A lanthanum element strengthened rhenium alloy material and preparation method thereof

Abstract

The invention discloses a lanthanum element strengthened rhenium alloy material and a preparation method thereof, which relates to the technical field of rhenium alloy materials. The lanthanum element strengthened rhenium alloy material comprises the following components by mass percentage: 5-10wt% tungsten, 1-3wt% hafnium, 0.1-0.3wt% osmium, 1-3wt% gallium, 0.05-0.15wt% niobium, 0.01-2wt% lanthanum oxide, 0.003-0.008wt% other rare earth elements, 0.001-0.003wt% nanofiller, and the balance is rhenium and other inevitable impurities. The lanthanum element strengthened rhenium alloy material disclosed by the invention has high high temperature strength, high high temperature creep resistance, low thermal expansion coefficient, and good bending resistance.

Description

Technical Field

[0001] The invention relates to the technical field of rhenium alloy materials, and in particular to a lanthanum element reinforced rhenium alloy material and a preparation method thereof. Background Art

[0002] Rhenium is a silvery white rare high melting point metal with high melting point, hardness, wear resistance, corrosion resistance, high strength, good plasticity and excellent mechanical stability. Rhenium has good creep resistance under high temperature and rapid cooling and heating conditions, and is suitable for ultra-high temperature and strong thermal shock working environment. Rhenium has very good thermal shock resistance at high temperature. At a high temperature of 2200℃, the engine nozzle made of rhenium can withstand 100,000 thermal fatigue cycles without failure. In addition, rhenium has very good wear resistance and corrosion resistance. Its wear resistance is second only to metallic osmium. It can maintain relatively good chemical inertness for most fuel gases except oxygen, will not be corroded by hot hydrogen, and has a low permeability to hydrogen. Due to its series of excellent properties, rhenium and its alloys are widely used in industries such as petrochemicals, electronics, and aerospace, becoming one of the extremely important new materials in the field of modern high technology.

[0003] Rhenium has a melting point of 3180℃, ranking second among all elemental metals. It is still plastic at high temperatures and will not crack. It is generally produced by powder metallurgy, so it is often used in structural parts in high temperature environments. However, as the temperature increases, its deformation resistance and strength decrease. In order to further expand its service life and application range, it is necessary to enhance its high temperature strength.

[0004] MOCVD (a new type of vapor phase epitaxial growth technology) is an important method for manufacturing semiconductor materials, devices and thin films. It has important applications in the chip manufacturing industry. The rhenium heating coil used in it needs to be used under rapid cooling and heating conditions. However, rhenium has a relatively high thermal expansion coefficient, which can easily cause irreversible deformation during rapid cooling and heating, affecting the heating effect and service life. Therefore, it is necessary to reduce its thermal expansion coefficient to increase its service life and expand its scope of use.

[0005] It can be seen that the development of a rhenium alloy material with high high-temperature strength, high high-temperature creep resistance, low thermal expansion coefficient and good bending resistance and its preparation method meets market demand, has broad market value and application prospects, and is of great significance to promoting the further development of the field of rhenium and its alloys. Summary of the invention

[0006] The main purpose of the present invention is to provide a lanthanum-reinforced rhenium alloy material with high high-temperature strength, high high-temperature creep resistance, low thermal expansion coefficient and good bending resistance and a preparation method thereof.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is: a lanthanum element reinforced rhenium alloy material, which comprises the following components by mass percentage: 0.01-2wt% of lanthanum oxide, and the balance is rhenium and other inevitable impurities.

[0008] Preferably, the lanthanum element reinforced rhenium alloy material also includes the following components: 5-10wt% tungsten, 1-3wt% hafnium, 0.1-0.3wt% osmium, 1-3wt% gallium, 0.05-0.15wt% niobium, 0.003-0.008wt% other rare earth elements, and 0.001-0.003wt% nanofiller; the other rare earth elements are a mixture of lanthanum, praseodymium, and gadolinium in a mass ratio of (3-5):(0.6-1):(0.3-0.6).

[0009] Preferably, the particle size of the nanofiller is 20-80 nm.

[0010] Preferably, the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of (2-4):1.

[0011] The present invention also provides a method for preparing the lanthanum element reinforced rhenium alloy material, comprising the following steps: mixing the components uniformly according to mass percentage, grinding to obtain the alloy powder, then putting the powder into a mold, isostatically pressing and molding the powder, and sintering the powder to obtain the lanthanum element reinforced rhenium alloy material.

[0012] Preferably, an organic binder having a mass of 1 / 20-1 / 40 of the mass of the alloy powder is added during the mixing process.

[0013] Preferably, the organic binder is glycerol and / or paraffin.

[0014] Preferably, the grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, the grinding time is 15-30 hours, and the mass ratio of the alloy powder to the hard tungsten ball is (0.1-0.5):1.

[0015] Preferably, the inert gas is any one of nitrogen, helium, neon and argon.

[0016] Preferably, the sintering is programmed temperature sintering, first heating to 680-720°C at a rate of 8-12°C / min, keeping warm for 1-3h, then heating to 1250-1500°C at a rate of 5-8°C / min, keeping warm for 2-4h, and then heating to 2000-2350°C at a rate of 10-15°C / min, keeping warm for 4-8h.

[0017] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0018] (1) The preparation method of the lanthanum element reinforced rhenium alloy material provided by the present invention can be made through the process of mixing, grinding and sintering, without the need for special equipment or complicated process flow, with low energy consumption, high preparation efficiency and finished product qualification rate, suitable for continuous large-scale production, low capital investment, and high promotion and application value.

[0019] (2) The lanthanum element reinforced rhenium alloy material provided by the present invention comprises the following components, in terms of mass percentage: 5-10wt% tungsten, 1-3wt% hafnium, 0.1-0.3wt% osmium, 1-3wt% gallium, 0.05-0.15wt% niobium, 0.01-2wt% lanthanum oxide, 0.003-0.008wt% other rare earth elements, 0.001-0.003wt% nanofiller, and the balance is rhenium and other inevitable impurities. By rationally selecting the types and formulas of the components, the components can better play a synergistic role, and they cooperate with each other and work together, so that the lanthanum element reinforced rhenium alloy material has high high temperature strength, high high temperature creep resistance, low thermal expansion coefficient, and good bending resistance.

[0020] (3) The lanthanum-reinforced rhenium alloy material provided by the present invention has lanthanum oxide particles pinned around the powder particles. During the sintering process, these lanthanum oxide particles greatly increase the driving energy required for grain boundary movement and hinder grain boundary movement at high temperatures, thereby achieving the effect of improving high-temperature strength and reducing its thermal expansion coefficient.

[0021] (4) The lanthanum element reinforced rhenium alloy material provided by the present invention can play a role in solid solution strengthening by adding nanofillers, further improving the high temperature strength, and can also improve the defects of thermal deformation by cooperating with other components. The other rare earth elements are a mixture of lanthanum, praseodymium, and gadolinium in a mass ratio of (3-5): (0.6-1): (0.3-0.6); through the interaction between these elements and between these elements and other components, the comprehensive performance and performance stability of the alloy material can be further improved, so that it has high high temperature strength, high high temperature creep resistance, low thermal expansion coefficient, and good bending resistance.

[0022] (5) The lanthanum element-reinforced rhenium alloy material provided by the present invention is prepared by adding other components to rhenium metal to form an alloy material, which not only improves the defects of the rhenium alloy and further improves the material performance, but also reduces the cost, thereby improving the cost performance of the material. DETAILED DESCRIPTION

[0023] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0024] Example 1

[0025] A lanthanum element reinforced rhenium alloy material comprises the following components in terms of mass percentage: 1wt% of lanthanum oxide, and the remainder is rhenium and other inevitable impurities.

[0026] A preparation method of the lanthanum element reinforced rhenium alloy material comprises the following steps: after mixing the components uniformly according to mass percentage, grinding to obtain the alloy powder, then putting it into a mold for isostatic pressing and sintering to obtain the lanthanum element reinforced rhenium alloy material; during the mixing process, an organic binder with a mass of 1 / 20 of the mass of the alloy powder is added; the organic binder is glycerol. The pressing force of the isostatic pressing is 350MPa, and the holding time of the isostatic pressing is 30min.

[0027] The grinding is performed in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, the grinding time is 15 hours, the mass ratio of the alloy powder to the hard tungsten ball is 0.1:1, and the inert gas is nitrogen.

[0028] The sintering is programmed temperature sintering, firstly heating to 680°C at a speed of 8°C / min, keeping the temperature for 1 hour, then heating to 1250°C at a speed of 5°C / min, keeping the temperature for 2 hours, and then heating to 2000°C at a speed of 10°C / min, keeping the temperature for 4 hours.

[0029] Example 2

[0030] A lanthanum element reinforced rhenium alloy material comprises the following components, measured by mass percentage: 6wt% of tungsten, 1.5wt% of hafnium, 0.15wt% of osmium, 1.5wt% of gallium, 0.07wt% of niobium, 0.08wt% of lanthanum oxide, 0.005wt% of other rare earth elements, 0.0015wt% of nano filler, and the balance is rhenium and other inevitable impurities.

[0031] The other rare earth elements are a mixture of lanthanum, praseodymium and gadolinium in a mass ratio of 3.5:0.7:0.4; the particle size of the nanofiller is 40nm; the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of 2.5:1.

[0032] A preparation method of the lanthanum element reinforced rhenium alloy material comprises the following steps: after uniformly mixing the components according to mass percentage, grinding to obtain the alloy powder, then putting it into a mold for isostatic pressing and sintering to obtain the lanthanum element reinforced rhenium alloy material; during the mixing process, an organic binder with a mass of 1 / 25 of the mass of the alloy powder is added; the organic binder is paraffin; the grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, and the grinding time is 20 hours; the mass ratio of the alloy powder to the hard tungsten ball is 0.2:1. The inert gas is helium. The pressing force of the isostatic pressing is 350MPa, and the holding time of the isostatic pressing is 30min.

[0033] The sintering is programmed temperature sintering, firstly the temperature is increased to 690°C at a speed of 9°C / min, kept at this temperature for 1.5h, then the temperature is increased to 1300°C at a speed of 6°C / min, kept at this temperature for 2.5h, and then the temperature is increased to 2150°C at a speed of 12°C / min, kept at this temperature for 5h.

[0034] Example 3

[0035] A lanthanum element reinforced rhenium alloy material comprises the following components, measured by mass percentage: 7.5wt% of tungsten, 2wt% of hafnium, 0.2wt% of osmium, 2wt% of gallium, 0.1wt% of niobium, 1wt% of lanthanum oxide, 0.006wt% of other rare earth elements, 0.002wt% of nano filler, and the balance is rhenium and other inevitable impurities.

[0036] The other rare earth elements are a mixture of lanthanum, praseodymium and gadolinium in a mass ratio of 4:0.8:0.45; the particle size of the nanofiller is 60nm; and the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of 3:1.

[0037] A preparation method of the lanthanum element reinforced rhenium alloy material comprises the following steps: after uniformly mixing the components according to mass percentage, grinding to obtain the alloy powder, then putting it into a mold for isostatic pressing and sintering to obtain the lanthanum element reinforced rhenium alloy material; during the mixing process, an organic binder with a mass of 1 / 30 of the mass of the alloy powder is added; the organic binder is glycerol; the grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, and the grinding time is 15-30h; the mass ratio of the alloy powder to the hard tungsten ball is 0.3:1. The inert gas is neon. The pressing force of the isostatic pressing is 350MPa, and the holding time of the isostatic pressing is 30min.

[0038] The sintering is programmed temperature sintering, firstly the temperature is increased to 700°C at a speed of 10°C / min, kept at this temperature for 2 hours, then the temperature is increased to 1400°C at a speed of 6.5°C / min, kept at this temperature for 3 hours, and then the temperature is increased to 2200°C at a speed of 13°C / min, kept at this temperature for 6 hours.

[0039] Example 4

[0040] A lanthanum element reinforced rhenium alloy material comprises the following components, measured by mass percentage: 9wt% of tungsten, 2.5wt% of hafnium, 0.25wt% of osmium, 2.5wt% of gallium, 0.13wt% of niobium, 0.18wt% of lanthanum oxide, 0.007wt% of other rare earth elements, 0.0025wt% of nano filler, and the balance is rhenium and other inevitable impurities.

[0041] The other rare earth elements are a mixture of lanthanum, praseodymium and gadolinium in a mass ratio of 4.5:0.9:0.55; the particle size of the nanofiller is 70nm; the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of 3.5:1.

[0042] A preparation method of the lanthanum element reinforced rhenium alloy material comprises the following steps: after mixing the components uniformly according to the mass percentage, grinding to obtain the alloy powder, then putting it into a mold for isostatic pressing and sintering to obtain the lanthanum element reinforced rhenium alloy material; during the mixing process, an organic binder with a mass of 1 / 35 of the mass of the alloy powder is added; the organic binder is glycerol; the grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, and the grinding time is 15-30h; the mass ratio of the alloy powder to the hard tungsten ball is 0.4:1; the inert gas is neon. The pressing force of the isostatic pressing is 350MPa, and the holding time of the isostatic pressing is 30min.

[0043] The sintering is programmed temperature sintering, firstly the temperature is increased to 710°C at a speed of 11°C / min, kept at this temperature for 2.5h, then the temperature is increased to 1450°C at a speed of 7.5°C / min, kept at this temperature for 3.5h, and then the temperature is increased to 2320°C at a speed of 14°C / min, kept at this temperature for 7h.

[0044] Example 5

[0045] A lanthanum element reinforced rhenium alloy material comprises the following components, measured by mass percentage: 10wt% tungsten, 3wt% hafnium, 0.3wt% osmium, 3wt% gallium, 0.15wt% niobium, 2wt% lanthanum oxide, 0.008wt% other rare earth elements, 0.003wt% nano filler, and the balance is rhenium and other inevitable impurities.

[0046] The other rare earth elements are a mixture of lanthanum, praseodymium and gadolinium in a mass ratio of 5:1:0.6; the particle size of the nanofiller is 80nm; and the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of 4:1.

[0047] A preparation method of the lanthanum element reinforced rhenium alloy material comprises the following steps: after mixing the components uniformly according to the mass percentage, grinding to obtain the alloy powder, then putting it into a mold for isostatic pressing and sintering to obtain the lanthanum element reinforced rhenium alloy material; adding an organic binder with a mass of 1 / 40 of the mass of the alloy powder during the mixing process; the organic binder is paraffin; the grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, the grinding time is 30 hours; the mass ratio of the alloy powder to the hard tungsten ball is 0.5:1. The pressing force of the isostatic pressing is 350MPa, and the holding time of the isostatic pressing is 30min.

[0048] The sintering is programmed temperature sintering, firstly heating to 720°C at a speed of 12°C / min, keeping the temperature for 3 hours, then heating to 1500°C at a speed of 8°C / min, keeping the temperature for 4 hours, and then heating to 2350°C at a speed of 15°C / min, keeping the temperature for 8 hours.

[0049] Comparative Example 1

[0050] This example provides a lanthanum-reinforced rhenium alloy material, the formula and preparation method of which are basically the same as those of Example 1, except that niobium and lanthanum oxide are not added.

[0051] Comparative Example 2

[0052] This example provides a lanthanum-reinforced rhenium alloy material, the formula and preparation method of which are basically the same as those of Example 1, except that no gallium and nanofiller are added.

[0053] Comparative Example 3

[0054] This example provides a tungsten-rhenium-copper alloy, which is made according to the method of Example 1 in CN 110396630 B.

[0055] In order to illustrate the technical effects of the embodiments of the present invention, the relevant performances of various products were tested with reference to the current national standards of my country. The test results are shown in Table 1.

[0056] As can be seen from Table 1, the lanthanum element reinforced rhenium alloy material disclosed in the embodiment of the present invention has greater high temperature strength and lower linear expansion coefficient than the comparative product. The addition of niobium, lanthanum oxide, gallium and nanofiller is beneficial to improving the above properties. The performance of the final product is the result of the synergistic effect of the raw material components.

[0057] Table 1

[0058] project 1000℃ yield strength Bending strength Deflection Average linear expansion coefficient (20-1000℃) unit MPa MPa mm <![CDATA[×10 -6 / ℃]]> Example 1 1320 2932 18.3 6.243 Example 2 1332 2950 19.1 6.013 Example 3 1347 2961 19.4 5.976 Example 4 1355 2970 19.6 5.855 Example 5 1360 2983 20.1 5.802 Comparative Example 1 1278 2760 15.3 8.621 Comparative Example 2 1185 2800 16.7 7.234 Comparative Example 3 1165 2812 17.8 9.105

[0059] The above implementation modes are only descriptions of the preferred implementation modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary engineering and technical personnel in the field should fall within the protection scope determined by the claims of the present invention.

Claims

1. A lanthanum element strengthened rhenium alloy material, characterized in that: The composition comprises the following components in terms of mass percentage: 0.01-2wt% of lanthanum oxide, and the balance is rhenium and other inevitable impurities; The following ingredients are also included: 5-10wt% tungsten, 1-3wt% hafnium, 0.1-0.3wt% osmium, 1-3wt% gallium, 0.05-0.15wt% niobium, 0.003-0.008wt% other rare earth elements, and 0.001-0.003wt% nanofiller; the other rare earth elements are a mixture of lanthanum, praseodymium, and gadolinium in a mass ratio of (3-5):(0.6-1):(0.3-0.6); the nanofiller is a mixture of titanium boride and silicon nitride in a mass ratio of (2-4):1; the lanthanum element strengthens rhenium The preparation method of the alloy material comprises the following steps: mixing each component uniformly according to mass percentage, grinding to obtain alloy powder, then putting it into a mold, isostatically pressing and forming it, and sintering to obtain a lanthanum element reinforced rhenium alloy material; the sintering is programmed temperature sintering, firstly heating to 680-720°C at a speed of 8-12°C / min, keeping the temperature for 1-3h, then heating to 1250-1500°C at a speed of 5-8°C / min, keeping the temperature for 2-4h, and then heating to 2000-2350°C at a speed of 10-15°C / min, and keeping the temperature for 4-8h.

2. The lanthanum-reinforced rhenium alloy material according to claim 1, characterized in that: The particle size of the nanofiller is 20-80 nm.

3. The lanthanum-reinforced rhenium alloy material according to claim 1, characterized in that: The grinding is carried out in an inert gas atmosphere, the grinding medium includes a hard tungsten ball, and the grinding time is 15-30 hours; the mass ratio of the alloy powder to the hard tungsten ball is (0.1-0.5):

1.

4. The method for preparing the lanthanum-reinforced rhenium alloy material according to claim 3, characterized in that: The inert gas is any one of nitrogen, helium, neon and argon.