阅读说明：本技术 一种钨钼合金及其制备方法 (Tungsten-molybdenum alloy and preparation method thereof ) 是由 缪兵 隋明侠 刘涛 于 2020-06-29 设计创作，主要内容包括：本专利公开了一种钨钼合金,包括如下质量百分比的组分：钼50-70%、钾0.0010-0.0100%、钨为余量。其制备方法如下：在钨中添加一定量的钾元素得到含钾钨粉,将钼粉预混合,再将预混合钼粉和含钾钨粉按比例固-固混合成钨钼钾混合粉,然后经过压制、烧结制成钨钼合金条。本发明制作的钨钼合金加工成丝材后,具有强度高、耐高温、耐磨、承受工作电流大的特点,用于线切割加工电极丝,具有使用寿命长、加工效率高的优点。(The patent discloses a tungsten-molybdenum alloy, which comprises the following components in percentage by mass: 50-70% of molybdenum, 0.0010-0.0100% of potassium and the balance of tungsten. The preparation method comprises the following steps: adding a certain amount of potassium element into tungsten to obtain tungsten powder containing potassium, premixing molybdenum powder, mixing the premixed molybdenum powder and the tungsten powder containing potassium in a solid-solid manner according to a certain proportion to obtain tungsten-molybdenum-potassium mixed powder, and pressing and sintering to obtain the tungsten-molybdenum alloy strip. After the tungsten-molybdenum alloy manufactured by the method is processed into wire materials, the tungsten-molybdenum alloy has the characteristics of high strength, high temperature resistance, wear resistance and large working current bearing capacity, is used for wire cutting processing of electrode wires, and has the advantages of long service life and high processing efficiency.)

1. The tungsten-molybdenum alloy is characterized by comprising the following components in percentage by mass: 50-70% of molybdenum, 0.0010-0.0100% of potassium and the balance of tungsten.

2. A method for preparing the tungsten-molybdenum alloy of claim 1,

the method comprises the following steps:

s1 mix preparation

S1-1, preparing potassium-containing tungsten powder: adding a potassium oxide solution into tungsten oxide, wherein the potassium oxide solution is prepared by dissolving potassium oxide in deionized water, and the weight ratio of potassium oxide: the proportion of tungsten oxide is 0.14-0.25%; drying, reducing, acid washing and water washing to obtain tungsten powder containing potassium;

s1-2, preparing molybdenum powder: pre-mixing molybdenum powder with different Fisher particle sizes; the mixed molybdenum powder has the Fisher granularity of 4.0-4.5 um;

s1-3 batch mixing: mixing tungsten powder containing potassium and premixed molybdenum powder according to the weight ratio of 30-50: mixing at a ratio of 50-70;

s2, pressing the mixture: isostatic pressing the mixture into a green compact;

and S3, sintering the pressed compact in a hydrogen protective atmosphere, and cooling to obtain the tungsten-molybdenum alloy.

3. A method of preparing the tungsten-molybdenum alloy of claim 2, wherein the steps of:

s1-1, the Fisher particle size of the potassium-containing tungsten powder is 2-3 um.

4. A method of preparing the tungsten-molybdenum alloy of claim 1, wherein the steps of:

the Fisher particle size of the S1-3 tungsten-molybdenum mixed powder is 3.0-4.0 um.

5. A method of preparing the tungsten-molybdenum alloy of claim 1, wherein the steps of:

the relative density of the S3 tungsten-molybdenum alloy after sintering is more than 95 percent.

Technical Field

The invention belongs to the field of powder metallurgy, and relates to a tungsten-molybdenum alloy with solid solution strengthening and potassium bubble strengthening of tungsten and molybdenum and a preparation method thereof.

Background

The tungsten-molybdenum alloy is an alloy composed of tungsten and molybdenum. The tungsten content of the common tungsten-molybdenum alloy is 30-50 percent (mass). The preparation method of the tungsten-molybdenum alloy is the same as that of a metal molybdenum material and a molybdenum alloy, namely, the rod, the plate, the wire or other sectional materials can be prepared by two methods of powder metallurgy sintering post-processing and smelting (arc smelting and ion beam bombardment) processing.

(1) In the article "molybdenum-tungsten alloy rotary swaging temperature optimization research", the gold-stacked city schisha et al prepared the Mo-50W alloy rod by a powder metallurgy method, and studied the influence of different rotary swaging temperatures on the yield and quality loss rate of the alloy rod, and the influence of different annealing temperatures on the metallographic structure of the alloy rod at the same rotary swaging temperature.

(2) The preparation and sintering process of the molybdenum-tungsten alloy powder is researched in the paper of "research on the structure and performance of the molybdenum-tungsten alloy" by the qi of the Jinchengcheng, and the molybdenum-tungsten alloy with the relative density of more than 96% and uniform component structure is obtained.

(3) The influence of the ball milling time on the physical properties and sintering characteristics of the molybdenum-tungsten alloy powder is introduced in the text of Jinchengchengwang Wanna et al, the molybdenum-tungsten alloy powder containing 30% of tungsten is prepared by a ball milling method, and the influence of different ball milling times on the physical properties and sintering characteristics of the molybdenum-tungsten powder, such as the micro-morphology, the apparent density, the Fisher granularity and the like, is analyzed.

(4) The patent of Zlingjie application of tungsten molybdenum company of Luoyancewi (application No. 201610989417.4) discloses a method for producing a tungsten molybdenum alloy rotary target, which comprises mixing tungsten powder with Fisher granularity of 3-7um and molybdenum powder with Fisher granularity of 1-10um according to the ratio of (3-5): (7-5) mixing in a double-cone mixer according to the mass ratio, then pressing, sintering, processing, annealing, performing surface treatment, and spraying tungsten-molybdenum alloy powder in the same proportion. The sputtering deposition coating of the obtained target material is more uniform, and the material utilization rate is greatly improved compared with that of a plane target material.

(5) A composite molybdenum wire for wire cutting and a manufacturing method thereof (application number CN 201511027765.5) applied by Xiamen Iru tungsten molybdenum industry Co Ltd, Pengfeng and the like discloses a wire cutting composite molybdenum wire and a manufacturing method thereof, wherein the composite molybdenum wire is made of molybdenum powder doped with solid solution metal elements and rare earth oxides, the solid solution metal elements are selected from at least one of Co, W, Ni, Hf or Re, and the weight content is 0.01-0.3%; the rare earth oxide is selected from at least one of La2O3 or Y2O3, and the weight content of the rare earth oxide is 0.05-0.2%; the manufacturing method comprises the following steps: carrying out secondary solid-liquid doping to obtain uniform doped molybdenum powder, and then carrying out pressing, sintering, rolling, drawing and intermediate annealing for multiple times to obtain the molybdenum powder. The prepared composite molybdenum wire for linear cutting can greatly improve the wear resistance, and has longer service life during cutting, faster cutting speed and higher yield.

(6) A patent of high-temperature-resistant tungsten-molybdenum alloy (application number 201710235021.5) applied by Wuhu Yangxiao new material science and technology service Limited company discloses a high-temperature-resistant tungsten-molybdenum alloy which comprises the following components in percentage by mass: 0.8-2% of carbon fiber composite material, 25-35% of molybdenum, 55-65% of tungsten, 0.5-1% of niobium, 2-3% of nickel-based alloy powder, 3-5% of rhenium and 1-2% of zirconium. According to the invention, nickel-based alloy powder, carbon fiber composite material and the like are added into the tungsten-molybdenum alloy, so that the obtained alloy has good high-temperature strength, the yield stress can reach 850-plus-one 1000MPa, the hardness can reach 220-plus-one 250HBS, and the tungsten-molybdenum alloy is particularly suitable for manufacturing high-temperature-resistant fittings such as filaments and the like.

The research results are based on tungsten-molybdenum bimetallic elements to prepare tungsten-molybdenum alloy products; or further adding Co, W, Ni, Nb, Hf, Re, La₂O₃、Y₂O₃One or more of them are made into metal product. The molybdenum wire invented in the invention of a composite molybdenum wire for wire cutting and a manufacturing method thereof is used for processing an electrode wire by wire cutting like the invention. Its disadvantage is that the content of tungsten metal element is low, so that the wear resistance and service life are not improved significantly compared with those of ordinary molybdenum wire. Other inventions or documents adopt the mode of adding carbon fiber materials to increase the alloy strength or prolonging the ball milling time to improve the relative density of the alloy, and more impurities such as carbon, oxygen and the like are introduced in the mode, so that the subsequent pressure processing and using effects of the alloy are influenced.

Disclosure of Invention

The invention aims to provide a tungsten-molybdenum alloy which has the relative density of more than 95 percent and good processability.

In order to solve the technical problems, the invention provides a tungsten-molybdenum alloy which comprises the following components in percentage by mass: 50-70% of molybdenum, 0.0010-0.0100% of potassium and the balance of tungsten.

Compared with the technical scheme of patent application No. 2015511027765.5, the tungsten content in the alloy is increased, and the wear resistance of the alloy is improved; compared with Mo-50W alloy introduced in the background technologies (1) and (2), the alloy wire has the advantages that the potassium element is added, and the high-temperature resistance of the alloy wire is improved.

The invention also provides a preparation method of the tungsten-molybdenum alloy. The method specifically comprises the following steps:

s1 mix preparation

S1-1, preparing potassium-containing tungsten powder: adding a potassium oxide solution into tungsten oxide, wherein the potassium oxide solution is prepared by dissolving potassium oxide in deionized water, and the weight ratio of potassium oxide: the proportion of tungsten oxide is 0.14-0.25%; drying, reducing, acid washing and water washing to obtain tungsten powder containing potassium, wherein the potassium content is 0.0060% -0.022%;

s1-2, preparing molybdenum powder: pre-mixing molybdenum powder with different Fisher particle sizes; the Ferris grain size of the molybdenum powder is 4.0-4.5 um.

S1-3 batch mixing: mixing tungsten powder containing potassium and premixed molybdenum powder according to the weight ratio of 30-50: mixing at a ratio of 70-50;

s2, pressing the mixture: isostatic pressing the mixture into a green compact;

and S3, sintering the pressed compact in a hydrogen protective atmosphere, and cooling to obtain the tungsten-molybdenum alloy.

Tungsten and potassium are added into the raw materials of the alloy, because the added potassium content is in a micro-scale level, potassium is doped into tungsten oxide powder in a potassium oxide solution mode, the prepared potassium-doped tungsten powder is uniform in distribution of potassium in the tungsten powder, the combination effect is better, the high-temperature resistance of the prepared alloy is better, the molybdenum powder is premixed, the Fisher particle size of the molybdenum powder is controlled to be 4.0-4.5um, the flowability of the molybdenum powder is improved, the subsequent mixing is more uniform, and the better comprehensive performance of the alloy is ensured.

Further optimization, step S1-1, the Fisher size of the potassium-containing tungsten powder is 2-3 um.

Adding a certain amount of potassium element into tungsten to obtain potassium-containing tungsten powder, wherein the Fisher particle size of the potassium-containing tungsten powder is controlled to be 2.0-3.0um, and the particle size of the selected tungsten powder is smaller than that of molybdenum powder, so that the alloying in the sintering process is facilitated.

Further optimizing, the Fisher particle size of the S1-3 tungsten-molybdenum mixed powder is 3.0-4.0 um;

further optimization, the relative density of the S3 tungsten-molybdenum alloy after sintering is more than 95%.

The premixed molybdenum powder and the tungsten powder containing potassium are mixed into the tungsten-molybdenum-potassium mixed powder in a solid-solid mode according to a proportion, the Fisher particle size of the tungsten-molybdenum-potassium mixed powder is controlled to be 3.0-4.0 mu m, and the purpose of controlling the Fisher particle size is to ensure that the density of a sintered product meets the requirement, so that good processing performance is obtained.

The tungsten-molybdenum alloy prepared by the method has relative density of more than 95 percent and good processability, and can be processed to phi 0.1mm wire material. The tungsten-molybdenum alloy prepared by the invention has the characteristics of high strength, high temperature resistance, wear resistance and large working current bearing after being processed into wire materials, is used for wire cutting and processing electrode wires, and has the advantages of long service life and high processing efficiency.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.