JPH0547512B2 - - Google Patents
Info
- Publication number
- JPH0547512B2 JPH0547512B2 JP5388489A JP5388489A JPH0547512B2 JP H0547512 B2 JPH0547512 B2 JP H0547512B2 JP 5388489 A JP5388489 A JP 5388489A JP 5388489 A JP5388489 A JP 5388489A JP H0547512 B2 JPH0547512 B2 JP H0547512B2
- Authority
- JP
- Japan
- Prior art keywords
- ceramics
- alloy
- metal
- layer
- joining
- 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.)
- Expired - Lifetime
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- 239000000919 ceramic Substances 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000010953 base metal Substances 0.000 claims description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 10
- 238000005304 joining Methods 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 4
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 229910018487 Ni—Cr Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 8
- 238000000635 electron micrograph Methods 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005548 dental material Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011351 dental ceramic Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Pressure Welding/Diffusion-Bonding (AREA)
- Ceramic Products (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は歯科用材料あるいはガスタービン用材
料のような耐熱高強度材料などの製造に適用でき
る金属とセラミツクスとの接合方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for joining metal and ceramics that can be applied to the production of heat-resistant, high-strength materials such as dental materials or gas turbine materials.
［従来の技術］
近年セラミツクスのもつ美観や耐熱姓と金属の
もつ強度や加工性とを兼備した材料として金属と
セラミツクスとの複合材料が種々開発されてい
る。[Prior Art] In recent years, various composite materials of metal and ceramics have been developed as materials that combine the beauty and heat resistance of ceramics with the strength and workability of metals.
例えば歯科補綴修復物は貴金属合金とセラミツ
クス（陶材）を接合させた審美性のある金属焼付
ポーセレンと称する材料が主流となつている。こ
の場合両者の接合は、貴金属材料をSn、Inある
いはFeなどの元素を微量添加した合金とし、セ
ラミツクス焼成時に微量添加元素が合金表面に析
出して形成した選択酸化物によつて、セラミツク
スと貴金属材料とを化学結合させる方法がとられ
ている。 For example, the mainstream of dental prosthetic restorations is an aesthetically pleasing material called metal-baked porcelain, which is made by bonding precious metal alloys and ceramics. In this case, the bond between the two is made by using an alloy containing small amounts of elements such as Sn, In, or Fe as the precious metal material, and by selective oxide formed by the small amount of added elements precipitating on the surface of the alloy during firing of the ceramics. A method of chemically bonding materials is used.
しかし最近では経済性の点あるいはセラミツク
スの強度を補う必要性から、弾性係数の高いNi
−Cr系、Co−Cr系、Fe系等の卑金属合金が利用
されている。 However, recently, due to economical reasons or the need to supplement the strength of ceramics, Ni, which has a high elastic modulus, has been used.
- Base metal alloys such as Cr-based, Co-Cr-based, and Fe-based are used.
［発明が解決しようとする課題］
卑金属合金をセラミツクスとの複合材料に用い
た場合には、貴金属合金材料と同様の接合方法を
行うと、合金表面に析出する酸化物と合金並びに
セラミツクスとの密着性が悪いために、合金とセ
ラミツクスとが剥離し易く、良好な接合体が得ら
れない。[Problems to be Solved by the Invention] When a base metal alloy is used in a composite material with ceramics, if the same joining method as for the noble metal alloy material is performed, oxides precipitated on the alloy surface will adhere to the alloy and ceramics. Due to the poor properties, the alloy and ceramics tend to separate, making it impossible to obtain a good joined body.
［課題を解決するための手段］
本発明は上記問題点を解決するためのものであ
り、卑金属合金成形体の表面に合金とセラミツク
スとの双方に接合し易い金属層を形成することに
よつて良好な接合体を得るものである。[Means for Solving the Problems] The present invention is intended to solve the above-mentioned problems by forming a metal layer on the surface of a base metal alloy compact that is easily bonded to both the alloy and ceramics. A good bonded product can be obtained.
すなわち、本発明は卑金属合金成形体を予備加
熱処理して表面に金属チタンをスパツタリングに
より積層した後、これにセラミツクスを焼成接合
することを特徴とする金属とセラミツクスとの接
合方法である。 That is, the present invention is a method for joining metal and ceramics, which comprises preheating a base metal alloy molded body, sputtering metal titanium on the surface thereof, and then firing and joining ceramics thereto.
卑金属合金としてはNi−10〜20％Cr系、Co−
Cr系、Fe系などの合金が用いられる。Fe系合金
の一例としてはFe33〜40％、Ni17〜20％、Cr17
〜20％、Co17〜20％、Mn1.3〜1.5％、Si0.4〜0.5
％、Mo6〜10％の組成のものが挙げられる。か
かる卑金属合金は例えばロストワツクス法により
成形し、ついで予備加熱処理をする。予備加熱処
理は鋳造応力の緩和、鋳造時の偏析除去、脱ガス
等を考慮した処理であるが、例えば900℃で５分
間行う。そしてスパツタリングにより形成する金
属チタンの膜厚は2000〜3000Åの範囲がよい。 Base metal alloys include Ni-10~20% Cr, Co-
Alloys such as Cr-based and Fe-based are used. Examples of Fe-based alloys include Fe33~40%, Ni17~20%, Cr17
~20%, Co17~20%, Mn1.3~1.5%, Si0.4~0.5
%, Mo6 to 10%. Such base metal alloys are formed by, for example, a lost wax method, and then subjected to a preliminary heat treatment. The preheating treatment is a treatment that takes into account relaxation of casting stress, removal of segregation during casting, degassing, etc., and is performed at 900° C. for 5 minutes, for example. The thickness of the metallic titanium film formed by sputtering is preferably in the range of 2000 to 3000 Å.
この金属チタンスパツタ膜は酸化物層の形成が
極力押えられるような条件で形成させる。 This metallic titanium sputter film is formed under conditions that suppress the formation of an oxide layer as much as possible.
ついでセラミツクス素材を該金属チタンスパツ
タ層に密着させて焼結する。使用するセラミツク
スは例えば歯科用の場合、SiO2、Al2O3、K2O、
ZrA2などを主成分とするフリツト磁器が挙げら
れる。その他耐熱性セラミツクス材料等が挙げら
れる。 Next, a ceramic material is brought into close contact with the sputtered titanium metal layer and sintered. For example, ceramics used for dental purposes include SiO 2 , Al 2 O 3 , K 2 O,
Examples include fritted porcelain whose main component is ZrA 2 . Other examples include heat-resistant ceramic materials.
焼結は通常下塗と上塗の２段階で行う。下塗は
低真空で500〜780℃、３〜４分ついで大気中で
780〜800℃、１分程度行い、上塗は低真空で500
〜770℃、３〜４分、ついで大気中で770〜800℃
１分程度行う。 Sintering is usually done in two stages: a base coat and a top coat. Undercoat at 500 to 780℃ in a low vacuum for 3 to 4 minutes, then in the air.
780 to 800℃ for about 1 minute, and the top coat is applied at 500℃ in a low vacuum.
~770℃, 3-4 minutes, then 770-800℃ in air
Do this for about 1 minute.
［作用］
卑金属合金成形体表面に積層した金属チタンス
パツタ層がセラミツクス層を密着させて焼成接合
する場合に、TiとCr、NiあるいはTiとCr、Fe、
CoさらにはNiと複合酸化物を形成して、合金層
とセラミツクスとの密着性を良くする。[Function] When the metallic titanium spatter layer laminated on the surface of the base metal alloy compact is bonded by firing with the ceramic layer in close contact, Ti and Cr, Ni or Ti and Cr, Fe,
Co and Ni form a composite oxide to improve the adhesion between the alloy layer and ceramics.
［実施例］
実施例 １
Ni−20wt％Cr合金を用いロストワツクス法に
より歯科用材料を作製した。次にセラミツクスと
の接合面を細いエメリペーパーで均一に仕上げ、
アルコールにて脱脂および超音波洗浄後、900℃
で５分間加熱の予備加熱処理を施す。[Examples] Example 1 A dental material was produced using a Ni-20wt%Cr alloy by the lost wax method. Next, finish the joint surface with the ceramics evenly with thin emery paper.
After degreasing with alcohol and ultrasonic cleaning, 900℃
Perform preheating treatment for 5 minutes.
次に前処理後の合金材表面にスパツタリング装
置を用いて金属チタンを2000〜3000Åの膜厚にな
るようにスパツタする。その際金属チタンが酸化
物に変化することのないようにする。 Next, titanium metal is sputtered onto the pretreated surface of the alloy material using a sputtering device to a thickness of 2000 to 3000 Å. At this time, make sure that titanium metal does not change into an oxide.
上記の方法により形成した金属チタンスパツタ
層に、SiO2、Al2O3、K2O、ZrO2を主成分とする
歯科用セラミツクスを被覆して800℃にて焼成し
た。 The metallic titanium sputter layer formed by the above method was coated with dental ceramics containing SiO 2 , Al 2 O 3 , K 2 O, and ZrO 2 as main components, and fired at 800°C.
第１図は金属チタンスパツタ層を形成したとき
の電子顕微鏡（日立製Ｓ−570型）写真と線分析
（KEVEX社製の分析器DELTAによる）結果を
示すものである。 FIG. 1 shows an electron microscope photograph (model S-570 manufactured by Hitachi) and the results of line analysis (using an analyzer DELTA manufactured by KEVEX) when a metallic titanium spatter layer was formed.
第２図はセラミツクスを被覆して焼成したもの
の電子顕微鏡写真と線分析結果を示すもので、合
金とセラミツクスとが強固に接合している様子が
うかがわれ、点分析の結果からもTi、Crなどが
界面から数μｍセラミツクス中に拡散しているこ
とが判る。 Figure 2 shows an electron micrograph and line analysis results of a ceramic coated and fired product, which shows that the alloy and ceramics are firmly bonded, and the point analysis also shows that Ti, Cr It can be seen that these substances are diffused into the ceramic several micrometers from the interface.
上記の方法により第３図に示すような合金１と
セラミツクス２との接合試験片をつくり、引張試
験を行つたところ、接合強さは330〜590Kgｆ／cm2
の値を示し、かつ破断状況も界面で剥離せず、セ
ラミツクス部で破断して良好な接合体が得られ
た。 A bonding test piece of Alloy 1 and Ceramics 2 as shown in Fig. 3 was prepared by the above method and a tensile test was conducted, and the bond strength was 330 to 590 Kgf/cm 2
A good bonded body was obtained, with no peeling at the interface and rupture at the ceramic part.
実施例 ２
Fe：33.5wt％、Ni：19.5wt％、Cr：19.5wt％、
Co：19.5wt％、Mo：6.0wt％、Mn1.5wt％、
Si：0.5wt％よりなるオーステナイト系合金を用
い、他は実施例１と同様にしてセラミツクスと接
合した。Example 2 Fe: 33.5wt%, Ni: 19.5wt%, Cr: 19.5wt%,
Co: 19.5wt%, Mo: 6.0wt%, Mn1.5wt%,
An austenitic alloy consisting of 0.5 wt% Si was used, and the other conditions were the same as in Example 1 to bond it to ceramics.
第４図は合金表面に金属チタンスパツタ層を形
成したときの電子顕微鏡写真並びに線分析結果を
示すものである。第５図はセラミツクスと焼成結
合したものについてのもので合金とセラミツクス
とが強固に接合している様子がうかがわれ、線分
析結果ではTi、Cr、Feなどがセラミツクスに含
まれているSiなどと拡散層を形成している様子が
うかがわれる。 FIG. 4 shows an electron micrograph and line analysis results when a metallic titanium sputter layer was formed on the alloy surface. Figure 5 shows the material bonded to ceramics by sintering, and it can be seen that the alloy and ceramics are strongly bonded, and the line analysis results show that Ti, Cr, Fe, etc. are included in the ceramics, such as Si, etc. It can be seen that a diffusion layer is formed.
この条件のものについて実施例１と同様に引張
試験を行つたところ、120〜480Kgｆ／cm2の接合強
さで、破断強度も界面剥離せず、セラミツクス部
で破談した。 When a tensile test was carried out under these conditions in the same manner as in Example 1, the bonding strength was 120 to 480 Kgf/cm 2 , and the breaking strength did not cause interfacial peeling, but fracture occurred at the ceramic portion.
比較例 １
Ni−20wt％Cr合金を用いて実施例１と同様に
して歯科用材料をつくり、前処理を施した。次に
前処理後の合金材表面にスパツタリング装置を用
いて金属Ti層をスパツタリングにより形成した。
この金属Ti層を800℃で60分酸化処理し、この上
に実施例１と同様に歯科用セラミツクス層を形成
し、同様の試験をしたところ、第６図に見られる
ように合金と酸化物層間のところどころに間〓が
認められた。これを第３図の試験片により引張試
験を行つたところ、酸化物層間あるいは酸化物層
内で剥離がおこつた。Comparative Example 1 A dental material was prepared in the same manner as in Example 1 using a Ni-20wt%Cr alloy, and pretreated. Next, a metal Ti layer was formed by sputtering on the pretreated alloy material surface using a sputtering device.
This metallic Ti layer was oxidized at 800°C for 60 minutes, a dental ceramic layer was formed on top of it in the same manner as in Example 1, and the same test was conducted. As shown in Figure 6, the alloy and oxide were Gaps were observed here and there between the layers. When this was subjected to a tensile test using the test piece shown in FIG. 3, peeling occurred between or within the oxide layers.
比較例 ２
実施例２のオーステナイト系合金を用い、比較
例１と同様にしてセラミツクスと接合した。第７
図および第８図はその電子顕微鏡写真で、これを
引張試験に付したところ、酸化物層間あるいは酸
化物層内で剥離が起つた。Comparative Example 2 The austenitic alloy of Example 2 was bonded to ceramics in the same manner as Comparative Example 1. 7th
Figure 8 and Figure 8 are electron micrographs of the same, and when this was subjected to a tensile test, peeling occurred between or within the oxide layers.
［発明の効果］
本発明によれば卑金属合金形成体とセラミツク
スとの良好な接合体が容易に得られ、歯科用材料
あるいは耐熱高強度などの製造に有用である。[Effects of the Invention] According to the present invention, a good joined body of a base metal alloy formed body and ceramics can be easily obtained, and it is useful for manufacturing dental materials or heat-resistant and high strength materials.
第１図は実施例１における金属チタンスパツタ
層を形成したときの組織を示す電子顕微鏡写真、
第２図はセラミツクスを接合したときの金属組織
を示す電子顕微鏡写真、第３図は試験片の平面図
並びに側面図、第４図は実施例２の金属チタンス
パツタ層を形成したときの組織を示す電子顕微鏡
写真、第５図は同じくセラミツクスを接合したと
きの金属組織を示す電子顕微鏡写真、第６図は比
較例における酸化処理後の金属組織を示す電子顕
微鏡写真、第７、８図は比較例２における酸化処
理後の金属組織を示す電子顕微鏡写真をそれぞれ
示す。
１……合金、２……セラミツクス。
FIG. 1 is an electron micrograph showing the structure when forming the metallic titanium sputter layer in Example 1;
Figure 2 is an electron micrograph showing the metallographic structure when the ceramics are bonded, Figure 3 is a plan view and side view of the test piece, and Figure 4 is the structure when the metallic titanium spatter layer of Example 2 is formed. Electron micrograph; Figure 5 is an electron microscope photograph showing the metal structure when ceramics are joined together; Figure 6 is an electron microscope photograph showing the metal structure after oxidation treatment in a comparative example; Figures 7 and 8 are comparative examples. Electron micrographs showing the metal structure after oxidation treatment in No. 2 are shown. 1...alloy, 2...ceramics.
Claims (1)
に金属チタンをスパツタリングにより積層した
後、これにセラミツクスを焼成接合することを特
徴とする金属とセラミツクスとの接合方法。 ２ 卑金属合金がNi−Cr系、Co−Cr系、Fe系の
合金である請求項１記載の金属とセラミツクスと
の接合方法。 ３ スパツタリングにより形成する金属チタンの
膜厚が2000〜3000Åである請求項１記載の金属と
セラミツクスとの接合方法。[Scope of Claims] 1. A method for joining metal and ceramics, which comprises preheating a base metal alloy molded body, sputtering metal titanium on the surface thereof, and then firing and joining ceramics thereto. 2. The method of joining metal and ceramics according to claim 1, wherein the base metal alloy is a Ni-Cr alloy, a Co-Cr alloy, or an Fe alloy. 3. The method of joining metal and ceramics according to claim 1, wherein the thickness of the titanium metal formed by sputtering is 2000 to 3000 Å.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5388489A JPH02233567A (en) | 1989-03-08 | 1989-03-08 | Jointing of metal to ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5388489A JPH02233567A (en) | 1989-03-08 | 1989-03-08 | Jointing of metal to ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02233567A JPH02233567A (en) | 1990-09-17 |
| JPH0547512B2 true JPH0547512B2 (en) | 1993-07-16 |
Family
ID=12955166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5388489A Granted JPH02233567A (en) | 1989-03-08 | 1989-03-08 | Jointing of metal to ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02233567A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5432568B2 (en) * | 2009-04-08 | 2014-03-05 | 株式会社豊田中央研究所 | Metal / ceramic bonded body and manufacturing method thereof |
-
1989
- 1989-03-08 JP JP5388489A patent/JPH02233567A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02233567A (en) | 1990-09-17 |
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