体積チのＷと５０体積
チの母材ＳｉｘＮ４セラミツクスと同−組第 ２
表
成の粉末の混合物の成形体を重ね、Ｎ２１ ａｔｍ 中
２ｏｏＫｙ／２の加圧下１７００℃でホットプレスし０
１ま
た。この時表面層成形体の厚さを変化させることにより
ホットプレス後の表面層の厚さが０．１〜２ｒｒｒｍの
各種属さになるように調整した。この表面層上にＮｉめ
っきを施しＨ２中９００℃でＮｉを拡散処理した後、Ｈ
２中６ペ０℃で鋼に銀鑞付けした。上記Ｓ ｉ ３Ｎａ
セラミックスと鋼の接合体の剪断試験の結果を第３表に
示す。Example 3゜Example 1. A molded body of S i 3N4 ceramics produced in the same manner as above was coated with 50 volume squares of W and 50 volume squares of the base material SixN4 ceramics, and the same set No. 2
The molded bodies of the surface powder mixture were stacked and hot pressed at 1700°C under pressure of 2ooKy/2 in N21 atm.
1 again. At this time, by changing the thickness of the surface layer molded body, the thickness of the surface layer after hot pressing was adjusted to various thicknesses of 0.1 to 2 rrrm. After applying Ni plating on this surface layer and diffusing Ni at 900°C in H2,
Silver brazing was applied to steel at 0°C. The above S i 3Na
Table 3 shows the results of the shear test of the ceramic-steel joint.
ホットプレス後の厚さが２ｍｍの表面層を形成した場合
にはホットプレスの冷却過程で発生する熱応力が母材Ｓ
ｉ３Ｎ４セラミックスの破壊強度を越え母材セラミック
ス内部に亀裂が生じた。When a surface layer with a thickness of 2 mm is formed after hot pressing, the thermal stress generated during the cooling process of hot pressing causes the base material S to
The fracture strength of the i3N4 ceramics was exceeded and cracks occurred inside the base ceramics.
これに対して表面層の厚さが１１１ｎ以下の場合には全
く同一の焼結条件でホットプレスしたにもかかわらず母
材セラミックス内部には亀裂が発生しなかった。この時
母材Ｓｉ３Ｎ４セラミツクスのホットプレス後の厚みが
全ての試料で５ｍｍになるように統一しておいた。銀鑞
付は後の剪断強度は第３表に示す結果となった。On the other hand, when the thickness of the surface layer was 111 nm or less, no cracks were generated inside the ceramic base material even though hot pressing was performed under exactly the same sintering conditions. At this time, the thickness of the base material Si3N4 ceramics after hot pressing was set to be 5 mm for all samples. The shear strength after silver brazing was as shown in Table 3.
第 ３ 表
（発明の効果）
以上説明したように本発明によれば鑞付接着強度の高い
ＳｉｘＮ４を主成分とするセラミックス成形体チ
によって得られる。Table 3 (Effects of the Invention) As explained above, according to the present invention, a ceramic molded body mainly composed of SixN4 having high brazing adhesive strength can be obtained.
手続補正書 昭和−印年９月７日 １、事件の表示 昭和５９ 年 特許 願第１５６１７４号事件よ。Procedural amendment Showa-India September 7th 1.Display of the incident 1982 Patent Application No. 156174.
関係 ね：ｉ’ｒ出願人
４、代理人
居嘲 所 け５３３ ） ＊Ｉ！ｌｉｉ ｉ’ｆｆ
＊ ｉ！川用：ａ′ｔ″ａｌＴＩＪ２０＃１２−５２
４号ユニゾーン新大阪５２４号室
７８、補正の内容
１）明細書中第１３頁の第６表と第１４頁上から１行目
の間に下記文章を追加する。Related: i'r applicant 4, agent Irika Tokoro ke533) *I! lii i'ff
*i! For river: a't''alTIJ20#12-52
No. 4 Unizone Shin-Osaka 524 Room 78 Contents of amendment 1) The following sentence is added between Table 6 on page 13 of the specification and the first line from the top of page 14.
１実施例４
平均粒径０．１μ雇のＳ ｉ ３Ｎ４粉末９０体積チと
平均粒径０．０５μｍのＡ／２０５粉末５体粉末５平積
チ径０．５μｍのＹ２Ｏ３粉末５体積チよりなる粉末を
ボールミルを用いてエチルアルコール中で３日間湿式混
合した。この混合粉末を金型プレスを用いて成形し、こ
の成形体上面にＭＯと上記のＳｉａＮａ−５体積チＡ／
２０５−５体積％Ｙ２Ｏ３混合粉末を第４表に示す割合
で混合した粉末を散布した後、更に軽く圧縮し表面層と
母材５１ｇＮ４セラミツクスを密着させた。この複合体
をＮ２１気圧中１８００℃で圧力を掛けずに焼結した。1 Example 4 Consisting of 90 volumes of S i 3N4 powder with an average particle size of 0.1 μm and 5 volumes of A/205 powder with an average particle size of 0.05 μm, 5 square blocks of Y2O3 powder with a diameter of 0.5 μm. The powder was wet mixed in ethyl alcohol using a ball mill for 3 days. This mixed powder was molded using a mold press, and MO and the above-mentioned SiaNa-5 volumetric silicon A/
After scattering a powder containing 205-5% by volume Y2O3 mixed powder in the ratio shown in Table 4, it was further lightly compressed to bring the surface layer and the base material of 51 g N4 ceramics into close contact. This composite was sintered at 1800°C in N21 atm without pressure.
焼結後の表面層の厚さは０，５膿であった。この表面層
とＨ。The thickness of the surface layer after sintering was 0.5 μm. This surface layer and H.
鋼の間に銀鑞をはさみ均気流中６５０℃で鑞付けを行っ
た。これらのＳ ｉ ３Ｎａセラミックスと鋼の接合体
の剪断試験の結果を第４表に示す。Silver solder was sandwiched between pieces of steel, and brazing was performed at 650°C in a uniform air flow. Table 4 shows the results of shear tests of these S i 3Na ceramic and steel joints.
表面層中に６０体積チ以下のＳｉ３Ｎａを含む試料では
ＳｉａＮａセラミツクスと鋼の接合強度が太きく剪断強
度が１０ Ｋｇ／ｍｒｄを越す試料があった。Among the samples containing 60 volumetric Ti or less of Si3Na in the surface layer, the bonding strength between the SiaNa ceramics and the steel was large, and the shear strength exceeded 10 Kg/mrd in some samples.
この時表面層中のＳｉｘＮ４の含有量によって破断する
部分が異なり表面層中に３０体積チ以下のＳ ｉ ＭＮ
４を含む試料では剪断試験でＳ ｉ ３Ｎ４セラミック
ス母材と表面層の界面で剥離し５１ｇＮ４が３０〜６０
体積チ含まれる試料では表面層中或は銀鑞中で破断した
。表面層中のＳ ｉ ３Ｎ４量が６０体積チを越す試料
では銀鑞と表面層の接着強度が低下するために剪断試験
を行うと銀鑞と表面層の界面で破断し強度が小さかった
。At this time, the part that breaks varies depending on the content of SixN4 in the surface layer.
In the sample containing 4, it peeled off at the interface between the S i 3N4 ceramic base material and the surface layer in a shear test, and 51 gN4 was 30 to 60
In the sample containing volumetric acid, the fracture occurred in the surface layer or in the silver solder. In a sample in which the amount of S i 3N4 in the surface layer exceeds 60 vol. H, the adhesive strength between the silver solder and the surface layer decreases, and when a shear test is performed, the adhesive breaks at the interface between the silver solder and the surface layer, resulting in low strength.
第４表
実施例５
平均粒径０．１μｍ Ｓ ｉ ＭＮ４粉末８５体積ヂと
平均粒径０．１ μｍノＩ’１２０ｂ粉末１０チ、平均
粒径０．５μｍ（ＤＣｅ０２粉末５体積チよりなる粉末
をボールミルを用いてエチルアルコール中で３日間湿式
混合した。この混合粉末を金型プレスを用いて成形しこ
の成形体上面に５０体積チのＮｂと５ｏ体積チの母材Ｓ
ｉ ３Ｎａセラミックスと同一組成の粉末の混合物の
成形体を重ねＮ２１気圧中２００ Ｋｆ／Ｃ，ｌの加圧
下１７００℃でホットプレスした。Table 4 Example 5 Powder consisting of 85 volumes of S i MN4 powder with an average particle size of 0.1 μm, 10 volumes of I'120b powder with an average particle size of 0.1 μm, and 5 volumes of DCe02 powder with an average particle size of 0.5 μm. were wet-mixed in ethyl alcohol using a ball mill for 3 days.The mixed powder was molded using a mold press, and 50 vol. of Nb and 50 vol. of base material S of 50 vol.
A molded body of a mixture of powders having the same composition as i 3Na ceramics was layered and hot pressed at 1700° C. under pressure of 200 Kf/C, l in N21 atmosphere.
第５表
この時表面層成形体の厚さを変化させることによりホッ
トプレス後の表面層の厚さが０．１〜２朋の各種属さに
なるように調整した。この表面層上にＮｉめつきを施し
Ｈ２中９００℃でＮｉ を拡散処理した後、Ｈ２中中５
０℃で鋼に銀鑞付けした。上記Ｓｉ３Ｎ４セラミツクス
と鋼の接合体の剪断試験の結果を第５表に示す。Table 5 At this time, the thickness of the surface layer molded product was varied so that the thickness of the surface layer after hot pressing was adjusted to various thicknesses of 0.1 to 2 mm. After applying Ni plating on this surface layer and performing Ni diffusion treatment in H2 at 900°C,
Silver brazing was carried out on steel at 0°C. Table 5 shows the results of the shear test of the Si3N4 ceramic and steel joint.
ホットプレス後の厚さが２ｍｍの表面層を形成した場合
にはホットプレスの冷却過程で発生する熱応力が母材５
１ｇＮａセラミックスの破壊強度を越え母材セラミック
ス内部に亀裂が生じた。When a surface layer with a thickness of 2 mm is formed after hot pressing, the thermal stress generated during the cooling process of hot pressing is applied to the base material 5.
The fracture strength of the 1gNa ceramic was exceeded, and cracks were generated inside the base ceramic.
これに対して表面層の厚さが１＋＋＋ｍ以下の場合には
全く同一の焼結条件でホットプレスしたにもかかわらず
母材セラミックス内部には亀裂が発生しなかった。この
時母材ＳｉｘＮ４セラミツクスのホットプレス後の厚み
が全ての試料で５＋＋＋ｍになるように統一しておいた
。銀鑞付は後の剪断強度は第５表に示す結果となった。On the other hand, when the thickness of the surface layer was 1+++ m or less, no cracks were generated inside the ceramic base material even though hot pressing was performed under exactly the same sintering conditions. At this time, the thickness of the base material SixN4 ceramics after hot pressing was made uniform for all samples to be 5+++ m. The shear strength after silver brazing was as shown in Table 5.
」 ２、特許請求の範囲を別紙の通りに訂正する。” 2. Amend the claims as shown in the attached sheet.
（１１Ｍｏ 、 Ｎｂ 、 Ｔａ 、 Ｔｉ 、Ｗ）ｉ
種又は２種以上及び／又はＳｉ 、Ｍｏ 、Ｎｂ 、Ｔ
ａ 、Ｔｉ 、 Ｗ、ＡＪ 、Ｍｇ並びに周期律表の■
１族元素の１種又は２種以上とＢ、Ｃ，Ｎ、００１種又
は２種以上を含む化合物群よりなる薄い組成物をその表
面に有することを特徴とするＳｉｘＮａを主成分とする
セラミックス複合組成物。(11Mo, Nb, Ta, Ti, W)i
species or two or more species and/or Si, Mo, Nb, T
a, Ti, W, AJ, Mg and ■ of the periodic table
A ceramic composite mainly composed of SixNa, characterized by having on its surface a thin composition consisting of a compound group containing one or more Group 1 elements and one or more B, C, N, and 001 elements. Composition.
（２１５１ｇＮ４を主成分とするセラミックス表面上の
薄い組成物に含まれている金属単体及び／又は化合物を
、全て原子に換算してＭｏ 、Ｎｂ 、Ｔａ 、 Ｔｉ
。(All elemental metals and/or compounds contained in the thin composition on the ceramic surface whose main component is 2151gN4 are Mo, Nb, Ta, Ti in terms of atoms.
.
Ｗの１種又は２種以上とＳｉのモル比が１以上である特
許請求の範囲第（１）項記載のセラミックス複合組成物
。The ceramic composite composition according to claim 1, wherein the molar ratio of one or more W and Si is 1 or more.
（３１５１ｇＮ４を主成分とするセラミックス表面の薄
い組成物層の厚さが１Ｗｎ以下である特許請求の範囲第
（１）項記載のセラミックス複合組成物。(The ceramic composite composition according to claim (1), wherein the thickness of the thin composition layer on the ceramic surface containing 3151 g N4 as a main component is 1 Wn or less.
（４］ 成形されたＳ ｉ ３Ｎ４を主成分とするセ
ラミックスノ上［ＭＯ，Ｎｂ、Ｔａ、Ｔｉ 、Ｗの１種
又は２種以上の粉末よりなる層、又はＭｏ 、 Ｎｂ
、 Ｔａ 、Ｔｉ 、 Ｗの１種又は２種以上とＳｉｘ
Ｎ４を主成分とするセラミックスの混合粉末よりなる層
を設けしかる後に焼結することを特徴とするセラミック
ス複合組成物の製造法。(4) Molded ceramic sheet containing Si3N4 as the main component [layer consisting of one or more powders of MO, Nb, Ta, Ti, W, or Mo, Nb
, Ta, Ti, and one or more of W and Six
1. A method for producing a ceramic composite composition, which comprises providing a layer made of a mixed ceramic powder containing N4 as a main component and then sintering it.
（５）特許請求の範囲第（４）項に記載のＭｏ 、 Ｎ
ｂ 、Ｔａ 。(5) Mo, N as described in claim (4)
b, Ta.
Ｔｉ、Ｗの１種又は２種以上とＳ ｉ ３Ｎ４を主成分
とするセラミックスの混合粉末よりなる層中に含まれる
金属単体及び／又は化合物を全て原子に換算しテＭｏ、
Ｎｂ、Ｔａ、Ｔｉ、 Ｗの１種又は２種以上とＳｉのモ
ル比が１以上である特許請求の範囲第（４）項記載のセ
ラミックス複合組成物の製造法。All elemental metals and/or compounds contained in a layer made of a mixed powder of ceramics whose main components are one or more of Ti and W and Si3N4 are converted into atoms,
The method for producing a ceramic composite composition according to claim 4, wherein the molar ratio of one or more of Nb, Ta, Ti, and W to Si is 1 or more.
（６）特許請求の範囲第（４）項に記載の焼結を行う際
に加圧しながら焼結する特許請求の範囲第（４）項記載
のセラミックス複合組成物の製造法。(6) A method for producing a ceramic composite composition according to claim (4), in which the sintering according to claim (4) is performed while pressurizing.
（７］ 特許請求の範囲第（４）項に記載の焼結を行
う際に、非酸化性雰囲気中で焼結する特許請求の範囲第
（４）項記載のセラミックス複合組成物の製造法。(7) A method for producing a ceramic composite composition according to claim (4), wherein the sintering according to claim (4) is performed in a non-oxidizing atmosphere.
（８）特許請求の範囲第（４）項に記載のＭｏ 、 Ｎ
ｂ 、 Ｔａ 。(8) Mo, N according to claim (4)
b, Ta.
Ｔｉ 、 Ｗの１種又は２種以上と混合するＳ ｉ ３
Ｎ４を主成分とするセラミックスが母材のＳｉ３Ｎ４を
主成分とするセラミックスと同一組成を持つ特許請求の
範囲第（４）項記載のセラミックス複合組成物の製造法
。S i 3 mixed with one or more of Ti and W
4. The method for producing a ceramic composite composition according to claim 4, wherein the ceramic containing N4 as a main component has the same composition as the base material ceramic containing Si3N4 as a main component.
Claims (8)
及び／又はＳｉ、Ｍｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗ、Ａｌ、
Ｍｇ並びに周期律表のIIIａ族元素の１種又は２種以上
とＢ、Ｃ、Ｎ、Ｏの１種又は２種以上を含む化合物群よ
りなる薄い組成物をその表面に有することを特徴とする
Ｓｉ＿３Ｎ＿４を主成分とするセラミックス複合組成物
。(1) One or more of Mo, Nb, Ta, Ti, W and/or Si, Mo, Nb, Ta, Ti, W, Al,
It is characterized by having on its surface a thin composition consisting of a compound group containing Mg, one or more of Group IIIa elements of the periodic table, and one or more of B, C, N, and O. A ceramic composite composition whose main component is Si_3N_4.
上の薄い組成物に含まれている金属単体及び／又は化合
物を、全て原子に換算してＭｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗ
の１種又は２種以上とＳｉのモル比が１以上である特許
請求の範囲第（１）項記載のセラミックス複合組成物。(2) All metal elements and/or compounds contained in the thin composition on the ceramic surface mainly composed of Si_3N_4 are converted into atoms such as Mo, Nb, Ta, Ti, and W.
The ceramic composite composition according to claim 1, wherein the molar ratio of one or more of the following and Si is 1 or more.
の薄い組成物層の厚さが１ｍｍ以下である特許請求の範
囲第（１）項記載のセラミックス複合組成物。(3) The ceramic composite composition according to claim (1), wherein the thin composition layer on the ceramic surface containing Si_3N_4 as a main component has a thickness of 1 mm or less.
ックスの上にＭｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗの１種又は２
種以上の粉末よりなる層、又はＭｏ、Ｎｂ、Ｔａ、Ｔｉ
、Ｗの１種又は２種以上とＳｉ３Ｎ４を主成分とするセ
ラミックスの混合粉末よりなる層を設けしかる後に焼結
することを特徴とする特許請求の範囲第（１）項記載の
セラミックス複合組成物の製造法。(4) One or two of Mo, Nb, Ta, Ti, and W are placed on the molded ceramic mainly composed of Si_3N_4.
A layer consisting of more than one type of powder, or Mo, Nb, Ta, Ti
The ceramic composite composition according to claim (1), characterized in that a layer is formed of a mixed powder of ceramics whose main components are one or more of W, and Si3N4, and then sintered. manufacturing method.
Ｔａ、Ｔｉ、Ｗの１種又は２種以上とＳｉ＿３Ｎ＿４を
主成分とするセラミックスの混合粉末よりなる層中に含
まれる金属単体及び／又は化合物を全て原子に換算して
Ｍｏ、Ｎｂ、Ｔａ、Ｔｉ、Ｗの１種又は２種以上とＳｉ
のモル比が１以上である特許請求の範囲第（４）項記載
のセラミックス複合組成物の製造法。(5) Mo, Nb according to claim (4),
All elemental metals and/or compounds contained in a layer made of a mixed powder of ceramics whose main components are one or more of Ta, Ti, and W and Si_3N_4 are Mo, Nb, Ta, and Ti in terms of atoms. , one or more types of W and Si
The method for producing a ceramic composite composition according to claim (4), wherein the molar ratio of is 1 or more.
に加圧しながら焼結する特許請求の範囲第（４）項記載
のセラミックス複合組成物の製造法。(6) A method for producing a ceramic composite composition according to claim (4), in which the sintering according to claim (4) is performed while pressurizing.
に、非酸化性雰囲気中で焼結する特許請求の範囲第（４
）項記載のセラミックス複合組成物の製造法。(7) When the sintering described in claim (4) is performed, the sintering is performed in a non-oxidizing atmosphere.
) The method for producing the ceramic composite composition described in item 2.
Ｔａ、Ｔｉ、Ｗの１種又は２種以上と混合するＳｉ＿３
Ｎ＿４を主成分とするセラミックスが母材のＳｉ＿３Ｎ
＿４を主成分とするセラミックスと同一組成を持つ特許
請求の範囲第（４）項記載のセラミックス複合組成物の
製造法。(8) Mo, Nb according to claim (4),
Si_3 mixed with one or more of Ta, Ti, and W
Si_3N base material is ceramics mainly composed of N_4
A method for producing a ceramic composite composition according to claim (4), which has the same composition as the ceramic whose main component is _4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59156174A JPS6140871A (en) | 1984-07-25 | 1984-07-25 | Solderable si3n4 ceramic composite composition and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59156174A JPS6140871A (en) | 1984-07-25 | 1984-07-25 | Solderable si3n4 ceramic composite composition and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6140871A true JPS6140871A (en) | 1986-02-27 |
| JPH044268B2 JPH044268B2 (en) | 1992-01-27 |
Family
ID=15621968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59156174A Granted JPS6140871A (en) | 1984-07-25 | 1984-07-25 | Solderable si3n4 ceramic composite composition and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6140871A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0174376U (en) * | 1987-11-09 | 1989-05-19 | ||
| JPH02153865A (en) * | 1988-12-03 | 1990-06-13 | Ngk Spark Plug Co Ltd | Silicon nitride sintered compact |
| US5164246A (en) * | 1985-09-13 | 1992-11-17 | Kabushiki Kaisha Toshiba | Highly thermoconductive ceramic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5551774A (en) * | 1978-10-06 | 1980-04-15 | Kyoto Ceramic | Composition and method for metallizing nonnoxide ceramic body |
| JPS5551777A (en) * | 1978-10-07 | 1980-04-15 | Ngk Spark Plug Co | Silicon nitride sintered body with metallized surface and its manufacture |
-
1984
- 1984-07-25 JP JP59156174A patent/JPS6140871A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5551774A (en) * | 1978-10-06 | 1980-04-15 | Kyoto Ceramic | Composition and method for metallizing nonnoxide ceramic body |
| JPS5551777A (en) * | 1978-10-07 | 1980-04-15 | Ngk Spark Plug Co | Silicon nitride sintered body with metallized surface and its manufacture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164246A (en) * | 1985-09-13 | 1992-11-17 | Kabushiki Kaisha Toshiba | Highly thermoconductive ceramic |
| JPH0174376U (en) * | 1987-11-09 | 1989-05-19 | ||
| JPH02153865A (en) * | 1988-12-03 | 1990-06-13 | Ngk Spark Plug Co Ltd | Silicon nitride sintered compact |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH044268B2 (en) | 1992-01-27 |
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