JPS62178331A - Composite structure of ceramics and metal - Google Patents
Composite structure of ceramics and metalInfo
- Publication number
- JPS62178331A JPS62178331A JP61020126A JP2012686A JPS62178331A JP S62178331 A JPS62178331 A JP S62178331A JP 61020126 A JP61020126 A JP 61020126A JP 2012686 A JP2012686 A JP 2012686A JP S62178331 A JPS62178331 A JP S62178331A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- ceramics
- composite structure
- ceramic
- thermal expansion
- 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
- 239000000919 ceramic Substances 0.000 title claims description 57
- 239000002131 composite material Substances 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 title claims description 21
- 239000002184 metal Substances 0.000 title claims description 19
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 24
- 239000007769 metal material Substances 0.000 claims description 24
- 238000005452 bending Methods 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 229910001018 Cast iron Inorganic materials 0.000 claims description 3
- 229910001208 Crucible steel Inorganic materials 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000002905 metal composite material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005382 thermal cycling Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- -1 rFz* Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Oxide Ceramics (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、金属弗化物を含んだセラミックスを用いた。[Detailed description of the invention] [Industrial application field] The present invention uses ceramics containing metal fluoride.
熱的環境下において信頼性のあるセラミックス・金属複
合構造物に関する。Concerning ceramic-metal composite structures that are reliable under thermal environments.
金属材料と比較して耐熱性、耐食性など、熱的、化学的
性質の点で優れているセラミックスは、近年、その使用
用途によっては、金属材料と代替するようになり、また
、機器の性能の限界を向上させるために使用されてきて
いる。しかし、セラミックスは、靭性が低く加工性が悪
いなどの点で金属材料に比べて劣っている。この問題に
対処するため、構造物において耐熱、耐食性などが必要
とされている部分には、セラミックスを、また、靭性や
、複雑形状が要求される部分には、金属材料を使用する
方法が提案され一部実用化されてきている。Ceramics have superior thermal and chemical properties such as heat resistance and corrosion resistance compared to metal materials. It has been used to improve the limits. However, ceramics are inferior to metal materials in terms of low toughness and poor workability. To address this problem, a method has been proposed in which ceramics are used for parts of structures that require heat resistance and corrosion resistance, and metal materials are used for parts that require toughness and complex shapes. Some of them have been put into practical use.
上記のセラミックスと金属材料からなる複合構造物を開
発するにあたり、異種材料間の接合部にス
おける熱膨張などの熱的性質の差心に十分注意を払わな
ければならないが、従来知られているセラミックスの熱
膨張係数は、約１３ ｘ １０−”／℃以下程度であり
、例えば、汎用性の高い金属性材料であるステンレス鋼
などと比較して小さい、このため、実用上接合部におけ
る熱膨張係数に差がありすぎ、熱的環境下においてされ
に起因する接合部のクラックの発生などの問題が発生し
ている。In developing the above-mentioned composite structures made of ceramics and metal materials, it is necessary to pay sufficient attention to the differences in thermal properties such as thermal expansion at the joints between different materials. The coefficient of thermal expansion of ceramics is about 13 x 10-"/°C or less, which is smaller than that of stainless steel, which is a highly versatile metallic material. Therefore, in practice, thermal expansion at joints is difficult. There are too many differences in the coefficients, leading to problems such as cracks in the joints due to cracking in a thermal environment.
例えば、従来は接合方法として、セラミックス表面にメ
タライソングを施し、Ｎｉメッキ等を行って、この上に
金属部材をロウ付して接合する方法などが採用されてい
るが、工程が煩雑であったり、また、熱膨張差に起因し
た破損がおこりやすかった。For example, conventional bonding methods include applying a metal lysong to the ceramic surface, plating with Ni, etc., and then brazing a metal member on top of this, but the process is complicated and Furthermore, damage caused by the difference in thermal expansion was likely to occur.
従来、セラミックスにおいて比較的大きい熱膨張係数を
有するものと′して、電子部品関連しては、Ｔ ｉ Ｏ
ｘ系（特開昭５６−１２７９２１、特開昭５７−１９１
２７２）や構造部品関連では、Ｚｒ０ｚ系（特開昭５８
−４９６６３ 、特開昭５７−１９１２７４）等がある
が、これらの熱膨張係数は、 １３ ｘ １０−’／’
Ｃ以下であり。Conventionally, T i O has been used in electronic components as a ceramic having a relatively large coefficient of thermal expansion.
x series (JP-A-56-127921, JP-A-57-191
272) and structural parts, the Zr0z series (JP-A-58
-49663, JP-A-57-191274), etc., but the thermal expansion coefficient of these is 13 x 10-'/'
C or lower.
ステンレス鋼等との接合に適用した場合、信頼性の高い
セラミックス・金属複合構造物を得ることは困難である
。When applied to bonding with stainless steel, etc., it is difficult to obtain a highly reliable ceramic-metal composite structure.
以上のごとく、鋳鉄、鋳鋼、炭素鋼、合金鋼、ステンレ
ス鋼などの鉄鋼、Ｎｉ及びその合金、銅及びその合金、
Ｃｏ基合金、アルミ合金、又はＦｅ系、Ｃｏ系、Ｎｉ系
アモルファス合金等の金属材料とセラミックスとの信頼
性の高い複合構造物は、今のところ開発されておらず、
その開発が強く要望されていた。As mentioned above, steel such as cast iron, cast steel, carbon steel, alloy steel, stainless steel, Ni and its alloys, copper and its alloys,
A highly reliable composite structure of ceramics and metal materials such as Co-based alloys, aluminum alloys, or Fe-based, Co-based, or Ni-based amorphous alloys has not been developed so far.
Its development was strongly requested.
本発明の目的は、耐食性、耐熱性、強度的に優れたセラ
ミックスと上記金属材料からなる高信頼性の複合構造物
を提供することにある。An object of the present invention is to provide a highly reliable composite structure made of ceramics excellent in corrosion resistance, heat resistance, and strength, and the above metal materials.
上記目的を達成するため、以下の手段を用いた。 In order to achieve the above objective, the following means were used.
本発明のセラミックスと金属材料との複合構造物は、セ
ラミックス部が、金属酸化物と、金属弗化物の混合相か
らなり、室温〜５００℃の範囲で熱膨張係数が１０〜２
０ ｘ １０−’／’Ｃの範囲にあり、金属材料部が鋳
鉄、鋳鋼、炭素鋼、合金鋼、ステンレス鋼などの鉄鋼、
Ｎｉ及びその合金、Ｃｕ及びその合金、Ｃｏ基合金アル
ミ合金、又は、Ｆｅ系、Ｃｏ系、Ｎｉ系、アモルファス
合金などの金属であることを特徴としている。In the composite structure of ceramics and metal materials of the present invention, the ceramic portion is composed of a mixed phase of metal oxide and metal fluoride, and has a coefficient of thermal expansion of 10 to 2 in the range of room temperature to 500°C.
It is in the range of 0 x 10-'/'C, and the metal material part is cast iron, cast steel, carbon steel, alloy steel, stainless steel, etc.
It is characterized by being made of metals such as Ni and alloys thereof, Cu and alloys thereof, Co-based alloys, aluminum alloys, Fe-based, Co-based, Ni-based, and amorphous alloys.
本発明者達の検討の結果、金属弗化物との金属酸化物の
粉末を粒径１μｍ以下に粉砕混合したものを焼結すれば
、比較的大きな強度を有し、且つ、熱膨張係数が１０〜
２０ ｘ １０−６／’Ｃと上記金属材料と同等の値を
示す複合焼結体が得れることが判った。なお、金属弗化
物として、弗素と構成金属元素の電気陰性度の差が２．
５以上の金属弗化物、例えば、ＭｇＦｚ、ＣａＦｚ、５
ｒＦｚ＊などのアルカリ類金屓の弗化物やＬａＦｓ、Ｃ
ｅＦｓなどの横木類の弗化物を用いると、その金属弗化
物のイオン結合性が強いことから熱膨張係数が比較的大
きく、上記の金属弗化物と金属酸化物から成るセラミッ
クス部において、比較的強度が小さい金属弗化物の組成
比を小さくすることができるため、好ましい。As a result of the studies conducted by the present inventors, it has been found that sintering a powder mixture of metal oxide and metal fluoride to a particle size of 1 μm or less has relatively high strength and a coefficient of thermal expansion of 10 ~
It was found that a composite sintered body having a value of 20 x 10-6/'C, which is equivalent to that of the above-mentioned metal material, could be obtained. As a metal fluoride, the difference in electronegativity between fluorine and the constituent metal elements is 2.
5 or more metal fluorides, such as MgFz, CaFz, 5
Fluorides of alkali metals such as rFz*, LaFs, C
When using a crosspiece fluoride such as eFs, the thermal expansion coefficient is relatively large due to the strong ionic bonding of the metal fluoride, and the ceramic part made of the metal fluoride and metal oxide described above has a relatively high strength. This is preferable because the composition ratio of the metal fluoride having a small value can be made small.
また、この複合焼結体を周知に方法で、熱膨張係数の類
似した前記金属材料と接合することにより、熱的環境下
で信頼性の高いセラミックス・金属複合構造物が得られ
ることがわかった。この時、セラミックス中の弗化物は
のり剤の効果を持ち、金属と特に強固な結合を形成する
ことが可能である。Furthermore, it was found that by joining this composite sintered body with the aforementioned metal material having a similar coefficient of thermal expansion using a well-known method, a ceramic-metal composite structure that is highly reliable in a thermal environment can be obtained. . At this time, the fluoride in the ceramic has the effect of a glue agent and can form a particularly strong bond with the metal.
なお１本発明のセラミックスの熱膨張係数は可変であり
、セラミック部における金属弗化物の種類、添加量を調
整することにより容易に、金属材料部の熱膨張係数に近
づけることができ、簡単に信頼性の高いセラミックス・
金属複合構造物でがきる。Note that the coefficient of thermal expansion of the ceramic of the present invention is variable, and by adjusting the type and amount of metal fluoride added in the ceramic part, it can be easily made close to the coefficient of thermal expansion of the metal material part, making it easy and reliable. High quality ceramics
Made of metal composite structures.
また、金属弗化物を加えることによって、金属酸化物が
有する好ましくない特性を一部改善することできる。例
えば、Ｚｒ０ｚの耐熱衝撃性、熱疲労特性に劣る欠点な
どを金属弗化物添加により向上させ得る。Furthermore, by adding a metal fluoride, some of the unfavorable characteristics of metal oxides can be improved. For example, the drawbacks of Zr0z, such as poor thermal shock resistance and thermal fatigue properties, can be improved by adding metal fluoride.
セラミックスの熱膨張係数を１０〜２０Ｘ１０−’／’
Ｃ（室温〜５００℃）としたのは、熱膨張係数がこの範
囲より低いと、一般に使用されている金属材料、例えば
、ステンレス鋼などの鉄鋼とセラミックスとの熱膨張係
数の差が大きすぎ、接合部の信頼性が低下する。また、
この範囲以上であれば、セラミックス部における金属弗
化物の含有量が多くなりすぎ、実用的な強度が得られな
い、なお、接合部の強度としては、構造用セラミックス
として広く利用されているＡ１１ａｙｓ並みの３００Ｍ
Ｐａ以上であることが特に望ましい。The thermal expansion coefficient of ceramics is 10 to 20X10-'/'
C (room temperature to 500°C) is because if the coefficient of thermal expansion is lower than this range, the difference in coefficient of thermal expansion between commonly used metal materials, such as steel such as stainless steel, and ceramics is too large. Joint reliability decreases. Also,
If it exceeds this range, the content of metal fluoride in the ceramic part will be too high and practical strength will not be obtained.The strength of the joint part is comparable to that of A11ays, which is widely used as a structural ceramic. 300M
It is particularly desirable that it is Pa or higher.
なお、金属弗化物の含有量を１０〜９０体積割合にした
のは、１０体積割合未満では、熱膨張増加の効果や、接
合時の３３剤としての効果が小さく、一方９０体積割合
より大では焼結体の実用的強度が得られないからである
。The reason why the content of metal fluoride is set to 10 to 90 volume ratio is that if the volume ratio is less than 10 volume, the effect of increasing thermal expansion or as a 33 agent during bonding will be small, while if the volume ratio is higher than 90 volume, the effect will be small. This is because the practical strength of the sintered body cannot be obtained.
また、セラミックス部と金属部の接合温度は。Also, what is the bonding temperature between the ceramic part and the metal part?
接合部の耐熱性、金属部の軟化を考慮した、５００℃付
近が適当であり、よって熱膨張係数の温度範囲は、室温
から５００℃までとし、この範囲で熱膨係数が１０〜２
０ Ｘ １０−６／℃であることが必要である。Considering the heat resistance of the joint and the softening of the metal part, a temperature around 500°C is appropriate.Therefore, the temperature range of the coefficient of thermal expansion should be from room temperature to 500°C, and within this range the coefficient of thermal expansion should be 10 to 2.
It is necessary that the temperature is 0 x 10-6/°C.
なお、この複合構造物において、金属材料部にステンレ
ス鋼を用いれば強度や耐食性に優れた複合構造物ができ
、また、Ｎｉ基合金、Ｃｏ基合金を用いれば強度、耐熱
性に優れた複合構造物ができる。In addition, in this composite structure, if stainless steel is used for the metal material part, a composite structure with excellent strength and corrosion resistance can be obtained, and if Ni-based alloy or Co-based alloy is used, a composite structure with excellent strength and heat resistance can be obtained. I can make things.
なお、この複合構造物において、セラミックス部におけ
る金属弗化物としてＣａ Ｆｚｅ Ｓ ｃ ＦｓｔＳｒ
Ｆ＊を用いれば耐食性に優れた複合構造物ができ、Ｃａ
Ｆａ、５ｒＦｚ、ＹｂＦａ、５ｃＦｓ。In addition, in this composite structure, Ca Fze S c FstSr is used as the metal fluoride in the ceramic part.
By using F*, composite structures with excellent corrosion resistance can be created, and Ca
Fa, 5rFz, YbFa, 5cFs.
ＣｅＦｓｅ ＮｄＦｓｅ ＳｍＦａ、ＥｕＦａを用いれ
ば。If CeFse NdFse SmFa, EuFa is used.
耐熱性に優れ５機械的強度のある複合構造物ができる。A composite structure with excellent heat resistance and mechanical strength can be produced.
以下実施例に基づき説明する。 The following will be explained based on examples.
以下の実施例で得られたセラミックス及びセラミックス
金属複合構造物の熱膨張係数１曲げ強さ、耐食性は下記
の方法により調べた。The thermal expansion coefficient 1 bending strength and corrosion resistance of the ceramics and ceramic-metal composite structures obtained in the following examples were examined by the following methods.
熱膨張係数・・・測定温度範囲は、５００℃付近で、セ
ラミックスと金属材料とを接合することを考慮し、室温
〜５００℃と決め、その間のセラミックスの平均熱膨張
係数を求めた。Thermal expansion coefficient: The measurement temperature range was set at around 500° C. Considering the bonding of ceramics and metal materials, it was determined to be from room temperature to 500° C., and the average thermal expansion coefficient of the ceramics was determined in that range.
曲げ強さ・・・室温において、４点曲げ強さ試験片方法
により求めた。接合部の曲げ強さを測定する場合には、
セラミック部と金属材料部の体積割合が等しくなるよう
試験片を作製し、接合部をスパンの中心にして４点曲げ
強さ試験を行った。Bending strength: Determined at room temperature using a 4-point bending strength test piece method. When measuring the bending strength of joints,
A test piece was prepared so that the volume ratio of the ceramic part and the metal material part was equal, and a four-point bending strength test was conducted with the joint part as the center of the span.
耐食性・・・３０％ＮａＯＨ水溶液中に、セラミックス
部を８０℃下に２４時間浸漬した後、表面状態の変化を
調べた。Corrosion resistance: After the ceramic part was immersed in a 30% NaOH aqueous solution at 80°C for 24 hours, changes in the surface condition were examined.
実施例１゜
５ｒＦｚ及び７．ｒＯｚ （ＹｚＯａ３ｍｏｕ％含有）
の粉末を所定量秤量し、ボールミルに溶媒を加え、数十
時間以上混合粉砕させた後、十分乾燥させ原料粉を作成
した。Example 1°5rFz and 7. rOz (contains 3mou% of YzOa)
A predetermined amount of the powder was weighed, a solvent was added to a ball mill, the mixture was mixed and ground for several tens of hours, and then thoroughly dried to prepare a raw material powder.
上記の方法により得られた原料粉の粒径は、１μｍ以下
であり、この粉砕により焼結温度の低下緻密化を図った
。この原料粉を加圧成形し、この成形体を１０００℃〜
１４００℃の温度範囲で。The particle size of the raw material powder obtained by the above method was 1 μm or less, and by this pulverization, the sintering temperature was lowered and the powder was densified. This raw material powder is pressure-molded, and the molded body is heated to 1000℃~
In a temperature range of 1400℃.
３０ＭＰａ以上の加圧で１〜３時間保持し、粒径２μｍ
以下の焼結体を得た。得られたセラミックスの室温から
５００℃の範囲の熱膨張係数及び。Hold for 1 to 3 hours under pressure of 30 MPa or more, particle size 2 μm
The following sintered body was obtained. The coefficient of thermal expansion of the obtained ceramics ranges from room temperature to 500°C.
室温の曲げ強さ及び、室温１０００℃の熱サイクルを１
００回おこなった後の室温での曲げ強さを第１表に示す
。Bending strength at room temperature and thermal cycle at room temperature 1000℃
Table 1 shows the bending strength at room temperature after 00 cycles.
また、得られたセラミックスと表面にＮｉメッキしたス
テンレス鋼（ＳＵＳ３０４）とを、真空中、１１００℃
で３０ｍ１ｎ圧着したセラミックス・金属複合構造につ
いて、接合部の室温での曲げ強さ、及び、室温５００℃
の熱サイクルを１００回行った後の曲げ強さを表に示す
、実施例走１〜３のセラミックス・金属複合構造物の接
合部は、熱サイクル後において、外観上なんら異状は、
認められなく、その室温での曲げ強さは、熱サイクル前
後において、参考例と比べて変化が小さく。In addition, the obtained ceramics and stainless steel (SUS304) whose surface was plated with Ni were heated at 1100°C in a vacuum.
The bending strength of the joint at room temperature and the bending strength at room temperature of 500°C for the ceramic-metal composite structure crimped to 30m1n at
The bending strength after 100 thermal cycles is shown in the table. The joints of the ceramic/metal composite structures of Examples 1 to 3 showed no abnormality in appearance after the thermal cycling.
No change was observed in the bending strength at room temperature before and after thermal cycling compared to the reference example.
実用上の強度を維持している。Maintains practical strength.
実施例２
実施例１と同様な方法により、金属弗化物として、５ｒ
Ｆｚ、ＥｕＦｇ＊ ５ｃＦａ、ＣａＦｚｅＳｍＦｓ、Ｎ
ｄ Ｆａ、Ｃｓ Ｆａ、ＹｂＦｓを用いたセミツクス金
属複合構造物を作製した。なお、この複合構造物の金属
材料部は、熱膨張係数が１０〜２０ ｘ １０−’／’
Ｃである金属材料を選び、また、これに対するセラミッ
クス部として、上記金属弗化物とＺｒ０ｚよりなり、金
属材料部と熱膨張係数が等しいか、違いが２ Ｘ １０
−６／’Ｃ以下になるように組成比を調整した。得られ
たセラミックスの熱膨張係数、接合部の曲げ強さ、熱サ
イクル（室温５００℃）を１００回繰り返した後の室温
での曲げ強さ、耐食性を第２表に示す、実施例４〜１１
における、熱サイクル後の曲げ強さの低下は、参考例３
に比べてはるかに小さく、また、参考例４，５は、熱サ
イクル後、接合部がはがれたのに対し、実施例４〜１１
は、接合部は、外観上異状はなかった。Example 2 5r was prepared as a metal fluoride by the same method as in Example 1.
Fz, EuFg* 5cFa, CaFzeSmFs, N
A semi-metal composite structure using dFa, CsFa, and YbFs was fabricated. The metal material portion of this composite structure has a thermal expansion coefficient of 10 to 20 x 10-'/'
A metal material C is selected, and the ceramic part thereof is made of the metal fluoride and Zr0z, and the coefficient of thermal expansion is the same as that of the metal material part, or the difference is 2 x 10.
The composition ratio was adjusted to be -6/'C or less. Table 2 shows the coefficient of thermal expansion of the obtained ceramics, the bending strength of the joint, the bending strength at room temperature after repeating the thermal cycle (room temperature 500°C) 100 times, and the corrosion resistance of Examples 4 to 11.
The decrease in bending strength after thermal cycling in Reference Example 3
In addition, in Reference Examples 4 and 5, the joint part peeled off after the thermal cycle, whereas in Examples 4 to 11
There was no apparent abnormality in the joint.
実施例３
実施例１と同様な方法により、金属弗化物としてＣａＦ
ｚを、また金属酸化物のうち、ＭｇＯ。Example 3 CaF was used as a metal fluoride by the same method as in Example 1.
z, and among metal oxides, MgO.
Ｇ ｅ Ｏｗ、 Ｆ ｅ Ｏｓ、ＷＯａ、ＣａＴｉ０ａ
＋ＭｇＦａｚＯａ。G e Ow, F e Os, WOa, CaTi0a
+MgFazOa.
のいずれかを用いたセラミックスより成るセラミックス
・金属複合構造物を作製した。なお、この複合構造物の
金属材料部としては、熱膨張係数が１０〜２０ Ｘ １
０−６／’Ｃである金属材料を選び。A ceramic-metal composite structure was fabricated using either of the above. The metal material part of this composite structure has a coefficient of thermal expansion of 10 to 20 x 1
Select a metal material with a temperature of 0-6/'C.
また、これに対するセラミックスとして、ＣａＦｚと上
記金属酸化物よりなり、金属材料部と熱膨張係数が等し
いか、違いが２ Ｘ １０−８／℃以下になるように組
成比を＊ｍｔ、たものを選んだ。得られたセラミックス
の熱膨張係数、接合部の曲げ強さ、熱サイクル（室温５
００”Ｃ）を１００回繰り返した後の室温での曲げ強さ
、を第３表に示す。実施例１２〜１７は、表２の実施例
４〜１１と同様に、参考例３〜５に比べて、接合部にお
ける熱応力及び熱サイクル疲労に強いものになっている
。In addition, ceramics for this purpose are made of CaFz and the above-mentioned metal oxides, and the composition ratio is *mt so that the coefficient of thermal expansion is the same as that of the metal material part, or the difference is 2 x 10-8/℃ or less. I chose. Thermal expansion coefficient of the obtained ceramics, bending strength of the joint, thermal cycle (room temperature 5
Table 3 shows the bending strength at room temperature after repeating 00''C) 100 times. In comparison, it is resistant to thermal stress and thermal cycle fatigue at the joint.
実施例４
金属弗化物としてＣａＦｚを、また、金属酸化物として
ＺｒＯｘ （ＹｚＯａ ：３＋＋ｏＱ％含有）とから成
るセラミックス複合材料をインサート材として。Example 4 A ceramic composite material consisting of CaFz as a metal fluoride and ZrOx (containing YzOa: 3++oQ%) as a metal oxide was used as an insert material.
ＳＵＳ ３１０とＺｒ５ｉＯ番とを加熱圧着した。SUS 310 and Zr5iO were heat-pressed.
ＣａＦｚの含有量が’１０ｖｏＱ％、２０ｖｏＱ％の２
種類の組成比より成る。それぞれの厚さがｌｌ１ｗ１の
インサート材をＳＵＳ ３１０とＺｒ５ｉＯ番の間に挟
み込み１０００℃で６０分間真空中で圧着した。2 with CaFz content of '10voQ% and 20voQ%
It consists of different composition ratios. Insert materials each having a thickness of ll1w1 were sandwiched between SUS 310 and Zr5iO and pressed together in a vacuum at 1000° C. for 60 minutes.
ＳＵＳ ３１０の熱膨張係数が１９ Ｘ １０−’／”
Ｃであるのに対し、ＺｒＳｉＯ４の熱膨張係数は、４．
２Ｘ１０−８／”Ｃと大きな差があるため、通常、接合
物は熱的環境下では、クラックが生じやすく、使用でき
ない。そのため、本発明では、金属弗化物の含有量が異
なるインサート材を２枚挟みこみ接合部の熱膨張係数に
勾配を付けることにより、耐熱サイクルの特性を改善さ
せ、熱応力に対する信頼性を向上させた。熱サイクル試
験後、接合部には、なんら異状が認められなかった。ま
た、曲げ試験による破壊も接合部ではなく、Ｚｒ５ｉＯ
ａ側で起った。同様な方法でアルミ合金とＡ １１ ｚ
ＯａとをＡ Ｉｌ Ｆ ａ／ Ａ Ｑ ２０ ｇより
成るインサート材を用いて６００℃３０分間加熱圧着さ
せた。アルミ合金の熱膨係数は、２３ ｘ １０−６／
”Ｃであり、Ａｇ２Ｏ３の熱膨張係数は７ Ｘ １０−
８／’Ｃと大きな差があるが、ＡＩＦｇを含むインサー
ト材を用いて接合することにより、上記と同様、破壊は
、ＡＱｚＯａ側で起こり、接合部の信頼性が向上した。The thermal expansion coefficient of SUS 310 is 19 x 10-'/”
C, whereas the thermal expansion coefficient of ZrSiO4 is 4.
2X10-8/"C, the bonded material is normally susceptible to cracking in a thermal environment and cannot be used. Therefore, in the present invention, two insert materials with different metal fluoride contents are used. By adding a gradient to the coefficient of thermal expansion of the sandwiched joint, we improved the heat cycle characteristics and increased the reliability against thermal stress.After the heat cycle test, no abnormalities were observed in the joint. Furthermore, the fracture caused by the bending test was not caused by the joint, but by the Zr5iO
It happened on side a. Aluminum alloy and A 11 z in the same way
Oa was heat-pressed at 600° C. for 30 minutes using an insert material consisting of 20 g of A Il Fa / A Q . The thermal expansion coefficient of aluminum alloy is 23 x 10-6/
"C, and the thermal expansion coefficient of Ag2O3 is 7 x 10-
Although there is a large difference from 8/'C, by joining using an insert material containing AIFg, the fracture occurred on the AQzOa side as in the above, and the reliability of the joint was improved.
なお、複合構造物において、セラミックス部を熱膨張係
数が小さい非酸化物系１例えば、ＳｒＣ。In addition, in the composite structure, the ceramic part is made of a non-oxide material 1 having a small coefficient of thermal expansion, for example, SrC.
５ｉａＮ４やサイアロン等とすることもできる。5iaN4, Sialon, etc. may also be used.
実施例５
第１表＆２の組成比を有する５ｒＦｚとＺｒＯｚ（Ｙｚ
Ｏａ３ｍｏＱ％含有）から成るセラミックスを実施例１
と同様な方法で作製し、第１図に示すようなセラミック
ス２と５ｔ７Ｓ３１６，１から成るバルブを作製した。Example 5 5rFz and ZrOz (Yz
Example 1 Ceramics consisting of Oa3moQ%
A bulb made of ceramic 2 and 5t7S316,1 as shown in FIG.
セラミックスと金属の接合には、焼ばめ法を用いたが、
この他の方法として、金属表面にＴ ｉ ／ Ｎ ｉ合
金を蒸着し、真空中、１０００〜１３００℃の温度でセ
ラミックスと圧着する方法、又は、金属を銅合金とした
場合、ペースト（カオリン：硫酸銅＝１ ： ｌ）をＮ
ｚ ＋ Ｈｘ気流中１０００〜１３００℃の温度で圧
着する方法を採ってもよい。得られたセラミックス・金
属複合構造を有するバルブにおいて金属棒１を回転軸と
してセラミックス円板２に約９００℃の排気ガスが当た
るようにし、ターボチャージャーのスクロール部内に設
置し、排気ガスの速さをコントロールできるようにし、
１０００時間エンジンテストを行った。テスト後バルブ
の接合部を調べた結果、異状は見られなかった。Shrink fit was used to join ceramics and metal, but
Other methods include vapor-depositing a Ti/Ni alloy on the metal surface and press-bonding it with ceramics at a temperature of 1000 to 1300°C in a vacuum, or when the metal is a copper alloy, using a paste (kaolin: sulfuric acid). Copper = 1: l) to N
A method of pressure bonding at a temperature of 1000 to 1300° C. in a z + Hx air flow may be adopted. In the valve having the obtained ceramic/metal composite structure, the exhaust gas at about 900°C hits the ceramic disk 2 using the metal rod 1 as the rotation axis, and is installed inside the scroll part of the turbocharger to control the speed of the exhaust gas. to be in control,
A 1000 hour engine test was conducted. After the test, the valve joints were inspected and no abnormalities were found.
本発明によれば、セラミック・金属複合構造物のセラミ
ックス部において、金属弗化物と金属酸化物よりなるセ
ラミックスを用いれば、金属材料部との接合強度が高く
、信頼性の高いセラミックス・金属複合構造物が得られ
、この結果として構造用セラミックスの適用用途が大幅
に拡大する。According to the present invention, if a ceramic made of a metal fluoride and a metal oxide is used in the ceramic part of a ceramic-metal composite structure, the bonding strength with the metal material part is high, and a highly reliable ceramic-metal composite structure can be obtained. As a result, the applications of structural ceramics are greatly expanded.
第１図は１本発明によるセラミックス・金属複合構造物
であるバルブの斜視図である。
１・・・金属、２・・・セラミックス。FIG. 1 is a perspective view of a valve which is a ceramic-metal composite structure according to the present invention. 1...Metal, 2...Ceramics.
Claims (1)
熱膨張係数が１０〜２０×１０＾−＾６／℃であるセラ
ミックスと金属とから成る複合構造物。 ２、特許請求の範囲第１項において、上記金属弗化物が
、弗素と構成金属元素との電気陰性度の差が２．５以上
である金属弗化物の内の少なくとも一つからなることを
特徴とするセラミックスと金属との複合構造物。 ３、特許請求の範囲第１項において、上記金属が鋳鉄、
鋳鋼、炭素鋼、合金鋼、ステンレス鋼などの鉄鋼、ニッ
ケル及びその合返、鋼及びその合金、Ｃｏ基合金、アル
ミ合金、又は、Ｆｅ系、Ｃｏ系、又はＮｉ系アモルファ
ス合金から選ばれることを特徴とするセラミックスと金
属との複合構造物。 ４、特許請求の範囲第１項、又は、第２項において、上
記セラミックス中の上記金属弗化物の含有率が１０〜９
０体積割合であることを特徴とするセラミックスと金属
との複合構造物。 ５、特許請求の範囲第１項において、上記セラミックス
の曲げ強さが３００ＭＰａ以上であることを特徴とする
セラミックスと金属との複合構造物。 ６、特許請求の範囲第１項において、セラミックスと金
属材料の熱膨張係数の差が２．０× １０＾−＾６／℃以下であることを特徴とするセラミッ
クスと金属との複合構造物。[Scope of Claims] 1. A composite structure made of ceramics and metal, which is mainly composed of a mixture of metal fluoride and metal oxide and has a coefficient of thermal expansion of 10 to 20 x 10^-^6/°C. 2. Claim 1, characterized in that the metal fluoride comprises at least one metal fluoride in which the difference in electronegativity between fluorine and the constituent metal elements is 2.5 or more. A composite structure of ceramics and metal. 3. In claim 1, the metal is cast iron,
Selected from iron steel such as cast steel, carbon steel, alloy steel, and stainless steel, nickel and its alloys, steel and its alloys, Co-based alloys, aluminum alloys, or Fe-based, Co-based, or Ni-based amorphous alloys. A composite structure of ceramics and metal. 4. Claim 1 or 2, wherein the content of the metal fluoride in the ceramic is 10 to 9.
A composite structure of ceramics and metal characterized by a volume ratio of 0. 5. A composite structure of ceramics and metal according to claim 1, wherein the ceramic has a bending strength of 300 MPa or more. 6. A composite structure of ceramics and metal according to claim 1, characterized in that the difference in coefficient of thermal expansion between the ceramic and the metal material is 2.0×10^-^6/°C or less.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020126A JPS62178331A (en) | 1986-02-03 | 1986-02-03 | Composite structure of ceramics and metal |
| DE8686309404T DE3681566D1 (en) | 1985-12-06 | 1986-12-03 | Ceramic sinter with high thermal expansion coefficient and a composite body made of the same and metal. |
| KR1019860010319A KR890002695B1 (en) | 1985-12-06 | 1986-12-03 | High thermal expansion coefficient ceramic sinter and composite body of the same and metal |
| EP86309404A EP0225781B1 (en) | 1985-12-06 | 1986-12-03 | High thermal expansion coefficient ceramic sinter and a composite body of the same and metal |
| US06/938,796 US5043305A (en) | 1985-12-06 | 1986-12-08 | High thermal expansion coefficient ceramic sinter and a composite body of the same and metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61020126A JPS62178331A (en) | 1986-02-03 | 1986-02-03 | Composite structure of ceramics and metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62178331A true JPS62178331A (en) | 1987-08-05 |
Family
ID=12018425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61020126A Pending JPS62178331A (en) | 1985-12-06 | 1986-02-03 | Composite structure of ceramics and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62178331A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02165943A (en) * | 1988-12-20 | 1990-06-26 | Seiko Instr Inc | Adhering method for metal-ceramics |
| KR100851518B1 (en) * | 2007-02-13 | 2008-08-11 | 오조니아인터내쇼날 | Ozone generator and an electrode therefor |
-
1986
- 1986-02-03 JP JP61020126A patent/JPS62178331A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02165943A (en) * | 1988-12-20 | 1990-06-26 | Seiko Instr Inc | Adhering method for metal-ceramics |
| KR100851518B1 (en) * | 2007-02-13 | 2008-08-11 | 오조니아인터내쇼날 | Ozone generator and an electrode therefor |
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