Method of manufacturing glass-impregnated fiber-reinforced...

Glass manufacturing – Processes – Sol-gel or liquid phase route utilized

Reexamination Certificate

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C165S091000, C165S045000, C427S397700, C427S397800, C427S398100, C427S452000

Reexamination Certificate

active

06460374

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a glass-impregnated fiber-reinforced ceramic suitable for use in a hot oxidizing atmosphere, and a method of manufacturing the same.
2. Description of the Related Art
Ceramics have become watched as lightweight, highly heat-resistant structural materials in recent years owing to their excellent heat resistance superior to that of metals, and their high specific strength. However, there are still problems in using ceramics as structural materials in respect of reliability because ceramics have low toughness as compared with that of metals. Efforts have been made for the development of fiber-reinforced ceramic composite materials having high toughness as well as the excellent characteristics of ceramic materials.
Generally, the toughness of a fiber-reinforced ceramic (hereinafter referred to sometimes as “FRC”) is most greatly dependent on the bonding strength of the interface between the fibers and the matrix of the FRC. The toughness is high if the bonding strength of the interface between the fibers and the matrix is low, and is low if the bonding strength of the interface between the fibers and the matrix is high. Such a characteristic of toughness is considered to be due to a fact that energy is consumed in extracting the fibers from the matrix if the bonding strength of the interface between the fibers and the matrix is low. Accordingly, when producing an FRC having a high toughness, the bonding strength of the interface between the fibers and the matrix of the FRC is reduced properly by, for example, coating the fibers.
The fiber-reinforced ceramic has a ceramic matrix, and inorganic fibers, i.e., reinforcing material, embedded in the ceramic matrix, and the ceramic matrix and the inorganic fibers are chosen out of various materials. The following are representative FRC manufacturing methods.
(a) Method which molds a mixture of fibers and a ceramic precursor, namely, a substance which can be converted into a ceramic material by thermal decomposition, in a molding and fires the molding.
(b) Method which forms a structure only from fibers, impregnates the structure with a ceramic precursor, and fires the structure impregnated with the ceramic precursor (Japanese patent application unexamined laid open No. 8-157271).
(c) Method which forms a structure only from fibers, impregnates the structure with a molten ceramic material, and fires the structure impregnated with the molten ceramic material.
Fiber-reinforced ceramics having excellent heat resistance, high specific strength and high toughness as mentioned above are used widely for various purposes. However, the following problems arise when conventional FRCs are used a hot oxidizing atmosphere.
Referring to
FIG. 5
showing a fiber-reinforced ceramic
1
manufactured by a conventional method in a typical sectional view, the fiber-reinforced ceramic
1
has a ceramic matrix
4
, and inorganic fibers
3
embedded in the ceramic matrix
4
, and the ceramic matrix
4
has voids
5
which develop unavoidably during a manufacturing process. If the inorganic fibers
3
are, for example, silicon carbide fibers, the ceramic matrix
4
is silicon carbide, and the FRC
1
is heated at 1200° C. in the atmosphere, oxygen permeates the FRC through the voids
5
, reaches the interfaces between the silicon carbide fibers and the silicon carbide matrix, and oxidizes the silicon carbide fibers and the silicon carbide matrix to produce SiO
2
glass in the interfaces. The SiO
2
glass formed in the interfaces bonds the silicon carbide fibers and the silicon carbide matrix firmly together, which reduces the toughness of the FRC
1
greatly. Therefore, the strength at elevated temperature of the FRC
1
in an oxidizing atmosphere or the strength of the same after the FRC
1
has been exposed to an oxidizing atmosphere is reduced greatly. Such a phenomenon is a problem common to FRC
1
consisting of easily oxidizable components. The notch effect of the voids
5
reduces the strength of the conventional FRC
1
.
The conventional art method proposed to solve the foregoing problem in Japanese patent application unexamined laid open No. 8-157271 coats the surface of an FRC with glass. This method improves the oxidation resistance and the room temperature strength of the FRC by the sealing effect of the glass. However, the properties of the FRC manufactured by this method are still below the level of properties required of structural materials for use in a hot oxidizing atmosphere.
SUMMARY OF THE INVENTION
The inventors of the present invention found through elaborate studies of the foregoing problems that the foregoing problem can be solved by impregnating the conventional fiber-reinforced ceramic with glass so that the voids are filled up with the glass and have made the present invention on the basis of the knowledge acquired through the studies.
The present invention has been made to solve the foregoing problems and it is therefore an object of the present invention to provide a glass-impregnated, fiber-reinforced ceramic having excellent oxidation resistance in a hot oxidizing atmosphere and high room temperature strength.
Another object of the present invention is to provide a method of manufacturing a glass-impregnated, fiber-reinforced ceramic having excellent oxidation resistance in a hot oxidizing atmosphere and high room temperature strength.
According to a first aspect of the present invention, a glass-impregnated, fiber-reinforced ceramic including a ceramic matrix having voids opening outside; inorganic fibers embedded in the ceramic matrix; and a glass matrix with which the voids of the ceramic matrix are filled.
When the glass-impregnated, fiber-reinforced ceramic is placed in a hot oxidizing atmosphere, the ceramic matrix and the inorganic fibers embedded in the ceramic matrix are insulated from oxygen contained in the hot oxidizing atmosphere because at least the voids in the ceramic matrix are filled up with the glass matrix. Therefore, even if the ceramic matrix and the inorganic fibers are subject to oxidation, the oxidation of the ceramic matrix and the inorganic fibers are protected surely from oxidation and hence a main cause of the reduction of the high-temperature strength and the oxidation resistance of the glass-impregnated, fiber-reinforced ceramic is eliminated. Accordingly, the high-temperature strength and the oxidation resistance of the glass-impregnated, fiber-reinforced ceramic of the present invention are far higher than those of the conventional fiber-reinforced ceramic not impregnated with glass. Since the cause of reduction of the strength due to the notch effect of the voids can be eliminated by the densifying effect of the impregnation with glass, the room temperature strength of the glass-impregnated, fiber-reinforced ceramic of the present invention is far higher than that of the conventional fiber-reinforced ceramic.
The glass matrix may be one of AlPO
4
, PbO, ZnO, SiO
2
, B
2
O
3
, Al
2
O
3
, Na
2
O, CaO, MgO, Li
2
O and K
2
O or a combination of some of those substances. A material of an appropriate composition having an appropriate softening point can be used as the glass matrix according to the temperature of the atmosphere in which the glass-impregnated, fiber-reinforced ceramic of the present invention is to be used because the glass matrix may be one of those substances or a combination of some of those substances. Therefore, voids can be effectively stopped up with the glass matrix at a working temperature and the glass matrix is able to exercise its oxygen intercepting effect effectively in a wide temperature range.
According to a second aspect of the present invention, a method for manufacturing a glass-impregnated, fiber-reinforced ceramic, comprising the steps of: producing a fiber-reinforced ceramic including a ceramic matrix having voids opening outside and inorganic fibers embedded in the ceramic matrix; impregnating the fiber-reinforced ceramic with glass precursor solution containing glass precursor to

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