JPS62132758A - High heat expansion ceramics - Google Patents
High heat expansion ceramicsInfo
- Publication number
- JPS62132758A JPS62132758A JP60273262A JP27326285A JPS62132758A JP S62132758 A JPS62132758 A JP S62132758A JP 60273262 A JP60273262 A JP 60273262A JP 27326285 A JP27326285 A JP 27326285A JP S62132758 A JPS62132758 A JP S62132758A
- Authority
- JP
- Japan
- Prior art keywords
- thermal expansion
- ceramics
- coefficient
- strength
- ceramic
- 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
Landscapes
- 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、室温から高温にかけて、金属材料、特に、ス
テンレス鋼など同等の熱膨脹係数を有する高熱膨脹セラ
ミックスに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to high thermal expansion ceramics having a coefficient of thermal expansion comparable to that of metallic materials, particularly stainless steel, from room temperature to high temperatures.
近年、金属材料と比較して高温で使用できるなどの理由
から、熱的特性に優れているセラミックスの用途が広が
ってきている。しかし、セラミックスは、加工性、靭性
、耐熱衝撃性などの点で。In recent years, the uses of ceramics, which have excellent thermal properties, have been expanding because they can be used at higher temperatures than metal materials. However, ceramics are inferior in terms of processability, toughness, thermal shock resistance, etc.
まだ問題がある。そのため１例えば、耐熱衝撃性を向上
させるために、低熱膨張セラミックスに関する研究開発
が、従来から、種々行われてきている。また、一方、磁
気ヘッドなどの電子部品や構造部品においては、金属材
料と組み合せて使用されることが多くなってきた。その
ためには、セラミックスと金属材料との複合設計が重要
である。There is still a problem. For this reason, for example, in order to improve thermal shock resistance, various research and developments have been conducted on low thermal expansion ceramics. On the other hand, in electronic parts and structural parts such as magnetic heads, they are increasingly being used in combination with metal materials. For this purpose, a composite design using ceramics and metal materials is important.
しかし、イオン結晶、井有結品よりなるセラミックスと
、金属結晶よりなる金属材料とでは、結晶構造自体が異
なり、それに起因するところの熱膨張は、通常２〜３倍
ぐらい差があり、両者の熱膨張差に起因する接合部のク
ラックの発生（ひいては、破壊に致る）が問題となって
いる。そこで、熱膨張差によって生ずる熱応力を緩和す
る方法が。However, the crystal structure itself is different between ceramics made of ionic crystals and Yukina Iyu and metal materials made of metal crystals, and the thermal expansion caused by this is usually about 2 to 3 times different. The occurrence of cracks (eventually leading to destruction) in the joints due to the difference in thermal expansion has become a problem. Therefore, there is a method to alleviate the thermal stress caused by the difference in thermal expansion.
従来□から種々考えられているが、用いる金属材料と同
等、またはそれに近い熱膨張を有するセラミックスを開
発することが一番有用であると考えられる。Although various ideas have been made in the past, it is thought that the most useful method would be to develop ceramics that have thermal expansion equal to or close to that of the metal material used.
例えば、磁気ヘッドのコアの熱膨脹係数に合わせた磁気
ヘッド用セラミックスが１種々間発されている。特公昭
６０−２９６６８においては、ＴｉＯを主成分とし、Ｂ
ａｄ、５ｉｆｔ、ＮｂｚＯｓ ｍおよびＺｎＯを加える
ことにより、熱膨脹係数値を６〜１２ Ｘ １０−６７
”Ｃの範囲で自由に選択することができ、焼成雰囲気変
化による色むらがなく、機械的強度が高く、ボア分布が
良好であり、フェライト同程度の摩耗性を有し、さらに
は、熱衝撃特性が良いことを特徴とするセラミックスを
提供している。他に磁気ヘッド関連の高熱膨脹セラミッ
クスとしては、特許昭４８−３１２１０．特開昭５０−
５５０６ 。For example, various types of ceramics for magnetic heads have been developed that match the coefficient of thermal expansion of the core of the magnetic head. In Japanese Patent Publication No. 60-29668, TiO is the main component and B
By adding ad, 5ift, NbzOs m and ZnO, the thermal expansion coefficient value is increased from 6 to 12 x 10-67
"C" can be freely selected within the range, there is no color unevenness due to changes in the firing atmosphere, high mechanical strength, good bore distribution, abrasion resistance comparable to ferrite, and furthermore, it has thermal shock resistance. We provide ceramics characterized by good properties.Other examples of high thermal expansion ceramics related to magnetic heads include Patent No. 48-31210 and Japanese Unexamined Patent Publication No. 1983-1989.
5506.
特開昭５２−５７２１８．特開昭５２−１３５３１８．
特開昭６０−２９６６９などがある。Japanese Patent Publication No. 52-57218. Japanese Patent Publication No. 52-135318.
There are Japanese Patent Application Laid-open No. 60-29669, etc.
構造部品用高熱膨脹セラミックスに関しては、エンジン
部品として、特公昭６０−１８６２１では、鋳鉄とほぼ
同等の熱膨脹係数（１０，３ｘ １０−’／℃）を有す
る高強度部分安定化ジルコニアを提供している。断熱性
、機械的強度に優れ（曲げ強さ５９８ＭＰａ）、熱膨張
率の温度特性が金属部品のそれとほぼ同じであることを
特徴としている。Regarding high thermal expansion ceramics for structural parts, Japanese Patent Publication No. 60-18621 provides high-strength partially stabilized zirconia with a thermal expansion coefficient almost equivalent to cast iron (10.3 x 10-'/°C) for engine parts. . It is characterized by excellent heat insulation and mechanical strength (flexural strength of 598 MPa), and temperature characteristics of the coefficient of thermal expansion that are almost the same as those of metal parts.
上記従来例のうち、特公昭６０−２９°６６８の磁気ヘ
ッド関連のセラミックスの熱膨脹係数は、１２×１０−
”／”Ｃ以下であり、フェライトと組み合せるには十分
であるが、炭素鋼（熱膨脹係数は、１３〜１４Ｘ１０″
″Ｂ／”Ｃ） 、合金鋼（熱膨脹係数は、〜２０×１０
−８７℃）、ステンレスｎｉ（熱膨脹係数は、１５〜２
０Ｘ１０″″Ｂ／℃）などと組み合せて、構造部品とし
ての拡大利用を考えると、熱膨脹係数が小さすぎる。ま
た、曲げ強さも、１６０ＭＰａ以下であり、構造部品と
して使用する場合を考えると強度的に不十分である。Among the above conventional examples, the thermal expansion coefficient of ceramics related to the magnetic head of Japanese Patent Publication No. 60-29°668 is 12 x 10-
``/''C or less, which is sufficient for combination with ferrite, but carbon steel (the coefficient of thermal expansion is 13~14X10''
"B/"C), alloy steel (coefficient of thermal expansion is ~20×10
-87℃), stainless steel (thermal expansion coefficient: 15-2
The coefficient of thermal expansion is too small when considering expanded use as a structural component in combination with 0x10''B/℃). Further, the bending strength is 160 MPa or less, which is insufficient in terms of strength when used as a structural component.
また、特公昭６０−１８６２１の構造部品用セラミック
スは１強度的には、高いほうであるが、熱膨脹係数の値
を自由に選択することが困難であるため、特定の金属材
料、すなわち、鋳鉄、としか組み合せられず、その用途
が限定されるという問題があった。また、熱膨脹係数が
１０．３ Ｘ １０−８／℃であるため、上記の特公昭
６０−２９６６８などと同様に。In addition, although the ceramics for structural parts of Japanese Patent Publication No. 60-18621 have a high strength, it is difficult to freely select the value of the coefficient of thermal expansion, so it is difficult to select the value of the coefficient of thermal expansion, so it is difficult to select the value of the coefficient of thermal expansion. There was a problem in that it could only be combined with , and its uses were limited. Also, since the coefficient of thermal expansion is 10.3 x 10-8/°C, it is similar to the above-mentioned Japanese Patent Publication No. 60-29668.
熱膨脹係数が低すぎて、炭素鋼、合金鋼、ステンレス鋼
合金などと組み合わせて利用することが困難である。The coefficient of thermal expansion is too low, making it difficult to use in combination with carbon steel, alloy steel, stainless steel alloy, etc.
〔発明が解決しようとする問題点３
以上のごとく、セラミックスと金属材料とを接合して用
いる場合には、セラミックスの熱膨張率を高め、金属材
料の熱膨張率に近づけることが有用であるが、従来にお
いて、開発された高熱膨脹セラミックスといっても、熱
膨脹係数は、せいぜい１２ Ｘ １０−’／’Ｃ止りで
あり、電子部品用として、また、構造部品用としても、
合金、炭素鋼。[Problem to be solved by the invention 3 As mentioned above, when ceramics and metal materials are bonded together, it is useful to increase the coefficient of thermal expansion of the ceramics so that it approaches the coefficient of thermal expansion of the metal materials. Even though high thermal expansion ceramics have been developed in the past, the coefficient of thermal expansion is no more than 12 x 10-'/'C, and they are not suitable for use in electronic parts or structural parts.
Alloy, carbon steel.
合金鋼、および、ステンレス鋼などと同等な熱膨脹係数
を有するセラミックスの開発が、強く要望されていた。There has been a strong demand for the development of ceramics that have a coefficient of thermal expansion equivalent to that of alloy steel and stainless steel.
本発明の目的は、耐酸化性および強度的にも優れ、金属
材料、例えば鋳鉄、Ｕ鋼、炭素鋼合金鋼、ステンレス鋼
などの鉄鋼、ニッケルおよびその合金、銅およびその合
金、Ｃｏ基合金、およびアルミ合金などの合金と同等、
または、それに近い熱膨張を有する高熱膨脹セラミック
スを提供することにある。The object of the present invention is to use metal materials, such as cast iron, U steel, carbon steel alloy steel, stainless steel, etc., nickel and its alloys, copper and its alloys, Co-based alloys, which have excellent oxidation resistance and strength. and equivalent to alloys such as aluminum alloys,
Another object of the present invention is to provide a high thermal expansion ceramic having a thermal expansion close to that.
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.
熱膨張は、融点、内容量、生成熱などの熱的特性や、結
晶構造、化学結合の強さなどと密接に関係しており、一
般に、次のようなことが言われている。Thermal expansion is closely related to thermal properties such as melting point, content, heat of formation, crystal structure, and strength of chemical bonds, and the following is generally said.
１）融点、生成熱が低い、また、熱容量が大きい物質は
、熱膨張は大きい。1) Substances with low melting point, low heat of formation, and large heat capacity have large thermal expansion.
２）共有結晶、イオン結晶、金属結晶の順で熱膨張が大
きくなる。2) Thermal expansion increases in the order of covalent crystals, ionic crystals, and metal crystals.
３）イオン結晶においては、結合強度の小さい、つまり
、陽イオンの原子価の小さいほど、また、配位数の大き
いほど熱膨張は大きい。3) In an ionic crystal, the smaller the bond strength, that is, the smaller the valence of the cation, and the larger the coordination number, the larger the thermal expansion.
以上のことを鑑みて、イオン結合性のかなり大きい結晶
を有する酸化物、ハロゲン化物の中から、酸化物として
は、８または６酸位構造をとり、熱膨張が比較的大きい
ＣａＦｚ型′構造、ペロブスカイト型構造、ＮａＣＱ型
構造、Ｒｅｄ、型構造など、いずれかをとる酸化物のう
ち、耐水性、耐酸化性に優れ、比較的低温（１４００℃
以下）で焼結可能で、熱膨脹係数が７ Ｘ １０−Ｂ／
’Ｃ（室温〜５００℃）以上あり１機械的特性も優れて
いる７、ｒＯＤ。In view of the above, among oxides and halides that have fairly large crystals with ionic bonding properties, oxides that have an 8- or 6-acid structure and a relatively large thermal expansion CaFz type' structure, Among oxides that have any of the perovskite structure, NaCQ structure, Red structure, etc., they have excellent water resistance and oxidation resistance, and are relatively low temperature (1400℃
) with a coefficient of thermal expansion of 7 x 10-B/
'C (room temperature to 500°C) or higher 1. Mechanical properties are also excellent 7. rOD.
ｌ３ａＴＩＯ：＋と、工業的に汎用性の高いコランダム
型構造のＡＱｚＯａが好ましい、これらの少なくと一種
に、機械的特性は比較的低いが、熱膨脹係数が１５ｘｌ
Ｏ−８／ ”Ｃ以上と金属材料と同等、または、それ以
上の値を示す弗化物のうち、化学的安定性に優れ、融点
が１０００℃以上である、Ｃａ Ｆ ｘ ｅＭ ｇ Ｆ
ｚ、 Ａ Ｑ Ｆａ、 Ｓ ｃ ＦＪＩ、 Ｙ Ｆａ、
およびＬａＦａのような希上超元素弗化物の少なくとも
一種が好ましく、これらを添加し、混合粉末を作成した
。これを加圧成型した後、９００〜１４００℃で０．５
〜３時間保持することにより１強度的にも十分な高熱膨
脹セラミックスを開発した。l3aTIO:+ and AQzOa with corundum type structure which is industrially versatile are preferred; at least one of these has relatively low mechanical properties but has a thermal expansion coefficient of 15xl.
Ca F
z, A Q Fa, S c FJI, Y Fa,
At least one kind of rare superelement fluoride such as and LaFa is preferable, and these were added to prepare a mixed powder. After pressure molding this, 0.5
We have developed a high thermal expansion ceramic that has sufficient strength when held for ~3 hours.
なお、用いる金属酸化物としては部分安定化７、 ｒ
Ｏｚを用いるのが最も望ましく、この隙特に高強度の高
熱膨脹セラミックスが得られる。Note that the metal oxide used is partially stabilized 7, r
It is most preferable to use Oz, as this provides particularly high strength and high thermal expansion ceramics.
さらに、焼結体の粒径は小さいほど、高強度でかつ耐熱
サイクル性が向上する傾向があり、実用上は２μｍ以下
の粒径であることが望ましい。Furthermore, the smaller the grain size of the sintered body, the higher the strength and the better the heat cycle resistance, and for practical purposes, the grain size is preferably 2 μm or less.
なお、この高熱膨脹セラミックスは、弗化物の量を調節
することにより、第３図のように、任意な熱膨脹係数を
得ることができ、また、第４表のように、弗化物の種類
を選ぶことにより、強度が同等でありながら、熱膨脹係
数を種々変えることができる０例えば、ＡＱｔＯｓに対
しＣａＦ２を７５体積割合加えると、熱膨脹係数が１７
ｘ １０６／℃（室温〜５００℃）となり、５ＵＳ３
０８Ｌ（７）熱膨脹係数１７．ＯＸ １０−’／”Ｃ（
室温〜５００℃）と等しいセラミックスとなる。また、
弗化物は、酸化物に比較して比重が小さいため、セラミ
ックスの軽量化にも役立つ。更に、焼結温度を下げるた
め、焼結助剤としても有用である。In addition, by adjusting the amount of fluoride, this high thermal expansion ceramic can obtain an arbitrary coefficient of thermal expansion as shown in Figure 3, and the type of fluoride can be selected as shown in Table 4. By doing so, the coefficient of thermal expansion can be varied while maintaining the same strength. For example, if 75 volume proportion of CaF2 is added to AQtOs, the coefficient of thermal expansion becomes 17.
x 106/℃ (room temperature to 500℃), 5US3
08L (7) Coefficient of thermal expansion 17. OX 10-'/”C(
(room temperature to 500°C). Also,
Fluorides have a lower specific gravity than oxides, so they are useful for reducing the weight of ceramics. Furthermore, it is useful as a sintering aid to lower the sintering temperature.
そして１本発明である高熱膨脹セラミックスを用いて、
周知の方法で、炭素鋼、合金鋼、ステンレス鋼などと接
合することにより、熱膨張差に起因する熱応力の発生を
軽減することができる。また、接合は従来に比べて容易
になり、信頼性の高いセラミックス、金属複合構造部品
が得られる。Using the high thermal expansion ceramics of the present invention,
By joining carbon steel, alloy steel, stainless steel, etc. using a well-known method, it is possible to reduce the occurrence of thermal stress caused by differences in thermal expansion. In addition, joining is easier than in the past, and highly reliable ceramic and metal composite structural parts can be obtained.
また、金属弗化物は、金属との接合の際、ロウ剤として
の働きを持つため、この高熱膨脹セラミックス、金属複
合構造部品の接合部の強度は、従来にくらべて格段と向
上し、より信頼性を高めている。In addition, since metal fluoride acts as a brazing agent when joining metal, the strength of the joints between high thermal expansion ceramics and metal composite structural parts is significantly improved compared to conventional methods, making them more reliable. It enhances sexuality.
また、リング状の前記金属にセラミックスを嵌合する場
合も本発明のセラミックスを用いることにより、セラミ
ックスが熱圧麗により破損するなどのおそれが少ない。Furthermore, when a ceramic is fitted to the ring-shaped metal, by using the ceramic of the present invention, there is less risk of the ceramic being damaged by heat compression.
以下１本発明を実施例に基づき説明する。なお、以下の
実施例で得られたセラミックスの熱膨脹係数、曲げ強さ
、耐酸化性、耐アルカリ性、および耐水性は、下記の方
法により調べた。The present invention will be explained below based on examples. The coefficient of thermal expansion, bending strength, oxidation resistance, alkali resistance, and water resistance of the ceramics obtained in the following examples were examined by the following methods.
熱膨脹係数・・・測定温度範囲は、ステンレス鋼などの
金属材料と接合することを考慮し、室温〜５００℃と決
め、その間の平均熱膨脹係数。Thermal expansion coefficient: The measurement temperature range is determined to be from room temperature to 500°C, taking into account that it will be bonded to metal materials such as stainless steel, and the average thermal expansion coefficient within that range.
曲げ強さ・・・室温において、４点曲げ強さ試験。Bending strength: 4-point bending strength test at room temperature.
耐酸化性・・・１０００℃大気中、２４時間放置後の単
位面積当りの重量変化。Oxidation resistance: Change in weight per unit area after being left in the air at 1000°C for 24 hours.
耐アルカリ性・・・７０℃、３％Ｎａ０１１水溶液中、
１２時間浸漬後の１重量変化。Alkali resistance...70℃, in 3% Na011 aqueous solution,
1 weight change after 12 hours immersion.
耐水性・・・７０℃、純水中、１２時間浸漬後の重量変
化。Water resistance: Change in weight after immersion in pure water at 70°C for 12 hours.
Ａ Ｑ ｚｏｓ、 Ｚ ｒ Ｏｘ、 ＢａＴｉ０ａと
Ｃａ Ｆｚ、 Ｍｇ Ｆｓ。A Q zos, Z r Ox, BaTi0a and Ca Fz, Mg Fs.
Ａ Ｑ Ｆａ、 Ｙ Ｆａ、 Ｌ ａ Ｆｘから選ばれ
た原料粉を第１．２．４表に示した実施例１〜３３の化
学組成を有するように秤量した。弗化物の含有量を１０
〜９０体積割合にしたのは、１０体積割合以下では、熱
膨張増加の効果や接合のロウ剤としてノ効果カ小さく、
一方、９０体積割合以上では、焼結体の実用的強度が得
られないためである７酸化物と弗化物の混合粉末をボー
ルミルに溶媒を加え、数十時間以上粉砕混合させた後、
十分乾燥させ原料粉を作成した。このようにして、酸化
物、弗化物の一方、または１両者の粒径を０．５μｍ以
下とし、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９００〜１４００℃の温度
範囲で圧力３００ｋｇ／ｍｍ” をかけ、０．５〜３時
間保持し、粒径２μｍ以下の焼結体を得た。そして、こ
の焼結体より各試験片を得た。Raw material powders selected from A Q Fa, Y Fa, and La Fx were weighed to have the chemical compositions of Examples 1 to 33 shown in Table 1.2.4. Fluoride content 10
The reason for setting the volume ratio to ~90 is that if the volume ratio is less than 10, the effect of increasing thermal expansion and the effect as a soldering agent for joining will be small.
On the other hand, if the volume ratio exceeds 90, the practical strength of the sintered body cannot be obtained.After adding a solvent to the mixed powder of heptaoxide and fluoride in a ball mill and pulverizing and mixing for more than several tens of hours,
It was thoroughly dried and a raw material powder was prepared. In this way, the particle size of one or both of the oxide and fluoride was reduced to 0.5 μm or less, thereby lowering the sintering temperature and achieving densification. This raw material powder was pressure molded, and the molded body was subjected to a pressure of 300 kg/mm'' in a temperature range of 900 to 1400°C and held for 0.5 to 3 hours to obtain a sintered body with a particle size of 2 μm or less. Each test piece was obtained from this sintered body.
なお、Ｚｒ０ｚ原料粉は、この場合４＋ａｏ１％のＹ２
Ｏ３を含むものを用いたが、Ｚｒ０ｚに対して、Ｙ ｚ
Ｏａを１〜８ｍ０１％添加したものを用いてよい。In addition, the Zr0z raw material powder is 4+ao1% Y2 in this case.
A material containing O3 was used, but compared to Zr0z, Yz
A material to which 1 to 8 m01% of Oa is added may be used.
第１表
ｆ５２ 表
第１表に前記の製法により得られた高熱膨脹セラミック
スの例を実施例１〜１５として示す。比較的１〜５に従
来から熱膨脹係数が大きく実用化されているセラミック
スを示す。実施例１〜１５は、比較例１〜５のいづれよ
りも大きい熱膨脹係数を示した。特に実施例９〜１５は
、熱膨脹係数が１３ Ｘ １０−”／’Ｃ〜１５ Ｘ
１０−８／”Ｃと大きな値を示し、参考例１〜３に示し
た炭素鋼、および。Table 1 f52 Table 1 shows examples of high thermal expansion ceramics obtained by the above manufacturing method as Examples 1 to 15. Ceramics that have been put into practical use and have comparatively large thermal expansion coefficients of 1 to 5 are shown. Examples 1-15 exhibited larger coefficients of thermal expansion than any of Comparative Examples 1-5. In particular, Examples 9 to 15 have thermal expansion coefficients of 13 x 10-''/'C to 15 x
The carbon steels which showed a large value of 10-8/''C and were shown in Reference Examples 1 to 3;
参考例４〜６に示した合金鋼の熱膨脹係数と同等の値を
示した。更に、実施例１〜８は、熱膨脹係数が１５ Ｘ
１０−６／”Ｃ以上の値を示し、参考例７〜１０に示
したステンレス鋼の熱膨脹係数と同等の値を示した。ま
た更に、実施例１〜４は、熱膨脹係数が１７．５ Ｘ
１０−８／’Ｃ以上の値を示し、参考例１１〜１３に示
した合金の熱膨脹係数と同等の値を示した。このことか
ら、炭素鋼、合金鋼、ステンレス鋼など合金のそれぞれ
の熱膨脹係数に合わせて、本発明の高熱膨脹セラミック
スを選ぶことができる。The thermal expansion coefficients were equivalent to those of the alloy steels shown in Reference Examples 4 to 6. Furthermore, Examples 1 to 8 have a thermal expansion coefficient of 15
It showed a value of 10-6/"C or more, and showed a value equivalent to the coefficient of thermal expansion of stainless steel shown in Reference Examples 7 to 10. Furthermore, in Examples 1 to 4, the coefficient of thermal expansion was 17.5
It showed a value of 10-8/'C or more, and a value equivalent to the coefficient of thermal expansion of the alloys shown in Reference Examples 11 to 13. From this, the high thermal expansion ceramics of the present invention can be selected according to the respective thermal expansion coefficients of alloys such as carbon steel, alloy steel, and stainless steel.
第３表
実施例１６〜２３に本発明のセラミックスの耐酸化性、
耐アルカリ性、耐水性を示す。これらは、比較例６〜８
の酸化物のそれに匹敵する。特に、弗化物としてＣａＦ
ｚを用いたものが、すぐれた特性を示す。Table 3 Examples 16 to 23 show the oxidation resistance of the ceramics of the present invention,
Shows alkali resistance and water resistance. These are Comparative Examples 6 to 8
comparable to that of the oxide. In particular, CaF as fluoride
Those using z show excellent characteristics.
第４表
実施例２４〜３０に本発明のセラミックスのうち、曲げ
強さが一般に広く用いられているＡ Ｑ ２０８セラミ
ツクスと同等の３００ Ｍ Ｐ ａ以上であるセラミッ
クスの例を示す。比較例１〜３と比べて、熱膨脹係数に
おいても、更に、曲げ強さにおいても優れている。しか
も、曲げ強さとして実用上充分な３００ Ｍ Ｐ ａ以
上有しながら、弗化物の種類を変えることにより、熱膨
脹係数を１３〜１．８ Ｘ１０−”／’Ｃの間で任意に
変えることができ、参考例７〜８に示したステンレス鋼
と同等の値とすることができる。Examples 24 to 30 of Table 4 show examples of ceramics of the present invention having a bending strength of 300 MPa or more, which is equivalent to AQ 208 ceramics, which is generally widely used. Compared with Comparative Examples 1 to 3, it is excellent in both the coefficient of thermal expansion and the bending strength. Furthermore, while having a bending strength of 300 MPa or more, which is sufficient for practical use, by changing the type of fluoride, the coefficient of thermal expansion can be arbitrarily changed between 13 and 1.8 X10-''/'C. It is possible to obtain a value equivalent to that of the stainless steel shown in Reference Examples 7 and 8.
第３図に、Ｚｒ０ｚ粉末に加えるＣａＦｚ粉末の体積割
合を種々に変えた場合の室温〜５００℃の熱膨張曲線を
示す。例えば、Ｓ Ｕ Ｓ ３０８ Ｔ、と同等な熱膨
脹係数を有するセラミックスが所望の場合、第３図から
ＺｒＯ２に６７体積割合のＣａＦｚを加えた原料粉を前
記の要領で製造すれば、実施例２５に示したように熱膨
脹係数が５ＵＳ３０８Ｌと同等な１７ Ｘ Ｌ ０−８
７℃を有するセラミックスを得ろことができろ。FIG. 3 shows thermal expansion curves from room temperature to 500° C. when the volume ratio of CaFz powder added to Zr0z powder is varied. For example, if a ceramic having a coefficient of thermal expansion equivalent to that of SUS 308 T is desired, if raw material powder containing ZrO2 and CaFz at a volume ratio of 67% is produced in the manner described above from FIG. 3, Example 25 can be obtained. As shown, the thermal expansion coefficient is equivalent to 5US308L, 17 X L 0-8
It is possible to obtain ceramics having a temperature of 7°C.
このように、炭素鋼、合金鋼、ステンレス鋼、などの金
属材料と複合利用を考える場合、相手側の金属材料の熱
膨脹係数が分かれば、その値と一致するように、酸化物
と弗化物を混ぜる険を容易に選ぶことができる。また、
このセラミックスの熱ｖ３脹係数の熱サイクルによる変
化は、Ｑ 、 ５ ％以下である６例えば、実施例２
５と参考例８の温度変化による熱膨張曲線の履歴の差は
、最大５％以下であった。これらのことより、接合する
ための加熱、冷却時にひずみの発生を極力おさえて接合
することができ、接合後、接合部は、熱サイクルに対し
て、信頼性のあるものができた。In this way, when considering combined use with metal materials such as carbon steel, alloy steel, and stainless steel, if the thermal expansion coefficient of the other metal material is known, oxides and fluorides can be used to match that value. You can easily choose the risks to mix. Also,
The change in the thermal v3 expansion coefficient of this ceramic due to thermal cycles is Q, 5% or less6 For example, Example 2
The difference in the history of thermal expansion curves due to temperature changes between Sample No. 5 and Reference Example 8 was 5% or less at maximum. As a result of these factors, it was possible to join with as little strain as possible during heating and cooling for joining, and after joining, the joint was able to be reliable against thermal cycles.
第４図は第３図で得られたＺ ｒ Ｏｚｌ Ｃａ ＦＺ
系系統上セラミックス室温における曲げ強度、および熱
膨強率の類似した鉄系材料（ＳｔＪＳ、鋳鉄など）と接
合した時の接合部の曲げ強度を示す。Figure 4 shows the Z r Ozl Ca FZ obtained in Figure 3.
Based on the system, the bending strength of ceramics at room temperature and the bending strength of the joint when joined to iron-based materials with similar thermal expansion coefficients (StJS, cast iron, etc.) are shown.
複合セラミックスの曲げ強度はＣａＦ２重と共に低下す
るが、ＣａＦｚ７５％以下では構造用部材としての実用
レベルの３００ Ｍ Ｐ ａ以上であり、また、９０％
以下では電子材料、電子部品に必要な２００ Ｍ Ｐ
ａ以上の強度を持つが、ＣａＦｚが９０％を越えると強
度は急激に低下する。一方、接合部の曲げ強度はＣａＦ
ｚが１０ｖｏ１％以上で実用上充分な大きさを持つが、
これはＣａＦｚのロウ剤としての働きによるものである
。なお、ＣａＦｚ８０％以上で接合部の強度がセラミッ
クスに一致し、ＣａＦｚ量と共に低下するが、これは接
合部強度がセラミックスの強度に支配されるためである
。同様な傾向が他の酸化物や弗化物との組合せの際にも
認められた。The bending strength of composite ceramics decreases with CaF2, but when CaFz is 75% or less, it is 300 MPa or more, which is the practical level for structural members, and 90%
The following is the 200MP required for electronic materials and electronic parts.
It has a strength of more than a, but the strength decreases rapidly when CaFz exceeds 90%. On the other hand, the bending strength of the joint is CaF
When z is 10vo1% or more, it has a sufficient size for practical use, but
This is due to the function of CaFz as a brazing agent. Note that the strength of the joint matches that of ceramics when CaFz is 80% or more, and decreases with the amount of CaFz, because the strength of the joint is dominated by the strength of ceramics. Similar trends were observed in combination with other oxides and fluorides.
また、第５表は本発明の複合セラミックスを各種金属に
接合した時の接合強度及び室温５００℃の熱サイクルを
１００回行った後の接合強度を示している。Further, Table 5 shows the bonding strength when the composite ceramic of the present invention was bonded to various metals and the bonding strength after 100 thermal cycles at room temperature of 500°C.
なお、高熱膨脹セラミックス・金属複合構造部品を作成
するに当り、次の接合方法を採用した。The following joining method was used to create the high thermal expansion ceramic/metal composite structural parts.
ステンレス鋼、または、炭素鋼などの鉄系金属と接合す
る場合、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。When joining with ferrous metals such as stainless steel or carbon steel, a Ti/Ni alloy is deposited on the metal surface,
Pressure bonding is performed with ceramics at a temperature of 1000 to 1300°C in a vacuum.
銅合金との接合は、表面にカオリン及び硫化鋼を含むペ
ースト（カオリン：硫化鋼＝１：１）を塗布し、Ｎ ｘ
＋ Ｈｚ気流中１０００〜１３００℃の温度でセラミ
ックスと圧着する。Ｎｉ基、または、ｃｏＪ＆合金との
接合は、表面を平滑に研摩したセラミックスを真空中１
０００〜１３００℃の温度で圧着する。上記メタライズ
を利用する以外にも、ステンレス鋼箔や各合金箔をイン
サート材として真空加熱圧着したり、加工に高精度が要
求されるが焼ばめ法を用いてもよい。For joining with copper alloy, apply a paste containing kaolin and sulfide steel (kaolin: sulfide steel = 1:1) to the surface, and apply N x
Pressure bonding with ceramics at a temperature of 1000-1300°C in +Hz air flow. For bonding with Ni-based or coJ&alloy, ceramics with a smooth surface are ground in vacuum.
Pressure bonding is carried out at a temperature of 000 to 1300°C. In addition to using the above-mentioned metallization, stainless steel foil or various alloy foils may be vacuum-heated and pressed as insert materials, or shrink-fitting may be used, although high accuracy is required for processing.
次に本発明のセラミックスと金属材料とを接合した複合
構造部品の実施例を第１図に示す。Next, FIG. 1 shows an example of a composite structural component in which ceramics and metal materials of the present invention are bonded.
第１図は、炭素ｍ製の金属スリーブ２２の内側に、Ｚｒ
０ｚとＣａＦｘ（体積割合は、Ｚｒ０ｚ：Ｃａ Ｆａ＝
４５ ： ５５）とからなる本発明のセラミックスより
作成されたライナー２１を焼ばめ法により嵌合して、シ
リンダーライナーを作った。このシリンダーライナーに
室温５００℃の熱負荷を１０００回繰り返すテストを行
った。テスト後、シリンダーライナーを点検したが、ス
リーブ２２とライナー２１間には、なんら異状はなく、
クラックの発生、および欠落も、無かった。なお、本発
明の高熱膨脹セラミックスは、平均粒径が２μｍ以下で
あるので、摺動に対し結晶粒の剥離が起りにくく、作動
時のクリアランスの増大による効率の低下を防げる。ま
た、大気中１０００℃に加熱しても、両部材は、剥れな
かった。これより、耐酸化性、耐摩耗性にもすぐれてい
るので、ライナーの材質に適している。In FIG. 1, Zr is placed inside a metal sleeve 22 made of carbon m.
0z and CaFx (volume ratio is Zr0z:CaFa=
A cylinder liner was made by fitting the liner 21 made of the ceramic of the present invention consisting of 45:55) by a shrink fit method. This cylinder liner was subjected to a test in which a heat load at a room temperature of 500°C was repeated 1000 times. After the test, the cylinder liner was inspected and there was no abnormality between the sleeve 22 and liner 21.
There were no cracks or defects. In addition, since the high thermal expansion ceramic of the present invention has an average grain size of 2 μm or less, crystal grains are less likely to peel off due to sliding, and a decrease in efficiency due to an increase in clearance during operation can be prevented. Further, even when heated to 1000° C. in the atmosphere, both members did not peel off. It also has excellent oxidation resistance and abrasion resistance, making it suitable as a material for liners.
また第２図は、実施例７のセラミックにより成るバルブ
シート３１を作成し、ＳＵＳ ３１６＠バルブ・ステム
３２との間にＴ ｉ ／ Ｎ ｉ合金箔を挟み、真空中
１０００℃で熱圧着して、高熱膨脹セラミックス・金属
複合体の排気バルブを作成した。このバルブをディーゼ
ルエンジンに組み込み、ガス温度を９００℃まで上昇さ
せて１０００時間エンジンテストを行った。テスト後、
バルブを調べた結果なんら異常は見られなかった。通常
、排気バルブの受熱の７０％は、燃焼ガスからの熱をバ
ルブシートに受け、また、高負荷運転時には、８００℃
を超える排気にさらされる。金属材料に比べて、熱伝導
率が低いため、バルブシート面積を大きくしても、バル
ブ温度上昇をおさえることができ、バルブ自体の慣性重
量の増加も、金属材料に比べて軽量にできる。Fig. 2 shows a valve seat 31 made of the ceramic of Example 7, a Ti/Ni alloy foil sandwiched between it and SUS 316@valve stem 32, and thermocompression bonded at 1000°C in vacuum. , created an exhaust valve made of high thermal expansion ceramic/metal composite. This valve was installed in a diesel engine, and an engine test was conducted for 1000 hours with the gas temperature raised to 900°C. After the test,
An inspection of the valve revealed no abnormalities. Normally, 70% of the heat received by an exhaust valve is received by the valve seat from the combustion gas, and during high-load operation, 70% of the heat received by the exhaust valve is 800℃.
exposed to exhaust gases exceeding Since it has lower thermal conductivity than metal materials, it is possible to suppress the rise in valve temperature even if the valve seat area is increased, and the increase in inertial weight of the valve itself can be reduced compared to metal materials.
第１表の実施例１に用いた原料粉末を混合し、粒径０．
５μｍ以下に粉枠した時、衆知のプラズマ溶射法を用い
て、第５図に示すように、５ＵＳ３１６ 製バルブ４２
の表面に溶射して、溶射膜４１を形成した。この実施例
では、バルブ材と溶射膜の熱膨張率がきわめて良く一致
しているため、従来の溶射膜（一般にＺｒＯ，）に較べ
て、格段に耐熱サイクル性の良い、セラミックス被覆バ
ルブが得られた。The raw material powders used in Example 1 in Table 1 were mixed and the particle size was 0.
When powdered to a size of 5 μm or less, a bulb 42 made of 5US316 was coated using a well-known plasma spraying method, as shown in Figure 5.
A sprayed film 41 was formed by thermal spraying on the surface of. In this example, since the coefficients of thermal expansion of the valve material and the thermally sprayed film match extremely well, a ceramic-coated valve with much better heat cycle resistance than a conventional thermally sprayed film (generally ZrO) can be obtained. Ta.
以上のように、本発明のセラミックスを用いた構造部品
は、従来と比べて優れており、内燃機関のシリンダー、
シリンダーライナー、ピストン、ピストン・ヘッド、タ
ーボチャージャー、ロッカーアーム、カム、タペット、
ベアリング等に有用である。また、ＩＣパッケージ基板
磁気ヘッド止め具等電子部品、バーナー、ブロワ−１お
よび、骨、歯に代わり得る生体材料としても有用である
。As described above, the structural parts using ceramics of the present invention are superior to conventional ones, and are suitable for use in internal combustion engine cylinders,
Cylinder liner, piston, piston head, turbocharger, rocker arm, cam, tappet,
Useful for bearings, etc. It is also useful as an electronic component such as an IC package substrate magnetic head stopper, a burner, a blower 1, and a biomaterial that can replace bones and teeth.
本発明のセラミックスは、炭素鋼、合金鋼、ステンレス
など、２種金属と同等の熱膨脹係数を示すので、セラミ
ックスと金属との一体構造において、熱応力に基づくり
クラックの発生しにくいものを提供でき、セラミックス
、金属複合構造物の信頼性を大幅に高めることができる
。Since the ceramic of the present invention exhibits a coefficient of thermal expansion equivalent to that of two types of metals such as carbon steel, alloy steel, and stainless steel, it is possible to provide an integrated structure of ceramic and metal that is less prone to cracking due to thermal stress. , ceramics, and the reliability of metal composite structures can be greatly improved.
第１図は、本発明の一実施例であるセラミック・金属複
合体より成るシリンダーライナーの斜視図、第２，５図
は、本発明の一実施例であるセラミック・金属複合体よ
り成る排気用バルブの斜視図、第３，４図は１本発明の
実施例のセラミックスの特性とＣａＦｚ含有量との関係
を示す曲線図である。Fig. 1 is a perspective view of a cylinder liner made of a ceramic-metal composite which is an embodiment of the present invention, and Figs. 2 and 5 are a perspective view of a cylinder liner made of a ceramic-metal composite which is an embodiment of the present invention. The perspective view of the bulb and FIGS. 3 and 4 are curve diagrams showing the relationship between the characteristics of the ceramic and the CaFz content in one embodiment of the present invention.
Claims (1)
炭化物及び硼化物の少なくとも１種と、（ｂ）金属の弗
化物１０〜９０体積％とからなる焼結体であることを特
徴とする高熱膨脹セラミックス。 ２、前記酸化物は、（ａ）Ａｌ＿２Ｏ＿３、ＺｒＯ＿２
、およびＢａＴｉＯ＿３の少なくとも一種、及び前記弗
化物は（ｂ）ＣａＦ＿２、ＭｇＦ＿２、ＡｌＦ＿３、Ｓ
ｃＦ＿３、ＹＦ＿３および、ＬａＦ＿３の少なくとも１
種からなる特許請求の範囲第１項に記載の高熱膨脹セラ
ミックス。 ３、特許請求の範囲第１項又は第２項において、室温〜
５００℃間の熱膨脹係数が、１５×１０＾−＾３／℃以
上であることを特徴とする高熱膨脹セラミックス。 ４、特許請求の範囲第１項において、焼結体の平均結晶
粒径が２μｍ以下であることを特徴とする高熱膨脹セラ
ミックス。[Claims] 1. The composition before sintering is (a) oxide, nitride, silicide,
A high thermal expansion ceramic characterized by being a sintered body comprising at least one of a carbide and a boride, and (b) 10 to 90% by volume of a metal fluoride. 2. The oxide is (a) Al_2O_3, ZrO_2
, and at least one of BaTiO_3, and the fluoride is (b) CaF_2, MgF_2, AlF_3, S
at least one of cF_3, YF_3 and LaF_3
A high thermal expansion ceramic according to claim 1, comprising seeds. 3. In claim 1 or 2, room temperature to
A high thermal expansion ceramic characterized by having a coefficient of thermal expansion at 500°C of 15×10^-^3/°C or more. 4. The high thermal expansion ceramic according to claim 1, characterized in that the average crystal grain size of the sintered body is 2 μm or less.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60273262A JPS62132758A (en) | 1985-12-06 | 1985-12-06 | High heat expansion ceramics |
| 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 |
| 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. |
| 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 |
|---|---|---|---|
| JP60273262A JPS62132758A (en) | 1985-12-06 | 1985-12-06 | High heat expansion ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62132758A true JPS62132758A (en) | 1987-06-16 |
| JPH0419182B2 JPH0419182B2 (en) | 1992-03-30 |
Family
ID=17525377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60273262A Granted JPS62132758A (en) | 1985-12-06 | 1985-12-06 | High heat expansion ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62132758A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012206913A (en) * | 2011-03-30 | 2012-10-25 | Ngk Insulators Ltd | Magnesium fluoride-sintered body, method for manufacturing the same, and member for semiconductor manufacturing apparatus |
| CN108218407A (en) * | 2018-01-24 | 2018-06-29 | 烟台金泰美林科技股份有限公司 | A kind of valve alumina composite ceramic and preparation method thereof |
-
1985
- 1985-12-06 JP JP60273262A patent/JPS62132758A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012206913A (en) * | 2011-03-30 | 2012-10-25 | Ngk Insulators Ltd | Magnesium fluoride-sintered body, method for manufacturing the same, and member for semiconductor manufacturing apparatus |
| CN108218407A (en) * | 2018-01-24 | 2018-06-29 | 烟台金泰美林科技股份有限公司 | A kind of valve alumina composite ceramic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0419182B2 (en) | 1992-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4485150A (en) | Metal ceramics composites and a method for producing said composites | |
| KR890002695B1 (en) | High thermal expansion coefficient ceramic sinter and composite body of the same and metal | |
| JPS5852451A (en) | Heat-resistant and heat-insulating light alloy member and its manufacture | |
| JPS6018621B2 (en) | engine parts | |
| JP2002538302A (en) | High temperature erosion resistant and wear resistant composite thermal barrier coating | |
| US4698271A (en) | Copper-silver-titanium filler metal for direct brazing of structural ceramics | |
| US4704338A (en) | Steel bonded dense silicon nitride compositions and method for their fabrication | |
| JPS58194782A (en) | Composite material coating material and application to article | |
| JPS62132758A (en) | High heat expansion ceramics | |
| JPH0515781B2 (en) | ||
| JPS6293359A (en) | Ceramic coating | |
| JPS61159566A (en) | Coating method of metallic or ceramic base material | |
| JPH0250994B2 (en) | ||
| JPH04147957A (en) | Heat insulating aluminum-based member | |
| JPH01184261A (en) | Ceramic heat-insulating member | |
| CN110643918A (en) | Coating material for internal combustion engine cylinder, preparation method thereof and internal combustion engine cylinder | |
| JPS63161150A (en) | Formation of heat insulating thermally sprayed layer | |
| JPS6046962A (en) | Sintering part | |
| JP3221180B2 (en) | Ceramic-metal bonded body and method of manufacturing the same | |
| JPS646274B2 (en) | ||
| JP3394844B2 (en) | Heat resistant material | |
| Hadian | Joining of silicon nitride-to-silicon nitride and to molybdenum for high-temperature applications | |
| JPH0673522A (en) | Heat insulating thermal spraying material | |
| JPS629768A (en) | Joining method for ceramics and metal | |
| JP3255354B2 (en) | Ceramic structure |