CN107313129B - Aluminum-copper-zirconium reinforced fiber, preparation method thereof and aluminum-copper-zirconium superplastic alloy based composite aluminum - Google Patents
Aluminum-copper-zirconium reinforced fiber, preparation method thereof and aluminum-copper-zirconium superplastic alloy based composite aluminum Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
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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
- C22C49/02—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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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention discloses an aluminum-copper-zirconium reinforced fiber, a preparation method thereof and aluminum-copper-zirconium superplastic alloy based composite aluminum. The material consists of (by weight) igneous rock 89-99%, copper oxide 0-9%, zirconium oxide 0-1% and carbon powder 1%; wherein, the content of the copper oxide and the content of the zirconium oxide are different and take a value of 0. The amorphous high-silicon aluminum copper zirconium reinforced fiber is generated by introducing the components of copper oxide and zirconium oxide on the basis of natural high-silicon aluminum igneous rock ore. The amorphous high-silicon aluminum copper zirconium reinforced fiber is compounded with the aluminum copper zirconium superplastic aluminum alloy, and silicon, aluminum, copper and zirconium components in the reinforced material can be subjected to molecular fusion with a metal solution, so that the bonding fastness of a composite interface is improved, namely the strength of the aluminum copper zirconium superplastic alloy based composite aluminum is improved.
Description
Technical Field
The invention relates to the field of preparation of aluminum-based composite materials, in particular to an amorphous high-silicon aluminum copper zirconium reinforced fiber and a preparation method thereof, and aluminum copper zirconium superplastic alloy-based composite aluminum reinforced by the fiber.
Background
The first generation of aluminum material was pure aluminum (1825, austte, denmark), the second generation was alloyed aluminum (1903, aluminum industries, usa), the third generation of aluminum material was ceramic-embedded aluminum (1950 s), and the fourth generation was amorphous inorganic material reinforced composite aluminum (2007, new materials science and technology ltd. Nanjing sky standing waves by antidune).
Compared with steel, the composite aluminum is lighter, stronger, more wear-resistant and more corrosion-resistant, can be used for replacing steel, and reduces the energy consumption of motor vehicles and ships. When the composite aluminum alloy is used for replacing steel shells of automobiles/ships, the ductility of the composite aluminum should be as close as possible to that of steel.
The composite aluminum reinforced material is a high-rigidity amorphous inorganic material. The aeronautical composite aluminum with 7050 as a matrix material obtained by melt-blown forming is added with only about 3 percent of reinforcing material in order to ensure that the elongation at break falls in the range of 4-5.5 percent.
Therefore, the prior art needs to be improved, and the composite aluminum still has higher elongation at break while the addition amount of the composite aluminum reinforcing material is increased.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an amorphous high-silicon aluminum copper zirconium reinforced fiber and a preparation method thereof, and the fiber is compounded with an aluminum copper zirconium superplastic alloy with high fracture elongation. Aims to improve the affinity (namely tensile strength) of a composite interface and ensure that the composite aluminum has higher elongation at break.
The technical scheme of the invention is as follows:
an amorphous high-silicon aluminum copper zirconium reinforced fiber, which comprises 89-99% of igneous rock, 0-9% of copper oxide, 0-1% of zirconium oxide and 1% of carbon powder in percentage by weight; wherein, the content of the copper oxide and the content of the zirconium oxide are different and take a value of 0.
The amorphous high-silicon aluminum copper zirconium reinforced fiber comprises, by weight, 90% -93% of igneous rock, 5% -8% of copper oxide, 0.5% -1% of zirconium oxide and 1% of carbon powder.
The amorphous high-silicon aluminum copper zirconium reinforced fiber comprises, by weight, 90.8% of igneous rock, 7.5% of copper oxide, 0.7% of zirconium oxide and 1% of carbon powder.
The amorphous high-silicon aluminum copper zirconium reinforced fiber comprises 98.3 wt% of igneous rock, 0.7 wt% of zirconium oxide and 1 wt% of carbon powder.
The amorphous high-silicon aluminum copper zirconium reinforced fiber comprises, by weight, 90.3% of igneous rock, 8% of copper oxide, 0.7% of zirconium oxide and 1% of carbon powder.
The amorphous high-silicon aluminum copper zirconium reinforced fiber is characterized in that on the basis of igneous rock, the total weight of ferric oxide and ferrous oxide contained in the igneous rock is less than 3%, and the total weight of silicon oxide and aluminum oxide contained in the igneous rock is more than 68%.
The preparation method of the amorphous high-silicon aluminum copper zirconium reinforcing fiber comprises the following steps:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and smelting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder to obtain a melt;
and then drawing the melt to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
The preparation method of the amorphous high-silicon aluminum copper zirconium reinforced fiber comprises the following steps:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and putting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder into a bottom-inserted-electrode all-electric smelting furnace for smelting to obtain a melt;
and then drawing the solution through a wire drawing bushing plate to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
The aluminum-copper-zirconium superplastic alloy-based composite aluminum is formed by mixing the amorphous high-silicon aluminum-copper-zirconium reinforcing fiber and the aluminum-copper-zirconium superplastic aluminum alloy.
The aluminum-copper-zirconium superplastic alloy-based composite aluminum is prepared by the following steps: putting the chopped amorphous high-silicon aluminum copper zirconium reinforced fibers into aluminum copper zirconium superplastic aluminum alloy liquid, then cooling, stirring and homogenizing, and finally heating and pouring to obtain aluminum copper zirconium superplastic alloy base composite aluminum; the weight ratio of the amorphous high-silicon aluminum copper zirconium reinforcing fiber to the aluminum copper zirconium superplastic aluminum alloy liquid is 3: 97.
Has the advantages that: according to the invention, on the basis of natural high-silicon aluminum igneous rock ore, the amorphous high-silicon aluminum copper zirconium reinforcing fiber is generated by introducing copper oxide and zirconium oxide. The amorphous high-silicon aluminum copper zirconium reinforced fiber is compounded with the aluminum copper zirconium superplastic aluminum alloy, and silicon, aluminum, copper and zirconium components in the reinforced material can be subjected to molecular fusion with a metal solution, so that the bonding fastness of a composite interface is enhanced, namely the mechanical strength of the aluminum copper zirconium superplastic alloy based composite aluminum is enhanced.
Detailed Description
The invention provides an amorphous high-silicon aluminum copper zirconium reinforced fiber and a preparation method thereof, and aluminum copper zirconium superplastic alloy based composite aluminum, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides an amorphous high-silicon aluminum copper zirconium reinforced fiber, which consists of 89-99% of igneous rock, 0-9% of copper oxide, 0-1% of zirconium oxide and 1% of carbon powder in percentage by weight; wherein, the content of the copper oxide and the content of the zirconium oxide are different and take a value of 0.
Compared with the prior art, the invention has the main improvement that on the basis of natural high-silicon aluminum igneous rock, copper oxide and zirconium oxide components are introduced to generate the amorphous high-silicon aluminum copper zirconium reinforced fiber. When the generated amorphous high-silicon aluminum copper zirconium reinforced fiber is compounded with the aluminum copper zirconium superplastic aluminum alloy, the matrix of the compound interface and the corresponding element of the fiber can generate molecular fusion, so that the compound activity and the bonding fastness of the interface are increased, and the mechanical strength of the aluminum copper zirconium superplastic alloy based compound aluminum is enhanced; and secondly, the reinforced fiber introduces copper oxide and zirconium oxide components, so that the fiber strength can be effectively improved. Tests show that the tensile strength of the amorphous high-silicon aluminum calcium reinforced fiber can reach 4000-6000MPa, while the stable tensile strength of the existing domestic carbon fiber is only 3500 MPa. Preferably, the amorphous high silicon aluminum copper zirconium reinforced fiber consists of 90-93 wt% of igneous rock, 5-8 wt% of copper oxide, 0.5-1 wt% of zirconium oxide and 1 wt% of carbon powder. Under the formula, the composite interface compatibility of the amorphous high-silicon aluminum copper zirconium reinforced fiber and the aluminum copper zirconium superplastic aluminum alloy is better, so that the mechanical strength of the aluminum copper zirconium superplastic alloy base composite aluminum is further enhanced.
In the invention, on the basis of igneous rock, the total weight of ferric oxide and ferrous oxide contained in the igneous rock is less than 3 percent, and the total weight of silicon oxide and aluminum oxide contained in the igneous rock is more than 68 percent. The igneous rock is selected to meet the sufficient conditions for producing the low-iron amorphous high-silicon aluminum copper zirconium reinforced fiber material.
The invention also provides a preparation method of the amorphous high-silicon aluminum copper zirconium reinforced fiber, which comprises the following steps:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and smelting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder to obtain a melt;
and then drawing the melt to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
Preferably, the preparation method of the amorphous high-silicon aluminum copper zirconium reinforced fiber specifically comprises the following steps:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and putting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder into a bottom-inserted-electrode all-electric smelting furnace for smelting to obtain a melt;
and then drawing the solution through a wire drawing bushing plate to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
Preferably, the smelting temperature is 1600-1800 ℃, and more preferably 1700 ℃.
The fiber length of the amorphous high-silicon aluminum copper zirconium reinforced fiber prepared by the method is 5-9 mm.
The invention also provides aluminum-copper-zirconium superplastic alloy-based composite aluminum, which is prepared by mixing the amorphous high-silicon aluminum-copper-zirconium reinforcing fiber and the aluminum-copper-zirconium superplastic aluminum alloy. The amorphous high-silicon aluminum copper zirconium reinforced fiber is compounded with the aluminum copper zirconium superplastic aluminum alloy, so that the high-strength aluminum copper zirconium superplastic alloy-based composite aluminum with excellent interface fusion performance can be obtained.
The preparation method of the aluminum-copper-zirconium superplastic alloy-based composite aluminum comprises the following steps: putting the chopped amorphous high-silicon aluminum copper zirconium reinforced fibers into an aluminum copper zirconium superplastic aluminum alloy solution (the temperature in the mixed solution is about 700 ℃), then cooling (reducing the temperature by about 5-50 ℃) to increase the viscosity, and stirring and homogenizing by using a stirrer at 300-30000 r/min for 3-10 min; finally, the temperature is increased (the temperature is increased to the initial temperature, namely 700 ℃) for casting, and the aluminum-copper-zirconium superplastic alloy base composite aluminum is obtained.
Based on the aluminum-copper-zirconium superplastic alloy-based composite aluminum, the weight ratio of the amorphous high-silicon aluminum-copper-zirconium reinforcing fiber is 1-30%, for example 3%, namely the weight ratio of the amorphous high-silicon aluminum-copper-zirconium reinforcing fiber to the aluminum-copper-zirconium superplastic aluminum alloy liquid is 3: 97.
Before the amorphous high-silicon aluminum copper zirconium reinforced fiber is compounded with the aluminum copper zirconium superplastic aluminum alloy, the method comprises the following steps: and carrying out short-cutting treatment on the amorphous high-silicon aluminum copper zirconium reinforced fiber. Specifically, the amorphous high-silicon aluminum copper zirconium reinforced fiber with the fiber length of 5-9 mm is cut into the amorphous high-silicon aluminum copper zirconium reinforced fiber with the fiber length of 1-3 mm by a chopping machine. The reason is that in the length range of the fiber, the amorphous high-silicon aluminum copper zirconium reinforced fiber can better pass through a high-pressure powder sprayer and be injected into the aluminum copper zirconium superplastic aluminum alloy solution.
According to the invention, the superplastic aluminum alloy with high ductility is selected as the matrix, and on the premise of ensuring the ductility, more reinforcing fibers are added, so that the strength of the aluminum-copper-zirconium superplastic alloy matrix composite aluminum is improved.
The present invention will be described in detail below with reference to examples.
Example 1
The amorphous high-silicon aluminum copper zirconium reinforced fiber consists of igneous rock 90.8 wt%, copper oxide 7.5 wt%, zirconium oxide 0.7 wt% and carbon powder 1.32 wt%, and the igneous rock contains ferric oxide and ferrous oxide 2.87 wt% and contains silicon oxide 63.93 wt%, aluminum oxide 17.51 wt% and magnesium oxide 1.32 wt%, and is suitable for producing low-iron amorphous reinforced material.
From the ratio of Cu to CuO molecular weight =63.55:79.545 equal to about 64:80, it is known that when copper oxide is 7.5%, the copper content is 6%. Similarly, when the zirconia content is 0.7%, the zirconium content is 0.5%. Tests show that the aluminum-6% of copper-0.5% of zirconium is the optimal proportion of the aluminum-copper-zirconium superplastic alloy, the optimal deformation temperature of the alloy is 430 ℃, and the maximum elongation is 3000%.
The igneous rock is from Hebei, and its composition is above 1% by weight, and includes 63.93% of silicon oxide, 17.51% of aluminium oxide, 1.32% of magnesium oxide, 4.80% of potassium oxide, 1.74% of cupric oxide, 6.04% of sodium oxide and 2.87% of ferric oxide/ferrous oxide.
Example 2
The amorphous high-silicon aluminum copper zirconium reinforced fiber consists of 98.3 wt% of igneous rock, 0.7 wt% of zirconium oxide and 1 wt% of carbon powder, wherein the igneous rock contains iron oxide and ferrous oxide accounting for 2.87 wt%, and the igneous rock contains 63.93 wt% of silicon oxide, 17.51 wt% of aluminum oxide and 1.32 wt% of magnesium oxide, so that the amorphous reinforced material with low iron content is produced.
The igneous rock is from Hebei, and comprises (by weight) silicon oxide 63.93%, aluminum oxide 17.51%, magnesium oxide 1.32%, potassium oxide 4.80%, copper oxide 1.74%, sodium oxide 6.04%, and ferric oxide/ferrous oxide 2.87%.
Example 3
The amorphous high-silicon aluminum copper zirconium reinforced fiber consists of 90.3 wt% of igneous rock, 8 wt% of copper oxide, 0.7 wt% of zirconium oxide and 1 wt% of carbon powder, wherein the igneous rock contains iron oxide and ferrous oxide accounting for 2.87 wt%, and the igneous rock contains 63.93 wt% of silicon oxide, 17.51 wt% of aluminum oxide and 1.32 wt% of magnesium oxide, so that the amorphous high-silicon aluminum copper zirconium reinforced fiber meets the sufficient conditions for producing low-iron amorphous reinforced materials.
The igneous rock is from Hebei, and comprises (by weight) silicon oxide 63.93%, aluminum oxide 17.51%, magnesium oxide 1.32%, potassium oxide 4.80%, copper oxide 1.74%, sodium oxide 6.04%, and ferric oxide/ferrous iron 2.87%.
Example 4
The igneous rock, the copper oxide, the zirconium oxide and the carbon powder which are uniformly mixed in the weight percentages of the embodiments 1, 2 and 3 are respectively smelted by a bottom-inserted electrode all-electric smelting furnace at the temperature of 1700 ℃, the obtained melt is drawn by a drawing bushing to produce the amorphous high-silicon aluminum copper zirconium reinforced fiber with the fiber length of 5-9 mm and the tensile strength of 4000-6000MPa, and then the amorphous high-silicon aluminum copper zirconium reinforced fiber is cut into the short amorphous high-silicon aluminum copper zirconium reinforced fiber with the fiber length of 1-3 mm. Uniformly spraying the amorphous high-silicon aluminum copper zirconium reinforced fibers with the thickness of 1-3 mm into the aluminum liquid through a high-pressure sprayer, then cooling and tackifying, and stirring for 6 minutes by using a stirrer at the speed of 2000 r/min until homogenization. And finally, heating to the initial temperature, and casting the aluminum alloy into composite aluminum, wherein the weight ratio of the amorphous high-silicon aluminum-copper-zirconium reinforced fiber to the aluminum-copper-zirconium superplastic aluminum alloy is 3: 97.
Tests show that after 3 wt% of the amorphous high-silicon aluminum copper zirconium reinforced fiber in the embodiment 1 is added, the tensile strength of the composite aluminum is improved from 260MPa to 310MPa at room temperature; and the elongation at break is 8 percent, which is just matched with the elongation at break of steel. The method is suitable for the working target of replacing steel with aluminum in a high-corrosion environment.
After 3% by weight of the amorphous high-silicon aluminum copper zirconium reinforced fiber of the embodiment 2 is added, the tensile strength of the composite aluminum is improved from 260MPa to 300MPa at room temperature; and elongation at break of 7%.
After 3% by weight of the amorphous high-silicon aluminum copper zirconium reinforced fiber of example 3 is added, the tensile strength of the composite aluminum is improved from 260MPa to 280MPa at room temperature; and an elongation at break of 6%.
In summary, according to the amorphous high-silicon aluminum copper zirconium reinforced fiber and the preparation method thereof provided by the invention, and the aluminum copper zirconium superplastic alloy based composite aluminum, the mixture of igneous rock, copper oxide, zirconium oxide and carbon powder is smelted by adopting a bottom-inserted electrode full-electric smelting furnace, and then the amorphous high-silicon aluminum copper zirconium reinforced fiber is obtained by a melt through a wire drawing bushing. The amorphous high-silicon aluminum copper zirconium reinforced fiber is chopped and then compounded with aluminum copper zirconium series superplastic aluminum alloy, so that high-strength composite aluminum with excellent interface fusion performance is obtained.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. An amorphous high-silicon aluminum copper zirconium reinforced fiber is characterized by comprising, by weight, 90% -93% of igneous rock, 5% -8% of copper oxide, 0.5% -1% of zirconium oxide and 1% of carbon powder;
the igneous rock pebbles are from Hebei, and the components with the weight percentage of more than 1 percent are as follows: 63.93% of silicon oxide, 17.51% of aluminum oxide, 1.32% of magnesium oxide, 4.80% of potassium oxide, 1.74% of copper oxide, 6.04% of sodium oxide and 2.87% of ferric oxide/ferrous iron.
2. The amorphous high silicon aluminum copper zirconium reinforcing fiber according to claim 1, characterized by consisting of, in weight percent, 90.8% igneous rock, 7.5% copper oxide, 0.7% zirconium oxide and 1% carbon powder.
3. The amorphous high silicon aluminum copper zirconium reinforcing fiber according to claim 1, characterized by consisting of, in weight percent, 90.3% igneous rock, 8% copper oxide, 0.7% zirconium oxide and 1% carbon powder.
4. The preparation method of the amorphous high silicon aluminum copper zirconium reinforcing fiber as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and smelting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder to obtain a melt;
and then drawing the melt to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
5. The method for preparing the amorphous high silicon aluminum copper zirconium reinforcing fiber according to claim 4, is characterized by comprising the following steps:
firstly, uniformly mixing igneous rock, copper oxide, zirconium oxide and carbon powder according to the formula, and putting the uniformly mixed igneous rock, copper oxide, zirconium oxide and carbon powder into a bottom-inserted-electrode all-electric smelting furnace for smelting to obtain a melt;
and then drawing the solution through a wire drawing bushing plate to obtain the amorphous high-silicon aluminum copper zirconium reinforced fiber.
6. An aluminum-copper-zirconium superplastic alloy based composite aluminum, which is characterized by being formed by mixing the amorphous high-silicon aluminum-copper-zirconium reinforcing fiber as claimed in any one of claims 1 to 3 and an aluminum-copper-zirconium superplastic aluminum alloy.
7. The aluminum-copper-zirconium superplastic alloy based composite aluminum according to claim 6, wherein the preparation method of the aluminum-copper-zirconium superplastic alloy based composite aluminum comprises the steps of: putting the chopped amorphous high-silicon aluminum copper zirconium reinforced fibers into aluminum copper zirconium superplastic aluminum alloy liquid, then cooling, stirring and homogenizing, and finally heating and pouring to obtain aluminum copper zirconium superplastic alloy base composite aluminum; the weight ratio of the amorphous high-silicon aluminum copper drill reinforcing fiber to the aluminum copper zirconium superplastic aluminum alloy liquid is 3: 97.
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| CN109183195A (en) * | 2018-08-23 | 2019-01-11 | 深圳市正佳科建科技有限公司 | Sial copper magnesium reinforcing fiber and preparation method and aluminum bronze magnesium super plastic alloy base clad aluminum |
| CN108998860A (en) * | 2018-08-23 | 2018-12-14 | 深圳市正佳科建科技有限公司 | Sial calcium zinc reinforcing fiber and preparation method and aluminium calcium zinc super plastic alloy base clad aluminum |
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