JPH0284242A - Manufacture of complexed material of ceramic and metal - Google Patents
Manufacture of complexed material of ceramic and metalInfo
- Publication number
- JPH0284242A JPH0284242A JP9762589A JP9762589A JPH0284242A JP H0284242 A JPH0284242 A JP H0284242A JP 9762589 A JP9762589 A JP 9762589A JP 9762589 A JP9762589 A JP 9762589A JP H0284242 A JPH0284242 A JP H0284242A
- Authority
- JP
- Japan
- Prior art keywords
- molded body
- layer
- ceramic
- ceramic molded
- metal
- 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 abstract description 138
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 105
- 239000002184 metal Substances 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 title description 7
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 229910000679 solder Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims description 40
- 239000002131 composite material Substances 0.000 claims description 28
- 230000035939 shock Effects 0.000 claims description 25
- 238000005266 casting Methods 0.000 claims description 23
- 238000005336 cracking Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 abstract description 7
- 230000008023 solidification Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 126
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 9
- 238000011835 investigation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 229910001060 Gray iron Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910001018 Cast iron Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910001296 Malleable iron Inorganic materials 0.000 description 1
- 229910017309 Mo—Mn Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はセラミックスと金属との複合体の製造方法に関
し、詳しくはセラミックスを溶融金属で鋳包んで構成さ
れる複合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a composite of ceramics and metal, and more particularly to a method for manufacturing a composite formed by casting ceramics with molten metal.
［従来の技術］
周知のようにセラミックスは、耐摩耗性や耐熱性に秀れ
た機能を発揮するが１強度が弱く、特に耐衝撃が劣ると
いう問題を抱えている。而してかかる問題を解決するた
めに金属製の基材の表面にセラミックスを固着し、前記
金属製の基材で前記セラミックスの強度、脆さ等を補強
することによっでセラミックスの利用範囲を拡げる試み
が近年積極的に行われている。[Prior Art] As is well known, ceramics exhibit excellent functions such as wear resistance and heat resistance, but suffer from the problem of low strength and particularly poor impact resistance. In order to solve this problem, the scope of use of ceramics has been expanded by fixing ceramics on the surface of a metal base material and reinforcing the strength, brittleness, etc. of the ceramics with the metal base material. Attempts to expand this field have been actively made in recent years.
前記固着方法としては、有機系あるいは無機系の接着剤
、又はろう材等を用いて接着固定する方法、超高圧法、
活性金属法５爆着法等で代表されるセラミックスと金属
との直接接合方法、ボルト締め、焼嵌め等による機械的
接合方法、及びセラミックスを溶融金属で鋳包み接合す
る方法などが一般的に知られている。The fixing method includes a method of adhesively fixing using an organic or inorganic adhesive or a brazing material, an ultra-high pressure method,
Activated metal method 5 Direct joining methods of ceramics and metals, such as the explosion bonding method, mechanical joining methods such as bolting and shrink fitting, and methods of joining ceramics by casting and joining them with molten metal are generally known. It is being
前述した固着方法において鋳包みは、複雑な形状への対
応が容易にできる上に、製造された製品の耐熱性が高く
、コストも低置で、しかも用いる金属種別による複合化
の機能を最大限に発揮できるなど多くの秀れた効果があ
る。ところがこの鋳包みでは、セラミックスと金属の熱
膨張率が著しく異なることから溶融金属の鋳造〜冷却過
程で熱応力が発生したり、また溶融金属鋳造時の急激な
熱衝撃でセラミックスの破損が頻発し、さらにセラミッ
クスと金属間に収縮差によるガタッキが発生し易く、こ
の結果接合強度も低いものとなりがちであるなどの問題
があり、実用化への大きな障害となっていた。Among the above-mentioned fixing methods, cast-in can easily handle complex shapes, the manufactured products have high heat resistance, are low in cost, and can maximize the functionality of composites depending on the type of metal used. It has many excellent effects, including: However, with this cast-in, thermal stress occurs during the casting and cooling process of the molten metal because the coefficient of thermal expansion of the ceramic and the metal is significantly different, and ceramics often break due to sudden thermal shock during casting of the molten metal. Furthermore, there are other problems such as looseness due to shrinkage difference between the ceramic and the metal, which tends to result in low bonding strength, which has been a major obstacle to practical application.
このため従来においても、例えば特開昭６２−２７５５
６２号公報で示されるように熱膨張率の差を吸収する弾
性の耐火性物質を用いた材料で取り囲んで溶融金属を注
入することによって前記熱衝撃を吸収する技術、特開昭
６２−２１４８６３号公報で示されるようにセラミック
ス成形体にほぼ一定間隔で貫通孔を設けて溶融金属を注
入することによりセラミックスと金属の接合強度を高め
る技術、特開昭６１−１７６４６２号公報で示されるよ
うに中空セラミックス成形体の外側に、鋳造される溶融
金属と同村又は同系材の金属製薄肉材を密着配置したの
ち溶融金属を注入して複合化する技術、等が提案されて
いる。For this reason, in the past, for example, Japanese Patent Application Laid-Open No. 62-2755
As shown in Japanese Patent Laid-Open No. 62-214863, a technique for absorbing the thermal shock by injecting molten metal into a surrounding material using an elastic fire-resistant material that absorbs the difference in coefficient of thermal expansion, as shown in Japanese Patent Application Laid-Open No. 62-214863 As shown in the publication, a technique to increase the bonding strength between ceramic and metal by providing through holes in a ceramic molded body at approximately regular intervals and injecting molten metal; A technique has been proposed in which a thin metal material of the same size or similar type as the molten metal to be cast is closely placed on the outside of a ceramic molded body, and then the molten metal is injected to form a composite.
しかしながらこのような従来技術ではいずれもコストの
高騰に繋がる上に、接合強度は満足すべきものとならず
、また耐熱性の点でも問題が多かった。However, all of these conventional techniques lead to an increase in cost, have unsatisfactory bonding strength, and have many problems in terms of heat resistance.
［発明が解決しようとする課題］
本発明は、セラミックスを溶融金属で鋳包んだ複合体を
製造するにあたり、前述した従来の鋳包み接合方法にお
ける問題点の抜本的な解決を図ることによって鋳包みの
特徴を最大限に発揮せしめることを目的とするものであ
る。[Problems to be Solved by the Invention] The present invention aims to fundamentally solve the problems in the conventional cast-in joining method described above when producing a composite body in which ceramics are cast in molten metal. The purpose is to maximize the characteristics of
［課題を解決するための手段］
本発明は、所定形状に成形されたセラミックス成形体を
、鋳型内に装着固定した後溶融金属を注入し、前記セラ
ミックス成形体を金属で鋳包むセラミックスと金属との
複合体製造方法において、前記セラミックス成形体の表
面に、層厚が０．００５〜２．４５＋ｍのソルダー層と
０．０５〜６．０ＩＩＩ１１のセラミックス系水性スラ
リー層とからなる中間層を、その総厚が０．０５５〜６
．００５ｍｍとなるよう形成し、乾燥処理した後、鋳型
内に装着固定することを特徴とするセラミックスと金属
との複合体製造方法に関し、また前記複合体製造方法に
おいて、予め、溶融金属とセラミックス成形体の種別毎
に、前記中間層厚と鋳包み時の熱衝撃割れ発生限界予熱
温度との関係を求めておき、セラミックス成形体を詩型
内に装着固定した後、当該鋳包み条件と前記割れ発生限
界予熱温度との関係より設定される予熱温度でセラミッ
クス成形体を予熱し、しかる後溶融金属を注入すること
を特徴とするものである。[Means for Solving the Problems] The present invention provides a method for combining ceramics and metal, in which a ceramic molded body formed into a predetermined shape is mounted and fixed in a mold, and then molten metal is injected, and the ceramic molded body is cast with metal. In the method for manufacturing a composite, an intermediate layer consisting of a solder layer having a thickness of 0.005 to 2.45+m and a ceramic aqueous slurry layer having a thickness of 0.05 to 6.0 m is provided on the surface of the ceramic molded body. Total thickness is 0.055~6
．． 0.005 mm, drying, and then mounting and fixing in a mold. For each type, the relationship between the intermediate layer thickness and the critical preheating temperature for thermal shock cracking during cast-in is determined, and after the ceramic molded body is installed and fixed in the mold, the relationship between the casting conditions and the crack occurrence is determined. The method is characterized in that the ceramic molded body is preheated at a preheating temperature set in relation to the limit preheating temperature, and then molten metal is injected.
［作用］
第１図は本発明の基本的な構成を説明するための断面構
造図である。本例は湾曲中空管の製造方法の一例を示す
もので、１が前記湾曲中空管状に形成されたセラミック
ス成形体である。このセラミックス成形体１の外表面に
は、第２図に示すようにソルダー層２とスラリー層３と
からなる中間層４が形成されている。ソルダー層２とし
ては、例えば酸化銅（Ｃｕ２０）とＳｉＯ２の混合物に
スクリーンオイルを添加混練したペーストを刷毛塗り、
あるいはスクリーン印刷したのち乾燥し、大気中で１０
００〜１１００℃に加熱する周知の酸化銅法によって形
成されるＣｕ、ＯとＳｉＯ□の酸化物のソルダー層、あ
るいはＭｏ−Ｍｎメタライズ法により形成される金属の
ソルダー層、あるいはＴｉ−Ｎｉ、Ｔｉ−Ｃｒ等の粉末
を塗布して形成される金属のソルダー層等を適用するこ
とができる。スラリー層３は前記ソルダー層２の上面、
つまり外表面に形成され、例えば５ｉｎ２． Ａ ｎ、
０３． Ｚｒ○３２等のセラミックス系の水性スラリー
を塗布して形成される。スラリー層３が形成されたセラ
ミックス成形体ｌは、後述する鋳包みの際における明渠
防止およびスラリー自体の接合による形状保持を狙いと
して、例えば大気中に放置して自然乾燥させるか、ある
いは加熱炉等で強制的に乾燥させ、スラリー層３の脱水
処理を行う。[Operation] FIG. 1 is a cross-sectional structural diagram for explaining the basic configuration of the present invention. This example shows an example of a method for manufacturing a curved hollow tube, and 1 is a ceramic molded body formed into the shape of the curved hollow tube. An intermediate layer 4 consisting of a solder layer 2 and a slurry layer 3 is formed on the outer surface of the ceramic molded body 1, as shown in FIG. As the solder layer 2, for example, a paste made by adding and kneading screen oil to a mixture of copper oxide (Cu20) and SiO2 is applied by brushing,
Alternatively, after screen printing, dry it in the atmosphere for 10 minutes.
A solder layer of Cu, O and SiO□ oxides formed by the well-known copper oxide method heated to 00 to 1100°C, or a metal solder layer formed by the Mo-Mn metallization method, or a Ti-Ni, Ti A metal solder layer formed by applying powder such as -Cr or the like can be applied. The slurry layer 3 is the upper surface of the solder layer 2,
That is, it is formed on the outer surface, for example, 5in2. An,
03. It is formed by applying a ceramic-based aqueous slurry such as Zr○32. The ceramic molded body l on which the slurry layer 3 has been formed is, for example, left in the air to dry naturally, or heated in a heating furnace, etc., with the aim of preventing spillage during casting and maintaining the shape by bonding the slurry itself, which will be described later. The slurry layer 3 is forcibly dried and dehydrated.
このような処理を終えたセラミックス成形体１は第１図
に示すように鋳型１１内に装着され、固定される。尚、
第１図において１２は中子であり、非鋳包み部への溶融
金属５０の流入を防止しつつ、前記セラミックス成形体
１を鋳型１１内で保存する。The ceramic molded body 1 that has undergone such treatment is placed in a mold 11 and fixed as shown in FIG. still,
In FIG. 1, reference numeral 12 denotes a core, which preserves the ceramic molded body 1 within the mold 11 while preventing the molten metal 50 from flowing into the non-cast-in portion.
本例の複合体はセラミックス成形体１の外周に金属層を
形成する構成とするために、セラミックス成形体１は鋳
型１１内に固定された状態でその外周側に所定厚の空間
１３を生成せしめて装着される。Since the composite of this example has a structure in which a metal layer is formed on the outer periphery of the ceramic molded body 1, the ceramic molded body 1 is fixed in the mold 11 and a space 13 of a predetermined thickness is created on the outer periphery side thereof. It is installed.
而して注入孔１４より溶融金属５０を注入すれば、溶融
金属５０が前記空間１３に充満され、セラミックス成形
体１を鋳包み、複合体１０を構成する。注入孔１４は通
常複数個設けられ、溶融金属５０の注入に用いない他の
注入孔１４は鋳造時のガス抜き、及び押湯としての機能
を発揮させる構造となっている。When the molten metal 50 is injected through the injection hole 14, the space 13 is filled with the molten metal 50, and the ceramic molded body 1 is cast-in to form the composite body 10. A plurality of injection holes 14 are usually provided, and the other injection holes 14 that are not used for injection of the molten metal 50 are designed to function as venting gas during casting and as a riser.
さて本発明においては、前述したようにセラミックス成
形体１の少なくとも溶融金属と接する側の表面に、中間
層４が形成され、この中間層４はセラミックス成形体上
に直接形成されるソルダー層２と、ソルダー層２上面に
形成されるスラリー層３とから構成されている。Now, in the present invention, as described above, the intermediate layer 4 is formed on at least the surface of the ceramic molded body 1 that is in contact with the molten metal, and this intermediate layer 4 is formed directly on the ceramic molded body 1 with the solder layer 2. , and a slurry layer 3 formed on the upper surface of the solder layer 2.
第３図はこのようなセラミックス成形体１を溶融金属５
０で鋳包むときの状態を模式的に示すものである。前記
第１図のようにセラミックス成形体ｌの外周に金属層を
形成する例でみると、鋳包み。FIG. 3 shows such a ceramic molded body 1 in a molten metal 5.
This figure schematically shows the state when casting at zero. An example of forming a metal layer on the outer periphery of a ceramic molded body l as shown in FIG. 1 is cast-in.
即ち鋳造時の溶融金属５０の高熱は矢印Ｘで示すように
セラミックス成形体１に加わる。この高熱は鋳包み開始
直後セラミックス成形体１に急激に加わり、セラミック
ス成形体１の表面温度も急上昇する。ところがセラミッ
クスは熱伝導率が極めて低いためセラミックス成形体１
の内部温度は前記表面温度に追従し得す、この結果セラ
ミックス成形体１は激しい熱衝撃を受けることとなる。That is, the high heat of the molten metal 50 during casting is applied to the ceramic molded body 1 as shown by the arrow X. This high heat is rapidly applied to the ceramic molded body 1 immediately after the start of casting, and the surface temperature of the ceramic molded body 1 also rises rapidly. However, since ceramics have extremely low thermal conductivity, ceramic molded bodies 1
The internal temperature can follow the surface temperature, and as a result, the ceramic molded body 1 is subjected to severe thermal shock.
この際に前記ソルダー層２は軟化、又は半溶融して熱′
＃撃を吸収する。またスラリー層３は前記溶融金属の高
熱を遮断（断熱）すると共に溶融金属が凝固収縮する際
の圧縮力に対し、それ自体が押し潰されるように収縮し
くこの現象を以下圧潰と言う）、前記ソルダー層２の機
能と相俟って金属とセラミックスの熱膨張差を効率的に
吸収する機能を発揮する。At this time, the solder layer 2 softens or semi-melts and heats up.
#Absorb the blow. In addition, the slurry layer 3 blocks (insulates) the high heat of the molten metal, and also contracts as if it were crushed by the compressive force when the molten metal solidifies and contracts (this phenomenon is hereinafter referred to as crushing), Together with the function of the solder layer 2, it exhibits a function of efficiently absorbing the difference in thermal expansion between metal and ceramics.
加えて前記ソルダー層２は、製品としての複合体が繰り
返しの熱変化を受けるような使用状態において、その熱
膨張差によってセラミックス成形体ｌと金属５（前記溶
融金属５０に対し、凝固した金属を以下金属５という）
との間に生じる後述する隙間（以下ガタッキという）を
防止する機能をも発揮する。In addition, when the solder layer 2 is used in such a way that the composite as a product undergoes repeated thermal changes, the difference in thermal expansion causes the solder layer 2 to cause a difference between the ceramic molded body 1 and the metal 5 (the solidified metal is different from the molten metal 50). (hereinafter referred to as metal 5)
It also has the function of preventing gaps (hereinafter referred to as backlash), which will be described later, that occur between the two.
而してソルダー層２としては鋳造される金属の種類に応
じ、例えばその融点近傍で軟化、又は半溶融するような
ものを選定し、かつ前記機能を発揮し得る厚みに設定さ
れるが、その厚みは後述するように０．００５〜２．４
５ｍｍの範囲内で設定されている。For the solder layer 2, a material that softens or semi-melts near its melting point is selected depending on the type of metal to be cast, and is set to a thickness that can exhibit the above function. The thickness is 0.005 to 2.4 as described later.
It is set within a range of 5mm.
第１表は鋳造される金属とソルダー層２の組合せの一例
を、低融点金属（Ａ Ｑ 、Ｃｕ、Ｚｎ等）と、高融点
金属（紡鋼、鋳鉄等）とを比較して表したものである。Table 1 shows examples of combinations of metals to be cast and solder layer 2, comparing low melting point metals (AQ, Cu, Zn, etc.) and high melting point metals (spun steel, cast iron, etc.) It is.
第 １ 表
スラリー層３は、前述したように鋳造時の高熱に対し熱
を遮蔽する断熱層としての機能に加えて金属の圧縮力の
緩衝層、さらには前記ソルダー層２の保持、保護層とし
ての機能をも発揮する。As mentioned above, the slurry layer 3 in Table 1 functions not only as a heat insulating layer that shields heat from the high heat during casting, but also as a buffer layer for the compressive force of the metal, and also as a retaining and protective layer for the solder layer 2. It also performs the functions of
ところで前記断熱層や緩衝層としての単純な機能のみで
あれば、例えばセラミックスファイバー等を用いること
も可能である。ところが本発明者らの経験では前記ファ
イバーでは熱伝達性のコントロールが難しく、層厚にも
ばらつきが大きく、このため局所的な温度差が生じて熱
衝撃性の割れが多発した。これを解決するためにファイ
バーの層厚を大きくすると前記割れの発生は軽減できて
も金属の凝固圧縮力を吸収し過ぎてガタッキが発生し、
セラミックスと金属間の接合力が弱まり、極端な場合、
金属からセラミックスが離脱したり、破損する事態が生
じることを本発明者らは経験した。By the way, if it only has a simple function as the above-mentioned heat insulating layer or buffer layer, it is also possible to use, for example, ceramic fiber or the like. However, in the experience of the present inventors, it is difficult to control the heat transfer properties of the above-mentioned fibers, and the layer thickness varies widely, resulting in local temperature differences and frequent cracking due to thermal shock. To solve this problem, increasing the thickness of the fiber layer may reduce the occurrence of cracks, but it will absorb too much of the solidification compressive force of the metal, causing looseness.
In extreme cases, the bonding force between ceramics and metal weakens.
The present inventors have experienced that ceramics may separate from metals or be damaged.
本発明のスラリー層３は、アルミナ、シリカなどのセラ
ミックスを主成分とし、リン酸アルミニウムやリン酸マ
グネシウム系のリン酸塩、ケイ酸アルカリ等をバインダ
ーとし、水で混練したセラミックス系の水性スラリーを
前述したソルダー層２の上面に、 Ｏ，ＯＳ〜６ 、０
ｍｍの層厚に塗布して形成される。この水性スラリーは
接着性を有し、乾燥過程で後述する気泡を生ずるなどの
種々の秀れた機能を発揮する。The slurry layer 3 of the present invention is a ceramic-based aqueous slurry that is mainly composed of ceramics such as alumina and silica, and has a binder such as aluminum phosphate or magnesium phosphate, an alkali silicate, etc., and is kneaded with water. On the upper surface of the solder layer 2 described above, O,OS~6,0
It is formed by coating to a layer thickness of mm. This aqueous slurry has adhesive properties and exhibits various excellent functions such as generating bubbles as described below during the drying process.
即ち前記水性スラリーを１例えば０．０１〜０．２ｍｍ
Ｚ回で順次塗布することにより均一な層厚が得られ、ま
た乾燥過程でスラリー層３に空気気泡が生成される。こ
の気泡は第４図に示すようにそれを覆う表層のスラリー
層３が溶融金属５０により押潰されるように圧壊し、溶
融金属５０が気泡３ａ内に差込むように浸入する。これ
により溶融金／Ｘ５０はアンカー効果を発揮し、接合強
度をより高めることができる。That is, the aqueous slurry has a thickness of, for example, 0.01 to 0.2 mm.
By sequentially applying Z times, a uniform layer thickness is obtained and air bubbles are generated in the slurry layer 3 during the drying process. As shown in FIG. 4, the bubbles are crushed so that the surface slurry layer 3 covering them is crushed by the molten metal 50, and the molten metal 50 penetrates into the bubbles 3a. As a result, the molten gold/X50 exhibits an anchor effect, and the bonding strength can be further increased.
さらにスラリー層３の下層部にセラミックスに比べ熱伝
導性の高いソルダー層２が形成されているためスラリー
層３に仮に局部的な高温が加わってもソルダー層２で均
等に分散され、セラミックス成形体１に温度むらの生じ
ることもなくなる。Furthermore, since the solder layer 2, which has higher thermal conductivity than ceramics, is formed below the slurry layer 3, even if a local high temperature is applied to the slurry layer 3, it is evenly dispersed in the solder layer 2, and the ceramic molded product is 1. Temperature unevenness will no longer occur.
尚前記水性スラリーを何回かに分けて塗布する場合、１
回の塗布が終了する毎に乾燥処理を行い、次回の塗布を
行うことが厚みの均一化、ガスによる鋳造不良抑制の点
から好ましい。特に５００℃程度の高温で乾燥すると完
全なガス抜きが可能となる上に、前述した気泡の生成が
効率的に行え、断熱効果の向上も図られ効果的である。In addition, when applying the aqueous slurry in several parts, 1
It is preferable to carry out a drying process after each application and then perform the next application from the viewpoints of making the thickness uniform and suppressing casting defects caused by gas. In particular, drying at a high temperature of about 500° C. is effective because it not only allows complete degassing, but also enables efficient generation of the bubbles described above and improves the heat insulation effect.
前記第４図において３ｂ□は第１Ｍ４目のスラリー層を
、３ｂ２は第２層目のスラリー層を示すものである。In FIG. 4, 3b□ represents the first M4th slurry layer, and 3b2 represents the second slurry layer.
以上のようなスラリー層３は、圧縮強度が１００〜５０
０ｋｇ／ｃｍ２で、耐熱温度はシリカ系が１２００℃、
アルミナ系が１３００℃、ジルコニヤ系では２４００℃
にも達する。而して要求される気泡の発生量、圧縮強度
、耐熱温度等に応じてその成分が調整され、また後述す
るようにその層厚が前記範囲内で決定される。The slurry layer 3 as described above has a compressive strength of 100 to 50.
0kg/cm2, heat resistance temperature is 1200℃ for silica type,
1300℃ for alumina type, 2400℃ for zirconia type
reach even. The components are adjusted according to the required amount of bubble generation, compressive strength, heat resistance temperature, etc., and the layer thickness is determined within the above range as described later.
さて次に、中間層４の厚み、及びソルダー層２、スラリ
ー層３の各々の層厚の設定法について説明する。Next, a method for setting the thickness of the intermediate layer 4 and the thicknesses of each of the solder layer 2 and the slurry layer 3 will be explained.
本発明の複合体製造に当って考慮しなければならないこ
とは、 （１）ＪＧ包み時の熱衝撃、（２）、溶融金属
が凝固する際の圧縮力、（３）、使用過程でのガタッキ
発生、の３点である。Things that must be considered when manufacturing the composite of the present invention are: (1) thermal shock during JG wrapping, (2) compressive force when molten metal solidifies, and (3) backlash during use. There are three points: occurrence.
先ずソルダー層２は前述した熱伝導性、及びそれ自身の
軟化、半溶融による熱吸収機能の他にも、スラリーの塗
布性向上の機能をも有している。First, the solder layer 2 has not only the above-mentioned thermal conductivity and a heat absorption function due to its own softening and semi-melting, but also the function of improving the coatability of the slurry.
かかる点からもその層厚は少なくとも０ 、００５ｍｍ
以上が必要である。またスラリー層３は前記ソルダー層
が軟化、半溶融したときにその流失を防止するために少
なくとも０．０５ｍｍ以上が必要である。From this point of view, the layer thickness is at least 0.005 mm.
The above is necessary. Further, the slurry layer 3 needs to be at least 0.05 mm thick to prevent the solder layer from flowing away when it becomes soft or semi-molten.
次に鋳包み時の熱衝撃について説明する。第５図はこの
肋包み開始直後の熱伝達状況を示すもので、Ｔｍが溶融
金属温度であり、Ｔｂがソルダー層２の表面温度、Ｔａ
がセラミックス成形体１の表面温度である。即ちセラミ
ックス成形体１の表面温度は溶融金属５０が注入される
ことによって、中間層４を介して直ちにＴａまで上昇す
る。一方セラミンクス成形体１の内部温度は、それ自体
の熱伝導率が前述したように極めて低いため鋳包み開始
前のＴｃのままである。Next, thermal shock during casting will be explained. Figure 5 shows the heat transfer situation immediately after the start of rib wrapping, where Tm is the molten metal temperature, Tb is the surface temperature of the solder layer 2, and Ta
is the surface temperature of the ceramic molded body 1. That is, the surface temperature of the ceramic molded body 1 immediately rises to Ta through the intermediate layer 4 as the molten metal 50 is injected. On the other hand, the internal temperature of the ceramic molded body 1 remains at Tc before the start of casting, since its own thermal conductivity is extremely low as described above.
従ってセラミックス成形体１には、［Ｔａ Ｔｃ＝△
Ｔ］の熱衝撃が加わることになる。この熱衝撃△Ｔに対
するセラミックス成形体１の耐用性は、セラミックスの
種別に応じて許容範囲があり、アルミナ系では２００〜
３００℃、サイアロン系では６００〜８００℃である。Therefore, in the ceramic molded body 1, [Ta Tc=△
T] thermal shock will be applied. The durability of the ceramic molded body 1 against this thermal shock ΔT has an allowable range depending on the type of ceramic, and for alumina type, it is 200~
300°C, and 600 to 800°C for Sialon type.
而して鋳包み時の熱衝撃ΔＴをセラミックスの種別に応
じて許容温度以下に押える必要があり、その方策の一つ
に中間層、とりわけスラリー層３の層厚の制御があり、
他の一つにセラミックス成形体１の予熱がある。Therefore, it is necessary to suppress the thermal shock ΔT during casting to a permissible temperature or lower depending on the type of ceramic, and one of the measures to do this is to control the layer thickness of the intermediate layer, especially the slurry layer 3.
Another method is preheating of the ceramic molded body 1.
予熱はセラミックス成形体１を全体的に同じ温度まで上
昇させる方法、あるいは前記第１図に示すように鋳型１
１内に装着されたセラミックス成形体１の非鋳包み部よ
りバーナー等で加熱し、非鋳包面の温度を意識的に鋳包
面より高くなるよう温度勾配を付けて行う方法等が採用
できる。Preheating can be carried out by heating the entire ceramic molded body 1 to the same temperature, or by heating the mold 1 as shown in FIG.
A method can be adopted in which the non-cast-in part of the ceramic molded body 1 mounted in the ceramic molded body 1 is heated with a burner, etc., and a temperature gradient is intentionally created so that the temperature of the non-cast-in surface is higher than that of the cast-in part. .
尚、第１図の例においては中子１２および鋳型１１にバ
ーナー導入孔１５ａが設けられており、この導入孔１５
ａにバーナーを挿入して加熱するものである。In the example shown in FIG. 1, the core 12 and the mold 11 are provided with burner introduction holes 15a.
A burner is inserted into the a to heat it.
１５ｂはバーナー加熱後の排気ガスを排出する排気孔の
機能を発揮する。而してこの非鋳包み部より加熱する方
法では、鋳包み直後のセラミックス成形体１の温度差が
全体加熱に比し小さくなり、この結果セラミックス成形
体１の平均予熱温度を１００〜２００°Ｃ程度下げるこ
とができる。第６図はこの予熱方法に基づく時間経過と
、鍔包み後のセラミックス成形体１の温度変化状況を示
すもので、実線ａ−１、破線ｂ−１が鋳包面温度を、実
線ａ−２、破線す−２が非鋳包面温度である。実線ａ−
１及びａ−２で示すセラミックス成形体１を全体的に同
温度に予熱する方法では、当初は温度差ΔＴ１は小さい
が時間の経過と共に大きくなる。これに対し破線ｂ−１
及びｂ−２で示す温度勾配を付けた予熱方法では当初の
温度差ΔＴ２は比較的大きいが時間の経過と共に小さく
なり、ある時間経過後逆転する。従って前記ΔＴ□の最
大値に対してこのΔＴ２の最大値は、低いものとなり、
この結果前述したようにセラミックス成形体ｌの平均予
熱温度を下げることが可能となる。15b functions as an exhaust hole for discharging exhaust gas after being heated by the burner. Therefore, in this method of heating from the non-cast-in part, the temperature difference in the ceramic molded body 1 immediately after the cast-in is smaller than that in the case of heating the entire ceramic body 1, and as a result, the average preheating temperature of the ceramic molded body 1 is reduced to 100 to 200°C. It can be lowered to a lesser extent. Fig. 6 shows the elapse of time based on this preheating method and the temperature change of the ceramic molded body 1 after wrapping the flange.The solid line a-1 and the broken line b-1 represent the casting surface temperature, and the solid line a-2 , the broken line S-2 is the non-cast iron surface temperature. Solid line a-
In the method of preheating the entire ceramic molded body 1 to the same temperature as shown in 1 and a-2, the temperature difference ΔT1 is small at first, but increases as time passes. On the other hand, the broken line b-1
In the preheating method with a temperature gradient shown in and b-2, the initial temperature difference ΔT2 is relatively large, but decreases over time and reverses after a certain period of time. Therefore, the maximum value of ΔT2 is lower than the maximum value of ΔT□,
As a result, as described above, it is possible to lower the average preheating temperature of the ceramic molded body l.
第７図は熱衝撃による割れを発生させないための予熱温
度とスラリー層厚との関係を調査した結果の一例を示す
図表である。本例は７０ｍｍφＸ ６０ｍｍφＸ ５０
！１１１０ Ｑの中空セラミックス成形体の外周に厚さ
５＋ａｍで溶融金属を鋳包んだときの熱衝撃割れ発生状
況を調査したものであって、第７図（ａ）はセラミック
ス成形体がアルミナ系セラミックスで、溶融金属がねず
み鋳鉄、第７図（ｂ）はセラミックス成形体がサイアロ
ン系セラミックスで、溶融金属がねずみ鋳鉄、第７図（
ｃ）はセラミックス成形体がアルミナ系セラミックスで
、溶融金属がアルミである。ソルダー層は、前述した酸
化銅を用い、第７図（ａ）及び第７図（ｂ）の例では０
．４ｍｍの層厚、第７図（Ｃ）の例では０ 、２ｍｍの
層厚で一定とした。スラリー層は、第７図（ａ）及び第
７図（ｂ）の例ではシリカ・アルミナ系スラリーを、第
７図（ｃ）の例ではアルミナ系スラリーをそれぞれ層厚
を変えて塗布した。また予熱方法はセラミックス成形体
を全体的に同温度に予熱する方法と、非紡包み部より加
熱し意識的に温度勾配を付ける予熱方法で実施した。而
してスラリー層厚が同一でもセラミックス成形体の予熱
温度、予熱方法が異なると熱衝撃割れの発生割合も変化
する。第７図において実線Ｃ工は全体的に同温度予熱の
、また実線ｃ２は温度勾配を付ける予熱方法における熱
衝撃割れ発生限界予熱温度を示し、この熱衝撃割れ発生
限界予熱温度は溶融金属の種別やセラミックス成形体の
種別毎に異なる。従って予め溶融金属およびセラミック
ス成形体の種別毎に前記中間層厚と鋳包み時の熱衝撃割
れ発生限界予熱温度ＱｌｌＣ２との関係を求めておくこ
とによって、当該鋳包み条件に応じた予熱温度を設定す
ることが可能となる。FIG. 7 is a chart showing an example of the results of an investigation into the relationship between preheating temperature and slurry layer thickness to prevent cracking due to thermal shock. This example is 70mmφX 60mmφX 50
! The occurrence of thermal shock cracking was investigated when molten metal was cast to a thickness of 5+ am around the outer periphery of a hollow ceramic molded body of 1110Q, and Figure 7 (a) shows that the ceramic molded body was made of alumina ceramic. , the molten metal is gray cast iron, and in Fig. 7(b), the ceramic molded body is Sialon ceramic, and the molten metal is gray cast iron, Fig. 7(b).
In c), the ceramic molded body is an alumina ceramic and the molten metal is aluminum. The solder layer uses the copper oxide described above, and in the examples shown in FIGS. 7(a) and 7(b),
．． The layer thickness was 4 mm, and in the example of FIG. 7(C), the layer thickness was constant at 0.2 mm. For the slurry layer, a silica-alumina slurry was applied in the examples shown in FIGS. 7(a) and 7(b), and an alumina-based slurry was applied in the example shown in FIG. 7(c), with varying layer thicknesses. The preheating method was carried out by preheating the entire ceramic molded body to the same temperature, and by heating the non-spun and wrapped part to intentionally create a temperature gradient. Even if the slurry layer thickness is the same, if the preheating temperature and preheating method of the ceramic molded body are different, the occurrence rate of thermal shock cracking will also change. In Fig. 7, the solid line C indicates the preheating temperature at which the temperature is the same throughout the process, and the solid line c2 indicates the preheating temperature at which the thermal shock cracks will occur in the preheating method with a temperature gradient. and differs depending on the type of ceramic molded body. Therefore, by determining the relationship between the intermediate layer thickness and the critical preheating temperature QllC2 for thermal shock cracking during cast-in for each type of molten metal and ceramic molded body, the preheating temperature can be set according to the cast-in conditions. It becomes possible to do so.
次に第８図は前述したアルミナ系水性スラリーを用いて
形成されたスラリー層の層厚とセラミックス成形体の熱
衝撃ΔＴの関係を調査した結果の一例を示すもので、破
ｍａが溶融金属がアルミ。Next, Figure 8 shows an example of the results of investigating the relationship between the thickness of the slurry layer formed using the alumina-based aqueous slurry mentioned above and the thermal shock ΔT of a ceramic molded body. Aluminum.
実線すが鋳鉄である。本例ではセラミックス成形体の予
熱を行わず、ソルダー層は酸化銅法によって形成される
Ｃｕ２ＯとＳ ｉｏ２の酸化物のソルダー（以下酸化銅
と略称する）でその層厚は０．２ｍｍで一定とした。こ
の第７図および第８図がら明らかなようにスラリー層厚
がある厚み以上であれば熱衝撃、および凝固収縮による
割れを防ぐことが可能となる。The solid line is cast iron. In this example, the ceramic molded body was not preheated, and the solder layer was a Cu2O and Sio2 oxide solder (hereinafter abbreviated as copper oxide) formed by the copper oxide method, and the layer thickness was constant at 0.2 mm. did. As is clear from FIGS. 7 and 8, if the slurry layer is thicker than a certain thickness, thermal shock and cracking due to solidification shrinkage can be prevented.
第２表はセラミックスの種別毎に前記熱衝撃△Ｔに対す
る許容温度以下にするためのスラリー層の最小層厚を示
すものであり、ソルダー層厚は前述した下限に０．００
５ｍｍにしている。この第２表および前記第８図から判
るように耐熱衝撃性の高いサイアロンにおいてはスラリ
ー層厚が０．０５ｆｆ＋ｍ以上であれば前述した割れ等
の欠陥を生ずることなく、鋳包み時の熱衝撃を効果的に
吸収することができた。Table 2 shows the minimum layer thickness of the slurry layer to keep the temperature below the permissible temperature for the thermal shock ΔT for each type of ceramic, and the solder layer thickness is 0.00% below the above-mentioned lower limit.
It is set to 5mm. As can be seen from Table 2 and Figure 8 above, in Sialon, which has high thermal shock resistance, if the slurry layer thickness is 0.05 ff+m or more, the above-mentioned defects such as cracks will not occur and thermal shock during casting will not occur. could be absorbed effectively.
第 ２ 表
成形体に比し数倍大きい。このためセラミックス成形体
は圧縮力を、金属は膨張力を受け、本発明の複合体にお
けるセラミックス成形体と金属との接合力を発揮する。It is several times larger than the molded product in Table 2. Therefore, the ceramic molded body is subjected to compression force, and the metal is subjected to expansion force, and the bonding force between the ceramic molded body and the metal in the composite of the present invention is exerted.
前記圧縮力は弾性変形域において次のような関係を満足
する。The compressive force satisfies the following relationship in the elastic deformation region.
ε ＝ｉｃ＋ ε阿
以上よりソルダー層、およびスラリー層の最小層厚は各
々０．００５ｍｍ、０．０５ｍｍに設定した。ε=ic+εa From the above, the minimum layer thicknesses of the solder layer and the slurry layer were set to 0.005 mm and 0.05 mm, respectively.
次に中間層厚の上限は使用過程でのガタッキ発生の要因
から決定される。Next, the upper limit of the intermediate layer thickness is determined based on the factors that cause looseness during use.
そこでこのガタッキ発生に大きな影響を与える圧縮力に
ついて説明する。Therefore, the compressive force that has a large effect on the occurrence of backlash will be explained.
鋳型内に注入された溶融金属は時間の経過に伴って温度
が低下し、凝固する。この凝固により溶融金属は収縮す
るが、その収縮率はセラミックス但し、εＣ：セラミッ
クス成形体の収縮量ＥＭ：金属収縮（見込み）量
ＥＭ：金属のヤング率
Ｅｃ：セラミックス成形体のヤング率
■Ｍ＝金属のポアソン比
■ｃ：セラミックス成形体のポアソン比Ｒ工：セラミッ
クス成形体の内径
Ｒ２：セラミックス成形体の外径
Ｒ１：！Ｊ造金金属外径
Ｐ ：圧縮力
εはセラミックスと金属の収縮量の和であり、圧縮力Ｐ
は以下のように求められる。The temperature of the molten metal injected into the mold decreases over time and solidifies. This solidification causes the molten metal to shrink, and the shrinkage rate is as follows: εC: Shrinkage amount of the ceramic molded body EM: Metal shrinkage (estimated) amount EM: Young's modulus of the metal Ec: Young's modulus of the ceramic molded body ■M= Poisson's ratio of metal c: Poisson's ratio of ceramic molded body R: Inner diameter R2 of ceramic molded body: Outer diameter R1 of ceramic molded body:! J Gold-formed metal outer diameter P: Compressive force ε is the sum of the shrinkage amount of ceramics and metal, and compressive force P
is calculated as follows.
Ｐ＝ Ｅ Ｘ ｆ（Ｒｏ、Ｒ２，Ｒ３）・・・・・・・
・（２）前述した中空管を例にとると下記（３）式に示
すように中間層の圧壊量を△εとすると、前記圧縮力Ｐ
は圧壊量△εの増加に比例して小さくなり、−法線形的
に変化する。P=EX f(Ro, R2, R3)・・・・・・
・(2) Taking the above-mentioned hollow tube as an example, as shown in equation (3) below, if the amount of collapse of the intermediate layer is Δε, the compressive force P
decreases in proportion to the increase in the amount of crushing △ε, and changes in a -normal linear manner.
” ” ｆ （Ｒ１＋Ｒｚ＋Ｒｉ）・・・・（３）Ｐ
＝
一方、セラミックス成形体の大きさも、前記圧縮力Ｐに
影響を与える。第９図はセラミックス成形体の外径と圧
縮力Ｐの調査結果の一例を示すもので、実線ｄは鋳造金
属の層厚が５ｍｍ、実線ｅは鋳造金属の層厚が１５ｍｍ
の例をそれぞれ表すものである。この第９図から判るよ
うにセラミックス成形体が大きくなるか、あるいはその
肉厚が厚くなるに伴い、圧縮力は増し、セラミックス成
形体と金属との接合力が大きくなる。"" f (R1+Rz+Ri)...(3)P
= On the other hand, the size of the ceramic molded body also affects the compressive force P. Figure 9 shows an example of the investigation results of the outer diameter and compressive force P of a ceramic molded body, where the solid line d indicates the thickness of the cast metal layer is 5 mm, and the solid line e indicates the layer thickness of the cast metal of 15 mm.
, respectively. As can be seen from FIG. 9, as the ceramic molded body becomes larger or its wall thickness increases, the compressive force increases and the bonding force between the ceramic molded body and the metal increases.
前記△εは、例えばスラリーを乾燥させると気孔率が１
０．４０％程度になり、この気孔率と比例して圧壊率が
増し、Δεを上げることができる。For example, when the slurry is dried, the porosity becomes 1.
The porosity is approximately 0.40%, and the crushing rate increases in proportion to this porosity, making it possible to increase Δε.
またソルダー層も高温状態となると、軟化あるいは半溶
融状態となり、溶融金属の収縮時に圧縮を受け、△εを
実質上アップし高温域における圧縮力軽減の機能を発揮
する。而して溶融金属の凝固収縮過程において高温域で
はソルダー層が軟化あるいは半溶融化して圧縮力を軽減
し、中、低温域ではスラリー層が圧壊して圧縮力の軽減
を図ることができる。Furthermore, when the solder layer reaches a high temperature state, it becomes soft or semi-molten, and is compressed when the molten metal contracts, substantially increasing Δε and exhibiting the function of reducing compressive force in the high temperature range. In the process of solidification and contraction of molten metal, the solder layer softens or becomes semi-molten in the high temperature range, reducing the compressive force, and in the medium to low temperature range, the slurry layer collapses, reducing the compressive force.
ところで周知のように金属は高温と低温の熱変化を繰り
返し受けると組織変化による膨張、あるいは収縮現象を
呈する。例えばねずみ鋳鉄では、６５０〜９５０℃の熱
変化を繰り返し受けると、第１０図に示すように粒成長
により次第に膨張する。このような使用環境下で用いら
れる複合体において、セラミックス成形体の表面にスラ
リー層のみを形成した場合、スラリー層は可逆性がない
ため使用時間の経過に伴ってセラミックス成形体と金属
間に隙間、つまりガタッキが発生し、その量が大きくな
ると離脱や破損等を生じる結果となる。このためスラリ
ー層およびソルダー層の厚みにはそれぞれ上限がある。By the way, as is well known, when metals are repeatedly subjected to thermal changes between high and low temperatures, they expand or contract due to structural changes. For example, when gray cast iron is repeatedly subjected to thermal changes of 650 to 950°C, it gradually expands due to grain growth, as shown in FIG. In composites used under such usage environments, if only a slurry layer is formed on the surface of the ceramic molded body, the gap between the ceramic molded body and the metal will increase over time because the slurry layer is not reversible. In other words, backlash occurs, and if the amount becomes large, it will result in detachment, breakage, etc. Therefore, the thickness of the slurry layer and the solder layer each has an upper limit.
第１１図は前記中間層厚の調査結果の一例を示すもので
、外径が２０〜３００ｍｍφ、長さが１５０〜１０００
ｍｍ、厚み５〜１５ｍｍのアルミナ系セラミックス成形
体を、ステンレス鋳鋼で鋳包んだとき実施例である。ア
ルミナ系セラミックスはセラミックスのなかでは最も圧
縮強度が弱く、またステンレス鋳鋼は凝固収縮条件の厳
しい金属である。このような製造条件でセラミックス成
形体又は金属に熱衝撃割れが発生せず、また使用中にお
けるガタッキが発生しない中間層厚を求めた。第１１図
（ａ）はセラミックス成形体が小型（２０ｍｍφＸ １
０ｍｍφＸ ５０ｎ＋ｍ）の、第１１図（ｂ）はセラミ
ックス成形体が大型（３００ｍｍφＸ ２７０ｍｍφＸ
１００１００Ｏの例を表すものである。FIG. 11 shows an example of the investigation results of the intermediate layer thickness.
In this example, an alumina ceramic molded body having a thickness of 5 to 15 mm was cast in stainless steel. Alumina ceramics have the lowest compressive strength among ceramics, and cast stainless steel is a metal that undergoes severe solidification and shrinkage conditions. Under these manufacturing conditions, the thickness of the intermediate layer was determined so that thermal shock cracking would not occur in the ceramic molded body or the metal, and no looseness would occur during use. Figure 11(a) shows that the ceramic molded body is small (20mmφX 1
0mmφX 50n+m), the ceramic molded body shown in FIG.
This represents an example of 100100O.
この第１１図から判るように中間層の下限厚みは前述し
た熱衝撃割れを防止する上からソルダー層厚は０．００
５ｍｍ以上、スラリー層厚は０ 、０５ｍｍ以上とする
必要があり、中間層の総厚は０．０５５ｍｍ以上とする
ことにより熱衝撃割れを防止できた。一方中間層厚が厚
くなるとガタッキの発生が生じるようになる。このガタ
ッキ発生について大型のセラミックス成形体では圧縮力
が強まることから中間層厚が６．００５ｍｍを越えると
ガタッキの発生率が急激に上昇する。これに対し小型の
セラミックス成形対では３ＩＩｌｆｆｌ以下であれば前
記ガタッキの発生は殆ど無かった。As can be seen from Fig. 11, the lower limit thickness of the intermediate layer is 0.00 to prevent the aforementioned thermal shock cracking, and the solder layer thickness is 0.00.
The thickness of the slurry layer must be 0.05 mm or more, and thermal shock cracking can be prevented by setting the total thickness of the intermediate layer to 0.055 mm or more. On the other hand, as the thickness of the intermediate layer increases, looseness will occur. Regarding the occurrence of backlash, since the compressive force is strong in large ceramic molded bodies, when the thickness of the intermediate layer exceeds 6.005 mm, the occurrence rate of backlash increases rapidly. On the other hand, in the case of small-sized ceramic molded pairs, the above-mentioned rattling hardly occurred when it was less than 3IIlffl.
圧縮強度が最も弱いアルミナ系セラミックスと、凝固収
縮条件の厳しいステンレス鋳鋼の組合せにおいて前記層
厚条件を満足することによって複合体の製造が可能であ
ることから、その他の組合せにおいても前記層厚条件を
満足すれば本発明で目的とする複合体を製造できること
が他の実験でも確認された。本発明においてソルダー層
厚を０．００５−２．４５ｍｍ、スラリー層厚を０．０
５−６．０ｍｍとし、その総厚が０．０５５〜６，００
５＋ｎｍとなるよう中間層を形成するとは係る理由から
である。Since it is possible to manufacture a composite by satisfying the above layer thickness condition in a combination of alumina ceramics, which has the lowest compressive strength, and stainless steel, which has severe solidification shrinkage conditions, it is possible to manufacture a composite by satisfying the above layer thickness condition in other combinations. It was confirmed in other experiments that the desired composite of the present invention can be produced if the conditions are satisfied. In the present invention, the solder layer thickness is 0.005-2.45 mm, and the slurry layer thickness is 0.0 mm.
5-6.0mm, and the total thickness is 0.055-6,00mm.
This is the reason why the intermediate layer is formed to have a thickness of 5+ nm.
第１２図はソルダー層が前記熱変化に与える影響を具体
的に調査した結果の一例を示すもので、３００℃から１
０００℃までの熱変化を加え、その熱変化回数と接合強
度との関係を調査したものである。Figure 12 shows an example of the results of a concrete investigation into the influence of the solder layer on the thermal change.
Thermal changes up to 000°C were applied, and the relationship between the number of thermal changes and bonding strength was investigated.
セラミックス成形体はアルミナ系セラミックスで２０ｍ
ｍφＸ５０ｍｍＱ（Ａ）、と３００ｍｍφＸ １０００
ｍｍ Ｑ （Ｂ ）とし、その外周に厚み５ｍ＋＋＋で
ねずみ鋳鉄を鋳包んだ。中間層におけるスラリー層厚は
０ 、５ｍｍで一定とし、ソルダー層厚を０．００２ｍ
ｍ（ａ）、 ０．００５ｍｍ（ｂ）、０．０２ｍｍ（ｃ
）とした。この第１２図から判るようにソルダー層厚が
０．００２ｍｍでは、大型のものでは５回の熱変化で、
また小型のものでも１０回程度で接合力が大幅に低下し
た。これに対しソルダー層厚が０．００５ｍｍ以上とな
ると熱変化を繰り返しても接合力の低下は極めて僅かで
あった。またソルダー層厚が２．４５ｍｍを越えると使
用中のみならず、使用前の接合力も大幅に低下した。The ceramic molded body is alumina ceramic and is 20m long.
mφX50mmQ(A), and 300mmφX 1000
mm Q (B), and gray cast iron was cast around its outer periphery to a thickness of 5 m++. The slurry layer thickness in the intermediate layer was constant at 0.5 mm, and the solder layer thickness was 0.002 m.
m(a), 0.005mm(b), 0.02mm(c
). As can be seen from Fig. 12, when the solder layer thickness is 0.002 mm, it takes 5 thermal changes for a large type.
Furthermore, even with a small size, the bonding force significantly decreased after about 10 times. On the other hand, when the solder layer thickness was 0.005 mm or more, the decrease in bonding strength was extremely small even after repeated thermal changes. Furthermore, when the solder layer thickness exceeded 2.45 mm, the bonding strength not only during use but also before use was significantly reduced.
［実施例］
第１３図〜第１７図に示すような複合体の製造において
本発明を実施した。[Example] The present invention was practiced in the production of composites as shown in Figures 13 to 17.
各複合体の種別、サイズ、及び中間層の種別、層厚等は
各図及び第３表に示す通であり、製造された複合体の割
れ、ガタッキ等の欠陥発生状況を調査した。The type and size of each composite, and the type and layer thickness of the intermediate layer are as shown in each figure and Table 3, and the occurrence of defects such as cracks and backlash in the manufactured composite was investigated.
尚、第１６図はチップ状のセラミックスを鋳包んだ例で
あり、適度の接合力を得るためにセラミックスチップに
は側面に溶融金属の入る隙間を形成したり、底面に窪み
が形成されている。この例においても溶融金属と接する
面には前述した中間層が形成されている。また第１７図
は多孔質セラミックスを鋳包んだ例でありこの例におい
ても前記第１６図と同様に中間層が形成され、溶融金属
が注入され複合体を製造した。更に溶融金属がアルミ
、可鍛鋳鉄などでは金属層の組織を調質することを狙い
として第３表に示す如き熱処理を行った。Fig. 16 shows an example of a ceramic chip being cast.In order to obtain an appropriate bonding force, the ceramic chip has a gap formed on the side surface for the molten metal to enter, and a depression formed on the bottom surface. . In this example as well, the aforementioned intermediate layer is formed on the surface in contact with the molten metal. Further, FIG. 17 shows an example in which porous ceramics were cast, and in this example as well, an intermediate layer was formed in the same manner as in FIG. 16, and molten metal was injected to produce a composite. Furthermore, the molten metal is aluminum.
, malleable cast iron, etc., were subjected to heat treatment as shown in Table 3 with the aim of refining the structure of the metal layer.
製造された複合体の評価方法としては製造時の割れ発生
、及び使用過程での割れ発生状況を調査し、百分率で表
した。同様に使用過程におけるガタッキ発生も調査し、
百分率で表した。As a method for evaluating the manufactured composites, the occurrence of cracks during manufacture and the occurrence of cracks during use were investigated and expressed as a percentage. Similarly, we investigated the occurrence of looseness during the usage process.
Expressed as a percentage.
この第３表から明らかなように本発明に基づく範囲内で
の実施では製造時の割れ発生率は殆どが５％以下であり
、又使用中の割れ発生率は最大でも７％程度で、殆ど４
％以下であった。さらせに使用中のガタッキ発生率も８
％以下となり、本発明の優れた効果が確認された。As is clear from Table 3, when the present invention is implemented within the scope of the present invention, the crack occurrence rate during manufacturing is mostly 5% or less, and the crack occurrence rate during use is about 7% at most, and most 4
% or less. Furthermore, the rattling occurrence rate during use is also 8.
% or less, confirming the excellent effects of the present invention.
［発明の効果］
本発明の実施により熱膨張率が著しく異なるセラミック
スと金属の鋳包みにおいてもセラミックスや金属の破損
を確実に防止でき、さらにセラミックスと金属間に収縮
差によるガタッキ発生も皆無とすることができた。[Effects of the Invention] By carrying out the present invention, it is possible to reliably prevent damage to ceramics and metals even when casting ceramics and metals that have significantly different coefficients of thermal expansion, and there is also no occurrence of backlash due to shrinkage differences between ceramics and metals. I was able to do that.
この結果セラミックスを溶融金属で鋳包んで構成される
複合体を低コストで、しかも接合強度が高く信頼性の高
いものとして製造することが可能となった。As a result, it has become possible to manufacture a composite body made by casting ceramics with molten metal at low cost, with high bonding strength and high reliability.
各図は本発明に基づ〈実施例を示すもので、第１図は本
発明の基本的な構成を説明するための断面構造図、
第２図は第１図のセラミックス成形体の詳細を示す断面
図、
第３図はセラミックス成形体を溶融金属で鋳包むときの
状態を示す模式図、
第４図はスラリー層と溶融金属の結合状態を示す断面構
造図、
第５図は鋳包み開始直後の熱伝達状況を示す図、第６図
はセラミックス成形体の予熱方法に基づく時間経過と、
鋳包み後のセラミックス成形体ｌの温度変化状況を示す
図、
第７図は熱ＷＩ撃による割れを発生させないための予熱
温度とスラリー層厚との関係を調査した結果の一例を示
す図、
第８図はスラリー層厚とセラミックス成形体の熱衝撃の
関係を調査した結果の一例を示す図、第９図はセラミッ
クス成形体の外径と圧縮力の調査結果の一例を示す図。
第１０図は金属が熱変化を繰り返し受けた結果の組織変
化による膨張、あるいは収縮現象を示す図、第１１図は
前記中間層厚の調査結果の一例を示す図、
第１２図はソルダー層が前記熱変化に与える影響を具体
的に調査した結果の一例を示す図、第１３図〜第１７図
は本発明に基づく複合体のそれぞれ異なった実施を示す
斜視図と断面図、である。
１：セラミックス成形体、 ２：ソルダー層、３ニスラ
リ−層、 ４：中間層、 ５：金属層、１０：複合体、
１１：鋳型、 １２：中子、 １３：空間、 １４：
注入孔、 １５ａ：バーナー導入孔、１５ｂ ：排気孔
、 ５０：溶融金属。
特許出願人 新日本製鐵株式会社Each figure shows an example based on the present invention. Figure 1 is a cross-sectional structural diagram for explaining the basic configuration of the present invention, and Figure 2 shows details of the ceramic molded body of Figure 1. Figure 3 is a schematic diagram showing the state when a ceramic molded body is cast in molten metal, Figure 4 is a cross-sectional structural diagram showing the bonding state of the slurry layer and molten metal, and Figure 5 is the start of casting. A diagram showing the heat transfer situation immediately after, Figure 6 shows the elapsed time based on the preheating method of the ceramic molded body,
Figure 7 is a diagram showing the temperature change status of the ceramic molded body l after casting. FIG. 8 is a diagram showing an example of the results of an investigation into the relationship between slurry layer thickness and thermal shock of a ceramic molded body, and FIG. 9 is a diagram showing an example of the results of an investigation of the outer diameter of the ceramic molded body and compressive force. Fig. 10 is a diagram showing the expansion or contraction phenomenon due to structural change as a result of repeated thermal changes in metal, Fig. 11 is a diagram showing an example of the investigation results of the intermediate layer thickness, and Fig. 12 is a diagram showing the phenomenon in which the solder layer is FIGS. 13 to 17 are perspective views and cross-sectional views showing different implementations of the composite according to the present invention, respectively, showing an example of the results of a concrete investigation into the influence on the thermal change. 1: Ceramic molded body, 2: Solder layer, 3 Nis slurry layer, 4: Intermediate layer, 5: Metal layer, 10: Composite,
11: Mold, 12: Core, 13: Space, 14:
Injection hole, 15a: Burner introduction hole, 15b: Exhaust hole, 50: Molten metal. Patent applicant Nippon Steel Corporation
Claims (2)
鋳型内に装着固定した後溶融金属を注入し、前記セラミ
ックス成形体を金属で鋳包むセラミックスと金属との複
合体の製造方法において、前記セラミックス成形体の表
面に、層厚が０．００５〜２．４５ｍｍのソルダー層と
０．０５〜６．０ｍｍのセラミックス系水性スラリー層
とからなる中間層を、その総厚が０．０５５〜６．００
５ｍｍとなるよう形成し、乾燥処理した後、鋳型内に装
着固定することを特徴とするセラミックスと金属との複
合体製造方法。(1) A ceramic molded body formed into a predetermined shape,
In a method for manufacturing a composite of ceramics and metal, in which the ceramic molded body is mounted and fixed in a mold, molten metal is injected, and the ceramic molded body is cast with metal, the ceramic molded body has a layer thickness of 0.005 to 2. The intermediate layer consisting of a .45 mm solder layer and a 0.05 to 6.0 mm ceramic aqueous slurry layer has a total thickness of 0.055 to 6.00 mm.
A method for manufacturing a composite of ceramics and metal, which comprises forming the composite to a thickness of 5 mm, drying it, and then fixing it in a mold.
鋳型内に装着固定した後溶融金属を注入し、前記セラミ
ックス成形体を金属で鋳包むセラミックスと金属との複
合体の製造方法において、前記セラミックス成形体の表
面に、請求項（１）に記載の中間層を形成し、予め、溶
融金属とセラミックス成形体の種別毎に、前記中間層厚
と鋳包み時の熱衝撃割れ発生限界予熱温度との関係を求
めておき、セラミックス成形体を鋳型内に装着固定した
後、当該鋳包み条件と前記割れ発生限界予熱温度との関
係より設定される予熱温度でセラミックス成形体を予熱
し、しかる後溶融金属を注入することを特徴とするセラ
ミックスと金属との複合体製造方法。(2) A ceramic molded body formed into a predetermined shape,
In a method for producing a composite of a ceramic and a metal, the ceramic molded body is injected with molten metal after being mounted and fixed in a mold, and the ceramic molded body is cast with metal. An intermediate layer is formed, and the relationship between the intermediate layer thickness and the critical preheating temperature for thermal shock cracking during casting is determined in advance for each type of molten metal and ceramic molded body, and the ceramic molded body is placed in the mold. After mounting and fixing, the ceramic molded body is preheated at a preheating temperature set based on the relationship between the casting conditions and the cracking limit preheating temperature, and then molten metal is injected. Composite manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9762589A JPH0284242A (en) | 1988-06-16 | 1989-04-19 | Manufacture of complexed material of ceramic and metal |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-147012 | 1988-06-16 | ||
| JP14701288 | 1988-06-16 | ||
| JP9762589A JPH0284242A (en) | 1988-06-16 | 1989-04-19 | Manufacture of complexed material of ceramic and metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0284242A true JPH0284242A (en) | 1990-03-26 |
Family
ID=26438789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9762589A Pending JPH0284242A (en) | 1988-06-16 | 1989-04-19 | Manufacture of complexed material of ceramic and metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0284242A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934555A (en) * | 2010-08-19 | 2011-01-05 | 杨永利 | Method for toughening ceramic layers at end parts of centrifugal self-propagating ceramic lining compound oil pipe |
-
1989
- 1989-04-19 JP JP9762589A patent/JPH0284242A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101934555A (en) * | 2010-08-19 | 2011-01-05 | 杨永利 | Method for toughening ceramic layers at end parts of centrifugal self-propagating ceramic lining compound oil pipe |
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