CN1250107A - Melting-casting process of preparing metal-base composite material through in-situ reaction and spray formation - Google Patents

Melting-casting process of preparing metal-base composite material through in-situ reaction and spray formation Download PDF

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CN1250107A
CN1250107A CN 99100510 CN99100510A CN1250107A CN 1250107 A CN1250107 A CN 1250107A CN 99100510 CN99100510 CN 99100510 CN 99100510 A CN99100510 A CN 99100510A CN 1250107 A CN1250107 A CN 1250107A
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杨滨
张济山
段先进
胡双春
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University of Science and Technology Beijing USTB
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Abstract

The present invention solves the problems of particle loss and inhomogeneous distribution of particles in alloy matrix in the preparation of metal-base composite material. The smelting of alloy matrix as well as the generation of reinforcing phase and the atomizing spraying formation of metal-base composite material blank are performed synchronously, and this can shorten the composite material preparing process obviously and reduce the production cost of metal-base composite material greatly. The present invention may be used in preparing various particle reinforced metal-base composite material including aluminium-base alloy, copper-base alloy, zinc-base alloy, titanium-base alloy and iron-base alloy.

Description

Method for preparing metal-based composite material by fusion casting-in-situ reaction spray forming
The invention is suitable for the field of metal matrix composite materials. Relates to a preparation process of fusion casting-in-situ reaction atomization spray forming metal-based composite material.
The atomization spray forming technology is a novel powder metallurgy material synthesis technology, has the outstanding advantages of having the capability of rapid solidification and near forming, and can directly form a blank with a certain shape and rapid solidification structure and performance characteristics by atomization and deposition of liquid metal so as to reduce or eliminate various high-cost manufacturing and processing intermediate links. The use of spray forming techniques to produce particle reinforced metal matrix composites is an important direction in the recent development of this technology. However, most of the existing techniques for preparing particle-reinforced metal matrix composites by spray forming at home and abroad are to spray a certain amount of reinforcing phase particles into an atomizing cone in the spray forming process, and then to deposit the particles on a depositor after the particles are forcibly mixed (or in-situ reacted) with metal molten drops to obtain a composite blank. The greatest disadvantage of this type of process is the low utilization of the reinforcing particles (it is estimated that more than about 50% of the reinforcing particles fail to enter the atomizing cone and are carried away by the air stream, causing considerable waste.
In recent years, new technology for preparing in-situ reaction (in-situ reaction) particle reinforced metal matrix composite materials is rapidly developed, and the in-situ reaction atomization spray forming technology is one of the latest and extremely important technologies, and the development speed of the in-situ reaction atomization spray forming technology is generally concerned by research units at home and abroad and the industry. Reactions that may be performed during in situ reactive spray forming to date include:
① gas-liquid reaction, i.e. mixing a certain proportion (or all) of reactive gas (such as N) into atomized gas during the atomized spray forming process2、O2Or CH4Etc.) to facilitate in situ generation of second phase particles by adjusting the composition of the atomizing gas and the molten metal.
During spray deposition the metal stream is atomized into very small droplets, the droplet size of which depends on the size of the nozzle and the flow rates of the metal and atomizing gas streams. Lubanska (JOM, 22(1970)45) derived the radius relationship for the predicted metal droplet size:
Figure A9910051000041
where η is the dynamic viscosity, j is the mass flow rate, NweIs the Weber number, which has a value of (T.W.Clyne and P.J.Withers, An Introduction to Metal Matrix Composites, Cambridge University Press, London (1993)):
Figure A9910051000051
where u is the droplet velocity and λ is the surface tension of the droplet. When aluminum is atomized with hydrogen gas, the average diameter of the droplets is about 100 to 200 μm as shown in formulas (1) and (2). The droplets have both a high temperature and a large surface area, which is deposited by sprayingThe chemical reaction in the process provides the driving force. The fine-grained reinforcing phase ceramic particles can be produced by means of chemical reactions between the droplets during flight and the atomizing gas and between the droplets and the added reactive particles during deposition and solidification on the substrate.
Lavernia et al (Scr. Metal. Mater., 29(1993)1341) at the university of California employs N2-O2Mixed gas atomizing spray forming Ni3Al alloy (containing Y and B) to obtain Al with fine dispersion distribution2O3And Y2O3Particle reinforced Ni3An Al-based composite material. By controlling the oxygen partial pressure in the mixed gas, the content of oxide particles and the size distribution thereof can be controlled, for example, the oxygen content in the mixed gas is increased or the dispersion degree of the aluminum liquid is increased (namely, the droplet size is reduced), and the oxidation degree of droplets can be improved, namely, the formation amount of the oxide is increased. The result of microscopic structure and mechanical property analysis shows that the thermal stability of the reaction synthesized composite material is obviously improved, for example, in the heat preservation process of 1200 ℃, crystal grains in the nitrogen atomization spray deposition forming material continuously grow along with the prolonging of the heat preservation time, and the crystal grains of the oxygen reaction atomization spray deposition forming material hardly change at all.
Perez et al (Scr. Metal. Mater., 31(1994)231) used N2-O2And atomizing, spraying and depositing the mixed gas to form the Cu-lat% Al alloy. About 1 vol% Al is formed in situ when the oxygen content is 8%2O3And about 2 to 4 vol% of CuO/Cu2O。
Pengzhong et Al (materials report, (2) (1993)72B) dispersed the molten aluminum into a large number of fine droplets in an oxidizing atmosphere to oxidize the surface to form Al2O3And (3) a membrane. These Al compounds2O3The film is broken and dispersed due to mutual collision among molten drops in the deposition process, and finally, Al in dispersed distribution is formed2O3A reinforced aluminum matrix composite.
② liquid-liquid reaction in which two liquid metals are mixed in an atomization process and high melting point particles are formed by the reaction Lee et al (Proc MRS, 132(1989)87) report the preparation of TiB by liquid-liquid reaction2Particle reinforcementExperimental results of the copper-based composite material. However, the application of this method is limited because a large amount of reaction heat is often released when forming high-melting particles by liquid-liquid reaction, which causes rapid heating of the melt and causes great difficulty in controlling the atomized spray deposition forming process.
③ liquid-solid reaction during atomisation spray deposition shaping there is some potential for liquid-solid reaction the sprayed particles dissolve during atomisation and react with one or more elements in the matrix to form a stable dispersed phase the size of the dispersed phase can be controlled by controlling the cooling rate of the spray and consequently the cooling rate of the blank, and according to Lawley et al (Powder metals, 37(1994)123) reference is made to the unpublished experimental results of AEA company, UK, of spraying Cr into Ti-containing 316L and 304 stainless steel droplets during nitrogen atomisation spray deposition shapingxN particles can form fine TiN dispersed phase with the diameter of about 20nm in the blank, and the mechanical property of the material is greatly improved as a result.
It is well known that the performance of particle reinforced metal matrix composites depends to a large extent on whether the particles are dispersed in the matrix. Because the gas-liquid reaction is mainly carried out on the outer surface of the molten drop, the reinforcing phase is easily gathered and distributed in a crystal boundary area, and the reinforcing effect of the reinforcing phase is weakened. The liquid-liquid reaction is often too violent to control, and limits the application of the method. The newly proposed technique of obtaining the desired reinforcing phase by liquid-solid reaction widens the route of preparation of in-situ reaction spray-formed metal matrix composites, but the problem is that it is necessary to find a supersaturated metastable (or highly reactive) solid state particle which is easily decomposed, which makes the selection of such solid state particles difficult in experiments. Moreover, as mentioned above, the reinforcing phase in the current home and abroad in-situ reaction atomization spray forming is generated by gas-liquid and liquid-solid reactions in the atomization chamber, and the utilization rate of the reinforcing phase particles generated by the method is still low.
The invention aims to provide a preparation method of an in-situ reaction atomization injection molding metal matrix composite material, which is simple and practical, has relatively low price and is convenient to popularize and apply. The method comprises the steps of putting the generation of a reinforcing phase into an alloy melt in a melting chamber to complete (called fusion casting-in-situ reaction), and then carrying out subsequent atomization spray forming to obtain the particle-reinforced metal matrix composite material with uniform dispersion distribution.
The invention is composed of: when the metal-based composite material is prepared by adopting a fusion casting-in-situ reaction spray forming method, the process mainly comprises three stages of preparation of a precast block, smelting of master alloy and atomization spray forming: (1) preparation of precast blocks
Selection of reactant species: according to the requirements of the composite system on the type of the particle reinforced phase, determining reactants participating in the reaction to form the hard particle phase, wherein the reactants comprise two types:
the first type: (3) wherein M represents a matrix element and an alloy thereof, such as Al, Cu, Zn, Ti, Fe, etc. and an alloy thereof; x represents a metallic element or a non-metallic element such as Ti, Ta, Zr, V, Nb, Hf, Mo, C, B, Si, etc.; y represents a non-metal element such as C, B, Si, etc. When X is a nonmetallic element, XY is a combination of two nonmetallic elements, such as C and B or C and Si, etc.
The second type: (4) wherein M represents a matrix element and an alloy thereof, such as Al and the like and an alloy thereof; n represents a transition metal such as Cu, Zn, Cr, etc.; the oxide MO is a class of compounds that are thermodynamically more stable than NO. The replaced transition group metal element N can be used as an alloy element to enter the matrix or react with a certain component in the matrix to generate a new intermetallic compound reinforcing phase. The metal elements, the nonmetal elements and the transition metal oxides in the first and second types are all powder, and the particle size ranges from 10 to 250 mu m.
When the two reactants are Ti and C, the proportion (weight ratio) is 1: 0.1-0.7; if the Ti and the B are combined, the proportion range (weight ratio) is 1: 0.1-0.8; if Al and CuO are combined, the proportioning range (weight ratio) is 1: 0.2-0.7. The preferred selection ratio range (weight ratio) is as follows: when the two reactants are Ti and C, the ratio is 1: 0.3-0.5; if the ratio of Ti to B is 1: 0.3-0.6; if Al and CuO are combined, the ratio is 1: 0.4-0.5.
A certain amount of catalyst or inhibitor can be added in the process of preparing the precast block according to the difficulty degree of the system reaction. The catalyst comprises powders of Al, Zn, Ni, Cu, Fe, Mn and rare earth, which can reduce the activation energy of the reaction between reactants and promote the reaction. The stopping agents include two types: aThe group is not involved in chemical reaction between reactants, and only acts as a diluent, such as Si, SiO2,Al2O3,ZrO2Etc.; the other is to participate in chemical reactions between reactants, such as chlorine salts, fluorine salts, and the like. The weight ratio of the catalyst to the two reactants is (0-0.8) to 1. When a stopping agent which plays a role of a diluent is added, the weight ratio of the stopping agent to the two reactants is (0.05-0.5) to 1; when a stopping agent (such as chlorine salt and fluorine salt) participating in a chemical reaction between reactants is added, the weight ratio of the chlorine salt to the fluorine salt to the two reactants is (0.03-0.20) to 1.
Mixing: the raw materials are put into a mixer according to a certain stoichiometric ratio and mixed evenly.
And (3) pressing and forming: and pressing and molding the uniformly mixed raw materials at room temperature, wherein the pressure range is 50-500 MPa. In order to improve the formability of the precast block, an organic volatile binder can be added into the uniformly mixed raw materials, and the weight ratio of the organic volatile binder to the uniformly mixed raw materials is (0.02-0.15): 1; these binders can be completely volatile or decompose at certain temperatures. (2) Smelting of composite master alloys
Smelting a base alloy: and (2) putting a proper amount of matrix alloy (such as Al, Cu, Zn, Ti, Fe and the like and alloys thereof) into a medium-frequency induction furnace for heating, wherein the heating temperature is 150-300 ℃ above the melting point of the alloy.
Adding a precast block: pressing a prefabricated block accounting for 1-20% of the weight of the alloy into the alloy melt by using a graphite bell jar, and preserving heat: 1-30 minutes. (3) Preparation of metal matrix composite blank by atomization spray forming
Because fine and thermodynamically stable reinforcing particles are generated in the melting chamber alloy melt, the subsequent atomization spray forming step in the invention can follow all the process parameters of the existing spray forming for preparing metal material blanks, including:
atomizing gas High purity nitrogen gas
Pressure of atomization (0.5-0.9)MPa
Degree of superheat of melt (150-300)℃
Catheter diameter (3.0-3.6)mm
Deposition distance (350-450)mm
The invention provides a method for generating a particle reinforced phase by introducing fusion casting-in-situ reaction in the preparation process of a spray forming metal-based composite material, which is the development of the preparation technology of the in-situ reaction spray forming metal-based composite material.
The invention has the advantages that: (1) the utilization rate of the reinforced particles is high, and the particles are uniformly distributed in thealloy matrix. The invention completes the generation of the reinforced particles in the melting chamber alloy melt, and fundamentally solves the problem of particle loss in the existing home and abroad in-situ reaction injection molding metal matrix composite material preparation technology. Furthermore, the particle size of the reinforcing phase produced by the present invention is mostly below 1 μm, and the sinking rate is small. The reinforced particles can be dispersed and distributed in the matrix very uniformly under the action of stirring of melt electromagnetic force and spray deposition of molten drop atomization. (2) Simple process, low cost and easy realization of industrialization. The prior art of in-situ reactive spray forming metal matrix composites has without exception the injection of certain reactive gases or highly reactive particles into the atomization chamber to achieve the desired reinforcement phase particles. The invention moves the generation of the enhanced particles from the atomizing chamber into the melting chamber alloy melt. The whole process of generating the particles is carried out in an atmospheric state, and the operation is simple and convenient. In addition, the invention can synchronously carry out the smelting of the matrix alloy, the generation of particles and the preparation of the spray-formed metal matrix composite, thereby obviously shortening the preparation process flow of the composite, reducing the preparation cost of the material and being easy to realize industrialization. (3) The refining and modification treatment technology in the cast alloy can be repeatedly used, and the comprehensive performance of the composite material is improved. The reinforcing phase produced by the method has small particle size and good wettability with the matrix alloy, and the particles can not float upwards along with bubbles in the matrix alloy and are brought to the surface of the molten liquid, so that the composite material master alloy melt can be refined and modified formultiple times by using refining and modification treatment technologies in casting alloys, and the comprehensive performance of the composite material is improved. (4) The technological parameters of the existing spray forming for preparing metal material blanks can be kept, and the equipment does not need to be changed. The subsequent spray forming process of the invention is completely similar to the process of preparing metal materials by the existing spray forming, and the equipment does not need to be changed.
Example 1
Spray formed 3 wt.% Ti/commercial pure aluminum composite was prepared. Weighing appropriate amount of Al powder, Ti powder and C powder with purity of 98%, 99.8% and 99.5% and particle size of 75 μm, 45 μm and 10 μm respectively according to the ratio of Al to Ti to C of 2: 70: 28, and mixing uniformly. Pressing into cylindrical prefabricated blocks with the diameter of 20X 30mm on a 50-ton press. 2 kg of industrial pure aluminum is melted in a medium frequency induction furnace and heated to 850 ℃. And pressing 0.06 kg of prefabricated block into the aluminum liquid by using a graphite bell jar, and keeping the temperature for 10 minutes. When the temperature is reduced to about 750 ℃, hexachloroethane accounting for 0.4 percent of the weight of the molten liquid is added for refining. And carrying out spray forming under the conditions that the atomizing gas is nitrogen, the atomizing pressure is 0.6MPa and the diameter of the liquid guide pipe is 3.0mm to obtain the 3 wt.% TiC particle reinforced industrial pure aluminum composite material. Composite material sigmabNot less than 140MPa and delta not less than 10%. Example 2
Preparation of 3 wt.% TiB2Industrial pure aluminum composite material. Weighing appropriate amount of Al powder, Ti powder and B powder with purity of 98%, 99.8% and 99.9%, and granularity of75 μm, 45 μm and 10 μm respectively, and appropriate amount of refining agent according to the ratio of Al to Ti to B of 30: 40: 30, and mixing uniformly. Pressing into cylindrical prefabricated blocks with the diameter of 20X 30mm on a 50-ton press. 2 kg of industrial pure aluminum is placed in a medium frequency induction furnace for melting and heated to 900 ℃. And pressing 0.06 kg of prefabricated block into the aluminum liquid by using a graphite bell jar, and keeping the temperature for 10 minutes. Adding hexachloroethane accounting for 0.3 percent of the weight of the molten liquid for refining. Spraying and forming under the conditions that the atomizing gas is nitrogen, the atomizing pressure is 0.6MPa and the diameter of the liquid guide pipe is 3.0-3.2 mm to obtain 3 wt.% of TiB2Industrial pure aluminum composite material. Composite material sigma after extrusionbNot less than 180 MPa. Example 3
And preparing a 5 wt.% TiC/Al-21Si-2.5Cu composite material for spray forming. Weighing appropriate amount of Al powder, Ti powder and C powder with purity of 98%, 99.8% and 99.5% and particle size of 75 μm, 45 μm and 10 μm respectively and appropriate amount of refining agent according to the ratio of Al to Ti to C of 3 to 72 to 25, and mixing uniformly. Pressing into cylindrical prefabricated blocks with the diameter of 20X 30mm on a 50-ton press. 4 kg of Al-21Si-2.5Cu alloy is put into a medium frequency induction furnace to be melted and heated to 950 ℃. 0.20 kg of preform is placed in a graphite bell jarThe block is pressed into the aluminum liquid and is kept warm for 10 minutes. Adding hexachloroethane accounting for 0.3 percent of the weight of the molten liquid for refining. And carrying out spray forming under the conditions that the atomizing gas is nitrogen, the atomizing pressure is 0.6-0.8 MPa and the diameter of the liquid guide pipe is 3.0-3.6 mm to obtain the 5 wt.% TiC/Al-21Si-2.5Cu composite material. Composite material sigmabNot less than 400 MPa. Example 4
Preparing the 8 wt% TiC/7075 composite material. Weighing appropriate amount of Al powder, Ti powder and C powder with purity of 98%, 99.8% and 99.5% and particle size of 75 μm, 45 μm and 10 μm respectively according to the ratio of Al to Ti to C of 2: 71: 27, and mixing uniformly. Pressing into cylindrical prefabricated blocks with the diameter of 20X 30mm on a 50-ton press. 5 kg of 7075 alloy was placed in a medium frequency induction furnace to melt and heated to 900 ℃. And pressing 0.40 kg of prefabricated blocks into the aluminum liquid by using a graphite bell jar, and keeping the temperature for 10 minutes. Adding hexachloroethane accounting for 0.3 percent of the weight of the molten liquid for refining. And carrying out spray forming under the conditions that the atomizing gas is nitrogen, the atomizing pressure is 0.6-0.7 MPa and the diameter of the liquid guide pipe is 3.0-3.6 mm to obtain the 8 wt.% TiC/7075 composite material. Composite material sigmabNot less than 550 MPa. Example 5
Preparing 5 wt% TiC/7075 composite material. Weighing appropriate amount of Al powder, Ti powder and C powder with purity of 98%, 99.8% and 99.5% and particle size of 75 μm, 45 μm and 10 μm respectively according to the ratio of Al to Ti to C of 2: 71: 27, and mixing uniformly. Pressing into cylindrical prefabricated blocks with the diameter of 20X 30mm on a 50-ton press. 4 kg of 7075 alloy was melted in a medium frequency induction furnace and heated to 900 ℃. And pressing 0.20 kg of prefabricated block into the aluminum liquid by using a graphite bell jar, and keeping the temperature for 10 minutes. Adding hexachloroethane accounting for 0.3 percent of the weight of the molten liquid for refining. And carrying out spray forming under the conditions that the atomizing gas is nitrogen, the atomizing pressure is 0.6-0.7 MPa and the diameter of the liquid guide pipe is 3.0-3.5 mm to obtain the 5 wt.% TiC/7075 composite material. Composite material sigma after extrusionbNot less than 650 MPa.

Claims (3)

1. A method for preparing a metal-based composite material by fusion casting-in-situ reaction spray forming is characterized by comprising the following steps: the process mainly comprises three stages of precast block preparation, master alloy smelting and atomized spray forming:
a. preparing a precast block: the reactants are first selected, two classes can be selected: the first type: wherein M represents a matrix element and an alloy thereof, such as Al, Cu, Zn, Ti, Fe, etc. and an alloy thereof; x represents a metallic element or a non-metallic element such as Ti, Ta, Zr, V, Nb, Hf, Mo, C, B, Si, etc.; y represents a non-metal element such as C, B, Si, etc. When X is a nonmetallic element, XY is a combination of two nonmetallic elements, such as C and B or C and Si, etc.; the second type: wherein M represents a matrix element and an alloy thereof, such as Al and the like and an alloy thereof; n represents a transition metal such as Cu, Zn, Cr, etc.; oxide MO is a class of compounds that are thermodynamically more stable than NO; the replaced transition group metal element N can be used as an alloy element to enter the matrix or react with a certain component in the matrix to generate a new intermetallic compound reinforcing phase. The metal elements, the nonmetal elements and the transition metal oxides in the first and second types are all powder, and the particle size ranges from 10 to 250 mu m;
when the two reactants are Ti and C, the proportion (weight ratio) is 1: 0.1-0.7; if the Ti and the B are combined, the proportionrange (weight ratio) is 1: 0.1-0.8; if Al and CuO are combined, the proportioning range (weight ratio) is 1: 0.2-0.7;
putting the raw materials into a mixer according to a certain stoichiometric ratio, uniformly mixing, and then pressing and forming the uniformly mixed raw materials at room temperature, wherein the pressure range is 50-500 MPa;
b, smelting of the composite material master alloy: putting a proper amount of matrix alloy (such as Al, Cu, Zn, Ti, Fe and the like and alloys thereof) into a medium-frequency induction furnace for heating, wherein the heating temperature is 150-300 ℃ above the melting point of the alloy: and pressing the prefabricated block accounting for 1-20% of the weight ratio of the alloy into the alloy melt by using a graphite bell jar, and preserving heat: 1-30 minutes;
c. the atomization spray forming can prepare metal matrix composite material blanks by using various process parameters of the existing spray forming metal material blanks.
2. The fusion-casting-in-situ reaction spray forming method for preparing metal matrix composites as claimed in claim 1, wherein: the catalyst comprises powders of Al, Zn, Ni, Cu, Fe, Mn, rare earth and the like, and can reduce the reaction activation energy among reactants and promote the reaction; the stopping agents include two types: one is not involved in chemical reaction between reactants and only acts as a diluent, such as Si, SiO2,Al2O3,ZrO2Etc.; the other is participating in chemical reaction between reactants, such as chlorine salt, fluorine salt and the like;the weight ratio of the catalyst to the two reactants is (0-0.8) to 1; when a stopping agent which plays a role of a diluent is added, the weight ratio of the stopping agent to the two reactants is (0.05-0.5) to 1; when a stoppingagent participating in chemical reaction between reactants is added, the weight ratio of the chlorine salt to the fluorine salt to the two reactants is (0.03-0.20) to 1; when the two reactants are Ti and C, the preferred selection range (weight ratio) is 1: 0.3-0.5; if the Ti and the B are combined, the preferred selection range (weight ratio) is 1: 0.3-0.6; if Al and CuO are combined, the preferable range (weight ratio) is 1: 0.4-0.5.
3. The method for producing a metal matrix composite by fusion casting-in-situ reaction spray forming according to claim 1 or 2, characterized in that: adding an organic volatile binder into the uniformly mixed raw materials, wherein the weight ratio of the organic volatile binder to the uniformly mixed raw materials is (0.02-0.15) to 1; these binders can be completely volatile or decompose at certain temperatures.
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