Method of bonding a metal oxide to a metal

Abstract: Inert non-magnetic metals are adhesively bonded to surfaces of metal oxides, for example ferrites, by means of a water vapour-hydrogen atmosphere. Reduction of the metal oxide only takes place at the interface of the inert metal and the metal oxide, after which the metal formed is partly dissolved in the inert metal.

Description: The invention relates to a method of bonding a surface of metal oxidic ceramic member to an inert metal layer, the inert metal layer being brought into contact with the surface of the ceramic member. A metal oxidic compound is to be understood to mean herein an oxidic compound of at least two metallic elements such as, for example, nickel ferrite NiFe₂O₄. Because of their magnetic properties ferrites are important ceramic compounds. Ferrites are used, inter alia, in magnetic heads for the purpose of magnetic recording. A thin non-magnetic metal layer is often applied between the two halves of the magnetic head, which metal layer serves as a so-called spacer. Such a method is described in United States Patent Specification US 3,793,705, in which titanium or chromium are applied to a ferrite by means of sputtering. Subsequently, the chromium layer is provided with a silver-containing brazing alloy. A non-magnetic metal is brought into contact herewith and the assembly is subsequently fired in an inert atmosphere, the bond between metal and ferrite being formed via the intermediate layer of chromium and the brazing alloy. A disadvantage of the known method is that metals such as titanium and chromium react with the oxygen present in the sputtering gas or residual gas instead of with the oxygen of the metal oxidic compound, as a result of which the bonding of these metals to the metal oxide is insufficient. Moreover, a brazing alloy is required for the bonding to a second non-magnetic metal. The brazing alloy may interact undesirably with the bonding layer and/or the metal layer. It is an object of the invention to provide a method of the type mentioned in the opening paragraph which overcomes the above disadvantages. According to the invention this object is achieved by a method as described in the opening paragraph, which is further characterized in that metal oxide of the ceramic member is subsequently reduced only at the interface ceramic member - inert metal layer to the corresponding metal by means of a reducing gas mixture including hydrogen and water vapour at a temperature between 800 and 1100 K and the partial pressure ratio between hydrogen and water vapour is smaller than 10⁻², said metal and the inert metal mixing, whereby a bond is formed between the ceramic member and the inert metal layer. The bonding of an inert metal Me to NiFe₂O₄ (nickel ferrite) is used as an example. The metal Me has been previously provided onto the surface of the ferrite, for example, by means of sputtering or vacuum evaporation. The reducing gas mixture contains gas in the reduced form G red and gas in the oxidised form G ox . The reaction taking place can be represented as follows: NiFe₂O₄ + G red + Me → Fe₂O₃ + G ox + [Ni] Me (I). In this equation [Ni] Me is a solid solution of Ni in the inert contact metal Me. In this case only NiO (least stable oxide) of NiFe₂O₄ is reduced to Ni: NiO → Ni + 1/2 O₂ - Q red . In this equation Q red is the required reduction energy. This reaction is brought about by the oxidation heat Q ox from G red to G ox and the heat of solution Q L of Ni in the metal Me: G red + 1/2 O₂ → G ox + Q ox Ni + Me → [Ni] Me + Q L . The reducing power (reduction potential) of the reducing gas mixture is determined by the ratio p(G red ): p(G ox ). Herein p is the partial pressure of the gas G. In combination with the heat of solution Q L the reduction potential is to be adjusted so that reduction of the metal oxide only takes place at the interface Me-metal oxide. Too strong a reducing power of the gas mixture would lead to reduction of the entire oxide, causing the loss of important properties such as magnetic properties. Q red , Q ox , Q L and solubilities of metals can be found in reference books. By calculating the free energy ΔG of the reaction (I) the ratio p(G ox ) : p(G red ) can be determined. According to the invention the reducing gas mixture comprises hydrogen and water vapour. In the foregoing G red denotes hydrogen and G ox denotes water vapour. Other reducing gas mixtures such as CO and CO₂ may alternatively be used. According to the invention the reduction takes place at a temperature between 800 and 1100 K and the partial pressure ratio between hydrogen and water vapour is smaller than 10⁻². Under these conditions a properly adhering bond between the inert metal and the oxidic surface is obtained in 5 minutes, the reduction of the metal oxide taking place only at the surface. An embodiment of the method according to the invention is characterized in that the inert metal is selected from the group formed by platinum, iridium and rhenium. Under the process conditions these metals are inert relative to oxygen and, moreover, they are non-magnetic so that they can suitably be used as a spacer layer in magnetic heads. Other non-magnetic metals such as Mo and W may alternatively be used. A suitable embodiment of the method according to the invention is characterized in that the inert metal is provided by means of sputtering or vacuum evaporation. Unlike chromium and titanium, the use of the above inert metals does not lead to oxidation of the metal by the sputtering gas or residual gas. A very suitable embodiment of the method according to the invention is characterized in that the ceramic member is a ferrite. Ferrites are ferromagnetic metal oxides of the general formula MFe₂O₄. In this formula, M is a bivalent metal. The metal M may be partly replaced by another bivalent metal. An embodiment of the method according to the invention is characterized in that the ferrite is nickel ferrite, nickel zinc ferrite or manganese zinc ferrite. The formula of nickel zinc ferrite is Ni x Zn 1/x Fe₂O₄ and the formula of manganese zinc ferrite is Mn x Zn 1-x Fe₂O₄. In this formula x is the molar fraction of Ni and Mn, respectively, in the ferrite. The invention will be explained by means of the following exemplary embodiments: Examples: Blocks of polycrystalline nickel-zinc ferrite Ni 0.1 Zn 0.9 Fe₂O₄ having the dimensions 10x6x2.5 mm are polished on one side (face 10 x 6 mm). These polished faces are cleaned by means of an Ar⁺ ion bombardment having an energy of 50 eV and a current density of 10 mA/cm². Subsequently a platinum layer having a thickness from 200 - 300 nm is provided on these faces by means of sputtering. The gas mixture in which the samples are heated, is prepared from boiling water at atmospheric pressure to which a mixture consisting of nitrogen and 7 % of hydrogen is added. The gas mixture obtained is led to a bell-jar via a pipe whose wall temperature is kept above 100°C. The samples are contained in a metal box in the bell-jar and are heated by means of a RF field at an overall pressure of 1 bar. The samples are heated at temperatures of 800 or 1100 K for 5 minutes. The ratio is adjusted to 10⁻¹, 10⁻² and 10 -3.3 , respectively. By means of AES and SIMS analyses concentration profiles of the metallic elements are measured in a direction perpendicular to the interface platinum-ferrite. To measure the strength of the bond between platinum and ferrite after the reduction treatment, the blocks are provided on the platinum side with two parallel gold wires having a diameter of 200 µm. An identical block is placed on these gold wires in such a manner that the platinum side faces the gold wires. This assembly is pressed together using a force of 300 N and heated in air for 10 minutes at 500°C. The bonding surface area is 4.8 mm². The tensile break is measured by means of a tensile strength tester. The results are listed in the following table. The table shows that the reducing power of the gas mixture used for the samples 1 and 2 is too large. Under these conditions reduction of the bulk of the ferrite takes place. The three oxides of zinc, nickel and iron are reduced to the corresponding metals which subsequently dissolve in platinum. In the case of the preparations 3 and 4 only reduction of zinc oxide to zinc takes place, the zinc formed dissolving in platinum. After the reduction treatment the platinum layer of a sample treated in accordance with Nos. 3 and 4 is polished as far as the original platinum-ferrite interface. By measuring the so-called Kerr-effect it is established that the reduction treatment has not changed the magnetooptical properties of the ferrite. In this measuring operation, polarised monochromatic light is reflected from the surface to be measured and the rotation of the plane of polarisation is determined. In the case of preparations treated in accordance with Nos. 1 and 2, however, the Kerr-effect can be measured clearly. On determining the tensile break it has been found that in all cases the ferrite is subject to breakage.

Claims: A method of bonding a surface of a metal oxidic ceramic member to an inert metal layer, the inert metal layer being brought into contact with the surface of the ceramic member, characterized in that metal oxide of the ceramic member is subsequently reduced only at the interface ceramic member - inert metal layer to the corresponding metal by means of a reducing gas mixture including hydrogen and water vapour at a temperature between 800 and 1100 K and the partial pressure ratio between hydrogen and water vapour is smaller than 10⁻², said metal and the inert metal mixing, whereby a bond is formed between the ceramic member and the inert metal layer. A method as claimed in Claim 1, characterized in that the inert metal is selected from the group formed by platinum, iridium and rhenium. A method as claimed in Claim 1 or 2, characterized in that the inert metal is provided by means of sputtering or vacuum evaporation. A method as claimed in Claim 1, 2 or 3, characterized in that the ceramic member is made from ferrite. A method as claimed in Claim 4, characterized in that the ferrite is nickel zinc ferrite or manganese zinc ferrite.

Inventors: CAERS FRANS JUSTIN MARIA, KLOMP JOHANNES THEODORUS, VAN DE VEN ADRIANUS JOHANNES C, CAERS, FRANS JUSTIN MARIA, KLOMP, JOHANNES THEODORUS, VAN DE VEN, ADRIANUS JOHANNES CORNELIS
Applicants: PHILIPS NV, N.V. PHILIPS' GLOEILAMPENFABRIEKEN
Application year: 1989
Main classification: C04B41
IPC codes: C23C26, C04B41, C23C14