JPH02233567A - Jointing of metal to ceramic - Google Patents

Abstract

PURPOSE:To accomplish easy, firm jointing between a base metal alloy form and a ceramic by pre-heat treatment of said base metal alloy form and sputtering metallic titanium on the surface of the form to effect lamination followed by jointing said ceramic thereto while carrying out baking. CONSTITUTION:A base metal alloy form such as of Ni-Cr alloy, Co-Cr alloy or Fe alloy is pre-heat treated and metallic titanium is sputtered on the resulting surface to effect lamination. The thickness of the metallic titanium layer formed is pref. 2000-3000Angstrom . Thence, a ceramic is jointed to said layer while carrying out baking, thus accomplishing the objective jointing. in this jointing process, a multiple oxide is formed from the Ti and base metal alloy; therefore, adherability between the alloy and the ceramic will be improved. The present jointing method is suitably applied to e.g. the jointing between an alloy material and a ceramic for dental use.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for joining metals and ceramics that can be applied to the production of heat-resistant, high-strength materials such as dental materials or gas turbine materials.

[Prior Art] In recent years, various composite materials of metal and ceramics have been developed as materials that have the beauty and heat resistance of ceramics and the strength and workability of metals.

For example, the mainstream of dental prosthetic restorations is an aesthetic material called metal-baked porcelain, which is made by bonding noble metal alloys and ceramics. In this case, the connection between the two is
The precious metal material is Sn. A method is used in which the ceramic and the noble metal material are chemically bonded by forming an alloy to which a trace amount of an element such as In or Fe is added, and a selective oxide is formed by precipitating the trace amount of the added element on the alloy surface during firing of the ceramic.

However, recently, from the point of view of economy or the need to supplement the strength of ceramics, Ni-Cr and Co-based materials, which have a high elastic modulus, have been
- Base metal alloys such as Cr-based and Fe-based alloys are usedb [Issue 2i to be solved by the invention] When base metal alloys are used in composite materials with ceramics, the same joining method as for noble metal alloy materials is used. If this is done, the adhesion between the oxide precipitated on the alloy surface and the alloy and ceramics is poor, making it easy for the alloy and ceramics to separate.
A good bonded body cannot be obtained.

[Means for Solving the Problems] The present invention is intended to solve the above-mentioned problems, and is capable of achieving good results 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 zygote is obtained.

That is, the present invention is a method for joining metals 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.

As the base metal alloy, alloys such as Ni-10 to 20% Cr-based, Co-Cr-based, Fe-based, etc. are used.

An example of Fe-based alloy is Fe33-40%, Ni17
~20%, Crt7~20%, Co17~20%, Mn
1.3-1.5%, Si0.4-0.5%
, Mo 8 to 10%. Such a base metal alloy is 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 polarization during casting, degassing, etc., and is carried out, for example, at 900° C. for 5 minutes. The thickness of the metallic titanium film formed by sputtering is 2000 to 3000.
Good range of people.

This metallic titanium sputtered film is formed under conditions that suppress the formation of an oxide layer as much as possible.

Then, the ceramic base is sintered in close contact with the metallic titanium backing layer. For example, in the case of dental use, the ceramics used include frit porcelain whose main components are Si02, A1203, K20, ZrOz, etc. Other examples include heat-resistant ceramic materials.

Sintering is usually done in two stages: a base coat and a top coat. Undercoat at 500-780℃ in low vacuum for 3-4 minutes, then 780-8℃ in air.
00℃ for about 1 minute, and the top coat is 500 to 770 in low vacuum.
℃ for 3 to 4 minutes, and then heated at 770 to 800℃ for about 1 minute in the air.

[Function] When the metallic titanium spatter layer laminated on the surface of the base metal alloy molded body is bonded by firing with the ceramic layer brought close together, T
A composite oxide is formed with i and CrSNi or Ti and C', FeSCo, and even Ni to improve the adhesion between the alloy layer and the ceramic.

Example L Example I Ni-20wt%C A dental material was produced by the lost wax method using the alloy. Next, the joint surface with the ceramics is uniformly finished with a thin emery bar, and after demolition with alcohol and ultrasonic cleaning, a preheating treatment is performed at 900° C. for 5 minutes.

Next, metal titanium is sputtered onto the pretreated surface of the alloy material using a sputtering device to a film thickness of 2000 to 3000 mm. At this time, make sure that titanium metal does not change into an oxide.

In the metallic titanium spatter layer formed by the above method, S
Dental ceramics containing tOz, A120, K20, and Zro2 as main components were coated and fired at 800°C.

Figure 1 shows an electron microscope photograph (Hitachi model S-570) and line segment tri (KEV
EX analyzer DELTAf. :． J) shows the results.

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 Ti1Cr etc. Several μl−+ from the interface: It can be seen that it is diffused into the ramix.

A bonding test piece of Alloy 1 and Ceramic 2 as shown in Fig. 3 was prepared by the above method and a tensile test was conducted, and the bond strength showed a value of 330 to 590 kgr/cm'', and there was no fracture condition. A good bonded body was obtained with no peeling at the interface and rupture at the ceramic part.

Example 2 Fe: 3L5wt%, Ni:
19.5wt%, C r :19.5vt%, C
o: 19.5wt%, Mo: 8.
Ovt%, Mn: 1.5vt%, St:
An austenitic alloy consisting of 0.5 wt % was used, and the other conditions were the same as in Example 1 to bond it to ceramics.

FIG. 4 shows an electron micrograph and line analysis results when a metallic titanium sputtered layer was formed on the alloy surface. Figure 5 shows the result of sintered bonding with ceramics, and shows that the alloy and ceramics are strongly bonded, and the line analysis results show that TL, Cr, Fe, etc. are contained in ceramics, such as Sl. It can be seen that a diffusion layer is formed.

A tensile test was conducted on the product under these conditions in the same manner as in Example 1.
In terms of bonding strength and breaking strength, there was no interfacial peeling, and the ceramic part broke.

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 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.

Comparative Example 2 The austenitic alloy of Example 2 was joined to ceramics in the same manner as Comparative Example 1.

FIGS. 7 and 8 are electron micrographs of the same. When this was subjected to a tensile test, peeling occurred between or within the oxide layers.

[Effects of the Invention] According to the present invention, a good joined body of a base metal alloy molded body and ceramics can be easily obtained, and is useful for manufacturing dental materials or heat-resistant high-strength materials.4. ! fWA”.”l=t
&Gate 1 Figure 1 is an electron microscope photograph showing the structure when the metallic titanium spatter layer was formed in Example 1, Figure 2 is an electron microscope photograph showing the structure when ceramics are bonded, and Figure 3 is an electron microscope photograph showing the structure when ceramics are bonded. Plan view and side view of the test piece, FIG. 4 is Example 2
Fig. 5 is an electron micrograph showing the structure when a metallic titanium spatter layer is formed, Fig. 5 is an electron micrograph showing the structure when ceramics are bonded together, and Fig. 6 is the structure after oxidation treatment in a comparative example. Electron micrographs, 7th and 8th
The figures show electron micrographs showing the structure after oxidation treatment in Comparative Example 2.

1...Alloy, 2...Ceramics.

5? II! I Figure 2 Figure 3 Patent applicant: Kodo Metal Industry Co., Ltd. Agent Patent Attorney Hidetake Komatsu

Claims (3)

[Claims] (1) A method for joining metals and ceramics, which comprises preheating a base metal alloy molded body, sputtering titanium metal onto the surface, and then firing and joining ceramics thereto. (2) The base metal alloy is Ni-Cr, Co-Cr, or Fe.
2. The method of joining a metal and ceramic according to claim 1, wherein the metal is an alloy of the above-mentioned type. (3) The method for joining metal and ceramics according to (1), wherein the thickness of the titanium metal formed by sputtering is 2000 to 3000 Å.