AU620862B2

AU620862B2 - Method of producing metal base composite material under promotion of matrix metal infiltration by fine pieces of third material

Info

Publication number: AU620862B2
Application number: AU33399/89A
Authority: AU
Inventors: Yoshiaki Kajikawa; Masahiro Kubo; Takashi Morikawa; Tetsuya Nukami; Tetsuya Suganuma; Atsuo Tanaka
Original assignee: Toyota Motor Corp
Current assignee: Toyota Motor Corp
Priority date: 1988-04-30
Filing date: 1989-04-26
Publication date: 1992-02-27
Anticipated expiration: 2009-04-26
Also published as: DE68913800D1; AU3339989A; EP0340957A3; CA1340883C; EP0340957B1; DE68913800T2; EP0340957A2

Description

1 1 _-1I1-

SAUSTRALIA

PATENTS ACT 1952 Form COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: SRelated Art: TO BE COMPLETED BY APPLICANT S Name of Applicant: TOYOTA JIDOSHA KABUSHIKI

KAISHA

S Address of Applicant: 1, TOYOTACHO

TOYOTA-SHI

AICHI-KEN

JAPAN

Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

SComplete Specification for the invention entitled: METHOD OF PRODUCING METAL BASE COMPOSITE MATERIAL UNDER PROMOTION OF MATRIX METAL INFILTRATION BY FINE PIECES OF THIRD MATERIAL The following statement is a full description of this invention including the best method of performing it known to me:- I

:A

li l METHOD OF PRODUCING METAL BASE COMPOSITE MATERIAL UNDER PROMOTION OF MATRIX METAL INFILTRATION BY FINE PIECES OF THIRD MATERIAL Background of the Invention Field of the Invention The present invention relates to a composite material, and more particularly, to a method of producing a metal base composite material comprising short fibers, whiskers or particles as a reinforcing material and an aluminum alloy or the like as a matrix material.

Description of the Prior Art As described in, for example, a paper titled "Forming of aluminum fiber reinforced material" distributed in the third Metal Forming Seminar held at Atami-shi on July 15-16, 1985 sponsored by 15 the Japanese Light Metal Institution, there are known several methods of producing fiber reinforced metal base composite materials including continuous fibers as a reinforcing fiber go material, such as diffusion binding method, plasma spray S• method, gas phase eduction method, melt infiltration 20 method, electric plating method, etc., and there are also known several methods of producing fiber reinforced metal base composite materials including discontinuous fibers as a fiber reinforcing material, such as powder metallurgy method, (2) compo-casting method, melt forging method, semi-melt working method, HIP method or the like.

~Particularly when the reinforcing fibers are short fibers, the above-mentioned melt forging method (high pressure casting method) has been commonly used for the reason that it is more suitable for the mass production as compared with other methods.

30 However, in the melt forging method it is required that a molten mass of matrix metal is pressurized to a very high pressure, and therefore a large scale production equipment is required, resulting in a high production cost of the composite materials, and thus presenting a principal obstacle for the practical use of this method.

Therefore, in the production of the composite materials including discontinuous fibers as the reinforcing fiber material 1 I II 111 r

I

t -2there is a demand for lowering of the pressure level required for the molten mass of matrix metal, or it is further demanded to dispense with pressurization of the molten matrix metal. For realization of these demands it is required that the affinity between the reinforcing fibers and the matrix metal is largely improved.

In view of these requirements it was proposed in, for example, Japanese Patent Laying-open Publication 61-295344 to use an aluminum alloy added with a particular element as a matrix metal. However, the affinity can not be improved enough by a mere adding of a particular element to the matrix metal. Further, this method is usable only with a very limited composition of matrix metal.

Various methods have been proposed to improve the affinity 15 between the reinforcing fibers and the matrix metal when the reinforcing fibers are continuous fibers. For example, in *Japanese Patent Laying-open Publication 49-42504 it is described to improve the affinity by painting a metal powder on the surface of the reinforcing fibers. In Japanese Patent Laying-open 20 Publications 50-109904, 52-28433, 53-38791, 57-169036 and 57- 169037 it is described to improve the affinity by coating the surface of fibers with metal.

As described in these publications, when the reinforcing fibers are continuous fibers which are generally disposed in a 0 25 common direction, the capillary action is available to infiltrate 0 a molten matrix metal into the interstices among the continuous fibers, and therefore the methods proposed in the above-mentioned 0. publications are effective.

However, when the reinforcing fibers are short fibers or a 0. 30 whisker, the infiltration of the molten matrix metal by the capillary action is not available. Therefore, the infiltration of the molten matrix metal into the short fibers or the whiskers is not improved by the method of increasing the affinity as applied to the continuous fibers as described in, for example, Japanese Patent Laying-open Publication 59-205464. Further, it is difficult to coat short fibers or whiskerswith a large amount of Smetal or to paint short fibers or whiskerswith a large amount of -3metal powder, and such a process requires a high production cost.

SThere are also these problems in the methods described in U.S.

Patent Specifications 4,376,803 and 4,569,886, wherein the surface of fibers is coated with a metal oxide.

Further, as described in Japanese Patent Laying-open Publication 57-31466 and Japanese Patent Laying-open Publication 62-67133, both being based upon the patent applications filed by the same applicant as the present application, it is already known to preheat a preform of the reinforcing material to a certain raised temperature and to infiltrate a molten matrix metal into the preform under pressure. According to this method the affinity between the reinforcing material and the molten matrix metal is increased by the preheating of the reinforcing material up to said certain temperature, so that the infiltration of the molten matrix 15 metal into the preform improved as compared with the case where go: the preform is not preheated. However, in this method the preheating of the preform is an indispensable condition, and a particular means is necessary for the preheating, and therefore the improvement for higher efficiency and lower cost of production 20 of the composite material is limited.

Further, as described in Japanese Patent Laying-open Publication 61-165265 based upon an application filed by the same applicant as the present application, it is already known to improve the infiltration of the molten matrix metal into the preform of the reinforcing material by utilizing oxidizing or deoxidizing reaction between a metal oxide included in the preform of the reinforcing material and a particular metal element included in the matrix metal. However, since the elements which react with one another in oxidizing or deoxidizing manner are 30 relatively limited, this method is not always applicable to the production of a composite material in which the matrix metal may have any optional composition.

In all of the above-mentioned conventional methods it is generally required that the molten mass of matrix metal is pressurized to a relatively high pressure. Therefore, in these conventional methods it is not possible to produce composite materials at low cost by dispensing with a pressurizing means such {f V. a a a 1i i Xr as mold or the like. FL., it is not avoidable that at each casting a relatively large amount of matrix metal solidifies around a preform in the mold cavity, thereby lowering the yield rate of the casting process.

In Japanese Patent Laying-open Publication 59-500973 and "Journal of Materials Science Letters" published in April 1985 it is described to produce a composite material by pretreating a preform of reinforcing fibers by a chemical agent including fluorine, and to infiltrate a molten matrix metal into the preform. However, this method is applicable only when the reinforcing fibers are carbon fibers or principally carbonic fibers or the fibers covered with carbon or carbide. Further, in this method it is also required that the preform of the reinforcing fibers is preheated before the infiltration of a 15 molten matrix metal.

Summary of the Invention In view of the above-mentioned problems in the conventional methods of producing composite materials, the inventors of the present application had conducted various experimental researches and found that the above-mentioned problems can be solved by mixing fine pieces of some determinate metals or metal oxides in the preform of reinforcing materials.

Therefore, it is a primary object of the present invention to propose, based upon the various experimental researches conducted by the inventors of the present application, a method of producing a composite material at high efficiency and low cost, wherein a matrix metal is infiltrated into a reinforcing material in good condition with no pressurization of a molten mass of the matrix metal.

It is another object of the present invention to provide a method of producing a composite material having a substantially predetermined shape and dimensions at very high efficiency, low cost and very high yielding rate with no need of a mold for pressurizing the molten matrix metal or a mold for producing a composite material having a predetermined shape.

According to the present invention, the above-mentioned objects are accomplished by a method of producing a metal base i i p.

1$ composite material comprising a first process of producing a porous preform from a reinforcing material selected from a group consisting of ceramic short fibers, ceramic whiskers, ceramic particles and mixtures thereof, and a second process of infiltrating a molten matrix metal into the interstices of said porous preform, wherein in said first process fine pieces of a metal having good affinity to the molten matrix metal and reactive with said molten matrix metal to generate heat are mixed in said porous preform, and in said second process at least a part of said preform is contacted with a molten mass of the matrix metal so that the molten matrix metal infiltrates into the interstices of said porous preform with no substantial pressure being applied thereto, said molten matrix metal infiltrated into the interstices of said porous preform being substantially reacted with said fine pieces so as to generate substantial heat for increasing fluidity of said molten matrix metal.

The third material for said fine pieces may be a 20 metal or metals selected from a group consisting of Ni, Fe, Co, Cr, Mn, Cu, Ag, Si, Mg, Al, Zn, Sn, Ti and an alloy or alloys including any one of these metals as a principal component when the matrix metal is Al or an Al alloy.

The third material for said fine pieces may be a metal or metals selected from a group consisting of Ni, Cr, Ag, Al, Zn, Sn, Pb-and an alloy or alloys including any one of these metals as a principal component when the matrix metal is Mg or a Mg alloy.

When said reinforcing material is particularly selected from a group consisting of short fibers, whiskers, particles and mixtures thereof made of an inorganic material other than metal, and the matrix metal is a metal selected from a group consisting of Al, Mg, Al alloy and Mg alloy, the material for said fine pieces may be an oxide or oxides of a metal or metals selected from a group consisting of W, Mo, Pb, Bi, V, Cu, Ni, Co, Sn, Mn, S B, Cr, Mg and Al and mixtures thereof.

1 According to the present invention, by the incorporation of such a metal having good affinity to the molten matrix metal being mixed in the reinforcing material in the form of fine pieces, the infiltration of the molten matrix metal into the interstices of the preform of reinforcing material is much promoted as helped by the affinity of the metal with the molten matrix metal.

Further, the molten matrix metal reacts with the fine pieces of the metal and generates heat which further improves the affinity between the molten matrix metal and oV ~4'r cC) 0°eo Pi -6a the reinforcing material, thereby further improving the infiltration of the molten matrix metal into the preform of reinforcing material.

According to the method of the present invention, it is not necessary to pressurize the molten matrix metal or to preheat the reinforcing material, and therefore no large scale equipment for pressurizing the molten matrix metal or for preheating the reinforcing material is required. Therefore, according to the present invention it is possible to produce a composite material including a matrix material well infiltrated in a reinforcing material at high efficiency and low cost.

Since the molten matrix metal infiltrates easily into the preform according to the method of the present invention, if the preform including a reinforcing material and fine pieces of the meki.

third ia is prepared to have a predetermined shape and dimensions, the whole body of the preform can be uniformly infiltrated with the molten matrix metal by a part of the preform being brought into contact with a molten mass of the matrix metal S so as immediately to provide a composite material having 20 substantially the predetermined shape and dimensions. Therefore, as compared with the conventional melt forging method requiring 9. pressurization of a molten matrix metal and a casting mold for 0. defining a predetermined shape of the product and still "9 unavoidably providing a large amount of matrix metal solidified 25 outside the composite material portion in the casting mold, a composite material having substantially a predetermined shape and dimensions can be produced at high efficiency and low cost with V very high yielding rate.

According to a result obtained by the experimental researches S. 30 conducted by the inventors of the present application, the infiltration of the molten matrix metal into the preform can be improved by incorporating fine pieces of a determinate metal or metals in any optional amount. However, when the matrix metal is Al or Al alloys, the molten matrix metal can infiltrate into the reinforcing material in good condition when the fine pieces of a determinate metal or metals are included in the reinforcing material at a ratio of more than 150% by weight relative to the -7amount of the reinforcing material. Therefore, according to a particular feature of the present invention, the matrix metal is Al or an Al alloy, and the fine pieces of a determinate metal or metals are iicorporated into the preform at a ratio more than 150% by weight relative to the amount of the reinforcing fibers.

Similarly, according to a result obtained by the experimental researches conducted by the inventors of the present application, the infiltration of the molten matrix metal into the preform can be improved by incorporating fine pieces of a determinate metal oxide or metal oxides in any optional amount. However, the molten matrix metal can infiltrate into the reinforcing material in good condition when the fine pieces of a determinate metal oxide or metal oxides are included in the reinforcing material at a ratio of more than 7.5% by weight, particularly more than 10% by weight, S 15 still more particularly more than 15% by weight, relative to the ooorin to amount of the reinforcing material. Therefore, according to a particular feature of the present invention, the fine pieces of a t' determinate metal oxide or metal oxides are incorporated into the preform at a ratio more than 7.5% by weight, particularly more S 20 than 10% by weight, still more particularly more than 15% by weight relative to the amount of the reinforcing fibers.

According to a result obtained by the experimental researches conducted by the inventors of the present application, when said *certain metal or metals provided in the form of fine pieces are more particularly any one of Ni, Fe, Co, Cu, Si, Zn, Sn, Ti or an alloy including one of these metals as a principal component, a molten Al or Al alloy can infiltrate into the preform in good condition. Therefore, according to another feature of the present invention, the metal to form the fine pieces of a certain to.. 30 determinate metal or metals ,s selected from a group consisting of Ni, Fe, Co, Cu, Si, Zn, Sn, Ti and an alloy including one of these metals as a principal component when the matrix metal is Al or an Al alloy.

Similarly, according to a result obtained by the experimental researches conducted by the inventors of the present application, when the metal or metals which form said certain metal oxide or metal oxides provided in the form of fine pieces are any one of W, -8- Mo, Pb, Bi, Cu, Ni, Co, Sn, Mn, Cr or an alloy including one of these metals as a principal component, particularly when the metal or the metals which form said certain metal oxide or metal oxides provided in the form of fine pieces are any one of W, No, Pb, Co, Mn or an alloy including one of these metals as a principal component, the molten matrix metal can infiltrate into the preform in good condition. Therefore, according to another feature of the present invention, the metal or metals to form the fine pieces of a certain determinate metal oxide or metal oxides is selected from a group consisting of W, Mo, Pb, Bi, Cu, Ni, Co, Sn, Mn, Cr or an alloy including one of these metals as a principal component, particularly a group consisting of W, Mo, Pb, Co, Mn or an alloy including one of these metals as a principal component.

Further, according to a result of the experimental researches 15 conducted by the inventors of the present application, when the "matrix metal is an Al alloy, if the Al alloy includes at least one of Mg, Zr and Ca by an amount more than the molten matrix 0* CC metal can more readily infiltrate into the preform. This composition is more effective to improve the affinity between the 20 reinforcing material and the matrix metal when the preform is preheated. Therefore, according to another detailed feature of the present invention, the matrix metal is an Al alloy including at least one of Mg, Zr and Ca by an amount more than Soo*** According to a result of the experimental researches conducted by the inventors of the present application, when the matrix metal is Mg or a Mg alloy, if the preform includes fine pieces of the above-mentioned determinate metal or metals, the infiltration of the molten matrix metal into the preform is improved. Particularly if the preform includes fine pieces of the 30 above-mentioned determinate metal or metals by an amount more than 130% by weight relative to the reinforcing material, the molten matrix metal can infiltrate into the preform in good condition.

Therefore, according to still another detailed feature of the present invention, the matrix metal is Mg or a Mg alloy, and the fine pieces of a certain determinate metal or metals is incorporated into the preform by an amount of more than 130% by weight relative to the reinforcing material in the preform.

-9- According to a result of the experimental researches conducted by the inventors of the present application, if the total volumetric ratio of the reinforcing material and the fine pieces of the determinate metal or metals in the preform is too low or too high, the good infiltration of the molten matrix metal into the preform is obstructed. Therefore, according to another detailed feature of the present invention, the total volumetric ratio of the reinforcing material and the fine pieces of the determinate metal or metals is set to 5-90%, desirably 7.5-85%.

Similarly, according to a result of the experimental researches conducted by the inventors of the present application, if the total volumetric ratio of the reinforcing material and the fine pieces of the determinate metal oxide or metal oxides in the preform is too low or too high, the good infiltration of the 0 15 molten matrix metal into the preform is obstructed. Therefore, according to another detailed feature of the present invention, the total volumetric ratio of the reinforcing material and the o 5 fine pieces of the determinate metal oxide or metal oxides is set 4-85%, desirably 5-80%.

SO SO S 20 According to a result of the experimental researches conducted by the inventors of the present application, even when the volumetric ratio of the fine pieces of the determinate metal or metals in the preform is high, the molten matrix metal can S'"infiltrate into the preform in good condition. However, the volumetric ratio of the reinforcing material decreases along with the amount of the fine pieces of the determinate metal or metals in the preform, and when the fine pieces are made of some certain metal or metals, the composition of the matrix metal is largely changed by the metal or metals of the fine pieces. Therefore, go.: 30 according to still another detailed feature of the present invention, the volumetric ratio of the fine pieces of the determinate metal of metals in the preform is desirably set to be less than Similarly, according to a result of the experimental researches conducted by the inventors of the present application, even when the volumetric ratio of the fine pieces of the determinate metal oxide or metal oxides in the preform is high, •l the molten matrix metal can infiltrate into the preform in good condition. However, when the fine pieces are made of some certain metal oxide or metal oxides, the composition of the matrix metal is largely changed by the metal oxide or metal oxides of the fine pieces. Therefore, according to still another detailed feature of the present invention, the volumetric ratio of the fine pieces of the determinate metal oxide or metal oxides in the preform is set to be less than 45%, desirably less than According to still another detailed feature of the present invention, the preform has a predetermined shape and dimensions, and only a part thereof is dipped into a bath of molten matrix metal. According to this method, a composite material having a predetermined shape and dimensions can be produced at high efficiency, low cost and very high yielding rate with no need of a 15 casting mold for pressurizing the molten matrix metal for defining the predetermined shape of the product.

C• Although the preheating of the preform is not necessary in :%Go, the present invention, the preform may be preheated to a :006 temperature which is lower than the conventional preheating 20 temperature in order to further improve the affinity of the reinforcing material to the matrix metal. Such a lower preheating temperature is desirable in order to avoid oxidization of the fine

CC..

t pieces of the determinate metal or metals. The fine pieces of the S..determinate metal or metals according to the present invention may be in an optional shape such as short fibers, whisker or powder.

8:00 Brief Description of the Drawings In the accompanying drawings, Fig. 'is a perspective view showing a preform made of a reinforcing material and fine pieces of a third material such as a 30 determinate metal or metal oxide; Fig. 2 is a schematic view showing the manner of production of a composite material from the preform shown in Fig. 1 according to the present invention; Fig. 3 is a perspective view showing a composite material produced by the method shown in Fig. 2;

A

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-11- Fig. 4 is a perspective view showing a cylindrical preform made of a reinforcing material and fine pieces of a third material such as a determinate metal or metal oxide; Fig. 5 is a schematic view showing the manner of dipping a lower end of the preform in a bath of a molten matrix metal; and Fig. 6 is a schematic view showing the manner of preform being raised from the bath of the molten matrix metal.

Description of the Preferred Embodiments The present invention will now be described with respect to some preferred embodiments with reference to the attached drawings.

Embodiment 1 As the reinforcing material alumina short fibers having 3 microns mean fiber diameter and 1mm mean fiber length ("Safil RG", 15 product of ICI, 95% Al 2 0 3 5% Si02), silicon carbide whiskers having 0.1-1.0 micron fiber diameter and 50-200 microns fiber length (product of Tokai Carbon Kabushiki Kaisha), and silicon nitride particles having 10 microns mean particle diameter (product of Kojundo Kagaku Kabushiki Kaisha) were prepared.

20 Further, metal fibers and metal powder as shown in Table 1 were prepared. Then the above-mentioned reinforcing material and the prepared. Thenrs or the above-mentioned reinforcing material and the metal fibers or the above-mentioned reinforcing material and the metal powder were mixed and formed into a preform of a rectangular parallelepiped shape of 20 x 20 x 40mm by compression. Fig. 1 shows such a preform 10 in a perspective view, wherein 12 indicates the reinforcing material and 14 indicates the metal fibers.

Two kinds of preforms were prepared by changing the mixing ratio of the reinforcing material and the metal fibers or the 30 metal powder so that in the first type preform the volumetric ratio of the reinforcing material is the mass ratio of the metal fibers or the metal powder relative to the reinforcing material is 600%, and the overall volumetric ratio of the preform is 13-62%, and in a second type preform the volumetric ratio of the reinforcing material is 15%, the mass ratio of the metal fibers or the metal powder relative to the reinforcin iaterial is 200%, and the overall volumetric ratio of the preform is 23-72%.

r I r -12- Then, except the preforms in which the metal fibers are Zn fibers and Sn fibers and the metal powder is Pb powder, each preform was preheated to 200 0 C and was then placed into a vessel 16 as shown in Fig. 2. Then a molten aluminum alloy was poured to form a bath^ thereof, and then the molten aluminum alloy was solidified with no pressurization. The aluminum alloy was prepared in seven differen, types which were JIS AC1A including 0.1% Mg, JIS AC4C including 0.3% Mg, JIS AC4D including 0.5% Mg, JIS AC8A including 1% Mg, JIS AC7B including 10% Mg, JIS AC4C added with 0.3% Ca, and JIS AC4C added with 0.3% Zr.

Then the composite material portion 20 corresponding to the portion of the preform was cut out from the solidified body, and the reinforcing material was cut along a phantom plane 22, and the cut section was polished and investigated by the naked eye and a 15 microscope to evaluate the quality of composite structure.

oI, .The results of the evaluation are shown in Tables 2-4. In I these tables a double circle indicates that both the 0 macroscopic composite condition and the microscopic composite condition were good, a single circle indicates that the 20 macroscopic composite condition was good, a triangle (z) indicates that only partial composite was accomplished, and a cross indicates that no composite structure was accomplished.

(These indications are the same in the subsequent Tables 5-7, and 11.) From Tables 2-4 it will be understood that, regardless of the types and the volumetric ratio of the reinforcing material and the composition of the aluminum alloy, when the preform includes the metal fibers or the metal powder made of Ni, Fe, Co, Cr, Mn, Cu, Ag, Si, Mg, Al, Zn, Sn, Ti or an alloy including one of these 30 metals as a principal component, a good composite quality is obtained, particularly when the metal fibers or the metal powder is made of Ni, Fe, Co, Cu, Si, Zn, Sn or an alloy including one of these metals as a principal component. Further, when the matrix aluminum alloy includes more than 0.5% Mg or more than 0.5% in total of Mg, Ca and Zr, a much better composite quality is obtained.

I

-13- Although not included in the shown embodiment, metal fibers or metal powder other than those shown in Table 1 and consisting of an alloy including the above-mentioned determinate metal as a principal component provides a good composite quality, and when the matrix metal includes more than 0.5% Ca or Zr, the composite quality is further improved.

Comparison Example 1 By the same alumina short fibers as used in Embodiment 1 preforms were prepared to include only the alumina short fibers at 15% and 30% by volume. Further, by the same silicon carbide whiskers as used in Embodiment 1 preforms were prepared to include only the silicon carbide whiskers at 15% anu 40% by volume.

Further, by the same silicon nitride particles as used in Embodiment 1 preforms were prepared to include only the silicon 15 nitride particles at 15% and 50% by volume. By using these preforms it was tried to produce composite materials in the same manner and under the same conditions as adopted in Embodiment 1.

S" No good composite material was obtained from these preforms.

Further, it was tried to produce composite materials from the 20 preforms of the above-mentioned comparison purpose with an aluminum alloy by employing a high pressure casting device in the same manner and under the same conditions as in Embodiment 1 except that the aluminum alloy was pressurized to various raised pressures. As a result it was found that in order to obtain a 25 composite material having good quality the molten aluminum alloy must be pressurized to at least 500kg/cm 2 Embodiment 2 SAlumina short fibers having 3 microns mean fiber diameter and i 1'Imm mean fiber length ("Safil RF", product of ICI, 96-97% A1 2 0 3 30 3-4% Si02), silicon nitride whiskers having 0.1-0.6 micron mean fiber diameter and 20-200 microns mean fiber length (product of Tateho Kagaku Kogyo Kabushiki Kaisha) and tungsten carbide particles having 10 microns mean particle diameter (product of Kojundo Kagaku Kabushiki Kaisha) were prepared. Further, the metal fibers and the metal powder shown in Table 1 were prepared as the metal fibers and the metal powder herein referred to. Then in the same manner as Embodiment 1 the above-mentioned reinforcing

I"

-14materials and the metal fibers or the metal powder were mixed, and preforms having 20 x 20 x 40 mm dimensions were prepared by compression forming.

By changing the mixing ratio between the reinforcing material and the metal fibers or the metal powder two types of preforms were prepared so that in a first type preform the volumetric ratio of the reinforcing material is the mass ratio of the metal fibers or the metal powder relative to the reinforcing material is 500%, and the overall volumetric ratio of the preform is 12-53%, and in a second type preform the volumetric ratio of the reinforcing material is 15%, the mass ratio of the metal fibers or the metal powder relative to the reinforcing material is 150%, and the overall volumetric ratio of the preform is 21-58%.

Then, in the same manner as in Embodiment 1, the preforms including Zn fibers and Sn fibers as the metal fibers were preheated to 150 the preform including Pb powder as the metal powder was preheated to 100 and other preforms were preheated *to 400 Then each preheated preform was placed in a vessel, and a molten magnesium alloy at 700 °C was poured into the vessel, 20 and solidified with no pressurizing. The magnesium alloy was prepared in three different types of MC-2, MC-7 and MC-8 according to JIS.

Then in the same manner as in Embodiment 1 the composite material portion was cut out from the solidified body corresponding to the preform portion, and then after polishing the cut out cross section the section was examined by the naked eye and microscope to evaluate the composite condition. The results of evaluation are shown in Tables 5-7.

From Tables 5-7 it will be understood that when the matrix 30 metal is a magnesium alloy, a good composite condition is obtained when the preform includes the metal fibers or the metal powder made of Ni, Cr, Ag, Zn, Sn, Pb or an alloy including one of these metals as a principal component.

Although not shown as embodiments, it has been confirmed that a good composite condition is obtained when the preform includes the metal fibers or the metal powder made of other alloys including one of Ni, Cr, Ag, Zn, Sn and Pb, or Al.

'I

Comparison Example 2 By the same aluminum short fibers as used in Embodiment 2 preforms were prepared to include only the aluminum short fibers at 15% and 40% by volume. Further, by the same silicon nitride whisker as used in Embodiment 2 preforms were prepared to include only bke silicon nitride whiskers at 15% and 40% by volume. Still further, by the same silicon carbide particles as used in Embodiment 2 preforms were prepared to include only the silicon carbide particles at 15% and 40% by volume. By using these preforms it was tried to produce composite materials in the same manner and under the saine conditions as adopted in Embodiment 2. No good composite material was obtained from these preforms.

Further, it was tried to produce composite materials from the preforms of the above-mentioned comparison purpose with a 15 magnesium alloy by employing a high pressure casting device in the same manner and under the same conditions as in Embodiment 2 •except that the magnesium alloy was pressurized to various "pressures. As a result it was found that in order to obtain a composite material having a good quality the molten magnesium 20 alloy must be pressurized at least to 500 kg/cm 2 Embodiment 3 As shown from the above Embodiments 1 and 2 it is desirable r000 •that the preform includes the determinate metal fibers or powder.

S .Therefore, investigations were conducted to determine what amount of the metal fibers or the metal powder is appropriate.

The reinforcing materials shown in Tables 8 and 9, and the matrix metals, the metal fibers and the metal powder shown in Table 10 and 11 were prepared. By using these materials composite materials were produced in the same manner as in Embodiments 1 and 30 2 with no preheating of the preforms. The composite materials thus obtained were evaluated about the composite conditions in the same manner as in Embodiments 1 and 2. The metal fibers and the metal powder were the same as those shown in Table 1. The mass ratio of the metal fibers or the metal powder relative to the reinforcing material was set to 50%, 100%, 150%, 200%, 250% and 300%. The results of evaluation are shown in Tables 10 and 11.

F-.

27 S S C.

S.

S *5 -16- From Tables 10 and 11 it will be understood that, regardless of the kinds of the reinforcing material, the metal fibers and the metal powder and the composition of the matrix metal, the mass ratio of the metal fibers or the metal powder relative to the reinforcing material should desirably be more than 150%, particularly more than 200%, when the matrix metal is an aluminum alloy, and more than 130%, particularly 180%, when the matrix metal is a magnesium alloy.

Embodiment 4 With regard to the combinations of the reinforcing material and the metal fibers or the metal powder which provided the good composite condition in Embodiment 1 (these combinations bearing the double circle mark or the circle mark in all of the Tables 2-4) cylindrical preforms such as 24 shown in Fig. 4 having 15 40 mm outer diameter, 30 mm inner diameter and 50 mm length were prepared in the same manner as in Embodiment 1 so that the volumetric ratio of the reinforcing material and the mass ratio of the metal fibers or the metal powder relative to the reinforcing material are the same as in the first type preform and the second 20 type preform in Embodiment 1. In Fig. 4, 26 indicates the reinforcing material, and 28 indicates the metal fibers. For the matrix metal the same seven kinds of molten aluminum alloys as those used in Embodiment 1 were prepared.

Then each preform was preheated to the same temperature as in 25 Embodiment 1, and then each preform 24 was held at a top portion thereof by a pincette-shaped holder 30 as shown in Fig. 5, and a bottom end portion of each preform was brought into contact with a bath of the molten aluminum alloy at 700 °C contained in a vessei 32. Then the molten aluminum alloy infiltrated into the whole body of each preform from the lower end to the upper end thereof in 3-10 seconds. After the molten aluminum alloy has completely iniiltrated into the whole body of the preform, the preform was removed from the bath of the molten aluminum alloy as shown in Fig. 6 and was held in that condition until the molten aluminum alloy solidified. During this process the molten aluminum alloy was maintained in the preform as attached thereto under the surface tension.

*1 -17- Then the dimensions of the composite material cylindrical body were measured. The outer diameter, the inner diameter and the length were 39-41 mm, 28-30 mm and 48-50 mm, respectively. It was confirmed that the composite material cylindrical body had substantially the same shape and dimensions as the preform. Each composite material cylindrical body was cut for the inspection of the composite condition. It was confirmed that in all of the composite material cylindrical bodies the aluminum alloy has sufficiently infiltrated up to all surfaces of the preform.

Embodiment With regard to the combinations of the reinforcing material and the metal fibers or the metal powder which provided the good composite condition in Embodiment 2 (these combinations bearing the double circle mark or the circle mark in all of the to* 15 Tables 5-7) cylindrical preforms having 80 mm outer diameter, m mm inner diameter and 40 mm length were prepared in the same manner as in Embodiment 2 so that the volumetric ratio of the S b reinforcing material and the mass ratio of the metal fibers or the 0* *e metal powder relative to the reinforcing material are the same as 20 in the first type preform and the second type preform in Embodiment 2. For the matrix metal the same three kinds of molten magnesium alloys as those used in Embodiment 2 were prepared.

Then each preform was preheated to the same temperature as in Embodiment 2, and then each preform 24 was brought into contact 25 with a bath of the molten magnesium alloy at 700 °C contained in a 400 vessel in the same manner as in Embodiment 4. Then the molten magnesium alloy infiltrated into the whole body of each preform from the lower end to the upper end thereof in 3-8 seconds. After the molten aluminum alloy has completely infiltrated into the 30 whole body of the preform, the preform was removed from the bath of the molten aluminum alloy and was held in that condition until the molten magnesium alloy solidified. During this process the molten magnesium alloy was maintained in the preform as attached thereto under the surface tension.

Then the dimensions of the composite material cylindrical body were measured. The outer diameter, the inner diameter and the length were 79.5-80.5 mm, 69-70 mm and 39-40 mm, respectively.

I

r t -18- It was confirmed that the composite material cylindrical body had substantially the same shape and dimensions as the preform. Each composite material cylindrical body was cut for the inspection of the composite condition. It was confirmed that in all of the composite material cylindrical bodies the aluminum alloy has sufficiently infiltrated up to all surfaces of the preform.

Embodiment 6 As the reinforcing material alumina short fibers having 3 microns mean fiber diameter and 1 mm mean fiber length ("Safil RG", product of ICI, 95% A1 2 0 3 5% Si02), silicon carbide whiskers having 0.1-1.0 micron fiber diameter and 50-200 microns fiber length (product of Tokai Carbon Kabushiki Kaisha), and silicon nitride particles having 10 microns mean particle diameter (product of Kojundo Kagaku Kabushiki !:aisha) were prepared.

15 Then the above-mentioned reinforcing material was mixed with a sol of oxides (Al 2 0 3 ZrO 2 Fe 2 0 3 CeO 2 SiO 2 (product of Nissan Kagaku Kabushiki Kaisha) and the mixture was formed under 4 S* pressure and dried, thereby producing a first type preform including the above-mentioned reinforcing material and fine pieces 20 of the above-mentioned oxides.

The above-mentioned reinforcing material was mixed with a water solution or an ethanol solution of chlorides (MnC1 2 4H 2 0, NiC12'6H 2 0, TiCl 4 CuCl 2 ZnC1 2 SnC12"2H 2 0) (product of Nihon Shinkinzoku Kabushiki Kaisha) and the mixture was formed under suction and heated in the atmosphere at 500 0 C so that the chlorides were converted into oxides, thereby producing a second type preform including the reinforcing material and fine pieces of the oxides converted from the above-mentioned chlorides.

The above-mentioned reinforcing material was mixed with Ta 2 0 30 powder having 1.5 micron mean particle diameter (product of Mitsui Kinzoku Kabushiki Kaisha), Nb 2 0 5 powder having 5 microns mean particle diameter (product of Mitsui Kinzoku Kabushiki Kaisha), PbO powder having 1-2 microns particle diameter (product of Kojundo Kagaku Kabushiki Kaisha), V 2 0 5 powder having 5 microns mean particle diameter (product of Kojundo Kagaku Kabushiki Kaisha), Bi 2 0 3 powder having 6 microns mean particle diameter (product of Kojundo Kagaku Kabushiki Kaisha), Co 3 0 4 powder having

-F

2

I

-19- 74 microns mean particle diameter (product of Sumitomo Kinzoku Kozan Kabushiki Kaisha) and MgO powder having 0.05 micron mean particle diameter (product of Ube Kosan Kabushiki Kaisha) in water, respectively, and the mixture was formed under compression and dried, thereby producing a third type preform including the above-mentioned reinforcing material and fine pieces of the abovementioned oxide.

The above-mentioned reinforcing material was mixed in a water solution including polyvinyl alcohol, and the well agitated mixture was formed to a body by suction and dried, and the formed body was soaked in a water solution dissolving Cr 2 0 3 (product of Nippon Denko Kabushiki Kaisha), H 3

BO

3 (product of Kenei Seiyaku Kabushiki Kaisha) and para-ammonium molybdate (product of Nihon Shinkinzoku Kabushiki Kaisha), and the water solution was heated 15 in the atmosphere to 500 0 C for an hour, so that fine pieces of o oxides of Cr, B and Mo are generated while water and polyvinyl alcohol were evaporated, thereby producing a fourth type preform S" including the above-mentioned reinforcing material and fine pieces of the Pbove-mentioned oxides.

20 Further, the above-mentioned reinforcing material was mixed into a water solution of polyvinyl alcohol and the well agitated mixture was formed to a body by suction and dried, and the body thus formed was soaked in a methane ammonium wolframate solution I al (product of Nihon Shinkinzoku Kabushiki Kaisha), and then the body o 25 was heated in the atmosphere to 700 0 C for one hour, so that fine pieces of oxide of W are generated while water was evaporated, thereby producing a fifth type preform including the abovementioned reinforcing material and fine pieces of the above- S* mentioned oxides.

30 The preform produced in the above-mentioned manner was also as shown in Fig. 1 by 10, wherein 12 also indicates the reinforcing material and 14 indicates in this case the fine pieces of the metal oxide. In this case, two kinds of preforms were prepared by changing the mixing ratio of the reinforcing material and the metal oxide powder so that in a first kind preform the volumetric ratio of the reinforcing material is 5% and the mass ratio of the metal oxide relative to the reinforcing material is I I and in a second kind preform the volumetric ratio of the reinforcing material is 15% and the mass ratio of the metal oxide relative to the reinforcing material is 15%. Each preform has a rectangular parallel piped shape of 20 x 20 x 40mm, and the fine pieces of the metal oxide were distributed substantially uniformly in the body of the preform.

Then the preform which includes an oxide of B as the metal oxide was preheated to 400 0 C while the other preforms were preheated to 600 0 C, and each said preform 10 was placed in a vessel 16 also as shown in Fig. 2, and then a molten matrix metal was poured into the vessel so as to form a bath 18 thereof, and then the molten matrix metal was solidifieu. The matrix alloy was prepared in eight different types of aluminum alloy which were JIS AC1A including 0.1% Mg, JIS AC4C including 0.3% Mg, JIS AC4D 15 including 0.5% Mg, JIS AC8A including 1% Mg, JIS AC7B including Mg, and JIS AC4C added with 0.3% Mg, 0.3% Ca, and 0.3% Zr, respectively, and magnesium alloys prepared in three different I types which were JIS FC-2, JIS MC-7 and JIS MC-8.

C Then a composite material 20 was cut out from the solidified 20 body prepared in the above-mentioned manner corresponding to the portion occupied by the preform, and then the composite material was cut also along a phantom plane 22 at a central portion thereof in Fig. 3. Then the cutout section was polished and investigated by the naked eye and a microscope for evaluation of the composite quality.

I The results of the evaluation are given in Tables 12-14 with respect to the composite materials in which the matrix metal was the aluminum alloy, and in Tables 15-17 with respect to the 30 composite materials in which the matrix metal was the magnesium 30 alloy. In these Tables a double circle indicates that both the macroscopic composite condition and the microscopic composite condition were goods, a single circle indicates that the macroscopic composite condition was good, a triangle (A) indicates that only partial composite was accomplished, and a cross indicates that no composite structure was accomplished.

(These indications are the same in the subsequent Table L 4

C

HB

21- 4 0 0 0 i.

9. S 0 0 S. S S t 6 5 d5 0 f0 S 0 1' From Table 12-17 it will be understood that regardless of the types and the volumetric ratio of the reinforcing material and the composition of the aluminum alloy, when the preform includes the fine pieces of an oxide or oxides of W, Mo,.Pb, Bi, V, Cu, Ni, Co, Sn, Mn, B, Cr, Mg or Al, particularly the fine pieces of an oxide or oxides of W, Mo, Pb, Co or Mn, a good composite quality is obtained. Further, when the matrix metal is an aluminum alloy, a much better composite quality is obtained when the aluminum alloy includes more than 0.5% Mg or more than 0.5% in total of Mg, Ca and Zr.

Although not included in the shown embodiment, it was confirmed that a good composite quality is obtained when the aluminum alloy includes more than 0.5 Mg, Ca or Zr.

Comparison Example 3 15 By the same alumina short fibers as used in Embodiment 6 preforms were prepared to include only the alumina short fibers at 15% and 309 by volume. Further, by the same silicon carbide whisker as used in Embodiment 6 preforms were prepared to include only te silicon carbide whiskers at 15% and 40% by volume.

Further, by the same silicon nitride particles as used in Embodiment 6 preforms were prepared to include only the silicon nitride particles at 15% and 50% by volume. By using these preforms it was tried to produca composite materials in the same manner and under the same conditions as adopted in Embodiment 6.

However, no good composite material was obtained from these preforms.

Further, it was tried to produce composite materials from the preforms of the above-mentioned comparison purpose with the matrix metal by employing a high pressure casting device in the same 30 manner and under the same conditions as in Embodiment 6 except that the matrix metal was pressurized to various raised pressures.

As a result it was found that in order to obtain a composite material having good quality the molten matrix metal must be pressurized to at least 500 g/cm 2 Embodiment 7 As shown from the above Embodiment 6 it is desirable that the preform includes fine pieces of a determinate metal oxide or metal ii I 'II 'I II ~-L1 ij .ii -22oxides. Therefore, investigations were conducted t- determine what amount of the metal oxide or metal oxides is appropriate.

Preforms were prepared from the reinforcing material shown in Tables 18 and 19 and the fine pieces of metal oxides shown in Table 20. Then by using these preforms with the molten matrix metals shown in Table 20 it was tried to produce composite materials in the same manner as in Embodiment 6. Then the composite condition of each composite material thus obtained was evaluated in the same manner as in Embodiment 6. The mass ratio of the fine pieces of the metal oxide relative to the reinforcing material was set to 10%, 15%, 20% and The results of evaluation are shown in Table From Table 20 it will be understood that, regardless of the kinds of the reinforcing material and the composition of the metal oxide, the mass ratio of the fine pieces of the metal oxide relative to the reinforcing material should be more than particularly more than 10%, and still more particularly more than Embodiment 8 S" 20 With regard to the combinations of the reinforcing material and the fine pieces of the metal oxides which provided the good composite condition in Embodiment 6 (these combinations bearing the double circle mark or the circle mark in all of the Tables 12-17) cylindrical preforms such as the one shown again in 25 Fig. 4 having 40 mm outer diameter, 30 mm inner diameter and 50 mm length were prepared in the same manner as in Embodiment 6 so that the volumetric ratio of the reinforcing material and the mass ratio of the metal oxide relative to the reinforcing material are the same as in the first kind preform and the second kind preform in Embodiment 6. In this case, also as seen in Fig. 4, 26 indicates the reinforcing material and 28 now indicates the fine pieces of the metal oxide. For the matrix metal the same eight kinds of molten aluminum alloys and the same three kinds of molten magnesium alloys as those used in Embodiment 6 were prepared.

Then each preform was preheated to the same temperature as in Embodiment 6, and then each preform 24 was held at a top portion thereof by a pincette-shaped holder 30 also as shown in Fig.

:-I

-23and a bottom end portion of each preform was brought into contact with a bath 34 of the molten matrix metal at 700 0 C contained in the vessel 32. Then the molten matrix metal infiltrated into the whole body of each preform from the lower end to the upper end thereof in 10-30 seconds. After the molten matrix metal had completely infiltrated into the whole body of the preform, the preform was removed from the bath of the molten matrix metal also as shown in Fig. 6 and was held in that condition until the molten matrix metal solidified. During this process the molten matrix metal was maintained in the preform as attached thereto under the surface tension.

Then the dimensions of the composite material cylindrical body were measured. The outer diameter, the inner diameter and the length were 40-41 mm, 29-30 mm and 49-50 mm, respectively. It was confirmed that the composite material cylindrical body had substantially the same shape and dimensions as the preform. Each composite material cylindrical body was cut for the inspection of the composite condition. It was confirmed that in all of the composite material cylindrical bodies the matrix metal has S 20 sufficiently infiltrated up to all surfaces of the preform.

S" ."From the foregoing it will be appreciated that according to .the present invention the composite material can be produced in high quality in which the matrix metal is sufficiently infiltrated into the interstices of the reinforcing material at high 25 efficiency and low cost with no need of pressurization of the molten matrix metal so that a composite material product having a predetermined shape and dimensions is directly produced at very high efficiency and yielding rate.

Further, although the preforms have been preheated in the above Embodiments 1, 2 and 4, it was confirmed that the composite material is obtained also in good condition when the preform is not preheated.

Although the invention has been described in detail with respect to some preferred embodiments thereof, it is to be noted that various other embodiments are possible within the scope of the present invention.

1.

S S SO C SS* S

S

*5 S. SC

S

S.

S

S.

S S

S

Fiber/Powder Ni f iber Stainless steel fiber(1) Ti fiber Cu-Zn fiber(2) Al-Mg fibcr(3) Zn f iber Sn f iber W powder Mo powder Ta powder Nb powder V powder Zr powder Co powder Mn powder Si powder Cr powder Ag powder Mg powder Pb powder Table 1 Dia. Length (uiM) (mmn) 20 1 20 1 20 1 60 3 60 3 90 3 90 3 1.0 10- 3- 6- 74- 2- 3 43- 2- 3 Manufacturer Tokyo Seikou K.K.

Aishin Seiki K.K.

Nihon Shinkinzoku K.K.

Koujundo Kagaku K.K.

FukudaKinzou K./ 500

S.

S. S 0* S S 5* e.g.

S.

0 Se S 5 0

S.

Notes: (1 (2) (3) JIS SUS430

LA

0~ 0 0 S *55 S S S S *5 555 S S 5 5 S S S S S *5 *e S S S S S S Table 2 Alumina sho.

f iber vol% 1 5 1 5 1 5 1- 5 1 5 1 5 rt Matrix metal

ACIA

AC4C AC4D AC8A

ACTB

AC4C 0. 3%Ca Ni SUS 0 0 0 0 Metal fiber Sn Cu-Zn Zn 0 0 0 Al-Mg 0 0 0 0 0 0Q0 Q0 00Q0X 0 0 0 0 0 0 000 00 x 0 0 0 0 0 0Q 0Q0aQ0X 0 0 @X 0 0 0 QOQOQ0 00 0X 0 0 0 9 @9 @x 0 0 @0 000 X 0 0 0 ©©00000@ 9A 0 0 0 9 9 @A 5 0 0 0 O O O X Metal powder Ti Co Si Cr Mn Mg Ag Nb QO0Q 0 00Q0X Notes: SUS: JIS SUS430 Cu-Zn: Al-Mg:

I

S OS S S S S S S S S S S S S 055 S S S C 55 .55 555 5 5 S S S S S S S S S S .5 S S S S S S S S 55 55

I

Table 3 SiC whisker volA.

1 5 1 5 1 5 1 5 1 5 1 5 Matrix mietal Ni

ACIA

AC4C AC4D AC8A AC7B AC4C+ 0. 3%Zr sus 0 Metal fiber Sn Cu-Zn Zn 0 o 0 0 o 0 0 Al-Mg 0 0 0 0 ©9 0 0 Ti Co 0 0 0 0 00 Metal powder Si Cr Mn Mg 0 00 0 0 00 0 @0 00 0 00 0 @0000 @0 00 @0000 @0 00 90 0 0 Notes: SUS: JIS SUS430 Cu-Zn: Al-Mg: 01- 44

I

00 00 0 00 0@ 0 0 000 0 Do@ 0* S0: ag 0 0 0. 0,0 see 000 00. 000 0 0 0 00000 0 0 000 0 0 0 00 00 0 0 00 0 0 0 0 0 00 @0 Table 4 Sis N 4 particle Matrix Vol.% metal AClA 1 5 AC4C 1 5 AC4D 1 5 AG8A 1 5 AC7B3 1 5 1 5 AC4C+ 0O. 3%Ca Ni SUS Metal fiber Sn Cu-Zn Zn 9 ©9 0 0 0 A I-Mg 0 0 0 Metal powder Ti Co Si Cr Mn Mg Ag (9 @00 0 00 0 0000C)0 0 ©D©©D00,0 0 @©©O00 00 @©©©0@000C Notes: SUS: JIS SUS430 Cu-Zn: Al-Mg:

C.

C C C es C C 0 C 0 S S C C C C C C C C C @4 0 0 0.W O C 0 C S C Table WC particle Matrix Vol.% mietal MC-2 1 5 MC-7 1 5 MC-8 1 5 A I-Mg 0 Metal fiber Sn Zn SUS

A

©9 A I Cu-Zn

A

Ti Cr A 00

A

A Metal powder Ag Pb Si Mu Mg Nb AA A x x x x ©A AA A ©9 X X X X AA A x x x x Notes: SUS: JIS SUS430 Cu-Zn: Al-Mg: *0

S..

S*

0 5 S 0 S S S S S SO S S *S 54 0 *0 *SS S S S S S S S S S S S 0 5 55 *S 0 S S S S 0 @0 00 Table 6 Si3 N 4 whisker Matrix Vol.% metal MC-2 1 5 MC-7 1 5 MC-8 1 5 A I -Mg Metal fiber Sn Zn SUS

A

Cu-Zn

A

Metal powder Ti Cr Ag Pb Si Mu Mg Nb Co A X X XX X X XX X Notes: SUS: JIS SUS430 Cu-Zn: Al-Mg: TablIe 7 Alumina short Matrix fiber vol metal MC-2 1 5 MC-7 1 5 MC-8 1 5 Al-Mg Metal fiber S n Z n SUS

A

Cu-Zn

A

AL

A©©©AAAA

I

Material Alumina-silica short fiber Potassium-Ti tanate whisker TiC particle Mineral fiber Si.3 N 4 whisker Graphite particle Cryst. alumina-silica short fiber Graphite whisker BN particle Glass fiber SiC whisker Cr3 G 2 particle Dimensions mean fiber dia. :2.8 am~mean fiber length:2mm fiber dia. :10 -30,am, fiber length: 80- 3'50pzm mean particle dia. :1.2 pm mean fiber dia. :5 ummean fiber length: 800p m fiber dia. 0. 1 0.6Bpmfiber length: 20- 200pum mean particle dia. :10 pm mean fiber dia. :2.8 ummean fiber length:2mm fiber dia. 0.1 l.Opamfiber length: 10- 200pum mean particle dia. 8 um mean fiber dia. 13 um.mean fiber, length:3mm fiber dia. :0.05 -1.5,umfiber length: 20-- 200pum mean particle dia.: 6 pm Manufacturer lsolite-Babcock Refractories K.K.

Kubota Tekko l(.K.

Nihon Shin Kinzoku K.K.

Nitto Boseki K.k.

Tateho Kagaku Kogyo K..

Nihon Kokuen Kogyo K.K.

lsolite-Babcock Refractories K.K.

Nikkiso K.K.

Showa Denko R.

Nihon Muki Seni Rogyo R.K.

Tateho Ragaku Rogyo R.R.

Nihon Shin Rinzoku K.K.

-LI

-j C C C C. C C C. C.

TablIe 9 Material Alumina short fiber SiC whisker TiC particle Cryst. alumina-silica short fiber Graphite whisker S3 N 4 particle ZrO 2 fiber Dimensions mean fiber dia. 3 gm~mean fiber length:2mm mean fiber dia. :O.2gim.meanl fiber length: 7jim mecan particle d La. 2jm mean fiber dia. 2.8 iim~mean fiber length: 2g m fiber dia. 1- 1.0um, fiber length: 10- 200ki'm mean pa rt iclIe d ia. l Oum mean f~ibe r d ia.: 5 gmmean fibe r Iength: 2mm Manufacturer Nichiasu K.K.

Shinetsu Kagaku K.K.

Nihon Shinkinzoku K.K.

lsolite-Babcock Refractories K.K.

Nikkiso K.l(.

Kojundo Kagaku K.K.

Shinagawa Shirorenga K.K.

S.

Sr.

S

S S a S S S S S S S St a See *OS S S 9s C S S S Sb S 0 r 55 55555 5 6 S S 50 4 Table 1 0 Reinforcing material Vol Alumina-silica short fiber Potassium-titanete whisker TIC particle Mineral fiber Si3 N 4 whisker Graphite particle Cryst. alumina-silica short fiber Graphite whisker BN particle Grass fiber SiC whisker Cr3 C 2 particle Matrix metal AC4D AC 8A AC 71B AC 71B ACN8A AC4D AC4C+0.3%Cu AC4D AC8A AC4C+0. 3%Zr AC7B AC4C+0. 2%Nog Metal fiber /Metal powder SUS fiber Ni particle uU fiber Sn fiber Zn fiber Co powder Si powder Cr powder Al-Mg fiber Mn powder Ag powder Mg powder Mass ratio relative to reinforcing material 100 150 200 A0 AL 0 S 00 00 A 0 A 0 AL 0 250 300 Li h1h, 71 a S.

~e 0 ~S S S a a 900: so: 00 0* 4, so SC 0 0 e aIC 0*0 9)B C a a a0,0 9.0g 000 0 Table 1 1 Reinforcing material Matrix vol metal Alumina short fiber MC-2 SIC whisker MC-7 TIC particle MC-8 Cryst. alumina-silica short fiber MC-2 Graphite whisker MC-7 Si3 N 4 particle MC-8 ZrO 2 fiber MC-5 Metal fiber /Metal powder Ni fiber Zn particle Cr fiber Al-Mg fiber Ag fiber Sn fiber Pb powder Mass ratio 0 30

XA'

X A x x X A X A x x x x relative to 80 130 A0 0

A

A 0 reinforcing 180 230 ©D material 280 r 0 0 -0 0 S. 0: 0 S0 S. ::0 0000 00©0 00© 0 0 0 05 S. Seeg 50 S S *5 +e mn mn mn m m m m In InDm r-i T- r-I i-I i i

CD

n O npm 90. 0 00 0 @00..

CADD

@D D @D @D @D CD

CDD

0* *0 00.

000.

0 0 0 0* 0 *0 0 0 000 0* S .0 *o

C

0.

S. 00 00 0 .0* 00 0O 0

S

S S S

S

555 S S S S S 55 S S S S S S *5 *S Ta blIe 1 Alumina short Matrix fiber Vol.%/O 1 5 1 5 1 m etalI W M o M C -2 (9 0 MC-7 00 M C- 8 ©9 Metal element forming oxide Pb Co Mn Bi Cu Ni Sn D C'

'©C

C' C' C' C C C' C' C' C C II I S S 5 S S S Table 1 6 SiC whisker Matrix Vol. metal MC-2 1 5 MC-7 1 5 MC-8 1 5 Metal elemnun' forming oxide W Mo Pb Co Mn Bi Cu Ni Sn Cr V B D ©9 ©0 0 0 0 0 0 0

I

a a a a a a. a a. 4., a a a. *.a T a bIe 1 7 Si3 N 4 particle Matrix Vol m et a MC-2 1 MC-7 1 MC-8 1 Metal element forming oxide W Mo Pb Co Mn BI Cu N i Sn C r V B 00 v,~ rV TablIe 1is Material Alumina-silica short fiber Potassium-Titanate whisker TiC particle Mineral fiber Glass fiber Si3 N 4 whisker Cr3 C 2 particle Dimensions mean fiber dia.: 2.8gpm,mean fiber length:2mm fiber dia. 10-'3Ozm, fiber length: 80~- 350/1m mean particle dia. :I.2pum mean f iber d ia. 5 pmmean f iber l engtLh: 800pUm mean f iber d ja. 13, l~m.mean f iber Ileng th: 3m f'iber d ia. 1- 0.6 um, f iber l ength: 20- 200,um, mean particle dia.:6pm Manufacturer Isolite-Babeock Refractories K.l(.

Kubota Tekkou K.K.

Nrihon Shin Kinzoku K.K.

Nitou Bouseki K.K.

Nihon Mukiseni Kogyo K.K.

Tateho Kagaku Kogyo K.K.

Nihon Shin Kinzoku K.K.

!P/3j~ Ta I' e 1 Alumina short fiber 813 N 4 whisker VC particle Cryst. alumina-silica short fiber ZrO 2 fiber Graphite particle BN particle SiC whisker TiC particle Dimensi on-s mean fiber dia. 3,u mmean fiber length: 2mm fiber dia. 1-0.6 u m, fiber length: 20-- 2001 jm mean particle dia. l0ki m mean f'iber d ia. 2. 8 um, mean f iber l eng th: 2,u m mean fi ber d ia. 5 5jmmean f'ibe r leng th: 2 u m mean particle dia. l0jim mean particle dia. :8im fiber dia. 0.05- L.5jimfiber length: 20-200mm mean pa rLi c Ie d ia. I.2,u m Manufacturer Nichiasu K.K.

Tateho Kagaku Kogyo N.K.

Nihon Shinkinzoku K.l(.

Isolite-Babeock Refractories K.K.

Shinagawa Shirorenga l(.K.

Nihon Kokuen K'ogyo K.K.

Showa Denkou K.K.

Tateho Kagaku Kogyo 1(1K.

Nihon Shinkinzoku K.l(.

S* .5 5* *S S S 5 S 55

I

i Table 2 0 Reinforcing material vol.% Alumina-silica short fiber Potassium-Titanate whisker TiC particle Alumina short fiber Sis N 4 whisker WC particle Mineral fiber Glass fiber Potassium-Titanate whisker Si3 N 4 whisker Cr3 C 2 particle Cryst. alumina-silica short fiber ZrO 2 fiber Graphite particle Alumina short fiber BN particle SiC whisker TiC particle Matrix Oxide Mass ratio relative to reinforcing material metal AC4D W oxide AC8A Mo oxide AC7B Pb oxide MC-2 Co oxide MC-7 Mn oxide MC-8 W oxide AC4C+0.3%Ca Mo oxide AC4C+0.2%Mg Cu oxide AC4C+0.3%Mg Sn oxide AC8A V oxide AC7B Mg oxide MC-8 Al oxide MC-8 B oxide MC-7 Cr oxide MC-7 Bi oxide MC-5 Ni oxide MC-2 Pb oxide MC-2 Mo oxide 2.5 5 A A x A x A A A A A x A A O A A x A x A x A A A A A A A A A x A x A x A x 7.5 10 15 20 30 O O 0 0 0 O 0 0 O O D C

Claims

1. A method of producing a metal base composite material comprising a first process of producing a porous preform from a reinforcing material selected from a group consisting of ceramic short fibers, ceramic whiskers, ceramic particles and mixtures thereof, and a second process of infiltrating a molten matrix metal into the interstices of said porous preform, wherein in said first process fine pieces of a metal having good affinity to the molten matrix metal and reactive with said molten matrix metal to generate heat are mixed in said porous preform, and in said second process at least a part of said preform is contacted with a molten mass of the matrix metal so that the molten matrix metal infiltrates into the interstices of said porous preform with no substantial pressure being applied thereto, said molten matrix metal .infiltrated into the interstices of said porous preform S.being substantially reacted with said fine pieces so as to "..generate substantial heat for increasing fluidity of said molten matrix metal.

2. A method as claimed in claim 1, wherein said fine pieces comprise a metal or metals selected from a group consisting of Ni, Fe, Co, Cr, Mn, Cu, Ag, Mg, Zn, Sn, Ti and an alloy or alloys including any one of these metals as a principal component when the matrix metal is Al or an Al alloy.

3. A method as claimed in claim 1, wherein said fine pieces comprise a metal or metals selected from a group consisting of Ni, Cr, Ag, Al, Zn, Sn, Pb and an alloy or alloys including any one of these metals as a principal component when the matrix metal is Mg or a Mg alloy.

4. A method as claimed in claim 2, wherein said fine pieces of a determinate metal or metals are incorporated into the preform at a ratio more than 150% by weight relative to the amount of the reinforcing material. I I Vi S i 4; 5* 4 27 45 A method as claimed in claim 2, wherein the metal to form said fine pieces is selected more particularly from a group consisting of Ni, Fe, Co, Cu, Zn, Sn, Ti and an alloy including one of these metals as a principal component.

6. A method as claimed in claim 1, wherein the matrix metal is an Al alloy including at least one of Mg, Zr and Ca by an amount more than

7. A method as claimed in claim 3, wherein said fine pieces of a certain determinate metal of metals are incorporated into the preform by an amount of more than 130% by weight relative to the reinforcing material in the preform.

8. A method as claimed in any one of claims 1, 2 and 3, wherein the total volumetric ratio of said reinforcing material and said fine pieces of a determinate metal or metals is set to 5-90%.

9. A method as claimed in any one of claims 1, 2 and 3, wherein the total volumetric ratio of said reinforcing material and said fine pieces of a determinate metal or metals is set to 7.5-85%.

10. A method as claimed in any one of claims 1, 2 and 3, wherein the volumetric ratio of said fine pieces of a determinate metal or metals in the preform is set to be less than

11. A method as claimed in any one of claims 1, 2 and 3, wherein the preform has a predetermined shape and dimensions, and only a part thereof is dipped into a bath of molten matrix metal. 1 S S S S.

55. S DATED THIS 5TH DAY OF DECEMBER, 1991 TOYOTA JIDOSHA KABUSHIKI KAISHA By Its Patent Attorneys: GRIFFITH HACK CO Fellows Institute of Patent Attorneys of Australia