CA1050305A - Composite material comprising reinforced aluminum or aluminum-base alloy - Google Patents
Composite material comprising reinforced aluminum or aluminum-base alloyInfo
- Publication number
- CA1050305A CA1050305A CA219,632A CA219632A CA1050305A CA 1050305 A CA1050305 A CA 1050305A CA 219632 A CA219632 A CA 219632A CA 1050305 A CA1050305 A CA 1050305A
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- Prior art keywords
- alumina
- fiber
- aluminum
- silica
- composite material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
- C04B35/62245—Fibres based on silica rich in aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/04—Light metals
- C22C49/06—Aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Laminated Bodies (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Abstract of the Disclosure A composite material, which comprises aluminum or an aluminum-base alloy as the matrix and an alumina fiber or an alumina-silica fiber having substantially no .alpha.-alumina reflection by X-ray diffraction as a reinforcement, said composite material having high tensile strength and high tensile modulus even at a high temperature. The composite material thus produced is light in weight but very strong and is therefore particularly useful as a construction material for the aerospace industry.
Description
- -~S~3~5 The present invention relates to a composite mate-rial, which comprises aluminum or an aluminum-base alloy con-taining an alumina fiber or an alumina-silica fiber as a re-inforcement.
With the recent technical developments ln the aero-space industries and various other industries, a very strong demand has developed for construction materials which combine lightness with superior mechanical strength, stiffness and heat resistance.
Such materials may be obtained by reinforcing a metal with a fiber material having a high mechanical strength and a high tensile modulus, and it has been already tried to reinforce aluminum, which is a light and conventional metal, ~ith a fiber ma~erial such as boron fiber, carbon fiber, alumina whisker or the like. Although many efforts have been made to produce such reinforced aluminum, none have been successful, bçcause the fibers so far used are not suitable for reinfsrcing aluminum. Thus, boron fiber has a diameter of more . . .
than 100 ~ and is inferior in flexibility and fur~her it easily reacts with aluminum even at a temperature lower than the melting point of aluminum of the matrix to result in the deterioration of the properties thereof. Accordingly, lt is not suitable for producing a composite material. The carbon fiber ls easily oxidl~ed and reacts with the aluminum of the matrix, and therefore, the composlte material must be prepared at a temperature lower than the melting point of aluminum - in a vacuum or in an atmosphere of an inert gas and further the ma~rix of the composite material thus obtained is gradually induced to electrolytical corrosion owing to the electrocon-ductivity of the fiber. Moreover, the carbon fiber is hardly wetted with fused aluminum, and th~refore, the production of ~L~51D305 the aluminum reinforced witl- the fiber is more difficult.
The alumina whisker is also hardly wetted with fused alumlnum, and therefore, it is difficult to produce the desired composite material having superior mechanical strength with less defects.
Moreover, the alumina whisker itse:Lf is expensive and it is very complicated to align the very short alumina whiskers in the desired direction which results in high cost for producing the composite material.
It is, therefore, the object of the present ivnention to overcome some of the above problems and provide a reinforced aluminum or aluminum-base alloy having superior mechanical strength and modulus over a wide temperature range, as well as having excellent fatigue characteristics, creep characteristics and impact resistance at a high temperature.
According to the present invention, it has b~en found that certain alumina or alumina-silica fibers, even without any specific surface treatment, are wetted very easily with fused aluminum or aluminum-based alloy and strongly bond to the matrix material, thereby making excellent reinforcing fibers. The particular fibers used are alumina fibers or alumina-silica fibers consisting essentially of 72 to 100~ by weight of alumina and 0 to 28~ by weight of silica and having substantially no ~-alumina reflection by X-ray diffraction.
Thus, the novel composite material of this invention comprises aluminum or an aluminum-base alloy reinforced by alumina fibers or alumina-silica fibers consisting essentially of 72 to 100%
by weight of alumina and 0 to 28% by weight of silica and having substantially no ~-alumina reflection by X-ray diffraction, the amount of the alumina fiber or alumina-silica fiber being 5 to 80%
by volume, A scanning electron microscopic photograph of the break section of the composite material of the invention shows the fibers to be closely bonded to the aluminum matrix and ~Qt3~5 further no fiber pull-out is observed, which characteristics are not observed for the conventional composite material reinforced wlth carbon fiber or a]umina whisker. These excellent characteristics of the a~lumina fibers and alumina-sil~ca fibers of the present invention are very important for obtaining the desired composite ma~erial, by which many difficulties encountered with the production of the conventional fiber-reinforced aluminum or aluminum alloy are overcome and the desired reinforced aluminum or aluminum-base alloy having excellent properties can be obtained.
The alumina fiber and alumina-silica fibers which are used have excellent mechanical properties, such as a tensile strength of 10 t/cm2 or more and a tensile modulus of 1,500 ~/cm2 or more, excellent oxidation resistance and hea~
resistance and further excellent wettability with a fused aluminum or aluminum-base alloy. Moreover, they can be obtained in the form of flexible continuous fibers and therefore can give the deslred-composite material having excellent mechanical properties without defects. Besides, the fibers have no electrical conducti~i~y and there is no problem of electrolytical corrosion, and therefore, ;the composite materlal produced by using the fibers is not deteriorated for a long time.
The al~lmina fibers and alumina-silica fibers, which are fully described in copending application Serial No. 192,993 filed February 19, 1974, may be produced by spinning a solution of polyaluminoxane or of a mixture of polyaluminoxane and an appropriate amount of a silicon-containing compound and then calcining the resulting precursor fiber. The detail of the production is as follows.
The polyaluminoxane used in the production is a poly-mer having a structural unit of the formula:
~OSQ3~5i -Al-0-y wherein Y is one or more kinds of the groups selected from an alkyl having 1 to ~ carbon atoms (e.g. methyl, ethyl, propyl, or butyl), an alkoxy hav:ing 1 to 6 carbon atoms (e.g. ethoxy, propoxy, or butyloxy), an acyloxy having 1 to 6 carbon atoms (e.g. formyloxy, acetoxy, propionyloxy or butyryloxy), a halogen (e.g. fluorine, or chlorine), hydroxy, phenoxy which may be substituted by alkyl, such as methyl, ethyl, propyl, and the like. To be soluble in the organic solvent it is necessary that not all of the Y groups in the polyaluminoxane by halogen or hydroxy. In other words, at least one Y group must represent an alkyl, alkoxy, acyloxy, phenoxy or substituted phenoxy.
The useful polyaluminoxane may have an alumina content of 10% or more, preferably of 20% or more by weight.
The alumina content means the numeral calculated by the following expression:
(51/molecular weight of the structural unit) X 100 (%) and when Y is two or more kinds of the groups~ the molecular weight means the average thereof. When a polyaluminoxane having an alumina content of less than 10% is used, it is very difficult to obtain a practically useful alumina f-ber or alumina-silica fiber having excellent strength, even though it is not impossible.
The most preferred group Y may be an alkyl, alkoxy and acyloxy having each not more than 4 carbon atoms since a polyaluminoxane having these groups has high alumina content and the precursor fiber made thereof may be easily hydroly~ed as described later.
~ _ 5 _ ~ ~05(~3~15 There is no specific limitation to the degree of polymerization of the polyaluminoxane and two or more degree of polymerization is enough. However, in view of ease of polymerization reaction, the compound having the degree of polymerization of not more than 1,000 may be preferable one.
The more preferable one may be the one having a degree of polymerization of from 10 to 200.
- Sa -~5~3~t~
The polyaluminoxane generally dissolve~ in an organic solvent such a~ ethyl ether, tetrahydrofuran, dioxane, benzene or toluene to give a viscous solution having large spinnability ln an appropriate concentration. The relation between the con-centration and the spinnability of the solution may vary in ac-cordance with the kind of the polyaluminoxan-e, the degree of polymerization thereof, the kind o~ the solvent and the kind and amount o~ the silicon-containing compound to be mixed with, but it may be preferable to use a solution having a viscosity of from 1 to 5,000 poises at room temperature for the pur~ose o~ spinning thereo~. Accordingly, the spinning solution must be prepared so that the viscosity thereo~ becomes within the range as mentioned above. Besides 9 the polyaluminoxane con-taining 1 to 20 ~o by mol, preferably 1 to 10 ~o by mol of the re~idue Y selected from palmitoyloxy and/or stearoyloxy is particularly preferable in view of its excellent spinna-bility.
As the silicon-containing compound to be mixed with~
there may be preferably used a polyorganosiloxane having a structural unit of the formula:
,. Rl --S i--O--wherein Rl and R2 are the same or different and represent ~ydrogen, an alkyl ~roup having 1 to 6 carbon atoms (e.g. methyl ethyl, propyl, and butyl)~ an alkenyl group having 1 to 6 carbon atoms (e.g. vinyl), an alkoxy group h~ving 1 to 6 carbon atoms (e.g. ethoxy), phenyl group, chlorine or the like1 and a poly-8ilicic acid ester having a structural unit of the foxmula:
3 0 oR3 --si--o--~ 4 3~5 wherein R3 and R4 are the same or different and represent hydrogen, an alkyl ~roup having 1 to 6 carbon atoms (e.g. methyl ethyl, propyl, and butyl)~ an alkenyl group havin~ 1 to 6 carbon atoms ~e.g. vinyl), phenyl group, chlorine or the like, but may be used an organosilane of the formula: R5Si(oR6)4 n wherein R5 and R6 are the same or different and represent hydrogen, an alkyl group having 1 to 6 carbon atoms (e.g. methyl and ethyl), an alkenyl group having 1 to 6 carbon atoms (e.g. vinyl~, phenyl group, chlorine or the like, and n is an integer of 1 to 4; a - silicic acid ester of the formula: Si(oR7)4 wherein R7 is - 13 hydrogen, an alkyl group h~ving 1 to 6 carbon atoms, phenyl group or the like; and any other silicon-containing compound.
The silicon-containing compound to be mixed with may be pre~erably dissolved homogeneously into a solution of the polyaluminoxane, but may be dispersed therein without dis-solving. Furthermore, the silicon~containing compound may be preferable to give a solution having spinnability when it is dissolved in the solution of the polyaluminoxane, but it is ... .
not essential.
20- ~urther-, to the spinnin~ solution there may be pre-ferably added a small amount of one or more kinds of the com-pounds containing an element such as lithium, beryllium, boron, ~odium, magnesium, phosphorus, potassium, calcium, titanium, ~hromium, manganese~ yttrium, zirconium, barium, lanthanum, or tungsten, by whlch the various characteristics of the alumina flber or alumina-silica fiber are improved.
When a solution of polyaluminoxane or of mixture of poiyaluminoxane and silicon-containing compound is spun, it may be conveniently carried out by dry-spinning method, but there may be also used any other conventional methods such as centri~ugal pot spinning or blow spinning.
~OS~30$
When the spinning is carried out in air, the poly-aluminoxane ~orming the precursor fiber may be gradually hydro ly~ed by moi~ture contained in air and thereby the organic component may be gradually 105t, by which the content of alumina in the precur~or fiber may be increased and further the mecha-nical properties of the alumina fiber or alumina silica fiber obtained by calcining thereof may be preferably improved. Ac-cordingly, the silicon-containing compound to be mixed with may ~e preferably the one being easily hydrolyzed, such as polysilicic acid ester. Furthermore, it may be preferable to contact positively the precursor fiber with a steam atmos~
phere or an acidic aqueous solution to promote the hydrolysis mentioned abo~e~
~ he precursor fiber produced by the present process may usually have an average diameter of 1 to 600 ~ but not limited thereto. The alumina or alumina-silica precursor fiber i~ composed in a homogeneous and continuous state wherein the alumina or silica forming materials are contained in a high concentration, and therefore it is very ef~ective for improv-ing the various characteristics of the final product. alumina fiber or alumina-silica fiber.
The alumina or alumina-silica precursor fiber ob-tained by contacting with moisture is not molten by heat, and therefore may be calcined in an atmosphere containing mole-cular oxygen gas, for instance in air, to gi~e readily the de~
sired alumina fiber or alumina-silica fiber without loosing the fiber form. The precu~sor fiber may be substantially changed to alumina fiber or alumina-silica fiber by calcining at about 700C in an atmosphere containing oxygen, e.g. in air, and may gi~e the desired alumina fiber or alumina-silica fiber being transparent and having excellent strength by calcinlng at about 1 ,(~00C, ~l~S~3~5 That is, when the precursor fiber i~ calcined in an atmosphere containing oxygen e.g. in air, it looses water and the organic components by about 600C, and the fiber strength increases with rai~ing the calcining temperature. However, when a pure alumina fiber containing no silica is calcined, the fiber-forming y-alumina phase is transformed into a-alumina phase at about 1,000 to 1,100C, by which the fiber strength may be significantly decreased. On the other hand, when an alumina fiber containing silica i9 calcined, the transforma-tion temperature may be moved to higher temperature with in-crease of the silica content thereof, and in case of the silicacontent being 25 to 28 % by weight, the transformation tempera-~ure is about 1,550C.
In order to obtain an alumina-silica fiber having excellent strength, the calcination temperature may be lower than the transformation temperature indicated abo~e.
The phases forming the fiber at a temperature of from ltO00C to the transformation temperature may be y-alumina phase, amorphous silica and mullite phase in case of the silica content being not more than 28 % by weight. These phases may
With the recent technical developments ln the aero-space industries and various other industries, a very strong demand has developed for construction materials which combine lightness with superior mechanical strength, stiffness and heat resistance.
Such materials may be obtained by reinforcing a metal with a fiber material having a high mechanical strength and a high tensile modulus, and it has been already tried to reinforce aluminum, which is a light and conventional metal, ~ith a fiber ma~erial such as boron fiber, carbon fiber, alumina whisker or the like. Although many efforts have been made to produce such reinforced aluminum, none have been successful, bçcause the fibers so far used are not suitable for reinfsrcing aluminum. Thus, boron fiber has a diameter of more . . .
than 100 ~ and is inferior in flexibility and fur~her it easily reacts with aluminum even at a temperature lower than the melting point of aluminum of the matrix to result in the deterioration of the properties thereof. Accordingly, lt is not suitable for producing a composite material. The carbon fiber ls easily oxidl~ed and reacts with the aluminum of the matrix, and therefore, the composlte material must be prepared at a temperature lower than the melting point of aluminum - in a vacuum or in an atmosphere of an inert gas and further the ma~rix of the composite material thus obtained is gradually induced to electrolytical corrosion owing to the electrocon-ductivity of the fiber. Moreover, the carbon fiber is hardly wetted with fused aluminum, and th~refore, the production of ~L~51D305 the aluminum reinforced witl- the fiber is more difficult.
The alumina whisker is also hardly wetted with fused alumlnum, and therefore, it is difficult to produce the desired composite material having superior mechanical strength with less defects.
Moreover, the alumina whisker itse:Lf is expensive and it is very complicated to align the very short alumina whiskers in the desired direction which results in high cost for producing the composite material.
It is, therefore, the object of the present ivnention to overcome some of the above problems and provide a reinforced aluminum or aluminum-base alloy having superior mechanical strength and modulus over a wide temperature range, as well as having excellent fatigue characteristics, creep characteristics and impact resistance at a high temperature.
According to the present invention, it has b~en found that certain alumina or alumina-silica fibers, even without any specific surface treatment, are wetted very easily with fused aluminum or aluminum-based alloy and strongly bond to the matrix material, thereby making excellent reinforcing fibers. The particular fibers used are alumina fibers or alumina-silica fibers consisting essentially of 72 to 100~ by weight of alumina and 0 to 28~ by weight of silica and having substantially no ~-alumina reflection by X-ray diffraction.
Thus, the novel composite material of this invention comprises aluminum or an aluminum-base alloy reinforced by alumina fibers or alumina-silica fibers consisting essentially of 72 to 100%
by weight of alumina and 0 to 28% by weight of silica and having substantially no ~-alumina reflection by X-ray diffraction, the amount of the alumina fiber or alumina-silica fiber being 5 to 80%
by volume, A scanning electron microscopic photograph of the break section of the composite material of the invention shows the fibers to be closely bonded to the aluminum matrix and ~Qt3~5 further no fiber pull-out is observed, which characteristics are not observed for the conventional composite material reinforced wlth carbon fiber or a]umina whisker. These excellent characteristics of the a~lumina fibers and alumina-sil~ca fibers of the present invention are very important for obtaining the desired composite ma~erial, by which many difficulties encountered with the production of the conventional fiber-reinforced aluminum or aluminum alloy are overcome and the desired reinforced aluminum or aluminum-base alloy having excellent properties can be obtained.
The alumina fiber and alumina-silica fibers which are used have excellent mechanical properties, such as a tensile strength of 10 t/cm2 or more and a tensile modulus of 1,500 ~/cm2 or more, excellent oxidation resistance and hea~
resistance and further excellent wettability with a fused aluminum or aluminum-base alloy. Moreover, they can be obtained in the form of flexible continuous fibers and therefore can give the deslred-composite material having excellent mechanical properties without defects. Besides, the fibers have no electrical conducti~i~y and there is no problem of electrolytical corrosion, and therefore, ;the composite materlal produced by using the fibers is not deteriorated for a long time.
The al~lmina fibers and alumina-silica fibers, which are fully described in copending application Serial No. 192,993 filed February 19, 1974, may be produced by spinning a solution of polyaluminoxane or of a mixture of polyaluminoxane and an appropriate amount of a silicon-containing compound and then calcining the resulting precursor fiber. The detail of the production is as follows.
The polyaluminoxane used in the production is a poly-mer having a structural unit of the formula:
~OSQ3~5i -Al-0-y wherein Y is one or more kinds of the groups selected from an alkyl having 1 to ~ carbon atoms (e.g. methyl, ethyl, propyl, or butyl), an alkoxy hav:ing 1 to 6 carbon atoms (e.g. ethoxy, propoxy, or butyloxy), an acyloxy having 1 to 6 carbon atoms (e.g. formyloxy, acetoxy, propionyloxy or butyryloxy), a halogen (e.g. fluorine, or chlorine), hydroxy, phenoxy which may be substituted by alkyl, such as methyl, ethyl, propyl, and the like. To be soluble in the organic solvent it is necessary that not all of the Y groups in the polyaluminoxane by halogen or hydroxy. In other words, at least one Y group must represent an alkyl, alkoxy, acyloxy, phenoxy or substituted phenoxy.
The useful polyaluminoxane may have an alumina content of 10% or more, preferably of 20% or more by weight.
The alumina content means the numeral calculated by the following expression:
(51/molecular weight of the structural unit) X 100 (%) and when Y is two or more kinds of the groups~ the molecular weight means the average thereof. When a polyaluminoxane having an alumina content of less than 10% is used, it is very difficult to obtain a practically useful alumina f-ber or alumina-silica fiber having excellent strength, even though it is not impossible.
The most preferred group Y may be an alkyl, alkoxy and acyloxy having each not more than 4 carbon atoms since a polyaluminoxane having these groups has high alumina content and the precursor fiber made thereof may be easily hydroly~ed as described later.
~ _ 5 _ ~ ~05(~3~15 There is no specific limitation to the degree of polymerization of the polyaluminoxane and two or more degree of polymerization is enough. However, in view of ease of polymerization reaction, the compound having the degree of polymerization of not more than 1,000 may be preferable one.
The more preferable one may be the one having a degree of polymerization of from 10 to 200.
- Sa -~5~3~t~
The polyaluminoxane generally dissolve~ in an organic solvent such a~ ethyl ether, tetrahydrofuran, dioxane, benzene or toluene to give a viscous solution having large spinnability ln an appropriate concentration. The relation between the con-centration and the spinnability of the solution may vary in ac-cordance with the kind of the polyaluminoxan-e, the degree of polymerization thereof, the kind o~ the solvent and the kind and amount o~ the silicon-containing compound to be mixed with, but it may be preferable to use a solution having a viscosity of from 1 to 5,000 poises at room temperature for the pur~ose o~ spinning thereo~. Accordingly, the spinning solution must be prepared so that the viscosity thereo~ becomes within the range as mentioned above. Besides 9 the polyaluminoxane con-taining 1 to 20 ~o by mol, preferably 1 to 10 ~o by mol of the re~idue Y selected from palmitoyloxy and/or stearoyloxy is particularly preferable in view of its excellent spinna-bility.
As the silicon-containing compound to be mixed with~
there may be preferably used a polyorganosiloxane having a structural unit of the formula:
,. Rl --S i--O--wherein Rl and R2 are the same or different and represent ~ydrogen, an alkyl ~roup having 1 to 6 carbon atoms (e.g. methyl ethyl, propyl, and butyl)~ an alkenyl group having 1 to 6 carbon atoms (e.g. vinyl), an alkoxy group h~ving 1 to 6 carbon atoms (e.g. ethoxy), phenyl group, chlorine or the like1 and a poly-8ilicic acid ester having a structural unit of the foxmula:
3 0 oR3 --si--o--~ 4 3~5 wherein R3 and R4 are the same or different and represent hydrogen, an alkyl ~roup having 1 to 6 carbon atoms (e.g. methyl ethyl, propyl, and butyl)~ an alkenyl group havin~ 1 to 6 carbon atoms ~e.g. vinyl), phenyl group, chlorine or the like, but may be used an organosilane of the formula: R5Si(oR6)4 n wherein R5 and R6 are the same or different and represent hydrogen, an alkyl group having 1 to 6 carbon atoms (e.g. methyl and ethyl), an alkenyl group having 1 to 6 carbon atoms (e.g. vinyl~, phenyl group, chlorine or the like, and n is an integer of 1 to 4; a - silicic acid ester of the formula: Si(oR7)4 wherein R7 is - 13 hydrogen, an alkyl group h~ving 1 to 6 carbon atoms, phenyl group or the like; and any other silicon-containing compound.
The silicon-containing compound to be mixed with may be pre~erably dissolved homogeneously into a solution of the polyaluminoxane, but may be dispersed therein without dis-solving. Furthermore, the silicon~containing compound may be preferable to give a solution having spinnability when it is dissolved in the solution of the polyaluminoxane, but it is ... .
not essential.
20- ~urther-, to the spinnin~ solution there may be pre-ferably added a small amount of one or more kinds of the com-pounds containing an element such as lithium, beryllium, boron, ~odium, magnesium, phosphorus, potassium, calcium, titanium, ~hromium, manganese~ yttrium, zirconium, barium, lanthanum, or tungsten, by whlch the various characteristics of the alumina flber or alumina-silica fiber are improved.
When a solution of polyaluminoxane or of mixture of poiyaluminoxane and silicon-containing compound is spun, it may be conveniently carried out by dry-spinning method, but there may be also used any other conventional methods such as centri~ugal pot spinning or blow spinning.
~OS~30$
When the spinning is carried out in air, the poly-aluminoxane ~orming the precursor fiber may be gradually hydro ly~ed by moi~ture contained in air and thereby the organic component may be gradually 105t, by which the content of alumina in the precur~or fiber may be increased and further the mecha-nical properties of the alumina fiber or alumina silica fiber obtained by calcining thereof may be preferably improved. Ac-cordingly, the silicon-containing compound to be mixed with may ~e preferably the one being easily hydrolyzed, such as polysilicic acid ester. Furthermore, it may be preferable to contact positively the precursor fiber with a steam atmos~
phere or an acidic aqueous solution to promote the hydrolysis mentioned abo~e~
~ he precursor fiber produced by the present process may usually have an average diameter of 1 to 600 ~ but not limited thereto. The alumina or alumina-silica precursor fiber i~ composed in a homogeneous and continuous state wherein the alumina or silica forming materials are contained in a high concentration, and therefore it is very ef~ective for improv-ing the various characteristics of the final product. alumina fiber or alumina-silica fiber.
The alumina or alumina-silica precursor fiber ob-tained by contacting with moisture is not molten by heat, and therefore may be calcined in an atmosphere containing mole-cular oxygen gas, for instance in air, to gi~e readily the de~
sired alumina fiber or alumina-silica fiber without loosing the fiber form. The precu~sor fiber may be substantially changed to alumina fiber or alumina-silica fiber by calcining at about 700C in an atmosphere containing oxygen, e.g. in air, and may gi~e the desired alumina fiber or alumina-silica fiber being transparent and having excellent strength by calcinlng at about 1 ,(~00C, ~l~S~3~5 That is, when the precursor fiber i~ calcined in an atmosphere containing oxygen e.g. in air, it looses water and the organic components by about 600C, and the fiber strength increases with rai~ing the calcining temperature. However, when a pure alumina fiber containing no silica is calcined, the fiber-forming y-alumina phase is transformed into a-alumina phase at about 1,000 to 1,100C, by which the fiber strength may be significantly decreased. On the other hand, when an alumina fiber containing silica i9 calcined, the transforma-tion temperature may be moved to higher temperature with in-crease of the silica content thereof, and in case of the silicacontent being 25 to 28 % by weight, the transformation tempera-~ure is about 1,550C.
In order to obtain an alumina-silica fiber having excellent strength, the calcination temperature may be lower than the transformation temperature indicated abo~e.
The phases forming the fiber at a temperature of from ltO00C to the transformation temperature may be y-alumina phase, amorphous silica and mullite phase in case of the silica content being not more than 28 % by weight. These phases may
2~ be transformed at the transformation temperature or higher tem-perature into -alumina phase and mullite phase.
Accordingly, the alumina fiber or alumina-silica flber having large fiber strength which contains 100 to 72 ~o ~y weight of alumina (A1203) and 28 to O % by wei~ht of silica (SiO2), must exhibit substantially no ~-alumina reflection by X-ray diffractionO
When the alumina fiber or alumina-silica fiber satis-~ies these conditions, the mechanical properties of the pure alumina fiber having no silica are tensile strength: about 10
Accordingly, the alumina fiber or alumina-silica flber having large fiber strength which contains 100 to 72 ~o ~y weight of alumina (A1203) and 28 to O % by wei~ht of silica (SiO2), must exhibit substantially no ~-alumina reflection by X-ray diffractionO
When the alumina fiber or alumina-silica fiber satis-~ies these conditions, the mechanical properties of the pure alumina fiber having no silica are tensile strength: about 10
3~ to 15 t/cm2 and tensile modulus: about 1,000 to 1,500 t/cm~ in '~
~15~3~
case of the fiber diameter being 10 ~. These numerical values lncrease with increase o- the silica content, and when the sillca content .,i9 about 10 to 25 ~ by weight, the tensile strength and the tensile modulus become about 25 to 30 t/cm2 and about 2,500 to 3~500 t/cm2, respectively.
According to the above proce~s, it i8 possible to pro-duce an alumina-silica fiber having a high silica con-tent, for instance a silica content of 50 % by weight. ~owever, the preferred alumina fiber or alumina-silica fiber used in the present invention has an alumina content of 72 to 100 %
by weight9 preferably 76 to 98 ~o by weight and a silica con-tent of 0 to 28 ~ by weight, preferabl~ 2 to 24 ~o by weight.
When the silica content is less than 2 ~ by weight, the fiber is a little inferior in the mechanical strength, and on the other hand, when the silica content is more than 24 ~o by weight, the fiber is inferior in the wettability with aluminum or aluminum-base alloy.
The alumina fiber and the alumina-silica fiber ob-tained by the ab:ove process have usually a diameter of from 0.6 to 400 ~1 on an average. When aluminum or an aluminum-base 2`0 alloy is reinfor;ced with these fibers, the diameter t~.ereof is not restricted. However, when the fiber having a diameter of more than 200 ~L iS used as the reinforcernent, it is not easy to prepare a thin) flexible composite sheet product because of the poor flexibility thereo~, and on the o*he~ hand, when the fiber having an extremely thin diameter is used as the reinforce-ment, the fiber is consumed by the formation of a reaction pro-duct of the fiber with the matrix metal as mentioned below and the effect of reinforcement is lowered~ There~ore, the diameter of the fiber used in the present invention is preferably not less than 6 ~.
- 10 ~
~OS~3~5 Besides, the alumina fiber and the alumlna-silica fiber uc~ed in the present invention should exhibit substantially no ~-alumina reflection by X-raY diffraction. G~ne-rally, when an inorganic fiber is heated nnd calcined up to an unfavQrably hi~h temperature, the fiber-formin~ inorganic materials crystallize into small ~rains which grow as the caicining temperature is raised, and since thesc ~rains are only weakly bonded with one another, the fiber becomes brittle breaking easily at the grain boundaries under stress to in-duce the significant lowerin~ of the fiber strength, More-over, with the growth of the crystalline grain3, the sur-~ace activity of the fibers decreases. When such fiber is used for reinforcing the aluminum, it shows inferior reinforc~
ing effect because of its inferior wettabïlity and inferior adhesiveness. It has been o~served by the present inventors that the growth of the crystalline grains is characterized by the appearance of a-alumina reflection in the X-ray diffrac-tion o~ the alumina or alumina-siiica fiber. Accordingly9 the alumina fiber and the alumina-silica fiber used in the present invention should be prepared so that no a-alumina re-- flection appears.
Thus, the alumina fiber and the alumina-silica fiber useful in the present invention have a very low degree of crystal-linity and comprise substantially y-alumina, amorphous silica and a slight amount of microcrystalline mullite. The surface of the fibers is comparatively active, and when a composite material is produced therefrom, an extremely thin layer of the reaction product of the fiber with the matrix (aluminum3 is ~ormed at the interface thereof, which may cause the excellent wettability of the fiber with the aluminum or aluminum-base alloy.
~5~3~S
The metals to be reinforced by t~e present invention include commercially available alumimum or aluminum~base alloy containing one or more kinds of metals selected from the group eonsisting of beryllium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, silicon, tin, titanium, æinc and zirconiumO
As explained above, the excellent wettablity of the present aluminn fiber or alumina-silica fiber ~rith aluminum or aluminum-base alloy o~les to the low crystallinity, and therefore, any alumina fiber or al~ina-silica fiber produced by any other process may be used unless it shows an a-alumina ~e~lection by X-ray diffraction. For instance, the useful fibers may be produced by calcining the following filaments or fibers at a temperature lower than the temperature at which u-alumina is formed, for instance, filaments being prepared by mixing an aluminum-containing compound ~e.g~ alumina sol or aluminum salt) and a silicon-containing compound (e.g. silica sol or ethyl silicate) with a solution of an organic high mole-cular compound (e.g. polyethylene oxide or polyvinyl alcohol) ... . .
and spinning the resulting viscous solution; fllaments being prepared by mixing a silieon-containing compound with an aque-ous solution of an aluminum salt of a carboxylic acid, concent-rating the solution and spinning the resulting viscous solution;
or organic fibers being prepared by dipping organic fibers in a solution of an aluminum salt and a solution containing silieon and thereby impregnating aluminum ~nd silicon thereto.
The volume amount of the alumina fiber or alumina silica fiber in the composite material according to the pre-sent invention is 5 to 80 ,~, prefcrably 30 to 60 $ by volume.
~35~30~
The composite material comprising a matrix of aluminum or an aluminum-base alloy and a rei.nforcement selected from the alumina fiber and the alumina-silica fiber may be produced by any conve~tional method which has been used for the produc-tion of a composite material by using a boron fiber or a carbon ~iber as the reinforcement, lor instance, an impregnation with fused matrix, a hot press of the ~iber,coated with the matrix, ~oil metallurgy, powder metallurgy, hot rolling, or the like. Particularly, since the present alumina -~iber and alumina-silica ~iber are chemically and thermally very stable, the im pregnation with fused matrix is effectively applicable, and therefore, the desired compos,ite material having excellent mechanical strength with least defects can be easily produced.
Owing to the excellent stabilities of the alumina fiber and the alumina-silica fiber, the desired composite ~aterial can be produced even at a temperature higher than the melting point of the matrix, and therefore, the composite material of the present inven,t,ion has larger volume fraction o~ the -reinforcement but less.defects in compariso.n with that pro-duced by using the conventional boron fiber or carbon fiber~
which is one o~,the characteristics o~ the present invsntion.
., . . . . . _ ...
The alumina fiber and the alumina-silica fiber may optionally be used together with the other conventional fibers such as boron fiber and carbon fiber.
The aluminum or aluminum-base alloy reinforced by the alumina fiber or alumina-silica fiber o~ the present in-vention has usually a density of 2.6 to 2.8 g/cm3, a tensile strength of 2 to 1~ t/cm2 and a tensile modulus of 800 to 2,000 ~cm g which values do almost not vary at a temperature of 20 ~o 500C.
The present invention is illustrated by the following ~xamples but not llmited thereto.
30~
Example 1 (a) In order to prepare alumina-~illca flber9 ethyl silicate was dissolved in a solution of polyethylaluminoxane in dioxane. The mixture was concentrated to give a solution containing the polyaluminoxane in concentration of about 60%
by weight. The viscosity of the solution thus obtained was about 200 poises at room temperature.
The solution thus obtained was used as a spinning solution. This solution was extracted from a 100~ diameter spinning nozzle at room temperature and the extruded fiber was wound at a rate of 50m/minute in air. The fiber thus obtained ~as contacted with saturated stream and calcined while raising the temperature from room temperature to 1200C
at a rate of 300C/hour in air to give transparent alumina-silica fiber containing 10% by weight of silica. The alumina-silica fiber thus obtained has a fiber diameter of 12~, a tensile strength of 30.1 t/cm2, a tensile modulus of 3,050 t/cm2 and a density of 3.1 g/cm3.
. (b) The fibers are bundled in a length of 120 m~ and the bundles thus obtained are put in an alumina tube having an inside diameter of 8 mm. One end of the alumina tube i~ dipped lneo fused aluminum being 99.~% in purity, which is kept at 800~C in an atmosphere of argon gas, and the pressure in the alumina tube is gradually reduced by sucking from the other end thereof, by which the fused aluminum is sucked up through the alumina tube to impregnate the fibers therewith. The whole system is gradually cooled to solidify the aluminum to give a unidirectionally reinforced aluminum pole.
According ts the above process, varlous composite materials having a volume fraction of fiber of 51 10, 20, 30, 40 or 50% are produced, on whlch the tensile s~rength and u ~L0S~3~5 the tensile modulus are measured ~t room temper~ture. The results are shown in Fi{~ure 1.
As made clear from the Figure 1, the tensile strength and the tensile modulus of the composite materials increase approximately linearly with the increase o-f the volume frac-tion of fiber, and when the volume fr~ction of fiber is 50 %, the reinforced aluminum thus obtained ha~ excellent mechanical properties, such as a tensile strength o~ 11.9 t/cm2, a tensile modulus of 1,800 t/cm2 and a density of 2.8 g/cm3. According to the scanning electron microscopic photo~raph of the break ~ection of the composite material, no fiber pull-out is ob-~erved, which means -that the ~ibers are closely bonded with the aluminum.
Example 2 The alumin~-silic~ fibers as used in ~xam~le 1 are laid in parallel with each other in sheet-like fashion and piled mutually and repeatedly with an aluminum foil having a purity of 99.5% and a thickness of 0O05 mm in a carbon mold, so that the volume fraction of fiber in the formed composite material is 45~. The resultant is pressed for 5 minutes at 620C under 20 - a pressure of 120 kg/cm in a vacuum of 10 Torr. The composite material thus obtained is cut to give a dumbbell specimen having a total length (in fiber direction) of 60 mm, a length of the parallel part of 7 mm, a width of 5 mm and a thickness of 3mm, on which the tensile strength is measured in a vacuum. The composite material obtained shows a tensile strength of 9.8, 908, 9.1 and 8.4 t/cm2 at room temperature, 300C, 400C and 550C, - respectively.
~0~03~5 Example ~
In the slmilar manner as described in ~xample 19 a composite material having a volume fraction of fiber of 50 /~
iB produced by using a matrix of aluminum-base alloy consist-ing of 3.7 ~ by weight of copper, 1.5 % by weight of magnesium, 2.0 % by weight of nickel and 92 % by weight of aluminum. The composite material thus obtained shows a tensile strength of 12.5 t/cm2 and a tensile modulus of 1~740 t/cm2 at 360Q~ in air.
... .
- ' ' ` .
~15~3~
case of the fiber diameter being 10 ~. These numerical values lncrease with increase o- the silica content, and when the sillca content .,i9 about 10 to 25 ~ by weight, the tensile strength and the tensile modulus become about 25 to 30 t/cm2 and about 2,500 to 3~500 t/cm2, respectively.
According to the above proce~s, it i8 possible to pro-duce an alumina-silica fiber having a high silica con-tent, for instance a silica content of 50 % by weight. ~owever, the preferred alumina fiber or alumina-silica fiber used in the present invention has an alumina content of 72 to 100 %
by weight9 preferably 76 to 98 ~o by weight and a silica con-tent of 0 to 28 ~ by weight, preferabl~ 2 to 24 ~o by weight.
When the silica content is less than 2 ~ by weight, the fiber is a little inferior in the mechanical strength, and on the other hand, when the silica content is more than 24 ~o by weight, the fiber is inferior in the wettability with aluminum or aluminum-base alloy.
The alumina fiber and the alumina-silica fiber ob-tained by the ab:ove process have usually a diameter of from 0.6 to 400 ~1 on an average. When aluminum or an aluminum-base 2`0 alloy is reinfor;ced with these fibers, the diameter t~.ereof is not restricted. However, when the fiber having a diameter of more than 200 ~L iS used as the reinforcernent, it is not easy to prepare a thin) flexible composite sheet product because of the poor flexibility thereo~, and on the o*he~ hand, when the fiber having an extremely thin diameter is used as the reinforce-ment, the fiber is consumed by the formation of a reaction pro-duct of the fiber with the matrix metal as mentioned below and the effect of reinforcement is lowered~ There~ore, the diameter of the fiber used in the present invention is preferably not less than 6 ~.
- 10 ~
~OS~3~5 Besides, the alumina fiber and the alumlna-silica fiber uc~ed in the present invention should exhibit substantially no ~-alumina reflection by X-raY diffraction. G~ne-rally, when an inorganic fiber is heated nnd calcined up to an unfavQrably hi~h temperature, the fiber-formin~ inorganic materials crystallize into small ~rains which grow as the caicining temperature is raised, and since thesc ~rains are only weakly bonded with one another, the fiber becomes brittle breaking easily at the grain boundaries under stress to in-duce the significant lowerin~ of the fiber strength, More-over, with the growth of the crystalline grain3, the sur-~ace activity of the fibers decreases. When such fiber is used for reinforcing the aluminum, it shows inferior reinforc~
ing effect because of its inferior wettabïlity and inferior adhesiveness. It has been o~served by the present inventors that the growth of the crystalline grains is characterized by the appearance of a-alumina reflection in the X-ray diffrac-tion o~ the alumina or alumina-siiica fiber. Accordingly9 the alumina fiber and the alumina-silica fiber used in the present invention should be prepared so that no a-alumina re-- flection appears.
Thus, the alumina fiber and the alumina-silica fiber useful in the present invention have a very low degree of crystal-linity and comprise substantially y-alumina, amorphous silica and a slight amount of microcrystalline mullite. The surface of the fibers is comparatively active, and when a composite material is produced therefrom, an extremely thin layer of the reaction product of the fiber with the matrix (aluminum3 is ~ormed at the interface thereof, which may cause the excellent wettability of the fiber with the aluminum or aluminum-base alloy.
~5~3~S
The metals to be reinforced by t~e present invention include commercially available alumimum or aluminum~base alloy containing one or more kinds of metals selected from the group eonsisting of beryllium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, silicon, tin, titanium, æinc and zirconiumO
As explained above, the excellent wettablity of the present aluminn fiber or alumina-silica fiber ~rith aluminum or aluminum-base alloy o~les to the low crystallinity, and therefore, any alumina fiber or al~ina-silica fiber produced by any other process may be used unless it shows an a-alumina ~e~lection by X-ray diffraction. For instance, the useful fibers may be produced by calcining the following filaments or fibers at a temperature lower than the temperature at which u-alumina is formed, for instance, filaments being prepared by mixing an aluminum-containing compound ~e.g~ alumina sol or aluminum salt) and a silicon-containing compound (e.g. silica sol or ethyl silicate) with a solution of an organic high mole-cular compound (e.g. polyethylene oxide or polyvinyl alcohol) ... . .
and spinning the resulting viscous solution; fllaments being prepared by mixing a silieon-containing compound with an aque-ous solution of an aluminum salt of a carboxylic acid, concent-rating the solution and spinning the resulting viscous solution;
or organic fibers being prepared by dipping organic fibers in a solution of an aluminum salt and a solution containing silieon and thereby impregnating aluminum ~nd silicon thereto.
The volume amount of the alumina fiber or alumina silica fiber in the composite material according to the pre-sent invention is 5 to 80 ,~, prefcrably 30 to 60 $ by volume.
~35~30~
The composite material comprising a matrix of aluminum or an aluminum-base alloy and a rei.nforcement selected from the alumina fiber and the alumina-silica fiber may be produced by any conve~tional method which has been used for the produc-tion of a composite material by using a boron fiber or a carbon ~iber as the reinforcement, lor instance, an impregnation with fused matrix, a hot press of the ~iber,coated with the matrix, ~oil metallurgy, powder metallurgy, hot rolling, or the like. Particularly, since the present alumina -~iber and alumina-silica ~iber are chemically and thermally very stable, the im pregnation with fused matrix is effectively applicable, and therefore, the desired compos,ite material having excellent mechanical strength with least defects can be easily produced.
Owing to the excellent stabilities of the alumina fiber and the alumina-silica fiber, the desired composite ~aterial can be produced even at a temperature higher than the melting point of the matrix, and therefore, the composite material of the present inven,t,ion has larger volume fraction o~ the -reinforcement but less.defects in compariso.n with that pro-duced by using the conventional boron fiber or carbon fiber~
which is one o~,the characteristics o~ the present invsntion.
., . . . . . _ ...
The alumina fiber and the alumina-silica fiber may optionally be used together with the other conventional fibers such as boron fiber and carbon fiber.
The aluminum or aluminum-base alloy reinforced by the alumina fiber or alumina-silica fiber o~ the present in-vention has usually a density of 2.6 to 2.8 g/cm3, a tensile strength of 2 to 1~ t/cm2 and a tensile modulus of 800 to 2,000 ~cm g which values do almost not vary at a temperature of 20 ~o 500C.
The present invention is illustrated by the following ~xamples but not llmited thereto.
30~
Example 1 (a) In order to prepare alumina-~illca flber9 ethyl silicate was dissolved in a solution of polyethylaluminoxane in dioxane. The mixture was concentrated to give a solution containing the polyaluminoxane in concentration of about 60%
by weight. The viscosity of the solution thus obtained was about 200 poises at room temperature.
The solution thus obtained was used as a spinning solution. This solution was extracted from a 100~ diameter spinning nozzle at room temperature and the extruded fiber was wound at a rate of 50m/minute in air. The fiber thus obtained ~as contacted with saturated stream and calcined while raising the temperature from room temperature to 1200C
at a rate of 300C/hour in air to give transparent alumina-silica fiber containing 10% by weight of silica. The alumina-silica fiber thus obtained has a fiber diameter of 12~, a tensile strength of 30.1 t/cm2, a tensile modulus of 3,050 t/cm2 and a density of 3.1 g/cm3.
. (b) The fibers are bundled in a length of 120 m~ and the bundles thus obtained are put in an alumina tube having an inside diameter of 8 mm. One end of the alumina tube i~ dipped lneo fused aluminum being 99.~% in purity, which is kept at 800~C in an atmosphere of argon gas, and the pressure in the alumina tube is gradually reduced by sucking from the other end thereof, by which the fused aluminum is sucked up through the alumina tube to impregnate the fibers therewith. The whole system is gradually cooled to solidify the aluminum to give a unidirectionally reinforced aluminum pole.
According ts the above process, varlous composite materials having a volume fraction of fiber of 51 10, 20, 30, 40 or 50% are produced, on whlch the tensile s~rength and u ~L0S~3~5 the tensile modulus are measured ~t room temper~ture. The results are shown in Fi{~ure 1.
As made clear from the Figure 1, the tensile strength and the tensile modulus of the composite materials increase approximately linearly with the increase o-f the volume frac-tion of fiber, and when the volume fr~ction of fiber is 50 %, the reinforced aluminum thus obtained ha~ excellent mechanical properties, such as a tensile strength o~ 11.9 t/cm2, a tensile modulus of 1,800 t/cm2 and a density of 2.8 g/cm3. According to the scanning electron microscopic photo~raph of the break ~ection of the composite material, no fiber pull-out is ob-~erved, which means -that the ~ibers are closely bonded with the aluminum.
Example 2 The alumin~-silic~ fibers as used in ~xam~le 1 are laid in parallel with each other in sheet-like fashion and piled mutually and repeatedly with an aluminum foil having a purity of 99.5% and a thickness of 0O05 mm in a carbon mold, so that the volume fraction of fiber in the formed composite material is 45~. The resultant is pressed for 5 minutes at 620C under 20 - a pressure of 120 kg/cm in a vacuum of 10 Torr. The composite material thus obtained is cut to give a dumbbell specimen having a total length (in fiber direction) of 60 mm, a length of the parallel part of 7 mm, a width of 5 mm and a thickness of 3mm, on which the tensile strength is measured in a vacuum. The composite material obtained shows a tensile strength of 9.8, 908, 9.1 and 8.4 t/cm2 at room temperature, 300C, 400C and 550C, - respectively.
~0~03~5 Example ~
In the slmilar manner as described in ~xample 19 a composite material having a volume fraction of fiber of 50 /~
iB produced by using a matrix of aluminum-base alloy consist-ing of 3.7 ~ by weight of copper, 1.5 % by weight of magnesium, 2.0 % by weight of nickel and 92 % by weight of aluminum. The composite material thus obtained shows a tensile strength of 12.5 t/cm2 and a tensile modulus of 1~740 t/cm2 at 360Q~ in air.
... .
- ' ' ` .
Claims (3)
1. A composite material, which comprises aluminum or an aluminum-base alloy reinforced by alumina fiber or alumina-silica fiber consisting essentially of 72 to 100% by weight of alumina and 0 to 28% by weight of silica and having substan-tially no .alpha.-alumina reflection by X-ray diffraction, the amount of the alumina fiber or alumina-silica fiber being 5 to 80% by volume.
2. The composite material according to claim 1, wherein the amount of the alumina fiber or alumina-silica fiber is 30 to 60% by volume.
3. The composite material according to claim 1, wherein the aluminum-base alloy contains at least one other metal selected from the group consisting of berillium, cobalt, chromium, copper, iron, magnesium, manganese, nickel, silicon, tin, titanium, zinc and zirconium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1643674A JPS5534215B2 (en) | 1974-02-08 | 1974-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050305A true CA1050305A (en) | 1979-03-13 |
Family
ID=11916170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,632A Expired CA1050305A (en) | 1974-02-08 | 1975-02-07 | Composite material comprising reinforced aluminum or aluminum-base alloy |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5534215B2 (en) |
| CA (1) | CA1050305A (en) |
| DE (1) | DE2505003C3 (en) |
| FR (1) | FR2260630B1 (en) |
| GB (1) | GB1484980A (en) |
| IT (1) | IT1030103B (en) |
| NL (1) | NL180335C (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1055733A (en) * | 1974-11-11 | 1979-06-05 | Paul G. Riewald | Reinforced aluminum alloy composite |
| US4047965A (en) * | 1976-05-04 | 1977-09-13 | Minnesota Mining And Manufacturing Company | Non-frangible alumina-silica fibers |
| JPS5610379U (en) * | 1979-07-04 | 1981-01-29 | ||
| JPS5625945A (en) * | 1979-08-06 | 1981-03-12 | Sumitomo Chem Co Ltd | Blank for metallic composite material reinforced with alumina fiber and its manufacture |
| JPS5629276U (en) * | 1979-08-10 | 1981-03-19 | ||
| JPS5732344A (en) * | 1980-07-31 | 1982-02-22 | Sumitomo Chem Co Ltd | Fiber reinforced metallic composite material |
| US4526616A (en) * | 1982-07-27 | 1985-07-02 | Dunlop Limited | Load-bearing thermal insulator |
| US4600481A (en) * | 1982-12-30 | 1986-07-15 | Eltech Systems Corporation | Aluminum production cell components |
| JPS6134156A (en) * | 1984-07-26 | 1986-02-18 | Nippon Gakki Seizo Kk | Composite material for ornamentation |
| JPS6199655A (en) * | 1984-10-18 | 1986-05-17 | Toyota Motor Corp | Mineral fiber reinforced metallic composite material |
| JPH0696188B2 (en) * | 1985-01-21 | 1994-11-30 | トヨタ自動車株式会社 | Fiber reinforced metal composite material |
| JPS61201745A (en) * | 1985-03-01 | 1986-09-06 | Toyota Motor Corp | Metallic composite material reinforced with alumina-silica fiber and mineral fiber |
| CA1287240C (en) * | 1985-09-14 | 1991-08-06 | Hideaki Ushio | Aluminum alloy slide support member |
| JPS62132407U (en) * | 1986-02-14 | 1987-08-21 | ||
| JPS62132408U (en) * | 1986-02-14 | 1987-08-21 | ||
| JPS62132406U (en) * | 1986-02-14 | 1987-08-21 | ||
| JPS6369930A (en) * | 1987-05-21 | 1988-03-30 | Sumitomo Chem Co Ltd | Production of stock for aluminous fiber reinforced composite metallic material |
| CN111574204A (en) * | 2020-05-20 | 2020-08-25 | 国装新材料技术(江苏)有限公司 | Alumina ceramic aerogel fiber and sol-gel spinning preparation method thereof |
-
1974
- 1974-02-08 JP JP1643674A patent/JPS5534215B2/ja not_active Expired
-
1975
- 1975-02-06 DE DE19752505003 patent/DE2505003C3/en not_active Expired
- 1975-02-06 FR FR7503694A patent/FR2260630B1/fr not_active Expired
- 1975-02-07 GB GB531575A patent/GB1484980A/en not_active Expired
- 1975-02-07 CA CA219,632A patent/CA1050305A/en not_active Expired
- 1975-02-07 IT IT6734075A patent/IT1030103B/en active
- 1975-02-10 NL NL7501567A patent/NL180335C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5534215B2 (en) | 1980-09-05 |
| NL180335B (en) | 1986-09-01 |
| GB1484980A (en) | 1977-09-08 |
| DE2505003B2 (en) | 1977-12-22 |
| DE2505003C3 (en) | 1978-08-24 |
| FR2260630B1 (en) | 1977-11-18 |
| NL7501567A (en) | 1975-08-12 |
| NL180335C (en) | 1987-02-02 |
| DE2505003A1 (en) | 1975-08-14 |
| FR2260630A1 (en) | 1975-09-05 |
| JPS50109903A (en) | 1975-08-29 |
| IT1030103B (en) | 1979-03-30 |
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