WO2019205231A1 - Method for preparing nanometer oxide particle reinforced metal composite material - Google Patents

Method for preparing nanometer oxide particle reinforced metal composite material Download PDF

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WO2019205231A1
WO2019205231A1 PCT/CN2018/089617 CN2018089617W WO2019205231A1 WO 2019205231 A1 WO2019205231 A1 WO 2019205231A1 CN 2018089617 W CN2018089617 W CN 2018089617W WO 2019205231 A1 WO2019205231 A1 WO 2019205231A1
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alloy powder
alloy
metal
powder
silver
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PCT/CN2018/089617
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French (fr)
Chinese (zh)
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喻学锋
康翼鸿
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中国科学院深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides

Definitions

  • the invention belongs to the field of new materials, and in particular to a method for preparing nano oxide particle reinforced metal composite materials.
  • the toughness and electrical conductivity of metallic silver are very good, but limited by the strength and wear resistance, it is difficult to use it alone as a structural metal.
  • the embedding of oxide particles in the metallic silver can be widely used to make electrical contact materials while maintaining good electrical conductivity while greatly improving the mechanical properties of the material.
  • the oxide particles uniformly dispersed inside the silver reach the nanometer order, various mechanical properties of the silver can be improved in all aspects.
  • the powder mixing method is to directly mix the silver powder and the oxide powder, and then prepare the silver tin oxide material by a powder metallurgy method, such as US Pat. No. 5,798,468, German Patent DE 19503182.2.
  • the internal oxidation method is further divided into a pre-oxidation method and a conventional internal oxidation method.
  • the pre-oxidation method is an internal oxidation of a silver alloy split, such as an AgSn alloy powder, and then an oxide-reinforced silver material is prepared by powder metallurgy, for example, CN1425790A. .
  • the conventional internal oxidation method is to first melt a silver alloy into a wire or a sheet, and then prepare an oxide-reinforced silver material by internal oxidation.
  • the chemical rule is to first prepare an oxide powder, then disperse the oxide powder in an aqueous solution and add a reducing agent, and then add the complexed silver ions to deposit silver on the surface of the oxidized powder, thereby preparing a composite oxide-reinforced silver powder, and then passing
  • the powder metallurgy process produces oxide-reinforced silver wires or sheets, such as CN1425789A, CN102633499A.
  • the grain size and microscopic strain are 20 nm and 0.55%, respectively.
  • the Ag-Zn alloy powder undergoes three stages of lamination, rupture of the lamellar structure, equilibrium of cracking and cold welding, and lamination of the lamellar structure during mechanical ball milling.
  • the internal oxidation rate of the Ag-Zn alloy powder increases with the ball milling time, and the ball milled for 100 h reaches the maximum oxidation degree within 0.5 h, which is 25% higher than that of the unmilled powder.
  • ZnO is formed on the surface and has a large size in the form of needles and flakes in the sample of non-ball-milled powder.
  • the powder is oxidized by mechanical ball milling, and ZnO is mainly present in the matrix in the form of needles.
  • the size is small.
  • the volume expansion generated by the ZnO is generated, and compressive stress is formed in the inner oxidation region, causing the silver atoms to diffuse to the surface of the powder to form a silver sphere.
  • CN1477219A discloses a method for preparing a silver metal oxide electrical contact material, which first prepares a silver-containing alloying or intermetallic compound or a remarkably refined powder by a high-energy ball milling method, and then is prepared by internal oxidation and molding. Into the electrical contacts.
  • the oxidation temperature in the invention is significantly reduced (from 600 to 900 ° C to 400 to 800 ° C), and the time is greatly reduced to significantly reduce the production cost; the present invention can obtain the nanometer amount by controlling the oxygen partial pressure and temperature of the internal oxidation process, respectively.
  • the uniform distribution of MeO neighbors fully utilizes the addition of components to improve the wettability of Ag and MeO and improve the performance of electrical contacts.
  • the object of the present invention is to overcome the deficiencies of the prior art, and the size effect of the sheet powder prepared by ball milling and the large number of dislocations introduced in the mechanical process greatly increase the internal oxidation rate while reducing the internal oxidation.
  • the size of the material using only the ball milling method and the surfactant, can produce a uniformly dispersed nano-sized oxide-reinforced silver composite under a dry air atmosphere.
  • a method for preparing a nano oxide particle reinforced metal composite material comprising the steps of:
  • the mass percentage of the main metal in the alloy powder is 60 to 90%
  • the secondary metal is at least one metal having an equilibrium oxygen partial pressure lower than that of the main metal.
  • the alloy powder is selected from one of a silver alloy, a nickel alloy, and a copper alloy.
  • the alloy powder is a silver alloy
  • the secondary metal component is selected from at least one of tin, indium, aluminum, titanium, chromium, cadmium, zirconium, and manganese
  • the alloy powder is a nickel alloy
  • the secondary metal component is selected from At least one of aluminum, manganese, titanium, zirconium, and chromium
  • the alloy powder is a copper alloy
  • the secondary metal component is at least one selected from the group consisting of aluminum, zirconium, chromium, manganese, and titanium.
  • the surfactant is added in an amount of from 0.1 to 10% by mass based on the mass of the alloy powder.
  • the surfactant is selected from at least one of polyethylene glycol, oleic acid, and cetyl alcohol.
  • the rotational speed at the time of ball milling is 300 to 1000 rpm.
  • the ball milling time is 2 to 9 hours.
  • the partial pressure of oxygen in the internal oxidation process is controlled so that the main metal in the alloy powder cannot be oxidized, but the secondary metal can be oxidized.
  • the thickness of the flake alloy powder is 0.1 to 5 ⁇ m.
  • the invention has simple operation, no need to use a high-pressure oxygen furnace, lower oxidation temperature than conventional internal oxidation method, shorter oxidation time, greatly reduced production cost, and preparation without using expensive nano powder as raw material.
  • the nanometer-scale oxide is uniformly dispersed in the interior of the main metal, such as silver, to achieve the effect of the nanoparticle oxide-enhancing metal, which greatly improves the material mechanics and electrical properties.
  • surface pure metals, such as silver layers, which affect the properties of the material are avoided. It is a low cost and efficient preparation method.
  • Example 1 is an electron micrograph of a sheet-like silver tin alloy prepared in Example 1;
  • Example 2 is a SEM cross-sectional view of the nano-sized oxide-reinforced silver composite material prepared in Example 1;
  • Figure 3 is a SEM cross-sectional view of a material close to the surface portion after oxidation in a silver-tin alloy sheet (100 ⁇ m thick) in a non-ball milling process of Comparative Example 1.
  • a method for preparing a nano oxide particle reinforced metal composite material comprising the steps of:
  • the alloy powder is one selected from the group consisting of a silver alloy, a nickel alloy, and a copper alloy.
  • the temperature of the heating is related to the type and composition of the alloy.
  • the heating temperature is generally 300 to 500 ° C; for the copper alloy, the heating temperature is generally 350 to 550 ° C; for the nickel alloy, the heating temperature is generally 450 to 700 ° C.
  • the mass percentage of the main metal in the alloy powder is 60 to 90%, and the secondary metal is at least one metal having an equilibrium oxygen partial pressure lower than that of the main metal.
  • the amount of secondary metal can be adjusted accordingly depending on the characteristics of the material.
  • the alloy powder is a silver alloy, and the secondary metal component is selected from at least one of tin, indium, aluminum, titanium, chromium, cadmium, zirconium, and manganese; the alloy powder is a nickel alloy, and the secondary metal component is selected from the group consisting of aluminum and manganese. At least one of titanium, zirconium and chromium; the alloy powder is a copper alloy, and the secondary metal component is at least one selected from the group consisting of aluminum, zirconium, chromium, manganese and titanium.
  • Silver alloys include, but are not limited to, silver tin alloys, silver indium alloys, silver cadmium alloys; nickel alloys include, but are not limited to, nickel aluminum alloys, nickel aluminum manganese alloys, nickel aluminum titanium alloys, nickel zirconium alloys, nickel chromium alloys; It is not limited to copper-titanium aluminum alloy, copper-zirconium alloy, and copper-chromium alloy.
  • the rotational speed at the time of ball milling is 300 to 1000 rpm.
  • the ball milling time is 2 to 9 hours.
  • the rotation speed of the ball mill and the time of ball milling can be adjusted according to the type of the alloy and the specific research effect, so that the thickness of the metal sheet prepared by ball milling is not more than 5 ⁇ m, preferably not more than 1 ⁇ m, and the size and thickness distribution are relatively uniform.
  • a softer alloy the ball milling time can be a little shorter, the speed can be slightly lower; and the harder alloy needs to properly extend the ball milling time and the ball milling speed.
  • the thickness of the flake alloy powder is 0.1 to 5 ⁇ m. This thickness of material can be oxidized internally to give a more uniform material.
  • the role of the surfactant is to avoid cold inlay between the metal particles during ball milling, which is advantageous for the preparation of the flake powder.
  • the surfactant is added in an amount of 0.1 to 10% by mass of the alloy powder.
  • the surfactant is preferably at least one of polyethylene glycol, oleic acid, and cetyl alcohol.
  • the ball milling media in the following examples were all stainless steel balls having a diameter of 1 cm, and the ball milling was carried out in a closed ball mill.
  • the size of the tin oxide particles in the composite material is generally less than 100 nm, and there is no silver enrichment on the surface.
  • the prepared sheet-shaped nickel-aluminum alloy powder is washed with ethanol and heated to 700 ° C under the equilibrium partial pressure of nickel oxide in a closed vessel.
  • Min a nano-scale oxide-reinforced nickel composite is obtained.
  • the equilibrium partial pressure of nickel oxide can be achieved by placing a mixture of nickel oxide powder and metallic nickel powder in a closed vessel.
  • a 100 ⁇ m thick silver tin alloy flake was placed in a dry air atmosphere and heated to 500 ° C for 10 min.
  • the SEM cross-section of the prepared composite near the surface portion is shown in Fig. 3. It can be seen that the surface has obvious silver enrichment, the oxidation is not complete, and the particle size inside the alloy obviously begins to increase to the order of micrometers.

Abstract

A method for preparing a nanometer oxide particle reinforced metal composite material, comprising: mixing alloy powder and a surfactant, and performing ball milling to obtain flaky alloy powder; placing the flaky alloy powder in a dry air atmosphere, heating to 300-500°C for undergoing internal oxidation for 10-60 min to obtain the nanometer oxide particle reinforced metal composite material. The method is simple in operation and does not require a high-pressure oxygen furnace; compared with a conventional internal oxidation method, the oxidation temperature is lower, the oxidation time is shorter, and the production costs are reduced; without using expensive nanometer powder as a raw material, nanoscale oxide is prepared, and is uniformly dispersed in the metal, so that the effect of reinforcing the metal by means of nanoparticle oxide is achieved; moreover, production of a surface pure metal layer affecting the material properties, such as a silver layer, is avoided.

Description

一种制备纳米氧化物颗粒增强金属复合材料的方法  Method for preparing nano oxide particle reinforced metal composite material
技术领域Technical field
本发明属于新材料领域，特别及一种制备纳米氧化物颗粒增强金属复合材料的方法。The invention belongs to the field of new materials, and in particular to a method for preparing nano oxide particle reinforced metal composite materials.
背景技术Background technique
金属银的韧性和导电性能非常好，但受限于其强度和耐磨性差的原因，很难单独作为结构金属使用。不过在金属银内部嵌入氧化物颗粒可以在保持良好导电性的同时，大幅提升材料的力学性能，从而被广泛地用于制作电接触材料。当均匀分散在银内部的氧化物颗粒达到纳米量级的时候，还可以全方面地提高银的各种力学性能。The toughness and electrical conductivity of metallic silver are very good, but limited by the strength and wear resistance, it is difficult to use it alone as a structural metal. However, the embedding of oxide particles in the metallic silver can be widely used to make electrical contact materials while maintaining good electrical conductivity while greatly improving the mechanical properties of the material. When the oxide particles uniformly dispersed inside the silver reach the nanometer order, various mechanical properties of the silver can be improved in all aspects.
为了在银中嵌入氧化物颗粒，主要的方法有三种：混粉法，内氧化法，化学法。混粉法是直接将银粉和氧化物粉末机械混合，再通过粉末冶金的方法制备银氧化锡材料，如美国专利US5798468，德国专利DE19503182.2。内氧化法又分为预氧化法和传统内氧化法，预氧化法是对银合金分体，例如AgSn合金粉，进行内氧化，然后再通过粉末冶金的方式制备氧化物增强银材料，例如CN1425790A。传统内氧化法是先把银合金熔化制备成线材或者板材，然后再通过内氧化制备氧化物增强银材料。化学法则是先制备氧化物粉末，然后在水溶液中将氧化物粉分散并加入还原剂，再加入络合的银离子使银沉积于氧化粉末表面，从而制备出复合的氧化物增强银粉，再通过粉末冶金的方法制备氧化物增强银线材或片材，如CN1425789A、CN102633499A。In order to embed oxide particles in silver, there are three main methods: mixed powder method, internal oxidation method, and chemical method. The powder mixing method is to directly mix the silver powder and the oxide powder, and then prepare the silver tin oxide material by a powder metallurgy method, such as US Pat. No. 5,798,468, German Patent DE 19503182.2. The internal oxidation method is further divided into a pre-oxidation method and a conventional internal oxidation method. The pre-oxidation method is an internal oxidation of a silver alloy split, such as an AgSn alloy powder, and then an oxide-reinforced silver material is prepared by powder metallurgy, for example, CN1425790A. . The conventional internal oxidation method is to first melt a silver alloy into a wire or a sheet, and then prepare an oxide-reinforced silver material by internal oxidation. The chemical rule is to first prepare an oxide powder, then disperse the oxide powder in an aqueous solution and add a reducing agent, and then add the complexed silver ions to deposit silver on the surface of the oxidized powder, thereby preparing a composite oxide-reinforced silver powder, and then passing The powder metallurgy process produces oxide-reinforced silver wires or sheets, such as CN1425789A, CN102633499A.
许灿辉，易丹青，吴春萍，等。机械球磨Ag-Zn合金粉末显微组织及内氧化性能[J]。稀有金属材料与工程，2010，39(1):85-89。利用XRD、SEM研究球磨时间对Ag-Zn合金粉末显微组织和内氧化性能的影响。先在氮气保护下进行球磨，之后在箱式电阻炉中进行氧化增重。结果表明:球磨初期，晶粒尺寸迅速减小，微观应变急剧增加，球磨25h后，变化趋于平缓，球磨100h后，晶粒尺寸和微观应变分别为20nm和0.55%。Ag-Zn合金粉末在机械球磨过程中经历了片层化、片层结构破裂细化、破裂和冷焊的平衡阶段以及片层组织焊合成团4个阶段。Ag-Zn合金粉末的内氧化速度随球磨时间延长而增加，球磨100h的粉末在0.5h内即达到最大氧化程度，与未球磨粉末相比提高了25%。Ag-Zn合金粉末在内氧化过程中，未球磨粉末样品中ZnO呈针状和片状形成于表面且尺寸较大;粉末经机械球磨后氧化，ZnO则主要以针状形式存在于基体中，尺寸较小。生成ZnO产生的体积膨胀，在内氧化区形成压应力，导致银原子向粉末表面扩散形成银球。Xu Canhui, Yi Danqing, Wu Chunping, et al. Microstructure and internal oxidation performance of mechanically ball-milled Ag-Zn alloy powder [J]. Rare Metal Materials and Engineering, 2010, 39(1): 85-89. The effects of milling time on the microstructure and internal oxidation properties of Ag-Zn alloy powders were investigated by XRD and SEM. Ball milling was first carried out under nitrogen protection, followed by oxidation weight gain in a box type resistance furnace. The results show that the grain size decreases rapidly and the microscopic strain increases sharply at the initial stage of ball milling. After 25 h of ball milling, the change tends to be gentle. After 100 h of ball milling, the grain size and microscopic strain are 20 nm and 0.55%, respectively. The Ag-Zn alloy powder undergoes three stages of lamination, rupture of the lamellar structure, equilibrium of cracking and cold welding, and lamination of the lamellar structure during mechanical ball milling. The internal oxidation rate of the Ag-Zn alloy powder increases with the ball milling time, and the ball milled for 100 h reaches the maximum oxidation degree within 0.5 h, which is 25% higher than that of the unmilled powder. In the internal oxidation process of Ag-Zn alloy powder, ZnO is formed on the surface and has a large size in the form of needles and flakes in the sample of non-ball-milled powder. The powder is oxidized by mechanical ball milling, and ZnO is mainly present in the matrix in the form of needles. The size is small. The volume expansion generated by the ZnO is generated, and compressive stress is formed in the inner oxidation region, causing the silver atoms to diffuse to the surface of the powder to form a silver sphere.
CN1477219A公开了一种银金属氧化物电触头材料的制备方法，用高能球磨方法首先制备出含银的合金化、或金属间化合物、或显著细化的粉末，再经内氧化及成型处理制备成电触头。本发明内氧化温度显著降低（从600～900℃降至400～800℃），时间大幅度减少使生产成本显著降低；本发明通过控制内氧化过程的氧分压与温度，可以分别获得纳米量级或微米量级的金属氧化物在银基体中的弥散分布；本发明氧化物和银基体间为自生成界面，界面结合好，提高了材料加工性能；另外本发明能够实现添加组元在Ag、MeO近邻的均匀分布，从而充分发挥添加组元改善Ag与MeO浸润性和提高电触头性能的作用。CN1477219A discloses a method for preparing a silver metal oxide electrical contact material, which first prepares a silver-containing alloying or intermetallic compound or a remarkably refined powder by a high-energy ball milling method, and then is prepared by internal oxidation and molding. Into the electrical contacts. The oxidation temperature in the invention is significantly reduced (from 600 to 900 ° C to 400 to 800 ° C), and the time is greatly reduced to significantly reduce the production cost; the present invention can obtain the nanometer amount by controlling the oxygen partial pressure and temperature of the internal oxidation process, respectively. Dispersion distribution of metal oxides of the order or micron order in the silver matrix; the self-generated interface between the oxide and the silver matrix of the invention has good interfacial bonding and improves the material processing property; and the invention can realize the addition of components in the Ag The uniform distribution of MeO neighbors fully utilizes the addition of components to improve the wettability of Ag and MeO and improve the performance of electrical contacts.
现有技术中，主要有三个问题：一个是在混粉法制备过程中，非常难做到纳米量级氧化物均匀分散在银内部，二是利用内氧化方法需要的氧化时间长（10-100小时）、氧化温度过高（500-800度）、氧化条件苛刻（高压氧氛围），氧化物颗粒大（大于1个微米），且很难氧化彻底。三是化学法的步骤繁琐，且需要化学还原剂。In the prior art, there are mainly three problems: one is that it is very difficult to uniformly disperse the nano-scale oxide in the silver during the preparation process of the mixed powder method, and the oxidation time required for the internal oxidation method is long (10-100). Hour), oxidation temperature is too high (500-800 degrees), oxidation conditions are harsh (high pressure oxygen atmosphere), oxide particles are large (greater than 1 micron), and it is difficult to completely oxidize. Third, the steps of the chemical process are cumbersome and require a chemical reducing agent.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足，利用球磨制备的片层粉末在厚度上的尺寸效应以及机械过程中引入的大量位错，在大幅度提高内氧化速度的同时又减小了内氧化物的尺寸，仅仅利用球磨方法和表面活性剂，在干燥空气的氛围下，即可制备出均匀分散的纳米量级氧化物增强银复合材料。The object of the present invention is to overcome the deficiencies of the prior art, and the size effect of the sheet powder prepared by ball milling and the large number of dislocations introduced in the mechanical process greatly increase the internal oxidation rate while reducing the internal oxidation. The size of the material, using only the ball milling method and the surfactant, can produce a uniformly dispersed nano-sized oxide-reinforced silver composite under a dry air atmosphere.
本发明所采取的技术方案是：The technical solution adopted by the present invention is:
一种制备纳米氧化物颗粒增强金属复合材料的方法，包括如下步骤：A method for preparing a nano oxide particle reinforced metal composite material, comprising the steps of:
1) 将合金粉末和表面活性剂混合，进行球磨，制备得到片状合金粉末；1) mixing the alloy powder and the surfactant, and performing ball milling to prepare a flake alloy powder;
2) 将片状合金粉末置于干燥空气氛中，加热到300～700℃ 10～60min进行内氧化，得到纳米氧化物颗粒增强金属复合材料。2) Place the flake alloy powder in a dry air atmosphere and heat to 300-700 °C. Internal oxidation was carried out for 10 to 60 minutes to obtain a nano-oxide particle reinforced metal composite material.
作为上述方法的进一步改进，合金粉末中主金属的质量百分含量为60～90%，次金属为平衡氧分压低于主金属的至少一种金属。As a further improvement of the above method, the mass percentage of the main metal in the alloy powder is 60 to 90%, and the secondary metal is at least one metal having an equilibrium oxygen partial pressure lower than that of the main metal.
作为上述方法的进一步改进，合金粉末选自银合金、镍合金、铜合金中的一种。As a further improvement of the above method, the alloy powder is selected from one of a silver alloy, a nickel alloy, and a copper alloy.
作为上述方法的进一步改进，合金粉末为银合金，次金属成分选自锡、铟、铝、钛、铬、镉、锆、锰中的至少一种；合金粉末为镍合金，次金属成分选自铝、锰、钛、锆、铬中的至少一种；合金粉末为铜合金，次金属成分选自铝、锆、铬、锰、钛中的至少一种。As a further improvement of the above method, the alloy powder is a silver alloy, the secondary metal component is selected from at least one of tin, indium, aluminum, titanium, chromium, cadmium, zirconium, and manganese; the alloy powder is a nickel alloy, and the secondary metal component is selected from At least one of aluminum, manganese, titanium, zirconium, and chromium; the alloy powder is a copper alloy, and the secondary metal component is at least one selected from the group consisting of aluminum, zirconium, chromium, manganese, and titanium.
作为上述方法的进一步改进，表面活性剂的添加量为合金粉末质量的0.1～10%。As a further improvement of the above method, the surfactant is added in an amount of from 0.1 to 10% by mass based on the mass of the alloy powder.
作为上述方法的进一步改进，表面活性剂选自聚乙二醇、油酸、十六醇中的至少一种。As a further improvement of the above method, the surfactant is selected from at least one of polyethylene glycol, oleic acid, and cetyl alcohol.
作为上述方法的进一步改进，球磨时的转速为300～1000 rpm。As a further improvement of the above method, the rotational speed at the time of ball milling is 300 to 1000 rpm.
作为上述方法的进一步改进，球磨的时间为2～9小时。As a further improvement of the above method, the ball milling time is 2 to 9 hours.
作为上述方法的进一步改进，控制内氧化过程中的氧分压使合金粉末中的主金属无法氧化，但次金属可以氧化。As a further improvement of the above method, the partial pressure of oxygen in the internal oxidation process is controlled so that the main metal in the alloy powder cannot be oxidized, but the secondary metal can be oxidized.
作为上述方法的进一步改进，片状合金粉末的厚度为0.1～5μm。As a further improvement of the above method, the thickness of the flake alloy powder is 0.1 to 5 μm.
本发明的有益效果是：The beneficial effects of the invention are:
本发明技术的操作简单，无需使用高压氧炉，比传统内氧化法所需的氧化温度更低，氧化时间更短，大幅降低制作成本，在不使用昂贵的纳米粉末为原料的情况下，制备出纳米量级氧化物，并且均匀分散在主金属，如银的内部，达到纳米颗粒氧化物增强金属的效果，大幅度提高材料力学和电学性能。同时又避免影响材料性能的表面纯金属，如银层的产生。是一种低成本、高效的制备方法。The invention has simple operation, no need to use a high-pressure oxygen furnace, lower oxidation temperature than conventional internal oxidation method, shorter oxidation time, greatly reduced production cost, and preparation without using expensive nano powder as raw material. The nanometer-scale oxide is uniformly dispersed in the interior of the main metal, such as silver, to achieve the effect of the nanoparticle oxide-enhancing metal, which greatly improves the material mechanics and electrical properties. At the same time, surface pure metals, such as silver layers, which affect the properties of the material, are avoided. It is a low cost and efficient preparation method.
附图说明DRAWINGS
图1是实施例1制得的片状银锡合金电镜图；1 is an electron micrograph of a sheet-like silver tin alloy prepared in Example 1;
图2是实施例1制得的纳米量级氧化物增强银复合材料的SEM截面图；2 is a SEM cross-sectional view of the nano-sized oxide-reinforced silver composite material prepared in Example 1;
图3是对比例1未经球磨过程的银锡合金薄片（100微米厚）内氧化后接近表面部分材料的SEM截面图。Figure 3 is a SEM cross-sectional view of a material close to the surface portion after oxidation in a silver-tin alloy sheet (100 μm thick) in a non-ball milling process of Comparative Example 1.
具体实施方式detailed description
一种制备纳米氧化物颗粒增强金属复合材料的方法，包括如下步骤：A method for preparing a nano oxide particle reinforced metal composite material, comprising the steps of:
1) 将合金粉末和表面活性剂混合，进行球磨，制备得到片状合金粉末；1) mixing the alloy powder and the surfactant, and performing ball milling to prepare a flake alloy powder;
2) 将片状合金粉末置于干燥空气氛中，加热到300～700℃ 10～60min进行内氧化，得到纳米氧化物颗粒增强金属复合材料。2) Place the flake alloy powder in a dry air atmosphere and heat to 300-700 °C. Internal oxidation was carried out for 10 to 60 minutes to obtain a nano-oxide particle reinforced metal composite material.
合金粉末选自银合金、镍合金、铜合金中的一种。The alloy powder is one selected from the group consisting of a silver alloy, a nickel alloy, and a copper alloy.
加热的温度和合金的种类和组成有关。对于银合金，其加热温度一般在300～500℃即可；对于铜合金，其加热温度一般要达350～550℃；对于镍合金，其加热温度一般要达到450～700℃。The temperature of the heating is related to the type and composition of the alloy. For the silver alloy, the heating temperature is generally 300 to 500 ° C; for the copper alloy, the heating temperature is generally 350 to 550 ° C; for the nickel alloy, the heating temperature is generally 450 to 700 ° C.
合金粉末中主金属的质量百分含量为60～90%，次金属为平衡氧分压低于主金属的至少一种金属。次金属的量可以根据材料的特性进行相应的调整。The mass percentage of the main metal in the alloy powder is 60 to 90%, and the secondary metal is at least one metal having an equilibrium oxygen partial pressure lower than that of the main metal. The amount of secondary metal can be adjusted accordingly depending on the characteristics of the material.
进一步的，合金粉末为银合金，次金属成分选自锡、铟、铝、钛、铬、镉、锆、锰中的至少一种；合金粉末为镍合金，次金属成分选自铝、锰、钛、锆、铬中的至少一种；合金粉末为铜合金，次金属成分选自铝、锆、铬、锰、钛中的至少一种。Further, the alloy powder is a silver alloy, and the secondary metal component is selected from at least one of tin, indium, aluminum, titanium, chromium, cadmium, zirconium, and manganese; the alloy powder is a nickel alloy, and the secondary metal component is selected from the group consisting of aluminum and manganese. At least one of titanium, zirconium and chromium; the alloy powder is a copper alloy, and the secondary metal component is at least one selected from the group consisting of aluminum, zirconium, chromium, manganese and titanium.
银合金包括但不限于银锡合金、银铟合金、银镉合金；镍合金包括但不限于镍铝合金、镍铝锰合金、镍铝钛合金、镍锆合金、镍铬合金；铜合金包括但不限于铜钛铝合金、铜锆合金、铜铬合金。Silver alloys include, but are not limited to, silver tin alloys, silver indium alloys, silver cadmium alloys; nickel alloys include, but are not limited to, nickel aluminum alloys, nickel aluminum manganese alloys, nickel aluminum titanium alloys, nickel zirconium alloys, nickel chromium alloys; It is not limited to copper-titanium aluminum alloy, copper-zirconium alloy, and copper-chromium alloy.
作为上述方法的进一步改进，球磨时的转速为300～1000 rpm。As a further improvement of the above method, the rotational speed at the time of ball milling is 300 to 1000 rpm.
作为上述方法的进一步改进，球磨的时间为2～9小时。As a further improvement of the above method, the ball milling time is 2 to 9 hours.
球磨的转速和球磨的时间，可以根据合金的种类和具体的研究效果进行相应的调整，以使球磨制备得到的金属片厚度不大于5μm，优选不大于1μm，且尺寸和厚度分布相对均匀。一般而言，质地较软的合金，球磨的时间可以稍短，转速可以稍低；而质地较硬的合金，则需要适当延长球磨时间和球磨转速。The rotation speed of the ball mill and the time of ball milling can be adjusted according to the type of the alloy and the specific research effect, so that the thickness of the metal sheet prepared by ball milling is not more than 5 μm, preferably not more than 1 μm, and the size and thickness distribution are relatively uniform. In general, a softer alloy, the ball milling time can be a little shorter, the speed can be slightly lower; and the harder alloy needs to properly extend the ball milling time and the ball milling speed.
作为上述方法的进一步改进，片状合金粉末的厚度为0.1～5μm。这种厚度的材料，可以内氧化得到更为均匀的材料。As a further improvement of the above method, the thickness of the flake alloy powder is 0.1 to 5 μm. This thickness of material can be oxidized internally to give a more uniform material.
表面活性剂的作用在于避免球磨过程中金属颗粒之间的冷镶嵌，利于片状粉末的制备，优选的，表面活性剂的添加量为合金粉末质量的0.1～10%。The role of the surfactant is to avoid cold inlay between the metal particles during ball milling, which is advantageous for the preparation of the flake powder. Preferably, the surfactant is added in an amount of 0.1 to 10% by mass of the alloy powder.
为进一步提高研磨效果，表面活性剂优选聚乙二醇、油酸、十六醇中的至少一种。In order to further improve the polishing effect, the surfactant is preferably at least one of polyethylene glycol, oleic acid, and cetyl alcohol.
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解到，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. In addition, it should be understood that various changes and modifications may be made by those skilled in the art in the form of the appended claims.
方便比较起见，以下实施例中的球磨介质均为直径为1cm的不锈钢球，球磨在密闭的球磨机内进行。For the sake of comparison, the ball milling media in the following examples were all stainless steel balls having a diameter of 1 cm, and the ball milling was carried out in a closed ball mill.
实施例1：Example 1:
1) 将30g粒径为50～100微米的球形银锡合金粉（锡的摩尔百分比为8%）和0.2g的表面活性剂（聚乙二醇）以及40个直径为1cm的不锈钢球混合放入球磨机，先300转/分钟转速球磨半小时，然后再使用500转/分钟转速球磨1小时，最后再使用800转/分钟转速球磨1小时，得到片状银锡合金（图1）；1) 30 g of spherical silver tin alloy powder having a particle size of 50 to 100 μm (mol% of tin is 8%) and 0.2 g of a surfactant (polyethylene glycol) and 40 stainless steel balls having a diameter of 1 cm are mixed into a ball mill Ball milled at 300 rpm for half an hour, then ball milled at 500 rpm for 1 hour, and finally ball milled at 800 rpm for 1 hour to obtain a flake-like silver-tin alloy (Fig. 1);
2) 取制得的片状银锡合金置于干燥空气氛围下，加热到500 ℃氧化10 min，得到纳米量级氧化物增强银复合材料（图2）。2) The obtained sheet-like silver-tin alloy is placed in a dry air atmosphere and heated to 500 ° C for oxidation. Min, a nano-sized oxide-reinforced silver composite was obtained (Fig. 2).
从图2可知，复合材料中氧化锡颗粒尺寸普遍小于100nm，表面没有银富集。It can be seen from Fig. 2 that the size of the tin oxide particles in the composite material is generally less than 100 nm, and there is no silver enrichment on the surface.
实施例2：Example 2:
1) 将30g粒径为50～100微米的球形镍铝合金粉（铝的摩尔百分比为8%）和0.4g的表面活性剂（油酸）以及40个直径为1cm的不锈钢球混合放入球磨机，先300转/分钟转速球磨半小时，然后再使用500转/分钟转速球磨1小时，最后再使用1000转/分钟转速球磨1小时得到片状镍铝合金；1) 30g of spherical nickel-aluminum alloy powder with a particle size of 50-100 microns (molar percentage of aluminum is 8%) and 0.4g of surfactant (oleic acid) and 40 stainless steel balls of 1cm diameter are mixed into the ball mill, first Ball milling at 300 rpm for half an hour, then ball milling for 1 hour at 500 rpm, and finally ball milling for 1 hour at 1000 rpm to obtain a sheet-like nickel-aluminum alloy;
2) 取制得的片状镍铝合金粉末用乙醇清洗后，在封闭容器内氧化镍的平衡分压下加热到700 ℃氧化30 min，得到纳米量级氧化物增强镍复合材料。氧化镍的平衡分压可以通过在封闭容器内放置氧化镍粉末和金属镍粉末混合物实现。2) The prepared sheet-shaped nickel-aluminum alloy powder is washed with ethanol and heated to 700 ° C under the equilibrium partial pressure of nickel oxide in a closed vessel. Min, a nano-scale oxide-reinforced nickel composite is obtained. The equilibrium partial pressure of nickel oxide can be achieved by placing a mixture of nickel oxide powder and metallic nickel powder in a closed vessel.
实施例3：Example 3:
1) 将30g粒径为50～100微米的镍铝锰合金粉（铝的摩尔百分比为8%，锰的摩尔百分比为8%）和0.2g的表面活性剂（聚乙二醇）以及40个直径为1cm的不锈钢球混合放入球磨机，先300转/分钟转速球磨半小时，然后再使用800转/分钟转速球磨2小时，得到片状镍铝锰合金；1) 30 g of nickel aluminum manganese alloy powder having a particle diameter of 50 to 100 μm (molar percentage of aluminum is 8%, molar percentage of manganese is 8%) and 0.2 g of surfactant (polyethylene glycol) and 40 diameters are 1cm stainless steel balls are mixed and placed in a ball mill, ball milled at 300 rpm for half an hour, and then ball milled at 800 rpm for 2 hours to obtain a sheet-like nickel aluminum manganese alloy;
2) 取制得的片状镍铝锰合金粉末用乙醇清洗并干燥后，在封闭容器内氧化镍的平衡分压下加热到700 ℃氧化15 min，得到纳米量级氧化物增强镍复合材料。2) The obtained sheet-like nickel aluminum manganese alloy powder is washed with ethanol and dried, and then heated to 700 ° C under the equilibrium partial pressure of nickel oxide in a closed container. Min, a nano-scale oxide-reinforced nickel composite is obtained.
实施例4：Example 4:
1) 将30g粒径为50～100微米的铜钛铝合金粉（铝的摩尔百分比为8%，钛的摩尔百分比为2%）和0.3g的表面活性剂（十六醇）以及40个直径为1cm的不锈钢球混合放入球磨机，先300转/分钟转速球磨半小时，然后再使用800转/分钟转速球磨2小时，得到片状铜钛铝合金；1) 30 g of copper-titanium aluminum alloy powder having a particle diameter of 50 to 100 μm (molar percentage of aluminum is 8%, molar percentage of titanium is 2%) and 0.3 g of surfactant (cetyl alcohol) and 40 diameters of 1 cm The stainless steel ball is mixed into a ball mill, ball milled at 300 rpm for half an hour, and then ball milled at 800 rpm for 2 hours to obtain a sheet-like copper-titanium alloy;
2) 取制得的片状铜钛铝合金粉末用乙醇清洗并干燥后，在封闭容器内氧化亚铜的平衡分压下加热到600 ℃氧化 20 min，得到纳米量级氧化物增强铜复合材料。氧化亚铜的平衡分压可以通过在封闭容器内放置氧化亚铜粉末和金属铜粉末混合物实现。2) The obtained sheet-shaped copper-titanium aluminum alloy powder is washed with ethanol and dried, and then heated to 600 ° C under the equilibrium partial pressure of cuprous oxide in a closed vessel. At 20 min, a nano-sized oxide-reinforced copper composite was obtained. The equilibrium partial pressure of cuprous oxide can be achieved by placing a mixture of cuprous oxide powder and metallic copper powder in a closed vessel.
实施例5：Example 5:
1) 将30g粒径为50～100微米的铜锆合金粉（锆的摩尔百分比为10%）和0.3g的表面活性剂（十六醇）以及40个直径为1cm的不锈钢球混合放入球磨机，先300转/分钟转速球磨半小时，然后再使用500转/分钟转速球磨3小时，得到片状铜钛铝合金；1) Mix 30g of copper-zirconium alloy powder with a particle size of 50-100 microns (10% by mole of zirconium) and 0.3g of surfactant (cetyl alcohol) and 40 stainless steel balls with a diameter of 1cm into the ball mill. Ball milling at 300 rpm for half an hour, and then ball milling for 3 hours at 500 rpm to obtain a sheet of copper-titanium aluminum alloy;
2) 取制得的片状铜钛铝合金粉末用乙醇清洗并干燥后，在封闭容器内氧化亚铜的平衡分压下加热到600 ℃氧化30 min，得到纳米量级氧化物增强铜复合材料。2) The prepared sheet-shaped copper-titanium aluminum alloy powder is washed with ethanol and dried, and then heated to 600 ° C for oxidation under a balanced partial pressure of cuprous oxide in a closed vessel. Min, a nano-scale oxide-reinforced copper composite is obtained.
对比例1：Comparative example 1:
取100μm厚的银锡合金薄片，置于干燥空气氛围下，加热到500 ℃氧化10 min。A 100 μm thick silver tin alloy flake was placed in a dry air atmosphere and heated to 500 ° C for 10 min.
制备得到的复合材料接近表面部分的SEM截面图如图3所示，可以看出，表面有明显的银富集，氧化不彻底，而且在合金内部的颗粒尺寸明显开始变大到微米量级。The SEM cross-section of the prepared composite near the surface portion is shown in Fig. 3. It can be seen that the surface has obvious silver enrichment, the oxidation is not complete, and the particle size inside the alloy obviously begins to increase to the order of micrometers.

Claims (10)

  1. 一种制备纳米氧化物颗粒增强金属复合材料的方法，包括如下步骤： A method for preparing a nano oxide particle reinforced metal composite material, comprising the steps of:
    1) 将合金粉末和表面活性剂混合，进行球磨，制备得到片状合金粉末；1) mixing the alloy powder and the surfactant, and performing ball milling to prepare a flake alloy powder;
    2) 将片状合金粉末置于干燥空气氛中，加热到300～700℃ 10～60min进行内氧化，得到纳米氧化物颗粒增强金属复合材料。2) Place the flake alloy powder in a dry air atmosphere and heat to 300-700 °C. Internal oxidation was carried out for 10 to 60 minutes to obtain a nano-oxide particle reinforced metal composite material.
  2. 根据权利要求1所述的方法，其特征在于：合金粉末选自银合金、镍合金、铜合金中的一种。 The method according to claim 1, wherein the alloy powder is one selected from the group consisting of a silver alloy, a nickel alloy, and a copper alloy.
  3. 根据权利要求2所述的方法，其特征在于：合金粉末中主金属的质量百分含量为60～90%，次金属为平衡氧分压低于主金属的至少一种金属。 The method according to claim 2, wherein the alloy powder has a mass percentage of the main metal of 60 to 90%, and the secondary metal is at least one metal having an equilibrium oxygen partial pressure lower than that of the main metal.
  4. 根据权利要求3所述的方法，其特征在于：合金粉末为银合金，次金属成分选自锡、铟、铝、钛、铬、镉、锆、锰中的至少一种；合金粉末为镍合金，次金属成分选自铝、锰、钛、锆、铬中的至少一种；合金粉末为铜合金，次金属成分选自铝、锆、铬、锰、钛中的至少一种。 The method according to claim 3, wherein the alloy powder is a silver alloy, and the secondary metal component is at least one selected from the group consisting of tin, indium, aluminum, titanium, chromium, cadmium, zirconium and manganese; and the alloy powder is a nickel alloy. The secondary metal component is at least one selected from the group consisting of aluminum, manganese, titanium, zirconium, and chromium; the alloy powder is a copper alloy, and the secondary metal component is at least one selected from the group consisting of aluminum, zirconium, chromium, manganese, and titanium.
  5. 根据权利要求1～4任一项所述的方法，其特征在于：表面活性剂的添加量为合金粉末质量的0.1～10%。 The method according to any one of claims 1 to 4, wherein the surfactant is added in an amount of from 0.1 to 10% by mass based on the mass of the alloy powder.
  6. 根据权利要求5所述的方法，其特征在于：表面活性剂选自聚乙二醇、油酸、十六醇中的至少一种。 The method of claim 5 wherein the surfactant is selected from at least one of polyethylene glycol, oleic acid, and cetyl alcohol.
  7. 根据权利要求1～4任一项所述的方法，其特征在于：球磨时的转速为300～1000 rpm。 The method according to any one of claims 1 to 4, characterized in that the rotational speed at the time of ball milling is 300 to 1000 rpm.
  8. 根据权利要求1～4任一项所述的方法，其特征在于：球磨的时间为2～9小时。 The method according to any one of claims 1 to 4, characterized in that the ball milling time is 2 to 9 hours.
  9. 根据权利要求1～4任一项所述的方法，其特征在于：控制内氧化过程中的氧分压使合金粉末中的主金属无法氧化，但次金属可以氧化。 The method according to any one of claims 1 to 4, characterized in that the partial pressure of oxygen in the internal oxidation process is controlled so that the main metal in the alloy powder cannot be oxidized, but the secondary metal can be oxidized.
  10. 根据权利要求1～4任一项所述的方法，其特征在于：片状合金粉末的厚度为0.1～5μm。 The method according to any one of claims 1 to 4, wherein the sheet-like alloy powder has a thickness of 0.1 to 5 μm.
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CN105458273A (en) * 2015-11-26 2016-04-06 浙江工业大学 Method for promoting oxidation of Ag-Sn alloy powder through high energy ball milling method
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CN107794389A (en) * 2017-10-20 2018-03-13 温州宏丰电工合金股份有限公司 A kind of silver-tin oxide or indium oxide contact material and preparation method thereof

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