CN110484803B - Mixed dispersion enhanced copper-tungsten-chromium electrical contact material and preparation method thereof - Google Patents
Mixed dispersion enhanced copper-tungsten-chromium electrical contact material and preparation method thereof Download PDFInfo
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Abstract
A mixed dispersion enhanced copper-tungsten-chromium electrical contact material is prepared by the following steps: and mixing and ball-milling the graphene oxide suspension subjected to ultrasonic dispersion with copper-aluminum powder, cuprous oxide powder, tungsten powder, chromium powder, cerium oxide powder and yttrium oxide powder, freeze-drying, and then performing vacuum hot-pressing sintering to obtain the graphene oxide powder. According to the electrical contact material, the graphene oxide and the rare earth oxide are added into the copper-aluminum-tungsten-chromium mixed powder to carry out vacuum hot-pressing sintering-simple internal oxidation process, so that the defects of poor affinity, interface binding force and conductivity of graphene oxide and poor conductivity of graphene oxide are overcome, and the comprehensive performance of the dispersed copper-tungsten-chromium electrical contact material is improved by the reduced graphene oxide under the vacuum high-temperature condition. In addition, the addition of the rare earth cerium oxide and yttrium oxide can effectively refine grains of the contact material, improve the strength and the hardness, reduce arc ablation, improve the fusion welding resistance of the contact and obviously improve the comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of preparation of electrical materials, and particularly relates to a rare earth oxide and graphene oxide doped and reinforced dispersed copper-tungsten-chromium electrical contact material and a preparation method thereof.
Background
The copper-based composite material is always considered as an ideal electrical contact material due to high conductivity, and the nano Al2O3 reinforced dispersion copper-based composite material prepared by the internal oxidation method not only has high strength and high conductivity, but also has high recrystallization temperature and good thermal stability, and is a functional material with excellent comprehensive performance. The tungsten has high melting point, large density and low expansion coefficient, and the electrical contact material prepared from the tungsten and the copper has high compressive strength and strong arc ablation resistance. Under the action of electric arc, tungsten particles are gradually gathered and sintered into a needle-shaped framework along with the evaporation and melting of copper, so that the flow of copper is limited, and the corrosion resistance of the contact is improved. Chromium has high melting point and hard and brittle characteristics, a low interception value and high breaking capacity, and has high affinity to oxygen, so that the good air suction capacity of the vacuum switch contact is ensured, and therefore, the copper-chromium contact is considered as an ideal electrical contact material in the medium-voltage high-power field.
Graphene is a two-dimensional material with a thickness of only one atomic layer, and has a honeycomb crystal structure formed by closely arranging sp2 hybridized carbon atoms. And the graphene is a crystal structure with the highest strength and hardness in the known two-dimensional material, the theoretical elastic modulus of the graphene is up to 1.1TPa through calculation, and the tensile strength of the graphene can reach 125 GPa. Graphene and its derivatives such as graphene oxide are attracting increasing attention as ideal metal matrix composite reinforcements. However, graphene has poor affinity and interface bonding force with a copper matrix, and is easy to agglomerate in the preparation process, and the dispersibility in the copper matrix and the wettability of the interface always restrict the application of graphene.
Chinese patent (publication No. CN105551839A) discloses a copper-plated graphene/copper-based electrical contact material and a preparation method thereof, wherein the electrical contact material comprises 0.1-2.0% of copper-plated graphene and 98.0-99.9% of copper-rare earth alloy, and the weight ratio of rare earth to the copper-rare earth alloy is 0.03-3.0%. The alloy material has high conductivity and low tensile strength. Chinese patent (publication No. CN 106498209A) discloses a preparation method of a doped graphene tungsten-copper alloy, which comprises the steps of mixing copper powder, tungsten powder and nickel-plated graphene powder, pressing and forming, and then carrying out high-temperature liquid-phase infiltration sintering to prepare the graphene tungsten-copper alloy, wherein the prepared alloy has higher hardness but lower conductivity.
Disclosure of Invention
The purpose of the invention is as follows: on the premise of simplifying the preparation process, the mixed dispersion enhanced copper-tungsten-chromium electrical contact material with remarkably improved tensile strength and hardness and excellent comprehensive performance is prepared and provided.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows: a mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following components in percentage by weight: 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide, 0.1-0.5% of yttrium oxide, 0.223-0.228% of aluminum, 35% of tungsten, 5% of chromium, and the balance of copper and inevitable impurity elements.
A preparation method of a mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following steps:
(1) ingredients
Respectively weighing 55.7-57% of copper-aluminum alloy powder, 35% of tungsten powder, 5% of chromium powder, 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide powder, 0.1-0.5% of yttrium oxide powder and 1.5-4% of cuprous oxide powder according to the mass percentage for later use;
(2) premixing of raw meal
Placing the copper-aluminum alloy powder, tungsten powder, chromium powder, cerium oxide powder, yttrium oxide powder and cuprous oxide powder weighed in the step (1) into a mixer for premixing for 1.5-4.5h to prepare a premix for later use;
(3) dispersion of graphene oxide
Adding the graphene oxide weighed in the step (1) into deionized water, and performing ultrasonic dispersion to prepare a graphene oxide suspension for later use;
(4) ball mill
Adding the premix prepared in the step (2) into the graphene oxide suspension prepared in the step (3), and then placing the mixed material into a ball milling tank for ball milling for 4-6 hours to prepare a mixed material for later use;
(5) freeze drying
Transferring the mixed material prepared in the step (4) into a vacuum freeze dryer for freeze drying for 20-28h, and then transferring into a material mixer again for mixing for 40-80min to prepare RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder for later use;
(6) vacuum hot pressing sintering
Transferring the RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder prepared in the step (5) into a graphite mold, placing the graphite mold into a sintering furnace with the vacuum degree of 0.04-0.08Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 8-12 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 28-32MPa when the temperature in the furnace is increased to 550-650 ℃, maintaining the pressure for 0.8-1.2h, then releasing the pressure, continuously heating to 900-1000 ℃ and then beginning to preserve the temperature, cooling along with the furnace after 0.8-1.2h, and taking out a sample when the temperature is reduced to room temperature, thus obtaining the finished product of the electrical contact material.
Preferably, in the step (1), the particle size of the copper-aluminum alloy powder is 38 μm, the particle size of the chromium powder is 44 μm, the particle sizes of the tungsten powder, the cuprous oxide powder, the cerium oxide powder and the yttrium oxide powder are all 2-5 μm, the graphene oxide used is single-layer graphene oxide, the sheet diameter is 0.5-5 μm, and the thickness is 0.8-1.2 nm.
Preferably, in the step (1), the weight ratio of Al in the copper-aluminum alloy powder is 0.4%.
Preferably, in the step (2) and the step (5), the mixer used is a V-shaped mixer.
Preferably, in the step (4), the ball-to-material ratio during ball milling is 10: 1, the rotating speed of the ball mill is 360 r/min.
Preferably, in the step (5), the vacuum freeze dryer used is a Lg-0.2 type vacuum freeze dryer, the freezing temperature during freeze drying is-20 ℃, and the cold trap temperature is-40 ℃.
Preferably, in the step (6), the adopted sintering furnace is a ZT-120-22Y type multifunctional sintering furnace.
The invention has the beneficial effects that:
1. the prepared dispersion copper-tungsten-chromium electrical contact material has the comprehensive effect of all components through the compounding of specific contents of aluminum, tungsten, chromium, cerium oxide, yttrium oxide and copper and the addition of graphene oxide, so that the comprehensive performance of the finished electrical contact material is obviously improved. The tensile strength of the finished copper-tungsten-chromium electrical contact material reaches more than 400Mpa, the hardness reaches more than 150HB, the density reaches more than 98%, the conductivity reaches more than 58% IACS, the comprehensive performance is excellent, and the use requirement of the electrical contact material can be better met.
2. According to the preparation process disclosed by the invention, a certain content of graphene oxide is added into the rare earth copper-aluminum-tungsten-chromium mixed powder, and a large number of hydrophilic groups such as hydroxyl, epoxy, carboxyl and the like exist in a molecular structure of the graphene oxide, so that the graphene oxide has good wettability, dispersibility and surface activity, and a bonding interface can be optimized during material mixing, thereby improving the performance of the composite material. However, the existence of these functional groups leads to the reduction of the excellent electric and thermal conductivity of graphene, so that the subsequent process steps adopt a 900-plus-1000 ℃ vacuum high-temperature sintering mode, so that the graphene oxide loses part of the functional groups in the vacuum high-temperature sintering process and is converted into the reduced graphene oxide, and the electric conductivity of the reduced graphene oxide is greatly improved due to the loss of oxygen-containing groups and the reconstruction of a carbon skeleton, so that the finished material has high conductivity. Meanwhile, the addition of the cerium oxide and yttrium oxide rare earth components in the contact material can effectively refine crystal grains of the contact material, improve the tensile strength and hardness of the finished material, and improve the high-temperature fusion welding resistance and other performances of the contact. In addition, the rare earth oxide can reduce the electron work function of the material and improve the electron emission capability of the alloy, thereby stabilizing the electric arc and improving the electric arc erosion resistance of the finished material.
3. The preparation method simplifies the internal oxidation process, overcomes the defects of poor affinity between graphene and a copper matrix, poor interface binding force and poor conductivity of the graphene oxide, improves the comprehensive performance of the dispersed copper-tungsten-chromium electrical contact material by sintering and reducing the graphene oxide under the vacuum high-temperature condition, ensures that the conductivity and the density of the material are better, the arc erosion resistance and the tensile strength are also obviously improved, and the comprehensive performance index is better than that of the same type of product. Meanwhile, part of C atoms are combined with Cr to generate Cr3C2 in situ in the high-temperature sintering process, and the contact material has a strengthening effect. The preparation method has the advantages of simple integral process, low energy consumption, obvious material performance improvement, high production efficiency and easy industrial production.
4. The electric contact material can meet the requirements of the medium-voltage vacuum switch contact market, has a great development prospect, obviously improves the comprehensive performance of the improved material, and is simple to operate, high in production efficiency and easy for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, 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.
The following examples are intended to illustrate the invention in further detail, but are not to be construed as limiting the invention in any way.
A mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following components in percentage by weight: 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide, 0.1-0.5% of yttrium oxide, 0.223-0.228% of aluminum, 35% of tungsten, 5% of chromium, and the balance of copper and inevitable impurity elements. The electric contact material is prepared by mixing and ball-milling a graphene oxide suspension subjected to ultrasonic dispersion with copper-aluminum powder, cuprous oxide powder, tungsten powder, chromium powder, cerium oxide powder and yttrium oxide powder, freeze-drying, and then carrying out vacuum hot-pressing sintering-internal oxidation process.
A preparation method of a mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following steps:
(1) ingredients
Respectively weighing 55.7-57% of Cu-0.4 wt.% Al alloy powder, 35% of W powder, 5% of Cr powder, 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide powder, 0.1-0.5% of yttrium oxide powder and 1.5-4% of Cu2O powder for later use;
wherein the grain diameter of the Cu-0.4wt% Al alloy powder is 38 mu m, the grain diameter of the tungsten powder is 2-5 mu m, the grain diameter of the chromium powder is 44 mu m, the grain diameter of the Cu2O powder is 2-5 mu m, the graphene oxide is single-layer graphene oxide, the sheet diameter is 0.5-5 mu m, the thickness is 0.8-1.2nm, the grain diameter of the CeO2 powder is 2-5 mu m, and the grain diameter of the Y2O3 powder is 2-5 mu m. Weighing each raw material (the calculation method of the weighing amount is the volume of the part, the theoretical density and the adding proportion). The raw material formulation of the electrical contact material is shown in table 1 below.
The mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following raw materials in percentage by mass:
(2) premixing of raw meal
Placing the copper-aluminum alloy powder, tungsten powder, chromium powder, cerium oxide powder, yttrium oxide powder and cuprous oxide powder weighed in the step (1) into a V-shaped mixer for premixing for 1.5-4.5 hours to prepare a premix for later use;
(3) dispersion of graphene oxide
Adding the graphene oxide weighed in the step (1) into 1000ml of deionized water, and performing ultrasonic oscillation dispersion by using an ultrasonic cleaning machine to prepare a graphene oxide suspension for later use;
(4) ball mill
Adding the premix prepared in the step (2) into the graphene oxide suspension prepared in the step (3), and then placing the mixed material into a ball milling tank for ball milling for 4-6h, wherein the ball-to-material ratio during ball milling is 10: 1, the rotating speed of the ball mill is 360r/min, and a mixed material is prepared for standby;
(5) freeze drying
And (4) transferring the mixed material prepared in the step (4) into an Lg-0.2 type vacuum freeze dryer for freeze drying for 20-28h, wherein the freezing temperature during freeze drying is-20 ℃, and the temperature of a cold trap is-40 ℃. Then, the mixture is transferred into a V-shaped mixer again for mixing for 40-80min to prepare RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder for later use;
(6) vacuum hot pressing sintering
Transferring the RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder prepared in the step (5) into a graphite mold, placing the graphite mold into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.04-0.08Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 8-12 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 28-32MPa when the temperature in the furnace is increased to 550-650 ℃, carrying out pressure relief after maintaining for 0.8-1.2h, continuously heating to 900-1000 ℃ and then beginning heat preservation, cooling with the furnace after 0.8-1.2h, and taking out a sample when the temperature is reduced to room temperature to obtain a finished product of the electrical contact material;
(7) performance testing
And analyzing the microstructure of the sintered sample by using a field emission scanning electron microscope and a transmission electron microscope. The conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage.
The graphene oxide added in the raw materials has the effects that a large number of hydroxyl, epoxy, carboxyl and other hydrophilic groups exist in the graphene oxide structure, and the groups enable the graphene oxide to have good wettability, dispersibility and surface activity, and can optimize a bonding interface so as to improve the performance of the composite material.
According to the preparation method and preparation method of the mixed dispersion enhanced copper-tungsten-chromium electrical contact material, graphene oxide is added on the basis of the dispersed copper-tungsten-chromium electrical contact material, part of functional groups of the graphene oxide are lost in the vacuum high-temperature sintering process and are converted into reduced graphene oxide, and in addition, part of C atoms are combined with Cr to generate Cr3C2 in situ, so that the contact material is enhanced; compared with an Al2O3-Cu/(35) W (5) Cr contact, the tensile strength of the contact material containing 0.3 wt% of GO and 0.5 wt% of GO in a sintering state is respectively improved by 45% and 34%, and the strengthening effect of the reduced graphene oxide on a matrix is obvious. The improved material has obviously improved comprehensive performance, and the preparation method has simple operation and high production efficiency and is easy for industrial production.
Example 1
Is prepared in the size of
0.1GO/Al2O3-Cu/(35) W (5) Cr electrical contact material doped with 0.1% graphene oxide.
The preparation method comprises the following steps:
step 1, proportioning
The respective amounts of copper-aluminum alloy powder, cuprous oxide powder, tungsten powder and chromium powder were calculated in proportion, the amount of copper-aluminum alloy powder equals 19.63cm3 × 10.53g/cm3 × 57.05% ═ 117.92g, the amount of tungsten powder equals 19.63cm3 × 10.53g/cm3 × 35% > -72.35 g, the amount of chromium powder equals 19.63cm3 × 10.53g/cm3 × 5% > -10.34 g, the amount of graphene oxide powder equals 19.63cm3 × 10.53g/cm3 × 2.85% > -5.89 g, and the amount of graphene oxide equals 19.63cm × 7319.53 g/cm × 23.3 g.
Step 2, mixing
Mixing the copper-aluminum alloy powder, the tungsten powder, the chromium powder and the cuprous oxide powder weighed in the step 1, filling the mixture into a self-made mixing bottle, and premixing the mixture for 4 hours on a V-shaped mixer for later use; and (3) putting the graphene oxide weighed in the step (1) into 1000ml of deionized water, ultrasonically oscillating and dispersing for 1h by using an ultrasonic cleaning machine, and adding the premixed powder into the dispersed graphene oxide solution for mixing.
Step 3, ball milling
And transferring the mixed solution to a ball milling tank for ball milling, wherein the ball material ratio is 10: 1, the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 5 hours in a ball milling tank.
Step 4, freeze drying
And putting the mixed material after ball milling into an Lg-0.2 type vacuum freeze dryer for freeze drying at the freezing temperature of-20 ℃, the cold trap temperature of-40 ℃ and the freezing time of 24 hours. After freezing, the mixture is transferred to a V-shaped mixer again to be mixed for 1h, and then 0.1GO/Cu-0.4 wt% Al/35W5Cr mixed powder can be obtained.
Step 5, high-temperature sintering
And (3) transferring the 0.1GO/Cu-0.4 wt% Al/35W5Cr composite powder prepared in the step (4) into a graphite mold, then placing the graphite mold into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.06Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 12 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 28MPa when the temperature in the furnace rises to 550 ℃, maintaining the pressure for 1.2h, then releasing the pressure, continuously heating to 1000 ℃, then beginning to preserve heat, cooling along with the furnace after 0.8h, and taking out a sample when the temperature is reduced to room temperature to obtain the finished product of the electrical contact material.
Step 6, performance test
The finished samples prepared in this example were tested for performance as follows:
the conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage. And testing the tensile strength and the compactness thereof. The test results are shown in table 2 below.
Example 2
Is prepared in the size of
0.3GO/Al2O3-Cu/(35) W (5) Cr electrical contact material doped with 0.3% graphene oxide.
The preparation method comprises the following steps:
step 1, proportioning
The amounts of copper-aluminum alloy powder, cuprous oxide powder, tungsten powder and chromium powder were calculated in proportion, the amount of copper-aluminum alloy powder was 19.63cm3 × 10.46g/cm3 × 56.85%: 116.73g, the amount of tungsten powder was 19.63cm3 × 10.46g/cm3 × 35%: 71.87g, the amount of chromium powder was 19.63cm3 × 10.46g/cm3 × 5%: 10.27g, the amount of cuprous oxide powder was 19.63cm × 10.46g/cm3 × 5%: 10.46g/cm3 × 2.84%: 5.83g, and the amount of graphene oxide was 19.63 × 19.63cm × 19.46 × 580 g.
Step 2, mixing
Mixing the copper-aluminum alloy powder, the tungsten powder, the chromium powder and the cuprous oxide powder weighed in the step 1, filling the mixture into a self-made mixing bottle, and premixing the mixture for 2.5 hours on a V-shaped mixer for later use; and (3) putting the graphene oxide weighed in the step (1) into 1000ml of deionized water, ultrasonically oscillating and dispersing for 1h by using an ultrasonic cleaning machine, and adding the premixed powder into the dispersed graphene oxide solution for mixing.
Step 3, ball milling
And transferring the mixed solution to a ball milling tank for ball milling, wherein the ball material ratio is 10: 1, the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 4 hours in a ball milling tank.
Step 4, freeze drying
And putting the mixed material after ball milling into an Lg-0.2 type vacuum freeze dryer for freeze drying at the freezing temperature of-20 ℃, the cold trap temperature of-40 ℃ and the freezing time of 20 hours. After freezing, the mixture is transferred to a V-shaped mixer again to be mixed for 80min, and then 0.3GO/Cu-0.4 wt% Al/35W5Cr mixed powder can be obtained.
Step 5, high-temperature sintering
And (3) transferring the 0.3GO/Cu-0.4 wt% Al/35W5Cr composite powder prepared in the step (4) into a graphite mold, then placing the graphite mold into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.08Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 8 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 32MPa when the temperature in the furnace rises to 650 ℃, maintaining the pressure for 1h, then releasing the pressure, continuously heating to 900 ℃, then beginning to preserve heat, cooling along with the furnace after 1.2h, and taking out a sample when the temperature drops to room temperature, thus obtaining the finished product of the electrical contact material.
Step 6, performance test
The finished samples prepared in this example were tested for performance as follows:
the conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage. And testing the tensile strength and the compactness thereof. The test results are shown in table 2 below.
Example 3
Is prepared in the size of
0.5GO/Al2O3-Cu/(35) W (5) Cr electrical contact material doped with 0.5% graphene oxide.
The preparation method comprises the following steps:
step 1, proportioning
The amounts of copper-aluminum alloy powder, cuprous oxide powder, tungsten powder and chromium powder were calculated in proportion, the amount of copper-aluminum alloy powder equals 19.63cm3 × 10.39g/cm3 × 56.67% ═ 115.58g, the amount of tungsten powder equals 19.63cm3 × 10.39g/cm3 × 35% >, the amount of chromium powder equals 19.63cm3 × 10.39g/cm3 × 5% >, the amount of graphene oxide equals 19.63cm3 × 10.39g/cm3 × 5% >, the amount of chromium powder equals 19.63cm × 10.39g/cm3 × 2.83% >, and the amount of graphene oxide equals 19.63cm × 5819.63 g/cm.
Step 2, mixing
And (3) mixing the copper-aluminum alloy powder, the tungsten powder, the chromium powder and the cuprous oxide powder weighed in the step (1), filling the mixture into a self-made mixing bottle, and premixing the mixture for 1.5 hours on a V-shaped mixer for later use. And (3) putting the graphene oxide weighed in the step (1) into 1000ml of deionized water, and ultrasonically oscillating and dispersing for 1h by using an ultrasonic cleaning machine. And adding the premixed powder into the dispersed graphene oxide solution and mixing.
Step 3, ball milling
And transferring the mixed solution to a ball milling tank for ball milling. Ball material ratio 10: 1, the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 6 hours in a ball milling tank.
Step 4, freeze drying
And putting the mixed material after ball milling into an Lg-0.2 type vacuum freeze dryer for freeze drying at the freezing temperature of-20 ℃, the cold trap temperature of-40 ℃ and the freezing time of 28 hours. After freezing, the mixture is transferred to a V-shaped mixer again to be mixed for 40min, and then 0.5GO/Cu-0.4 wt% Al/35W5Cr mixed powder can be obtained.
Step 5, high-temperature sintering
And (3) transferring the 0.5GO/Cu-0.4 wt% Al/35W5Cr composite powder prepared in the step (4) into a graphite mold, then placing the graphite mold into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.04Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 10 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 30MPa when the temperature in the furnace rises to 600 ℃, carrying out pressure relief after maintaining for 0.8h, starting heat preservation after continuously heating to 950 ℃, cooling along with the furnace after 1h, and taking out a sample when the temperature drops to the room temperature to obtain the finished product of the electrical contact material.
Step 6, performance test
The finished samples prepared in this example were tested for performance as follows:
the conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage. And testing the tensile strength and the compactness thereof. The test results are shown in table 2 below.
Example 4
Is prepared in the size of
0.1Ce2O0.1Y2O3/0.1GO// Al2O3-Cu/35W5Cr composite material doped with 0.1% Ce2O, 0.1% Y2O3 and 0.1% graphene oxide.
The preparation method comprises the following steps:
step 1, proportioning
The amounts of copper-aluminum alloy powder, cuprous oxide powder, tungsten powder, chromium powder, cerium oxide powder and yttrium oxide powder are calculated according to the proportions, the proportion of copper-aluminum alloy powder added according to the volume of the part multiplied by the theoretical density multiplied by 19.63cm3 multiplied by 10.50g/cm3 multiplied by 56.85% is 117.18g, the proportion of tungsten powder added according to the volume of the part multiplied by the theoretical density multiplied by 19.63cm3 multiplied by 10.50g/cm3 multiplied by 35% is 72.14g, the proportion of chromium powder added according to the volume of the part multiplied by the theoretical density multiplied by 3 multiplied by 10.50g/cm3 multiplied by 5% is 10.31g, the proportion of cuprous oxide powder added according to the volume of the part multiplied by the theoretical density multiplied by 19 cm3 multiplied by 10.50g/cm 24 multiplied by 2.85% is 5.87g, the proportion of graphene oxide multiplied by the volume multiplied by 10.63 cm multiplied by 10 cm 3cm is 19.8.35 g/cm, the proportion of the theoretical density multiplied by 6850.19 cm 3cm, the proportion of the part multiplied by 19 cm 3cm 3.19.19 g/cm, the amount of yttrium oxide powder is 19.63cm3 × 10.50g/cm3 × 0.1% and 0.21 g.
Step 2, mixing
And (2) mixing the copper-aluminum alloy powder, the tungsten powder, the chromium powder, the cuprous oxide powder, the cerium oxide powder and the yttrium oxide powder weighed in the step (1), filling the mixture into a self-made mixing bottle, and premixing the mixture for 4.5 hours on a V-shaped mixer for later use. And (3) putting the graphene oxide weighed in the step (1) into 1000ml of deionized water, and ultrasonically oscillating and dispersing for 1.5h by using an ultrasonic cleaning machine. And adding the premixed powder into the dispersed graphene oxide solution and mixing.
Step 3, ball milling
And transferring the mixed solution to a ball milling tank for ball milling. Ball material ratio 10: 1, the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 5 hours in a ball milling tank.
Step 4, freeze drying
And putting the mixed material subjected to ball milling into an Lg-0.2 type vacuum freeze dryer for freeze drying at the freezing temperature of-20 ℃, the cold trap temperature of-40 ℃ and the freezing time of 23 h. After freezing, the mixture is transferred to a V-shaped mixer again to be mixed for 50min, and then 0.1Ce2O0.1Y2O3/0.1GO/Cu-0.4 wt% Al/35W5Cr mixed powder can be obtained.
Step 5, high-temperature sintering
And (3) transferring the 0.1Ce2O0.1Y2O3/0.1GO/Cu-0.4 wt% Al/35W5Cr composite powder prepared in the step (4) into a graphite mold, then placing the graphite mold into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.04Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 10 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 30MPa when the temperature in the furnace rises to 600 ℃, carrying out pressure relief after 1h of pressure maintenance, continuously heating to 930 ℃ and then beginning to carry out heat preservation, cooling along with the furnace after 1h, and taking out a sample when the temperature falls to room temperature to obtain the finished product of the electrical contact material.
Step 6, performance test
The finished samples prepared in this example were tested for performance as follows:
the conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage. And testing the tensile strength and the compactness thereof. The test results are shown in table 2 below.
Example 5
Is prepared in the size of
0.3Ce2O0.3Y2O3/0.3GO// Al2O3-Cu/35W5Cr composite material doped with 0.3% Ce2O, 0.3% Y2O3 and 0.3% graphene oxide.
The preparation method comprises the following steps:
step 1, proportioning
The amounts of copper-aluminum alloy powder, cuprous oxide powder, tungsten powder, chromium powder, cerium oxide powder and yttrium oxide powder are calculated according to the proportions, the proportion of copper-aluminum alloy powder added according to the volume of the part multiplied by the theoretical density multiplied by 19.63cm3 multiplied by 10.50g/cm3 multiplied by 56.28% is 116g, the proportion of tungsten powder added according to the volume of the part multiplied by the theoretical density multiplied by 19.63cm3 multiplied by 10.50g/cm3 multiplied by 35% is 72.14g, the proportion of chromium powder added according to the volume of the part multiplied by the theoretical density multiplied by 19.63cm3 multiplied by 10.50g/cm3 multiplied by 10.31g is 10.31g, the proportion of cuprous oxide powder added according to the volume of the part multiplied by the theoretical density multiplied by 19 cm3 multiplied by 10.50g/cm3 multiplied by 2.82% is 5.81g, the proportion of graphene oxide multiplied by the volume multiplied by 10.63 cm 3cm multiplied by the theoretical density multiplied by 19 cm 3cm 3.63 g/3663 g, the amount of yttrium oxide powder is 19.63cm3 × 10.50g/cm3 × 0.1% and 0.63 g.
Step 2, mixing
And (2) mixing the copper-aluminum alloy powder, the tungsten powder, the chromium powder, the cuprous oxide powder, the cerium oxide powder and the yttrium oxide powder weighed in the step (1), filling the mixture into a self-made mixing bottle, and premixing the mixture for 2 hours on a V-shaped mixer for later use. And (3) putting the graphene oxide weighed in the step (1) into 1000ml of deionized water, and ultrasonically oscillating and dispersing for 1h by using an ultrasonic cleaning machine. And adding the premixed powder into the dispersed graphene oxide solution and mixing.
Step 3, ball milling
And transferring the mixed solution to a ball milling tank for ball milling. Ball material ratio 10: 1, the rotating speed of the ball mill is 360r/min, and the ball milling is carried out for 5 hours in a ball milling tank.
Step 4, freeze drying
And putting the mixed material after ball milling into an Lg-0.2 type vacuum freeze dryer for freeze drying at the freezing temperature of-20 ℃, the cold trap temperature of-40 ℃ and the freezing time of 24 hours. After freezing, the mixture is transferred to a V-shaped mixer again to be mixed for 60min, and then 0.3Ce2O0.3Y2O3/0.3GO/Cu-0.4 wt% Al/35W5Cr mixed powder can be obtained.
Step 5, high-temperature sintering
And (3) transferring the 0.3Ce2O0.3Y2O3/0.3GO/Cu-0.4 wt% Al/35W5Cr composite powder prepared in the step (4) into a graphite mould, then placing the graphite mould into a ZT-120-22Y type multifunctional sintering furnace with the vacuum degree of 0.06Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 10 ℃/min, continuously carrying out uniaxial pressurization on the graphite mould while heating, controlling the uniaxial pressure on the graphite mould to be 30MPa when the temperature in the furnace rises to 600 ℃, carrying out pressure relief after 1h of pressure maintenance, starting heat preservation after continuously heating to 950 ℃, cooling along with the furnace after 1h, and taking out a sample when the temperature falls to room temperature to obtain the finished product of the electrical contact material.
Step 6, performance test
The finished samples prepared in this example were tested for performance as follows:
the conductivity of the as-sintered test specimens was tested using a Sigma2008B1 digital conductivity meter. Brinell hardness testing was performed using a HB-3000B Brinell hardness tester, in accordance with the provisions of GB/T231.1-2009. The density was measured and calculated using a hydrostatic balance using archimedes drainage. And testing the tensile strength and the compactness thereof. The test results are shown in table 2 below.
Example 6
Is prepared in the size of
0.5Ce2O0.5Y2O3/0.5GO// Al2O3-Cu/35W5Cr composite material doped with 0.5% Ce2O, 0.5% Y2O3 and 0.5% graphene oxide.
The preparation method is the same as example 4.
The results of the performance tests performed on the finished samples obtained in this example are shown in table 2 below.
Example 7
Is prepared in the size of
0.5Ce2O0.5Y2O3/0.1GO// Al2O3-Cu/35W5Cr composite material doped with 0.5% Ce2O, 0.5% Y2O3 and 0.1% graphene oxide.
The preparation method is the same as example 4.
The results of the performance tests performed on the finished samples obtained in this example are shown in table 2 below.
Example 8
Is prepared in the size of
0.5Ce2O0.5Y2O3/0.3GO// Al2O3-Cu/35W5Cr composite material doped with 0.5% Ce2O, 0.5% Y2O3 and 0.3% graphene oxide.
The preparation method is the same as example 4.
The results of the performance tests performed on the finished samples obtained in this example are shown in table 2 below.
Example 9
Is prepared in the size of
0.3Ce2O0.3Y2O3/0.5GO// Al2O3-Cu/35W5Cr composite material doped with 0.3% Ce2O, 0.3% Y2O3 and 0.5% graphene oxide.
The preparation method is the same as example 4.
The results of the performance tests performed on the finished samples obtained in this example are shown in table 2 below.
Table 2 is a table of results of performance tests of examples 1 to 9
The dispersed copper 35W5Cr in the above table is the performance parameter of the material used as the matrix, which is known in the prior art.
From the table above, the rare earth oxide-doped and graphene oxide-doped mixed reinforced dispersion copper-tungsten-chromium electrical contact material prepared by the invention is superior to the copper-tungsten-chromium electrical contact material without the addition of graphene oxide in the aspects of hardness, tensile strength and the like, and the main performance of the contact material with the addition of rare earth cerium oxide and yttrium oxide is superior to that of the copper-tungsten-chromium electrical contact material without the addition of rare earth graphene oxide. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A mixed dispersion enhanced copper-tungsten-chromium electrical contact material is characterized by comprising the following components in percentage by weight: 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide, 0.1-0.5% of yttrium oxide, 0.223-0.228% of aluminum, 35% of tungsten, 5% of chromium, and the balance of copper and inevitable impurity elements;
the preparation method of the mixed dispersion enhanced copper-tungsten-chromium electrical contact material comprises the following steps:
(1) ingredients
Respectively weighing 55.7-57% of copper-aluminum alloy powder, 35% of tungsten powder, 5% of chromium powder, 0.1-0.5% of graphene oxide, 0.1-0.5% of cerium oxide powder, 0.1-0.5% of yttrium oxide powder and 1.5-4% of cuprous oxide powder according to the mass percentage for later use;
(2) premixing of raw meal
Placing the copper-aluminum alloy powder, tungsten powder, chromium powder, cerium oxide powder, yttrium oxide powder and cuprous oxide powder weighed in the step (1) into a mixer for premixing for 1.5-4.5h to prepare a premix for later use;
(3) dispersion of graphene oxide
Adding the graphene oxide weighed in the step (1) into deionized water, and performing ultrasonic dispersion to prepare a graphene oxide suspension for later use;
(4) ball mill
Adding the premix prepared in the step (2) into the graphene oxide suspension prepared in the step (3), and then placing the mixed material into a ball milling tank for ball milling for 4-6 hours to prepare a mixed material for later use;
(5) freeze drying
Transferring the mixed material prepared in the step (4) into a vacuum freeze dryer for freeze drying for 20-28h, and then transferring into a material mixer again for mixing for 40-80min to prepare RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder for later use;
(6) vacuum hot pressing sintering
Transferring the RGO/GO/Cu-0.4wt% Al/35W5Cr composite powder prepared in the step (5) into a graphite mold, placing the graphite mold into a sintering furnace with the vacuum degree of 0.04-0.08Pa for vacuum hot-pressing sintering, controlling the heating rate in the sintering furnace to be 8-12 ℃/min, continuously carrying out uniaxial pressurization on the graphite mold while heating, controlling the uniaxial pressure on the graphite mold to be 28-32MPa when the temperature in the furnace is increased to 550-650 ℃, maintaining the pressure for 0.8-1.2h, then releasing the pressure, continuously heating to 900-1000 ℃ and then beginning to preserve the temperature, cooling along with the furnace after 0.8-1.2h, and taking out a sample when the temperature is reduced to room temperature, thus obtaining the finished product of the electrical contact material.
2. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (1), the particle size of the copper-aluminum alloy powder is 38 μm, the particle size of the chromium powder is 44 μm, the particle sizes of the tungsten powder, the cuprous oxide powder, the cerium oxide powder and the yttrium oxide powder are all 2-5 μm, the adopted graphene oxide is single-layer graphene oxide, the sheet diameter is 0.5-5 μm, and the thickness is 0.8-1.2 nm.
3. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (1), the weight ratio of Al in the copper-aluminum alloy powder is 0.4%.
4. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (2) and the step (5), the mixer used is a V-shaped mixer.
5. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (4), the ball-to-material ratio during ball milling is 10: 1, the rotating speed of the ball mill is 360 r/min.
6. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (5), the adopted vacuum freeze dryer is an Lg-0.2 type vacuum freeze dryer, the freezing temperature during freeze drying is-20 ℃, and the cold trap temperature is-40 ℃.
7. The mixed dispersion enhanced copper-tungsten-chromium electrical contact material as recited in claim 1, wherein: in the step (6), the adopted sintering furnace is a ZT-120-22Y type multifunctional sintering furnace.
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| CN112210690B (en) * | 2020-08-31 | 2021-09-07 | 河南科技大学 | Multi-order-degree load type GO-mixed copper-chromium electrical contact material and preparation method thereof |
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