Preparation method of high-strength molybdenum alloy wire and high-strength molybdenum alloy wire

Abstract

The invention discloses a preparation method of a high-strength molybdenum alloy wire and the high-strength molybdenum alloy wire. The technical problem that in the prior art, a molybdenum alloy wire is small in tensile strength is solved. The preparation method of the high-strength molybdenum alloy wire comprises the following steps that molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide are subjected to ball milling and mixing; adding a mixed solution containing cerium ions, yttrium ions and lanthanum ions into the ball-milled and mixed slurry, and continuing ball-milling and mixing; carrying out spray drying on the slurry to obtain composite powder; performing high-temperature hydrogen reduction treatment to obtain multi-component doped molybdenum powder; and the high-strength molybdenum alloy wire is obtained through compression molding treatment, high-temperature sintering treatment, high-temperature rotary swaging and wire drawing treatment.

Description

Technical Field

[0001] The present invention relates to the technical field of molybdenum alloy wires, and in particular to a preparation method of high-strength molybdenum alloy wires and the high-strength molybdenum alloy wires. Background Art

[0002] Molybdenum alloys have been widely used in high-temperature heating elements, radiation shielding, high-temperature heating molds, integrated circuit connectors, and spray coatings due to their excellent properties such as high density and melting point, low vapor pressure and thermal expansion coefficient, and good high-temperature strength. As an important product type of molybdenum, molybdenum alloy wires have been widely used as wire cutting wires, heating elements, and automotive parts spraying, especially as electric spark wire cutting wires, which are widely used in electric spark cutting of various materials.

[0003] As a common metal cutting method, wire EDM mainly generates high temperature and certain pressure to melt and erode metal through high-frequency electric spark discharge between molybdenum wire and workpiece surface. Long-life stable cutting is very important for wire EDM production. In addition to the influence of EDM cutting parameters, the tensile strength of molybdenum wire will also directly affect the quality and service life of wire EDM.

[0004] At present, the strengthening method of molybdenum alloy wire mainly relies on doping with a second phase for strengthening. For example, Chinese invention patent CN115505809B discloses a high-strength and durable molybdenum wire for wire cutting and its production process, which strengthens the molybdenum alloy by adding transition metal elements such as chromium, nickel, manganese and transition metal oxides such as ZrO 2 Multi-element doping strengthening is performed, but the tensile strength of the obtained molybdenum alloy wire is only 546-603Mpa. In addition, the molybdenum alloy wire faces a local short-term or long-term high temperature environment during service, and the melting points of transition metal elements such as chromium, nickel, and manganese are low, which is not suitable for use in the high temperature environment of electric spark wire cutting, which is not conducive to the service performance of the molybdenum alloy wire. Summary of the invention

[0005] The main purpose of the present invention is to provide a preparation method of a high-strength molybdenum alloy wire and a high-strength molybdenum alloy wire, so as to solve the technical problem of low tensile strength of molybdenum alloy wire in the prior art.

[0006] In order to achieve the above object, the present invention first provides a method for preparing a high-strength molybdenum alloy wire, and the technical scheme is as follows:

[0007] The method for preparing high-strength molybdenum alloy wire comprises the following steps:

[0008] Molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide are ball-milled and mixed;

[0009] Adding a mixed solution containing cerium ions, yttrium ions and lanthanum ions to the ball-milled slurry, and continuing the ball-milling;

[0010] The slurry is spray-dried to obtain a composite powder;

[0011] The multi-component doped molybdenum powder is obtained by high-temperature hydrogen reduction treatment;

[0012] The high-strength molybdenum alloy wire is obtained through pressing, high-temperature sintering, high-temperature rotary forging and wire drawing.

[0013] As a further improvement to the above-mentioned method for preparing high-strength molybdenum alloy wire: the average particle size of the molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide is 50-900 nm.

[0014] As a further improvement of the above-mentioned method for preparing high-strength molybdenum alloy wire: the mixed solution is a mixed aqueous solution of cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0015] As a further improvement to the preparation method of the above-mentioned high-strength molybdenum alloy wire: molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed for 48 to 96 hours, with a ball-to-material mass ratio of (6 to 15):1; after adding the mixed solution, the ball-milling mixing is continued for 12 to 36 hours.

[0016] As a further improvement of the above-mentioned method for preparing high-strength molybdenum alloy wire: the high-temperature hydrogen reduction treatment is a reduction reaction at 900-1100° C. in flowing hydrogen for 2-4 hours.

[0017] As a further improvement of the above-mentioned method for preparing high-strength molybdenum alloy wire: the high-temperature sintering treatment is sintering at 2000-2300° C. for 3-5 hours.

[0018] As a further improvement to the above-mentioned method for preparing high-strength molybdenum alloy wire, the high-temperature rotary forging and wire drawing treatment are carried out at 1000-1400°C.

[0019] In order to achieve the above object, the present invention secondly provides a high-strength molybdenum alloy wire, and the technical solution is as follows:

[0020] The high-strength molybdenum alloy wire is prepared by the method for preparing the high-strength molybdenum alloy wire described in the first aspect.

[0021] As a further improvement of the above-mentioned high-strength molybdenum alloy wire: the sum of the mass fractions of rhenium, ruthenium and tungsten is 0.3-3.5%, the sum of the mass fractions of cerium, yttrium, lanthanum and oxygen is 0.1-1.5%, and the balance is molybdenum; the mass ratio of cerium, yttrium and lanthanum is (5-6):(1-2):(3-4).

[0022] As a further improvement of the above-mentioned high-strength molybdenum alloy wire: the mass fraction of the molybdenum element is 97.5%, the mass fraction of the rhenium element is 0.5%, the mass fraction of the ruthenium element is 0.5%, the mass fraction of the tungsten element is 1%, the sum of the mass fractions of the cerium element, the yttrium element, the lanthanum element, and the oxygen element is 0.5%, and the mass ratio of the cerium element, the yttrium element, and the lanthanum element is 5:2:3.

[0023] The preparation method of the high-strength molybdenum alloy wire and the high-strength molybdenum alloy wire of the present invention have the following advantages:

[0024] The present invention adopts molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide and a mixed solution containing cerium ions, yttrium ions and lanthanum ions as raw materials for multi-component synergistically doped high-strength molybdenum alloy. On the one hand, the pre-solidification of rhenium, ruthenium and tungsten in molybdenum is achieved through ball milling mixing of metal oxides and hydrogen co-reduction, and further high-temperature sintering is performed to achieve the purpose of uniform distribution of rhenium, ruthenium and tungsten atoms and solid solution strengthening of the alloy; on the other hand, fluorite structure cerium oxide / yttrium / lanthanum (Ce, Y, La) O with uniform composition can be synthesized through synergistic mixing, drying and reduction of the mixed solution of cerium ions, yttrium ions and lanthanum ions. 2 ) enhanced phase, (Ce, Y, La)O 2 It can not only absorb impurities, but also regulate the interface bonding ability between oxides and molybdenum alloys, thereby improving the strength of molybdenum alloy materials. Finally, the present invention uses multi-element solid solution doping of rhenium, ruthenium, and tungsten and fluorite structure (Ce, Y, La)O 2 The strengthening effect of the doped composite second phase realizes the synthesis of high-strength molybdenum alloy wires and solves the technical problem of low tensile strength of molybdenum alloy wires in the prior art.

[0025] Compared with the Chinese invention patent CN115505809B, the present invention takes into account that molybdenum alloy wires are often faced with local short-term or long-term high-temperature environments during service and that the addition of low-melting-point metal elements is not conducive to the service performance of molybdenum alloy wires. Rhenium, ruthenium, tungsten, cerium, yttrium and lanthanum that can withstand high-temperature environments are used for dual doping modification. On the basis of improving the tensile strength of the molybdenum alloy wires, the high-temperature stability of the molybdenum alloy wires is also guaranteed, which helps to improve the service performance of the molybdenum alloy wires.

[0026] The present invention is further described below by way of specific embodiments. Additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be learned through practice of the present invention. DETAILED DESCRIPTION

[0027] The present invention is described clearly and completely below. A person skilled in the art will be able to implement the present invention based on these descriptions. Before describing the present invention, it should be noted that:

[0028] The technical solutions and technical features provided in each part of the present invention, including the following description, may be combined with each other if there is no conflict.

[0029] In addition, the embodiments of the present invention involved in the following description are generally only a part of the embodiments of the present invention, rather than all the embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0030] About the terms and units in the present invention: The terms "include", "have" and any variations thereof in the description and claims of the present invention and related parts are intended to cover non-exclusive inclusions.

[0031] Example 1

[0032] According to the mass fraction of molybdenum element being 99.4%, the mass fraction of rhenium element being 0.1%, the mass fraction of ruthenium element being 0.1%, the mass fraction of tungsten element being 0.3%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 0.5%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 0.1%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 6:2:2, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0033] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 10:1 and a ball-milling time of 72 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray-dried to obtain a mixed powder. Then, the reduction reaction is carried out at 1000°C in flowing hydrogen for 3 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2100°C and a sintering time of 4 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1350°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0034] The test shows that the tensile strength of the molybdenum alloy wire is 750MPa.

[0035] Example 2

[0036] According to the mass fraction of molybdenum element being 98.9%, the mass fraction of rhenium element being 0.3%, the mass fraction of ruthenium element being 0.3%, the mass fraction of tungsten element being 0.4%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 1%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 0.1%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 6:1:3, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0037] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 12:1 and a ball-milling time of 72 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray-dried to obtain a mixed powder. Then, a reduction reaction is carried out at 1000°C in flowing hydrogen for 3 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2050°C and a sintering time of 5 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1350°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0038] The test shows that the tensile strength of the molybdenum alloy wire is 780MPa.

[0039] Example 3

[0040] According to the mass fraction of molybdenum element being 98.5%, the mass fraction of rhenium element being 0.3%, the mass fraction of ruthenium element being 0.3%, the mass fraction of tungsten element being 0.4%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 1%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 0.5%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 5:1:4, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0041] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 12:1 and a ball-milling time of 80 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray dried to obtain a mixed powder. Then, a reduction reaction is carried out at 1000°C in flowing hydrogen for 3 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2100°C and a sintering time of 5 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1400°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0042] The test shows that the tensile strength of the molybdenum alloy wire is 810MPa.

[0043] Embodiment 4 (optimum embodiment)

[0044] According to the mass fraction of molybdenum element being 97.5%, the mass fraction of rhenium element being 0.5%, the mass fraction of ruthenium element being 0.5%, the mass fraction of tungsten element being 1%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 2%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 0.5%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 5:2:3, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0045] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 12:1 and a ball-milling time of 90 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray-dried to obtain a mixed powder. Then, a reduction reaction is carried out at 1100°C in flowing hydrogen for 3 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2200°C and a sintering time of 4 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1400°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0046] The test shows that the tensile strength of the molybdenum alloy wire is 865MPa.

[0047] Example 5

[0048] According to the mass fraction of molybdenum element being 99.6%, the mass fraction of rhenium element being 0.1%, the mass fraction of ruthenium element being 0.1%, the mass fraction of tungsten element being 0.1%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 0.3%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 0.1%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 5:2:3, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0049] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 12:1 and a ball-milling time of 90 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray-dried to obtain a mixed powder. Then, a reduction reaction is carried out at 900°C in flowing hydrogen for 4 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2000°C and a sintering time of 5 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1000°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0050] The test shows that the tensile strength of the molybdenum alloy wire is 745MPa.

[0051] Example 6

[0052] According to the mass fraction of molybdenum element being 95%, the mass fraction of rhenium element being 1%, the mass fraction of ruthenium element being 1%, the mass fraction of tungsten element being 1.5%, the sum of the mass fractions of rhenium element, ruthenium element and tungsten element being 3.5%, the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element being 1.5%, wherein the mass ratio of cerium element, yttrium element and lanthanum element is 5:2:3, calculate and weigh the corresponding molybdenum oxide, rhenium oxide, ruthenium oxide, tungsten oxide, cerium nitrate, yttrium nitrate and lanthanum nitrate.

[0053] First, molybdenum oxide, rhenium oxide, ruthenium oxide, and tungsten oxide are ball-milled and mixed, with a ball-to-material mass ratio of 12:1 and a ball-milling time of 90 hours. Then, a mixed solution of cerium nitrate, yttrium nitrate, and lanthanum nitrate is added to the slurry, and the ball milling is continued for 24 hours. The mixed slurry is spray-dried to obtain a mixed powder. Then, a reduction reaction is carried out at 1000°C in flowing hydrogen for 3 hours to obtain a composite powder. The obtained composite powder is placed in a cold isostatic press to press a molybdenum alloy rod-shaped compact at a pressure of 300MPa. The compact is then placed in an induction heating furnace for high-temperature sintering at a sintering temperature of 2300°C and a sintering time of 3 hours. After cooling, a molybdenum alloy rod is obtained. The molybdenum alloy rod is subjected to a 1150°C rotary forging and wire drawing process to obtain a molybdenum alloy wire with a diameter of 0.5 mm.

[0054] The test shows that the tensile strength of the molybdenum alloy wire is 740MPa.

[0055] Comparative Example 1

[0056] Compared with Example 4, this comparative example has the difference that cerium nitrate, yttrium nitrate and lanthanum nitrate are not used.

[0057] The test shows that the tensile strength of the molybdenum alloy wire is 620MPa.

[0058] Comparative Example 2

[0059] Compared with Example 4, the difference of this comparative example is that rhenium oxide, ruthenium oxide and tungsten oxide are not used.

[0060] The test shows that the tensile strength of the molybdenum alloy wire is 635MPa.

[0061] In the above embodiments and control examples, a universal mechanical testing machine was used to test the tensile strength of the molybdenum alloy wire according to "Tensile Test of Metallic Materials Part 1: Room Temperature Test Method" (GB / T 228.1-2021).

[0062] The above is a description of the relevant contents of the present invention. A person skilled in the art will be able to implement the present invention based on these descriptions. Based on the above contents of the present invention, all other embodiments obtained by a person skilled in the art without creative work shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing a high-strength molybdenum alloy wire, characterized in that: The following steps are involved: Molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide are ball-milled and mixed; Adding a mixed solution containing cerium ions, yttrium ions and lanthanum ions to the ball-milled slurry, and continuing the ball-milling; The slurry is spray-dried to obtain a composite powder; The multi-component doped molybdenum powder is obtained by high-temperature hydrogen reduction treatment; The high-strength molybdenum alloy wire is obtained through pressing, high-temperature sintering, high-temperature rotary forging and wire drawing.

2. The method for preparing a high-strength molybdenum alloy wire according to claim 1, characterized in that: The average particle sizes of the molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide are all 50-900nm.

3. The method for preparing the high-strength molybdenum alloy wire according to claim 1, characterized in that: The mixed solution is a mixed aqueous solution of cerium nitrate, yttrium nitrate and lanthanum nitrate.

4. The method for preparing a high-strength molybdenum alloy wire according to claim 1, characterized in that: Molybdenum oxide, rhenium oxide, ruthenium oxide and tungsten oxide are ball-milled and mixed for 48 to 96 hours, with a ball-to-material mass ratio of (6 to 15):1; after adding the mixed solution, the ball-milling and mixing are continued for 12 to 36 hours.

5. The method for preparing the high-strength molybdenum alloy wire according to claim 1, characterized in that: The high temperature hydrogen reduction treatment is a reduction reaction at 900-1100° C. in flowing hydrogen for 2-4 hours.

6. The method for preparing a high-strength molybdenum alloy wire according to claim 1, characterized in that: The high temperature sintering treatment is sintering at 2000-2300° C. for 3-5 hours.

7. The method for preparing a high-strength molybdenum alloy wire according to claim 1, characterized in that: The high temperature rotary forging and wire drawing treatment are performed at 1000-1400°C.

8. High-strength molybdenum alloy wire, characterized by: The high-strength molybdenum alloy wire is prepared by the preparation method of the high-strength molybdenum alloy wire according to any one of claims 1 to 7.

9. The high-strength molybdenum alloy wire according to claim 8, characterized in that: The sum of the mass fractions of rhenium, ruthenium and tungsten is 0.3-3.5%, the sum of the mass fractions of cerium, yttrium, lanthanum and oxygen is 0.1-1.5%, and the remainder is molybdenum; the mass ratio of cerium, yttrium and lanthanum is (5-6):(1-2):(3-4).

10. The high-strength molybdenum alloy wire according to claim 8, characterized in that: The mass fraction of molybdenum element is 97.5%, the mass fraction of rhenium element is 0.5%, the mass fraction of ruthenium element is 0.5%, the mass fraction of tungsten element is 1%, and the sum of the mass fractions of cerium element, yttrium element, lanthanum element and oxygen element is 0.5%; the mass ratio of cerium element, yttrium element and lanthanum element is 5:2:3.