WO2017070808A1 - 一种碳化钛颗粒增强铜基复合合金材料及其制造方法 - Google Patents

一种碳化钛颗粒增强铜基复合合金材料及其制造方法 Download PDF

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WO2017070808A1
WO2017070808A1 PCT/CN2015/000869 CN2015000869W WO2017070808A1 WO 2017070808 A1 WO2017070808 A1 WO 2017070808A1 CN 2015000869 W CN2015000869 W CN 2015000869W WO 2017070808 A1 WO2017070808 A1 WO 2017070808A1
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copper
mass
alloy material
based composite
titanium carbide
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PCT/CN2015/000869
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French (fr)
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陆海荣
孙飞
赵勇
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苏州天兼新材料科技有限公司
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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
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

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  • the invention relates to a titanium carbide particle reinforced copper-based composite alloy material, in particular to a high-strength titanium carbide particle reinforced copper-based composite alloy material for heavy equipment, and to a method for manufacturing the copper-based composite alloy material.
  • GB/T 1176-1987 copper alloy ZCuSn5Zn5Pb5 is a multi-purpose cast bronze material with good wear resistance, corrosion resistance, processing properties, casting properties and air tightness. Therefore, it is widely used to manufacture wear-resistant and corrosion-resistant parts that work at higher loads and moderate sliding speeds (4 m/s), such as bushings, bushings, cylinder liners, pistons, clutches, pump glands, turbines, etc. .
  • the service life is limited, so the application in heavy equipment is greatly limited.
  • Titanium carbide TiC has the advantages of high melting point, good thermal conductivity, high hardness, good chemical stability, no hydrolysis, high temperature oxidation resistance, etc.
  • High-purity titanium carbide powder is usually made of TiO 2 and carbon black in a carbon tube furnace with hydrogen gas or The reaction is carried out in a frequency-controlled vacuum furnace at a high temperature of 1600 ° C to 1800 ° C. Due to its good mechanical properties such as hardness and high temperature strength of titanium carbide, it is an important raw material for the production of hard alloys. It is commonly used in the manufacture of wear-resistant materials, cutting tool materials, mechanical parts, and metals such as tin, lead, cadmium and zinc. crucible.
  • Particle reinforced composite materials are one of the research hotspots in recent years.
  • the elastic modulus, strength, wear resistance, high temperature strength and fracture toughness of the alloy can be effectively improved by uniformly dispersing particles of a micron-sized carbide, nitride, boride or the like in the alloy.
  • titanium carbide particles to improve copper-based alloys.
  • the present invention proposes to add a high-purity titanium carbide particle powder to strengthen the ZCuSn5Zn5Pb5 alloy to improve its mechanical properties such as strength and hardness, and prolong the service life.
  • the present invention achieves the object by the following means:
  • a copper-based composite alloy material comprising 5% by mass of Sn, 5% by mass of Zn, 5% by mass of Pb, the balance being Cu and unavoidable impurities,
  • the alloy material was further added with titanium carbide particles having a particle diameter of 7 ⁇ m.
  • the titanium carbide particles of the copper-based composite alloy material are preferably added in an amount of from 0 to 5.0% by mass.
  • the amount of the titanium carbide particles added to the copper-based composite alloy material is further preferably from 0 to 4.0% by mass.
  • the titanium carbide particles of the copper-based composite alloy material are preferably added in an amount of from 0.5 to 3.5% by mass.
  • the titanium carbide particles of the copper-based composite alloy material are preferably added in an amount of from 3.0 to 3.5% by mass.
  • Step 1 Adding 5 mass% of Sn, 5 mass% of Zn, 5 mass% of Pb, and 85 mass% of electrolytic copper to an electric furnace protected by an argon atmosphere, and controlling the volume of copper water to be less than 99% of the volume of the furnace during the melting. Maintain the melting temperature of 1000-1100 ° C for 5-6 hours;
  • Step 2 After the above holding time, determine that the chemical composition is within the requirements of the national standard
  • Step 3 adding titanium carbide particles to the tested copper alloy melt and turning on the vibration device of the power frequency electric furnace, stirring, further raising the temperature to 1200-1250 ° C and maintaining for 25-30 minutes;
  • Step 4 The smelted alloy material is kept for 20-25 minutes, and the alloy is cast into an alloy rod by continuous casting, and the casting temperature is 950-1000 ° C;
  • Step 5 The finished casting and the alloy bar are subjected to surface processing to obtain a finished product.
  • the method for preparing the copper-based composite alloy material according to the above claims is further stirred in a third step using a graphite rod.
  • Figure 1 Flow chart of the preparation process of the alloy of the present invention.
  • the alloy of the present invention is obtained by the following steps:
  • Step 1 Experimental conditions According to the national standard GB/T 1176-2013, the copper alloy is added with 5% by mass of Sn, 5% by mass of Zn, and 5% by mass of Pb to the electric furnace protected by argon atmosphere according to the chemical composition of ZCuSn5Zn5Pb5. 85 mass% of electrolytic copper, the volume of copper water is controlled to be less than 99% of the volume of the furnace during the smelting, and the smelting temperature is maintained at 1000-1100 ° C for 5-6 hours to make it sufficiently uniform.
  • Step 2 After the above holding time, the smelted copper alloy melt is subjected to component detection by using a Spike direct reading spectrometer to determine that its chemical composition is within the requirements of the national standard. If there is a case where the predetermined component is deviated due to burning of one of the above elements, the corresponding element is added to continue the heat preservation until the composition meets the standard.
  • Step 3 Add different content of titanium carbide particles with a particle size of 7 ⁇ m to the tested ZCuSn5Zn5Pb5 copper alloy liquid, turn on the vibration device of the power frequency electric furnace and stir with a graphite rod to uniformly mix; further increase the temperature to 1200 -1250 ° C and hold for 25-30 minutes.
  • Step 4 Insulation and casting, the smelted alloy material is kept for 20-25 minutes, and the alloy is cast into an alloy rod by continuous casting, and the casting temperature is 950-1000 °C.
  • Step 5 The finished casting and the alloy bar are subjected to surface processing to obtain a finished product.
  • the inventors obtained the ingots of ZCuSn5Zn5Pb5 containing no different boron carbide particles and boron carbide particles in the same manner as described above. Sampling from different parts of the ingot, using XRF (X-ray fluorescence spectrometry) instrumentation of the German model Bruker S2PUMA The composition of the components was checked to ensure that the chemical composition of the ingot was uniform, and there was no significant influence on the segregation of the mechanical properties test.
  • the chemical compositions are shown in Table 1 below:
  • the samples were taken by electric spark cutting from the middle of the ingots with different compositions, and the EDM cutting effect layer was sanded, and further 400 mesh, 600 mesh, 800 mesh, 1200 mesh were used respectively. After the 2000-mesh sandpaper was polished, the polishing treatment was performed, and the Brinell hardness of the above alloy was measured by a Brinell hardness tester of the model MC010-HBS-3000.
  • the pressed material used in the measurement process was a hardened steel ball with a diameter of 10 mm, and a load of 3000 kg was applied. Each sample was averaged after being measured at five different positions.
  • Tensile strength and elongation measurement The sample was cut by electric spark cutting from the ingot, and the sample was cut by electric spark cutting.
  • the electrospark cutting effect layer was removed by sandpaper and further Polishing was performed after grinding with 400 mesh, 600 mesh, 800 mesh, 1200 mesh, and 2000 mesh sandpaper, respectively. After that, the tensile strength and elongation of the above alloys were measured by the tensile rate of 3 mm/min of the WDW-500E/600E microcomputer-controlled electronic universal testing machine.
  • the hardness, strength and elongation of ZCuSn5Zn5Pb5 copper alloy can be effectively improved by adding titanium carbide, and the hardness and strength of the alloy increase with the addition of titanium carbide, but when the addition amount of titanium carbide exceeds 3.5 After the mass%, the amount of addition of titanium carbide is continuously increased, and the elongation rate is somewhat lowered. Therefore, from the viewpoint of economy and overall performance, the amount of titanium carbide added in the present invention is particularly preferably from 2.5 to 3.5% by mass.
  • the titanium carbide particle reinforced copper matrix composite alloy material of the invention Compared with the traditional copper alloy ZCuSn5Zn5Pb5, the titanium carbide particle reinforced copper matrix composite alloy material of the invention has obvious improvement in strength, hardness and tensile properties, and can be used for manufacturing wear resistance under high load and medium sliding speed. Corrosion resistant parts. It fills the research gap in the current use of titanium carbide particles to improve the mechanical properties of copper alloys, and has broad application prospects.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

一种碳化钛颗粒增强铜基复合合金材料，该铜基复合合金材料含有5质量％的Sn、5质量％的Zn、5质量％的Pb，余量为Cu及不可避免的杂质，其中所述铜基复合合金材料进一步添加有粒径为7μm的碳化钛颗粒。

Description

一种碳化钛颗粒增强铜基复合合金材料及其制造方法 技术领域
本发明涉及一种碳化钛颗粒增强铜基复合合金材料，特别涉及一种重型装备用高强度的碳化钛颗粒增强铜基复合合金材料，本发明还涉及该铜基复合合金材料的制造方法。
背景技术
国标GB/T 1176-1987铜合金ZCuSn5Zn5Pb5是一种多用途的铸造青铜材料，具有较好的耐磨性、耐蚀性、加工性能、铸造性能、气密性。因此，其广泛用于制造在较高负荷、中等滑动速度(4m/s)下工作的耐磨、耐蚀零件，如轴瓦、衬套、缸套、活塞、离合器、泵件压盖、涡轮等。但是，由于该材料自身强度和硬度不足，导致使用寿命有限，因此在重型装备中的应用受到较大限制。
碳化钛TiC具有熔点高、导热性能好、硬度大、化学稳定好、不水解、高温抗氧化性好等优点，高纯度的碳化钛粉末通常由TiO2与炭黑在通氢气的碳管炉或调频真空炉内于1600℃～1800℃高温下反应制得。由于碳化钛硬度、高温强度等力学性能良好，因此它成为硬质合金的重要生产原料，通常用于制造耐磨材料、切削刀具材料、机械零件、以及熔炼锡、铅、镉、锌等金属的坩埚。
颗粒增强复合材料是近年来的研究热点之一。通过采用微米级别的碳化物、氮化物、硼化物等的颗粒均匀分散于合金中能够有效改善合金的弹性模量、强度、耐磨性、高温强度和断裂韧性。但目前未见采用采用碳化钛颗粒来改善铜基合金的报道。
发明内容
本发明鉴于以上所述，提出加入高纯度碳化钛颗粒粉末来增强ZCuSn5Zn5Pb5合金，以提高其强度和硬度等力学性能，延长使用寿命。
具体地，本发明通过以下方式实现了所述目的：
根据本发明的一个实施方式，提供了一种铜基复合合金材料，其含有5质量％的Sn、5质量％的Zn、5质量％的Pb，余量为Cu及不可避免的杂质，所述合金材料进一步添加有粒径为7μm碳化钛颗粒。
根据本发明的一个实施例，所述铜基复合合金材料的碳化钛颗粒的添加量优选为0～5.0质量％。
根据本发明的一个实施例，所述铜基复合合金材料的所述碳化钛颗粒的添加量进一步优选为0～4.0质量％。
根据本发明的一个实施例，所述铜基复合合金材料的所述碳化钛颗粒的添加量优选为0.5～3.5质量％。
根据本发明的一个实施例，所述铜基复合合金材料的所述碳化钛颗粒的添加量优选为3.0～3.5质量％。
根据本发明的一个实施方式，进一步提供了一种用于制备以上所述铜基复合合金材料的方法，其特征在于，包括如下步骤：
步骤一：向氩气氛保护的电炉中添加5质量％的Sn、5质量％的Zn、5质量％的Pb及85质量％的电解铜，熔炼期间控制铜水体积在熔炉体积的99％以下，保持熔炼温度1000-1100℃，持续时间5-6小时；
步骤二：在上述保温时间之后，确定其化学成分在国标要求范围之内；
步骤三：向经检验合格的铜合金熔体加入碳化钛颗粒并开启工频电炉的震动装置，进行搅拌，进一步升高温度至1200-1250℃并保持25-30分钟；
步骤四：将熔炼完成的合金材料进行保温，时间为20-25分钟，采用连续铸造的方式将此合金铸造成合金棒材，铸造温度为950-1000℃；
步骤五：将铸造完成和合金棒材进行表面车加工处理，获得成品。
根据本发明的一个实施例，所述用于制备权利要求以上所述铜基复合合金材料的方法，进一步在步骤三中采用石墨棒进行搅拌。
附图说明
图1：本发明的合金的制备过程流程图。
具体实施方式
本发明的合金通过如下步骤制取：
步骤一：实验条件根据国标GB/T 1176-2013的标准，铜合金根据ZCuSn5Zn5Pb5的化学成分，向氩气氛保护的电炉中添加5质量％的Sn、5质量％的Zn、5质量％的Pb及85质量％的电解铜，熔炼期间控制铜水体积在熔炉体积的99％以下，保持熔炼温度1000-1100℃，持续时间5-6小时，以使其充分均匀。
步骤二：在上述保温时间之后，采用斯派克直读光谱仪对熔炼完成的铜合金熔体进行成分检测，以确定其化学成分在国标要求范围之内。如果存在因上述某种元素烧损而偏离预定成分的情况，则补充相应的元素继续进行保温，直至成分符合标准。
步骤三：分别向经检验合格的ZCuSn5Zn5Pb5铜合金液体加入不同含量的颗粒尺寸为7μm的碳化钛颗粒，开启工频电炉的震动装置并用石墨棒进行搅拌，使其均匀混合；进一步升高温度至1200-1250℃并保持25-30分钟。
步骤四：保温与铸造，将熔炼完成的合金材料进行保温时间为20-25分钟，采用连续铸造的方式将此合金铸造成合金棒材，铸造温度为950-1000℃。
步骤五：将铸造完成和合金棒材进行表面车加工处理，获得成品。
发明人采用如上所述的步骤，分别制取了不含碳化硼颗粒及碳化硼颗粒含量不同的ZCuSn5Zn5Pb5的铸锭。从所述铸锭的不同部位取样，采用德国布鲁克公司产型号为S2PUMA的XRF(X射线荧光光谱分析)仪检 验其成分含量，以确保铸锭化学成分均匀，无明显影响表征其力学性能测试的偏析发生，其化学成分分别如下表1所示：
表1：熔炼所得各合金的元素含量
Figure PCTCN2015000869-appb-000001
由上表1可见，所熔炼的各铸锭成分均在误差要求范围内，符合实验要求。
布氏硬度测量：分别从所得不同成分的铸锭中部，采用电火花切割的方式截取试样，采用砂纸磨去电火花切割影响层，并进一步分别采用400目、600目、800目、1200目、2000目砂纸打磨之后进行抛光处理，对上述合金分别采用型号为MC010-HBS-3000的布氏硬度计测量布氏硬度。测量过程中采用的压入材料为直径10mm的淬硬钢球，施加载荷为3000kg力，每个试样在5个不同位置测量后取平均值。
拉伸强度和拉伸率测量：从所述铸锭采用电火花切割的方式截取采用电火花切割的方式截取试样，采用砂纸磨去电火花切割影响层，并进一步 分别采用400目、600目、800目、1200目、2000目砂纸打磨之后进行抛光处理。之后，采用WDW-500E/600E微机控制电子万能试验机3mm/min的拉伸速率对上述合金分别测拉伸强度与拉伸率，
所述力学性能具体结果如下表2所示：
表2：不同合金的力学性能
Figure PCTCN2015000869-appb-000002
由上表2可见，通过添加碳化钛能够有效提高ZCuSn5Zn5Pb5铜合金的硬度、强度和拉伸率，并且随着碳化钛的添加量合金的硬度和强度不断提高，但当碳化钛的添加量超过3.5质量％之后，继续增大碳化钛的添加量，拉伸率存在一定程度上的降低。因此，从经济性和综合性能的角度考虑，本发明特别优选碳化钛的添加量为2.5～3.5质量％。
关于以上所述的仪器及操作步骤和参数，应理解的是，其为描述性而非限定性的，可通过等价置换的方式在以上说明书及权利要求所述的范围 内做出修改。即，本发明的范围应参照所附权利要求的全部范围而确定，而不是参照上面的说明而确定。总之，应理解的是本发明能够进行多种修正和变化。
产业上的实用性
本发明的碳化钛颗粒增强铜基复合合金材料与传统铜合金ZCuSn5Zn5Pb5相比，强度、硬度及拉伸性能均得到明显的改善，可用于制造在较高负荷、中等滑动速度下工作的耐磨、耐蚀零件。填补了目前采用碳化钛颗粒改善铜合金的力学性能方面的研究空白，具有广阔的应用前景。

Claims (7)

  1. 一种铜基复合合金材料，其特征在于，所述铜基复合合金材料含有5质量％的Sn、5质量％的Zn、5质量％的Pb，余量为Cu及不可避免的杂质，其中所述铜基复合合金材料进一步添加有粒径为7μm碳化钛颗粒。
  2. 根据权利要求1所述的铜基复合合金材料，其特征在于，所述碳化钛颗粒的添加量为0～5.0质量％。
  3. 根据权利要求1或2所述的铜基复合合金材料，其特征在于，所述碳化钛颗粒的添加量为0～4.0质量％。
  4. 根据权利要求1或2所述的铜基复合合金材料，其特征在于，所述碳化钛颗粒的添加量为0.5～3.5质量％。
  5. 根据权利要求1或2所述的铜基复合合金材料，其特征在于，所述碳化钛颗粒的添加量为3.0～3.5质量％。
  6. 一种用于制备权利要求1～5的任一项所述的铜基复合合金材料的方法，其特征在于，包括如下步骤：
    步骤一：向氩气氛保护的电炉中添加5质量％的Sn、5质量％的Zn、5质量％的Pb及85质量％的电解铜，熔炼期间控制铜水体积在熔炉体积的99％以下，保持熔炼温度1000-1100℃，持续时间5-6小时；
    步骤二：在上述保温时间之后，确定其化学成分在国标要求范围之内；
    步骤三：向经检验合格的铜合金熔体加入碳化钛颗粒并开启工频电炉的震动装置，进行搅拌，进一步升高温度至1200-1250℃并保持25-30分钟；
    步骤四：将熔炼完成的合金材料进行保温，时间为20-25分钟，采用连续铸造的方式将此合金铸造成合金棒材，铸造温度为950-1000℃；
    步骤五：将铸造完成和合金棒材进行表面车加工处理，获得成品。
  7. 根据权利要求6所述的方法，其特征在于，在步骤三中进行搅拌所 采用的是石墨棒。
PCT/CN2015/000869 2015-10-30 2015-12-04 一种碳化钛颗粒增强铜基复合合金材料及其制造方法 WO2017070808A1 (zh)

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