JPS5813777A - Surface coating of inorganic fiber for reinforcing titanium and nickel - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for surface coating inorganic fibers used in the production of inorganic fiber reinforced titanium and nickel.

In recent years, metal materials compositely reinforced with inorganic fibers such as carbon fibers, alumina fibers, and silicon carbide fibers have been attracting attention as materials that are required to be high strength, heat resistant, and lightweight for aircraft components. It's here.

However, in the production of this type of fiber-reinforced metal material, composites of inorganic fibers and inorganic fibers that minimize the interfacial reaction between fibers and metals are currently not put to practical use.

The present invention is a surface coating method for inorganic fibers to facilitate and strengthen the composite of titanium or nickel with inorganic fibers. After coating the surface of the inorganic fiber with a solution containing dextrin as necessary and the remainder being water or an organic solvent, it is heated to 1300 to 17
It is characterized by heat treatment at 00°C. More specifically, titanate ester (T i (OR)
4. 1 part by weight of R: alkylmatahaaryl group) and boric acid ester (B (OR')n(OH) s
-n, n=1.2. a, a': alkyl group) 1
~・5 parts by weight of tetraalkylammonium (R', N-OH) dissolved in an organic solvent such as methanol or water
, R,': alkyl group) 10 to 30 parts by weight - 1 to 3 parts by weight of the solution and mixed to prepare a treatment liquid. Furthermore, dextrin may be added in an amount of 0.5 to 7% by weight based on the weight of the treatment liquid. If the composition of the treatment liquid is outside the above range, the viscosity of the line treatment liquid is 1N.
4 or it is too dilute, which is inconvenient when coating the surface of inorganic fibers; and it is not preferable that it does not form the following combination of titanium and boron during heat treatment.

Inorganic fibers (hereinafter referred to as fibers) such as carbon fibers (including graphite fibers), alumina fibers, silicon carbide fibers, potassium titanate fibers, boron fibers, and tungsten fibers are immersed in this treatment solution or A coating layer of about 0.05 to 3 μm is formed on the fiber surface by passing it through the fiber, and then, after drying if necessary, it is heated to 1300 to 1700°C in an inert or non-oxidizing atmosphere such as argon, helium, or nitrogen. The fiber surface is coated by heat treatment.

If the heat treatment temperature is lower than 1,300°C, the coating will be insufficient, and if it exceeds 1,700°C, the fibers will deteriorate, both of which are disadvantageous when forming composites.

A heat treatment time of about 10 to 60 seconds is sufficient.

The titanium and boron attached to the fiber surface by coating with the treatment liquid are removed by heat treatment, partly as linear oxides and partly as a compound with a non-stoichiometric composition of titanium/boron, and in addition to the treatment liquid to which dextrin is added. In the case of i, and in the case of carbon fiber, there is mold on the surface.

In the case of silicon carbide fibers in which a large amount of carbon is present, some of the carbon is attached to the fiber surface as carbide, and the entire surface of the fiber is coated with gold. This coating exhibits minimal reaction at the fiber/metal interface upon combination of the fibers with titanium and nickel, resulting in a good composite.

In addition, the present invention is a method in which the fiber surface is first coated using a liquid phase method and then heat treated at a relatively low temperature in a short time, so it can be easily carried out using simple equipment and does not require complicated operations. be.

In particular, titanium tends to react with fibers when coating them, and there is a concern that the surface of the fibers will become rough when coated with titanium, but the presence of boron has the effect of turning it into ductiles and will not weaken the fibers. - The presence of boron has a similar effect when combining fibers with titanium.

The effects of the present invention will be specifically described below using Examples.

Example 1 Tetraisoprovir titanate) (((CHs) 2C
H) a T t O4) 1 part by weight and 3 parts by weight of isopropylboreide (B(OCR(CH3)2)3) were combined with nato2methylammonium/1hydroxide (((C
A treatment solution was prepared by adding and mixing 2 parts by weight of a 20% by weight methanol solution of H3)4N)OH).

In this treatment solution, silicon carbide fibers (trade name "Nicalon" manufactured by Nippon Carbon) 500 filaments, fiber diameter 1
The fiber surface was coated with the treatment solution by continuously dipping the fiber (5μ) in the treatment solution, dried in air at 200°C for 30 seconds, and then heat-treated at 1400°C for 15 seconds in a nitrogen atmosphere to form the coating of the present invention. As a result of measuring this coating layer with an X@microanalyzer, the presence of boron and titanium was confirmed.

Example 2 Carbon fibers (part name "Carboron Z" manufactured by Nippon Carbon ■, 300G filament fiber diameter 7J1) were continuously immersed in the same treatment solution used in Example 1 to coat the fiber surface with the treatment solution, and then exposed to air. The coating of the present invention was formed by drying the inner shell at 50° C. for 40 seconds and then heat-treating it at 1600° C. for 20 seconds in a nitrogen atmosphere. This coating layer was tested for the presence of boron and titanium by the same method as in Example 1.

Example 3 Tetrabutyl titanate (T I (OCa H9)4
) 1 part by weight and triethylborate (B(QC) 1°C)
I3) 2 parts by weight of 3) were added to 3 parts by weight of a 30% by weight ethanol solution of tetramethylammonium hydroxide and mixed, and then 02 parts by weight of dextrin was added to prepare a treatment liquid.

Alumina fibers (200 filaments, fiber diameter 20μ) were immersed in this treatment solution to coat the fiber surface with the treatment solution, dried at 180°C for 40 seconds, and then heated at 150°C in a helium atmosphere.
Coating was performed by heat treatment at 0° C. for 50 seconds.

The presence of boron and titanium in this coating layer was confirmed by the same method as in Example 1.

Examples 4 to 9 The fibers having the coating layer of the present invention obtained in Examples 1 to 3 were used as reinforcing fibers, and composited with nickel and titanium, respectively, by the following method to obtain fiber reinforced nickel and titanium. Its characteristics are shown in Table 1.

■Composite method with nickel: Arrange the fibers and apply nickel chemical plating to coat the fiber surface with nickel (coating thickness is 3μ for silicon carbide fiber, 2μ for carbon fiber, 5μ for alumina fiber)
μ) After that, this was laminated with polystyrene resin as an adhesive, and hot pressed at 800℃ and molding pressure 500℃.
Hold for 1 hour and combine with titanium. Titanium powder (under 325 mesh) is dispersed in a polystyrene resin solution, and the fibers are continuously immersed in this solution to attach the titanium powder. Then, after aligning the fibers and laminating them, they were placed in a pot press at 850°C and a molding pressure of 700 min for 40 minutes to form a composite.

Comparative Examples 1 to 6 The same silicon carbide fibers, carbon fibers, and alumina fibers used in Examples 1 to 3 were combined without any surface coating in the same manner as in Comparative Examples 4 to 9. did. Its characteristics are shown in Table 1.

Table 1 Comparative Examples 7 to 8 The silicon carbide fibers used in Example 1 were continuously immersed in the same treatment solution as in Example 1 to coat the fiber surface with the treatment solution, and then heated in air at 200°C for 30 seconds. After drying, coating was performed by heat treatment under a nitrogen atmosphere at the temperature and time shown in Table 2. The coated fibers were composited with nickel in the same manner as in Example 4 to obtain fiber-reinforced nickel. The results are shown in Table 2.

As shown in Table 2, the present invention exhibits excellent effects using a relatively simple method, and is extremely useful industrially.

Patent applicant Nippon Carbon Co., Ltd. Representative Toshiko Ishikawa Procedural amendment November 30, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono1, Indication of the case 1982 Patent Order No. 1077212, Name of the invention Titanium and Surface coating method for nickel-reinforced inorganic fibers 3, relationship with the amended case Patent applicant address (residence) 2-6-1 Hatchobori, Chuo-ku, Tokyo
Issue □ 5. Number of inventions covered by the amendment 16. Subject of the amendment 7. Contents of the amendment (1) Claim 2 on page 1, lines 13 to 17 of the specification is corrected as follows. .

Method for coating the surface of inorganic fibers with a solution containing ◇” (2) “For an additional $4, titanate ester” on page 3, lines 2-3 of the same, is corrected as follows. "More specifically, the preferred composition of the solution for coating the surface of the inorganic edge is 0.1 to 0.9 parts by weight of titanate nitroxide and 0.7 to 2.7 parts by weight of water and organic solvent. This solution is a titanate ester.''(#) Correct ``methanol, etc.'' in line 6 of the same page to ``methanol, xylene, acetone, petroleum ether, etc.''

0) Oka, same page, line 10, "Adjust the processing solution 0 and the weight of the processing solution" to "It is preferable to adjust 0 and the weight of this solution" 0φ) Oka, same page, line 12, "Adjust the processing solution 0 and the weight of the processing solution""Composition" is corrected to "Composition of the solution (hereinafter referred to as treatment liquid)".

(6) "Titanium" on page 5, line 14 is corrected to "nickel".

(Te) Same, page 9, line 7, “Comparative Examples 4 to 9” was changed to “Example 4”
~9”.

Patent applicant: Nippon Carbon Co., Ltd.

Claims (1)

[Claims] 1) The surface of the inorganic fiber is coated with a solution containing a titanate ester, a borate ester, and a tetraalkylammonium hydroxide, the remainder being water or an organic solvent, and then heated under an inert or non-oxidizing atmosphere for 1300~ A method for surface coating inorganic fibers for reinforcing titanium and nickel, characterized by heat treatment at 1700°C. 2. Titanium according to claim 1, which is obtained by coating the surface of inorganic fibers with a solution obtained by adding 0.5 to 7 weight of dextrin based on the weight of the iron solution to the solution described in claim 1. and a surface coating method for nickel-reinforced inorganic fibers.