CN115533093A - Composite powder material for rapidly preparing bronze ware - Google Patents

Composite powder material for rapidly preparing bronze ware Download PDF

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Publication number
CN115533093A
CN115533093A CN202211118766.0A CN202211118766A CN115533093A CN 115533093 A CN115533093 A CN 115533093A CN 202211118766 A CN202211118766 A CN 202211118766A CN 115533093 A CN115533093 A CN 115533093A
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powder
percent
copper
bronze
tin
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潘春旭
刘恒星
赵成
李孟钊
张国栋
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Zaozhuang Dacheng Bronze Art Co ltd
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Zaozhuang Dacheng Bronze Art Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a composite powder material for rapidly preparing a bronze ware, which is prepared from the following raw materials in percentage by mass: 8 to 25 percent of aluminum powder, 12 to 45 percent of copper-tin-phosphorus brazing powder, 1 to 10 percent of copper-zinc-tin brazing powder, 1 to 5 percent of copper-zirconium intermediate alloy powder, 2 to 5 percent of copper-silicon intermediate alloy powder, 0.5 to 1 percent of borax powder, 3 to 6 percent of salt powder, 0.5 to 3 percent of potassium tetrafluoroaluminate, 9 to 30 percent of magnesium sulfate powder, 18 to 40 percent of copper oxide powder, 2 to 5 percent of nickel oxide powder, 5 to 15 percent of stannous oxide powder and 2 to 8 percent of ferrochrome powder. The bronze ware has obvious energy-saving effect in the preparation process, is simple and rapid to operate, does not generate pollution and carbon emission, and has safe and stable process; the prepared bronze ware or bronze landscape sculpture has the advantages of clean and smooth appearance, uniform components, no defects of cracks, air holes and the like in the interior, higher strength, no fracture, excellent corrosion resistance in the atmosphere or seawater atmosphere and difficult oxidative discoloration.

Description

Composite powder material for rapidly preparing bronze ware
Technical Field
The invention relates to the technical field of bronze ware manufacturing, in particular to a composite powder material for rapidly preparing a bronze ware.
Background
Due to the development of science and technology, the manufacturing process of the modern antique bronze wares and the manufacturing of the antique bronze wares are different from the same day. The patent CN 110090929A provides a manufacturing process of an antique bronze ware, which comprises sixteen processes of sculpturing a model, smelting, casting and the like; particularly, the smelting and roasting system is efficient and advanced, and not only can a more exquisite antique bronze ware be manufactured, but also the manufacturing efficiency is greatly improved. However, the material formula adopted by the patent is a traditional formula, wherein the red copper accounts for 75-90%, and the tin or tin lead accounts for 10-25%, and the materials need to be put into a crucible and smelted in a gas smelting furnace, and after the smelting is finished, the alloy liquid is scooped out and cast into a gypsum casting mold. Obviously, the mixed material needs large-scale equipment such as a gas type smelting furnace and the like in the smelting process, the equipment investment is huge, and a large amount of electric energy needs to be consumed. Patent CN 105921694A proposes a bronze ware copying and manufacturing process, which combines the traditional process with the use of new materials, such as a shell manufacturing process; manufacturing a brick powder mold, and synthesizing and manufacturing powder of blue bricks and red bricks; quartz powder quartz sand is used as a shell material for manufacturing, and glass water and high bauxite are used as auxiliary materials; the main materials of the gypsum mold are high-strength gypsum material, borax, industrial ammonium chloride and industrial magnesium chloride which are used as auxiliary materials. The patented technology can be widely applied to modern production, and is particularly suitable for manufacturing special-shaped products and workpieces. However, the materials used in this patent also use bronze alloys of conventional formulation, still requiring an electric furnace to heat and melt the metal liquid, with a heating temperature of 1350 degrees, consuming a large amount of electrical energy.
Based on this, the existing manufacturing process of the antique bronze wares has the following disadvantages: 1. a complicated smelting facility such as an electric furnace, a coal furnace or a natural gas furnace is required. 2. The consumption of energy sources, such as electric energy or gas energy, is needed, carbon dioxide CO2 and sulfur dioxide SO2 are generated when chemical energy sources are combusted, the emission of flue gas pollutes the atmosphere, animal and plant growth and human health are damaged, and metal equipment is corroded. 3. Because of the limitation of heating condition, the temperature of the copper alloy liquid is only 1100-1350 ℃, which is about 300 ℃ higher than the melting point of copper, the heat is quickly dissipated during casting, and the cast bronze device is easy to delaminate, generate air holes and crack defects and be easily damaged. 4. The existing bronze ware is made of a single material component, is composed of copper, tin and lead, has poor corrosion resistance, is easy to rust in the environment, and is particularly easy to rust spots when being used as a bronze landscape sculpture.
In recent years, the preparation process of copper alloy based on self-propagating high-temperature reaction synthesis technology has become a research hotspot. The technology is a new method for preparing inorganic compound high-temperature material, which utilizes the self-heating and self-conduction action of chemical reaction heat between reactants to synthesize the material, and when the reactants are ignited, the reactants automatically spread to an unreacted area until the reaction is complete. The raw material cost required by the self-propagating high-temperature synthesis of the copper alloy is low, the chemical energy of the system can be fully utilized to meet the energy-saving requirement, the equipment is simple, and the process flow is short, so that the method obtains higher and higher attention in the field of bronze ware preparation. However, the existing self-propagating material for preparing copper alloy often has the defects of single component, over-narrow solidification temperature range, more air hole cracks, layering in the solidification process, incomplete slag-liquid separation and serious segregation, so that the mechanical property is poor, the corrosion resistance is poor, and the copper alloy is easy to corrode and damage after being exposed in the atmosphere for a long time.
Based on the above, the inventor intends to provide a powder material which is low in comprehensive cost, good in adaptability, stable in reaction, free of pollution discharge, free of layering of the obtained bronze ware, free of pore and crack defects, attractive in appearance formation and good in corrosion resistance, and is prepared by bronze ware imitation and bronze landscape sculpture rapidly, and a chemical formula of the powder material.
Disclosure of Invention
The invention aims to provide a composite powder material for rapidly preparing a bronze ware, so as to solve the technical problem.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite powder material for rapidly preparing bronze wares is prepared from the following raw materials in percentage by mass: 8 to 25 percent of aluminum powder, 12 to 45 percent of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 1 to 10 percent of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 1 to 5 percent of copper-zirconium intermediate alloy powder (CuZr 40), 2 to 5 percent of copper-silicon intermediate alloy powder (CuSi 50), 0.5 to 1 percent of borax powder, 3 to 6 percent of salt powder, 0.5 to 3 percent of potassium tetrafluoroaluminate, 9 to 30 percent of magnesium sulfate powder, 18 to 40 percent of copper oxide powder, 2 to 5 percent of nickel oxide powder, 5 to 15 percent of tin oxide powder and 2 to 8 percent of ferrochrome powder.
Preferably, the granularity of the raw materials is 50-200 meshes.
Preferably, the raw materials are sufficiently and uniformly stirred and mixed by using a powder mixer or a ball mill, and the powder material is dehydrated by heating to 100 ℃ in an argon atmosphere.
Preferably, the using amount m of the powder material depends on the quality G of the simulated bronze ware and the bronze landscape sculpture, and the calculation formula is as follows: g = 1.8.
Preferably, before use, the composite powder material is ignited by adopting a fire-ignition material, wherein the fire-ignition material is composed of four raw materials in a mass ratio: 40 percent of aluminum magnesium powder, 20 percent of charcoal powder, 10 percent of sulfur powder and 30 percent of potassium permanganate, the granularity is 50 meshes, and the usage amount of the ignition material is 0.1 percent of the mass of the powder material.
The invention has the beneficial effects that: the complex smelting equipment, the electric furnace, the coal furnace or the gas furnace are not needed in the process of preparing the copper alloy liquid, the operation is simple and convenient, and the mass production is easy.
The preparation process does not need the consumption of energy sources, including electric energy or gas energy. Based on self-propagating exothermic reaction, obtaining high-temperature molten metal similar to the copper-tin alloy of the bronze relic substrate, and solidifying the molten metal into the bronze ware with a specific shape in a packaging mould.
No pollution such as carbon dioxide CO2 and sulfur dioxide SO2 is generated in the reaction process, the growth of animals and plants and the health of human beings are not harmed, and metal equipment is not corroded.
The powder was MgSO 4 The reaction heat is sufficient due to multiple exothermic reactions of the + Al system, the CuO + Al system, the SnO + Al system and the NiO + Al system, the adiabatic temperature can reach 2000-2200 ℃ through calculation and is far higher than the heating temperature (about 1300 ℃) of smelting equipment, and the method avoids the phenomenon that the heat insulation temperature is too highAvoids the layering phenomenon of the bronze device after casting, and the air holes overflow rapidly.
The copper tin phosphorus (BCu 86 SnP) brazing powder and the copper zinc tin (BCu 58 ZnSn) are added to have multiple functions, so that the concomitant addition of tin, zinc and copper is realized, the tin and zinc content is ensured, and the tissues and the components are uniformly distributed. The second addition process is stable, and the phenomenon of gasification and splashing during separate addition is avoided. Thirdly, P is an excellent deoxidizer, can effectively remove O ions in the alloy and improve the yield of castings. Fourthly, cu-P, cu-Sn, cu-Zn and the like form various eutectic crystals, the fluidity is excellent, and the quality of the casting is further improved.
NaCl is convenient and easy to obtain, and the cost is low. The borax in the welding powder is beneficial to flowing of molten metal, meanwhile, the welding surface can be protected from being oxidized easily, B2O3 obtained by decomposing the borax at high temperature on the other surface can be combined with NaCl and potassium tetrafluoroaluminate to be used as a diluent and a slagging constituent, the protection capability of a slag system on molten pool metal is improved, and oxidation and slag inclusion of the high-temperature molten metal are avoided.
Adding copper-zirconium intermediate alloy powder (CuZr 40) and copper-silicon intermediate alloy powder (CuSi 50), on one hand, the addition of copper is ensured, on the other hand, the composite addition is more stable than the addition of simple substance elements, and in addition, the addition of Zr and Si strengthens welding seams and enhances deoxidation; the added silicon is converted into silicon oxide at high temperature, so that the solid-liquid conversion temperature range of the liquid metal can be expanded, and the flowing and wetting properties of the liquid metal are improved.
The addition of Ni, zr, cr and Fe and the excess of Al not only can improve the strength of the bronze ware or bronze sculpture, but also greatly improves the corrosion resistance of the bronze ware or bronze sculpture. For example, a Cu-Al-Ni-Fe quaternary alloy containing 8 to 12% of Al,4 to 6% of Ni,4 to 6% of Fe, exhibits a K phase in its structure, and when the Ni content is larger than the Fe content, the K phase is precipitated in a layered form, and when the Fe content > the Ni content, the K phase is in a lump form, and only when the Ni content is about the Fe content, the K phase is in a uniformly dispersed fine particle form, which is advantageous in obtaining excellent mechanical properties, and remarkably improving the atmospheric and seawater corrosion resistance. Chromium oxide is preferentially generated when Cr is oxidized, and the oxidation resistance and corrosion resistance of the bronze ware are further improved.
The bronze landscape sculpture has wide application range, can be prepared from bronze landscapes with various shapes, sizes and specifications besides bronze ware imitation, and adds bright colors to cities.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The mass of a certain bronze ware is 300g, and when the bronze ware is imitated, the chemical composition of the adopted composite powder material is as follows: 8% of aluminum powder, 24% of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 10% of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 1% of copper-zirconium intermediate alloy powder (CuZr 40), 2% of copper-silicon intermediate alloy powder (CuSi 50), 1% of borax powder, 5% of salt powder, 1% of potassium tetrafluoroaluminate, 10% of magnesium sulfate powder, 23% of copper oxide powder, 2% of nickel oxide powder, 11% of stannous oxide powder and 2% of ferrochrome powder.
The usage amount m of the powder material depends on the quality G of the imitated bronze ware and the bronze landscape sculpture, and the calculation formula is as follows: g =1.8 to 4.2, taking 2. The total mass of the powder was 750g, in terms of mass percentage. The components are as follows: 60g of aluminum powder, 180g of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 75g of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 7.5g of copper-zirconium intermediate alloy powder (CuZr 40), 15g of copper-silicon intermediate alloy powder (CuSi 50), 7.5g of borax powder, 37.5g of salt powder, 7.5g of potassium tetrafluoroaluminate, 75g of magnesium sulfate powder, 172.5g of copper oxide powder, 15g of nickel oxide powder, 82.5g of stannous oxide powder and 15g of ferrochrome powder.
The granularity of each raw material in the powder material is 100 meshes. The powder is fully and uniformly stirred and mixed by using a powder mixer or a ball mill, and the powder material is heated to 100 ℃ in an argon atmosphere to be dehydrated.
The powder was MgSO 4 The multiple exothermic reactions of the + Al system, the CuO + Al system, the SnO + Al system and the NiO + Al system have sufficient reaction heat, and the adiabatic temperature can reach 2200 ℃ by calculation and is far higher than that of a smelting deviceThe hot temperature (about 1300 ℃) avoids the layering phenomenon of the bronze device after casting, and the air holes overflow rapidly. The copper tin phosphorus (BCu 86 SnP) brazing powder and the copper zinc tin (BCu 58 ZnSn) are added to have multiple functions, so that the concomitant addition of tin, zinc and copper is realized, the tin and zinc content is ensured, and the tissues and the components are uniformly distributed. The second addition process is stable, and the phenomenon of gasification and splashing during separate addition is avoided. Thirdly, P is an excellent deoxidizer, can effectively remove O ions in the alloy and improve the yield of castings. Fourthly, cu-P, cu-Sn, cu-Zn and the like form various eutectic crystals, the fluidity is excellent, and the quality of the casting is further improved. Adding copper-zirconium intermediate alloy powder (CuZr 40) and copper-silicon intermediate alloy powder (CuSi 50), so that on one hand, the addition of copper is ensured, on the other hand, the addition of composite addition is more stable than the addition of simple substance elements, and in addition, the addition of Zr and Si strengthens welding seams and enhances deoxidation; the added silicon is converted into silicon oxide at high temperature, so that the solid-liquid conversion temperature range of the liquid metal can be expanded, and the flowing and wetting properties of the liquid metal are improved. The addition of Ni, zr, cr and Fe and the excess of Al not only can improve the strength of the bronze ware or bronze sculpture, but also greatly improves the corrosion resistance of the bronze ware or bronze sculpture. For example, a Cu-Al-Ni-Fe quaternary alloy containing 8 to 12% of Al,4 to 6% of Ni,4 to 6% of Fe, in which a K phase appears in the structure, when the Ni content is larger than the Fe content, the K phase is precipitated in a layered form, and when the Fe content is larger than the Fe content>When the Ni content is about equal to the Fe content, the K phase is in a uniformly dispersed fine particle shape, so that good mechanical properties can be obtained, and the atmospheric and seawater corrosion resistance of the alloy is remarkably improved. Cr is preferentially generated during oxidation to further improve oxidation and corrosion resistance of the bronze ware.
The powder material is ignited by adopting an ignition material before use, the ignition material comprises 40% of aluminum magnesium powder, 20% of charcoal powder, 10% of sulfur powder, 30% of potassium permanganate (all are 50-mesh coarse particles) and the like in mass ratio, and the usage amount of the ignition material is 0.1% and about 0.75g of the mass of the powder material. The ignition is safe, convenient and quick.
In this example, 750g of the powder material was reacted to obtain about 400g of a high-temperature mixed copper liquid having a temperature of 2000 ℃ in consideration of combustion and splash loss.
Example 2
The mass of a certain bronze ware is 15Kg, and when the bronze ware is imitated, the adopted powder material comprises the following chemical compositions: 20% of aluminum powder, 20% of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 2% of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 2% of copper-zirconium intermediate alloy powder (CuZr 40), 4% of copper-silicon intermediate alloy powder (CuSi 50), 1% of borax powder, 6% of salt powder, 2% of potassium tetrafluoroaluminate, 15% of magnesium sulfate powder, 18% of copper oxide powder, 2% of nickel oxide powder, 5% of stannous oxide powder and 3% of ferrochrome powder.
The usage amount m of the powder material depends on the quality G of the imitated bronze ware and the bronze landscape sculpture, and the calculation formula is as follows: g =1.8 to 4.2, taking 3. The total mass of the powder was 2000g, in terms of mass percent. The components are as follows: 400g of aluminum powder, 400g of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 40g of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 40g of copper-zirconium intermediate alloy powder (CuZr 40), 80g of copper-silicon intermediate alloy powder (CuSi 50), 20g of borax powder, 120g of salt powder, 40g of potassium tetrafluoroaluminate, 300g of magnesium sulfate powder, 360g of copper oxide powder, 40g of nickel oxide powder, 100g of stannous oxide powder and 60g of ferrochrome powder.
The particle size of each raw material in the powder material is 200 meshes. The powder is fully and uniformly stirred and mixed by using a powder mixer or a ball mill, and the powder material is heated to 100 ℃ in argon atmosphere to be dehydrated.
The powder was MgSO 4 The reaction heat is sufficient due to multiple exothermic reactions of the + Al system, the CuO + Al system, the SnO + Al system and the NiO + Al system, the adiabatic temperature can reach 2200 ℃ through calculation and is far higher than the heating temperature (about 1300 ℃), the layering phenomenon of the bronze device after casting is avoided, and air holes overflow rapidly. The copper tin phosphorus (BCu 86 SnP) brazing powder and the copper zinc tin (BCu 58 ZnSn) are added to have multiple functions, so that the concomitant addition of tin, zinc and copper is realized firstly, the tin and zinc content is ensured, and the tissue and the component distribution are uniform. The second addition process is stable, and the phenomenon of gasification and splashing during separate addition is avoided. Thirdly, P is an excellent deoxidizer, can effectively remove O ions in the alloy and improve the yield of castings. Fourthly, cu-P, cu-Sn, cu-Zn and the like form various eutectic crystals, so that the fluidity is excellent, and the quality of the casting is further improved. Adding copper-zirconium intermediate alloy powder(CuZr 40) and copper-silicon intermediate alloy powder (CuSi 50), on one hand, the addition of copper is ensured, on the other hand, the composite addition is more stable than the addition of simple substance elements, and in addition, the addition of Zr and Si strengthens the welding line and enhances deoxidation; the added silicon is converted into silicon oxide at high temperature, so that the solid-liquid conversion temperature range of the liquid metal can be expanded, and the flowing and wetting properties of the liquid metal are improved. The addition of Ni, zr, cr and Fe and the excess of Al not only can improve the strength of the bronze ware or bronze sculpture, but also greatly improves the corrosion resistance of the bronze ware or bronze sculpture. For example, a Cu-Al-Ni-Fe quaternary alloy containing 8 to 12% of Al,4 to 6% of Ni,4 to 6% of Fe, in which a K phase appears in the structure, when the Ni content is larger than the Fe content, the K phase is precipitated in a layered form, and when the Fe content is larger than the Fe content>When the Ni content is about equal to the Fe content, the K phase is in a uniformly dispersed fine particle shape, so that good mechanical properties can be obtained, and the atmospheric and seawater corrosion resistance of the material is remarkably improved. Chromium oxide is preferentially generated when Cr is oxidized, and the oxidation resistance and corrosion resistance of the bronze ware are further improved.
The powder material is ignited by adopting an ignition material before use, the ignition material comprises 40% of aluminum magnesium powder, 20% of charcoal powder, 10% of sulfur powder, 30% of potassium permanganate (all are 50-mesh coarse particles) and the like in mass ratio, and the usage amount of the ignition material is 0.1% and about 2g of the mass of the powder material. The ignition is safe, convenient and fast.
In this example, 2000g of the powder material was reacted to obtain about 1350g of a high-temperature mixed copper liquid having a temperature of 2200 ℃ in consideration of the combustion and the spatter loss.
Example 3
The mass of a certain bronze spherical landscape sculpture is 20Kg, and when the bronze sculpture is prepared, the chemical components of the adopted powder materials are as follows: 25% of aluminum powder, 15% of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 3% of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 1% of copper-zirconium intermediate alloy powder (CuZr 40), 3% of copper-silicon intermediate alloy powder (CuSi 50), 1% of borax powder, 3% of salt powder, 3% of potassium tetrafluoroaluminate, 9% of magnesium sulfate powder, 26% of copper oxide powder, 2% of nickel oxide powder, 7% of stannous oxide powder and 2% of ferrochrome powder.
The usage amount m of the powder material depends on the quality G of the imitated bronze ware and the bronze landscape sculpture, and the calculation formula is as follows: g =1.8, 5 to 4.2, taking 2.5. The total mass of the powder is 40Kg according to the mass percentage. The components are as follows: 10Kg of aluminum powder, 1.2Kg of copper-tin-phosphorus (BCu 86 SnP) brazing powder, 0.4Kg of copper-zinc-tin (BCu 58 ZnSn) brazing powder, 0.4Kg of copper-zirconium intermediate alloy powder (CuZr 40), 1.2Kg of copper-silicon intermediate alloy powder (CuSi 50), 0.4Kg of borax powder, 1.2Kg of salt powder, 1.2Kg of potassium tetrafluoroaluminate, 3.6Kg of magnesium sulfate powder, 10.4Kg of copper oxide powder, 0.8Kg of nickel oxide powder, 2.8Kg of stannous oxide powder and 0.8Kg of ferrochrome powder.
The granularity of each raw material in the powder material is 150 meshes. The powder is fully and uniformly stirred and mixed by using a powder mixer or a ball mill, and the powder material is heated to 100 ℃ in an argon atmosphere to be dehydrated.
The powder was MgSO 4 The reaction heat is sufficient due to multiple exothermic reactions of the + Al system, the CuO + Al system, the SnO + Al system and the NiO + Al system, the adiabatic temperature can reach 2200 ℃ through calculation and is far higher than the heating temperature (about 1300 ℃), the layering phenomenon of the bronze device after casting is avoided, and air holes overflow rapidly. The copper tin phosphorus (BCu 86 SnP) brazing powder and the copper zinc tin (BCu 58 ZnSn) are added to have multiple functions, so that the concomitant addition of tin, zinc and copper is realized, the tin and zinc content is ensured, and the tissues and the components are uniformly distributed. The second addition process is stable, and the phenomenon of gasification and splashing during separate addition is avoided. Thirdly, P is an excellent deoxidizer, can effectively remove O ions in the alloy and improve the yield of castings. Fourthly, cu-P, cu-Sn, cu-Zn and the like form various eutectic crystals, so that the fluidity is excellent, and the quality of the casting is further improved. Adding copper-zirconium intermediate alloy powder (CuZr 40) and copper-silicon intermediate alloy powder (CuSi 50), on one hand, the addition of copper is ensured, on the other hand, the composite addition is more stable than the addition of simple substance elements, and in addition, the addition of Zr and Si strengthens welding seams and enhances deoxidation; the added silicon is converted into silicon oxide at high temperature, so that the solid-liquid conversion temperature range of the liquid metal can be expanded, and the flowing and wetting properties of the liquid metal are improved. The addition of Ni, zr, cr and Fe and the excess of Al not only can improve the strength of the bronze ware or bronze sculpture, but also greatly improves the corrosion resistance of the bronze ware or bronze sculpture. For example, comprise8-12% of Al, 4-6% of Ni, 4-6% of a Cu-Al-Ni-Fe quaternary alloy of Fe, in which the structure exhibits a K phase which precipitates in layers when the Ni content is greater than the Fe content, and the Fe content>When the Ni content is about equal to the Fe content, the K phase is in a uniformly dispersed fine particle shape, so that good mechanical properties can be obtained, and the atmospheric and seawater corrosion resistance of the alloy is remarkably improved. Chromium oxide is preferentially generated when Cr is oxidized, and the oxidation resistance and corrosion resistance of the bronze ware are further improved.
The powder material is ignited by adopting an ignition material before use, the ignition material comprises 40% of aluminum magnesium powder, 20% of charcoal powder, 10% of sulfur powder, 30% of potassium permanganate (all are 50-mesh coarse particles) and the like in mass ratio, and the usage amount of the ignition material is 0.1% of the mass of the powder material and is about 40g. The ignition is safe, convenient and fast.
In this example, 40Kg of the powder material was reacted to obtain about 21.6Kg of the high-temperature mixed copper liquid having a temperature of 2150 deg.C, taking into consideration the combustion and splash loss.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. The composite powder material for rapidly preparing the bronze ware is characterized by being prepared from the following raw materials in percentage by mass: 8 to 25 percent of aluminum powder, 12 to 45 percent of copper-tin-phosphorus brazing powder, 1 to 10 percent of copper-zinc-tin brazing powder, 1 to 5 percent of copper-zirconium intermediate alloy powder, 2 to 5 percent of copper-silicon intermediate alloy powder, 0.5 to 1 percent of borax powder, 3 to 6 percent of salt powder, 0.5 to 3 percent of potassium tetrafluoroaluminate, 9 to 30 percent of magnesium sulfate powder, 18 to 40 percent of copper oxide powder, 2 to 5 percent of nickel oxide powder, 5 to 15 percent of stannous oxide powder and 2 to 8 percent of ferrochrome powder.
2. The composite powder material for the rapid preparation of bronze wares according to claim 1, wherein the particle sizes of the raw materials are all 50-200 mesh.
3. The composite powder material for the rapid preparation of the bronze ware according to claim 1, wherein the composite powder material is prepared by sufficiently and uniformly stirring and mixing raw materials by using a powder mixer or a ball mill, and the powder material is dehydrated by heating to 100 ℃ in an argon atmosphere.
4. The composite powder material for the rapid preparation of bronze wares according to claim 1, wherein the amount of powder material used m depends on the quality of simulated bronze wares and bronze landscape sculptures G, and the calculation formula is: g = 1.8.
5. The composite powder material for the rapid preparation of the bronze ware according to claim 1, wherein the composite powder material is ignited by a pilot material before use, and the pilot material is composed of four raw materials in a mass ratio of: 40 percent of aluminum magnesium powder, 20 percent of charcoal powder, 10 percent of sulfur powder and 30 percent of potassium permanganate, the granularity is 50 meshes, and the usage amount of the ignition material is 0.1 percent of the mass of the powder material.
CN202211118766.0A 2022-09-15 2022-09-15 Composite powder material for rapidly preparing bronze ware Withdrawn CN115533093A (en)

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Application publication date: 20221230