A high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy and its preparation method

Abstract

The present invention relates to the field of titanium alloys, and in particular to a high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy and a preparation method thereof. In terms of mass percentage, the Zr content is 3.8-4.2%, the Nb content is 23.8-24.2%, the Sn content is 7.8-8.2%, the mass fraction of oxygen is 0.05-0.4%, and the balance is Ti. The present invention regulates the stability of the titanium alloy and the phase stability of the constituent phases through the combined action of component limitation and processing technology regulation, so that the alloy produces a special modulated decomposition structure. By limiting the subsequent heating, cooling, and heat preservation processes, the temperature coefficient of resistance and the lattice mismatch of the modulated decomposition structure are regulated, thereby playing a role in regulating the overall temperature coefficient of resistance and strength of the alloy. Thus, the problem that there is currently no relevant technology that can provide a titanium alloy material with both high strength and extremely low temperature coefficient of resistance is solved.

Description

Technical Field

[0001] The present invention relates to the field of titanium alloys, in particular to a high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy and a preparation method thereof. Background Art

[0002] Precision instruments often rely on highly accurate resistance performance. If the resistance of the materials used in these instruments changes due to temperature fluctuations, the electrical signal will become unstable and affect signal accuracy. Therefore, materials with extremely low temperature coefficients of resistance are extremely important in the field of precision instruments.

[0003] According to the authoritative metal materials database https: / / www.nessengr.com / techdata / metalresis.html, the temperature coefficient of resistance (TCR) of conventional titanium alloys is approximately 350 ppm / K. Furthermore, the resistance of conventional titanium alloys fluctuates dramatically with temperature and does not possess a low TCR (see Materials Properties Handbook: Titanium Alloys [M], ASM International, 1993).

[0004] Conventional techniques for obtaining low-TCR alloy materials in related fields involve the preparation of thin film materials and the adjustment of the composition ratio of the composite materials. For example, cobalt-germanium alloys are prepared into thin films (publication number CN113481484A), nickel-chromium-silicon alloys are prepared into thin films (publication number CN106435478A), glass-ceramic composites are prepared and the ceramic components are adjusted (publication number CN207663866U), FeGa alloys are prepared and the Ga content is adjusted (publication number CN103214246A), titanium alloys are prepared and the aging heat treatment system is adjusted (publication number CN115627381A). None of these techniques involve the combined effects of Nb, Zr, Sn, and O composition control, thermal processing, heating, cooling, and insulation processes on the TCR. At the same time, the low-TCR materials provided by the above-mentioned technical solutions do not have high strength, which limits the application scenarios of such materials. Summary of the Invention

[0005] The purpose of the present invention is to provide a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance and a preparation method thereof, so as to solve the problem that there is currently no relevant technology that can provide a titanium alloy material with both high strength and an extremely low temperature coefficient of resistance.

[0006] The technical solution of the present invention is:

[0007] A high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance comprises, by mass percentage, 3.8-4.2% Zr, 23.8-24.2% Nb, 7.8-8.2% Sn, 0.05-0.4% oxygen, and the remainder Ti.

[0008] The method for preparing the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy is carried out in sequence by the following steps:

[0009] Step 1: Regulating the alloy stability so that the mass percentage of Nb in the alloy is 23.8-24.2%;

[0010] Step 2: Suppressing the formation of metastable phases in the alloy so that the mass percentage of Zr in the alloy is 3.8-4.2%, the mass fraction of Sn is 7.8-8.2%, and the mass fraction of oxygen is 0.05-0.4%;

[0011] Step 3: vacuum melting;

[0012] Step 4: hot forging, the temperature of the blank is controlled at 600-1200℃;

[0013] Step 5: Cooling, controlling the cooling rate to 10-50°C / min, cooling to 20°C;

[0014] Step 6: Hot working, the hot working temperature is controlled at 400-800℃;

[0015] Step 7: heat preservation treatment at 300-700°C for 5-15 minutes;

[0016] Step 8: Hot working, the hot working temperature is controlled at 200-500℃;

[0017] Step 9: Heat preservation treatment at 200-400℃ for 20 minutes;

[0018] Step 10: Cooling, controlling the cooling rate to 0.1-1°C / s, cooling to 20°C;

[0019] Step 11: heating at a rate of 5 to 10°C / s to a temperature of 100 to 300°C below the α-phase transition temperature;

[0020] Step 12: Keep warm for 5 to 720 minutes;

[0021] Step 13: Cooling, controlling the cooling rate to 0.1-1°C / s, and cooling to 20°C;

[0022] Step 14: Keep warm for 24 to 48 hours;

[0023] Step 15: Cooling, controlling the cooling rate at 2-4°C / min, to -260°C;

[0024] Step 16: heating at a rate of 2-4°C / min to 80°C;

[0025] Step 17: Cooling down, controlling the cooling rate to 10-30°C / min, and cooling down to 20°C;

[0026] Step 18: Obtain a high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy.

[0027] In the method for preparing the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy, in step 6, the hot working is hot rolling, and the deformation amount is 20-60%.

[0028] In the method for preparing the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy, in step 7, the hot working is hot rolling, and the deformation amount is 10-50%.

[0029] In the method for preparing the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy, the holding temperature in step 7 is greater than the hot working temperature in step 8. After step 7, the cooling rate is controlled to be 5-25°C / min, and the alloy is cooled to the hot working temperature and hot worked.

[0030] In the method for preparing the high-strength and extremely low temperature coefficient of resistance titanium, niobium, zirconium and tin alloy, in step 18, the temperature coefficient of resistance of the high-strength and extremely low temperature coefficient of resistance titanium, niobium, zirconium and tin alloy is -50 to 50 ppm / K in the range of -260 to 80°C.

[0031] In the method for preparing the high-strength and extremely low temperature coefficient of resistance titanium, niobium, zirconium, and tin alloy, in step 18, the tensile strength of the high-strength and extremely low temperature coefficient of resistance titanium, niobium, zirconium, and tin alloy is 900 to 1350 MPa.

[0032] The working principle of the present invention is as follows:

[0033] The present invention regulates the electromagnetic properties of titanium alloys by limiting the composition and regulating the processing technology. By limiting the composition to only contain Ti, Nb, Zr, Sn, and O, the alloy can produce a special modulated decomposition structure under this technical solution (see Appendix). Figure 1By limiting the subsequent heating, cooling, and holding processes, the TCR and lattice mismatch of the decomposed structure are regulated, further affecting the overall TCR of the alloy and improving its strength. The stability of the microstructures responsible for TCR regulation in this technology is strictly dependent on the processing temperature, holding temperature / time, and cooling rate. Therefore, cold working, solution treatment, and water quenching can destroy these microstructures, preventing the alloy from achieving low TCR performance. Therefore, the preparation method should not include processes such as cold working, solution treatment, and water quenching.

[0034] In addition, during the vacuum melting process, the mass fraction of oxygen is controlled to be 0.05-0.4%, which has the following functions: optimizing the electromagnetic properties of the alloy and inhibiting the generation of high-resistance precipitation phases during subsequent alloy hot working.

[0035] The beneficial effects of the present invention are as follows:

[0036] 1. The present invention provides a titanium alloy material with excellent performance, which has an extremely low temperature coefficient of resistance of -50 to 50 ppm / K in the temperature range of -260 to 80°C, effectively solving the demand for low temperature coefficient of resistance in the field of precision devices;

[0037] 2. The present invention provides a method for preparing a material with a low temperature coefficient of resistance. This method does not require complex steps such as cold working, solution treatment, and water quenching, thereby simplifying the preparation process of the low-resistance alloy material and improving the preparation efficiency.

[0038] 3. The titanium alloy material provided by the present invention has both high strength and low temperature coefficient of resistance, solving the problem of low strength of current low temperature coefficient of resistance materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 : Modulated decomposition structure morphology of the alloy produced in Example 1.

[0040] Figure 2 : Curve of the temperature coefficient of resistance of the alloy of Example 1 changing with temperature.

[0041] Figure 3 : Tensile curve of the alloy of Example 1. DETAILED DESCRIPTION

[0042] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention and the accompanying drawings. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative efforts should fall within the scope of protection of the present invention.

[0043] Embodiment 1:

[0044] In this embodiment, a method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance is as follows:

[0045] Step 1: Regulating the alloy stability so that the mass percentage of Nb in the titanium alloy is 23.8%;

[0046] Step 2: Suppressing the formation of metastable phases in the alloy, so that the mass percentage of Zr in the titanium alloy is 3.8%, the mass fraction of Sn is 7.8%, and the mass fraction of oxygen is 0.05%;

[0047] Step 3: vacuum melting;

[0048] Step 4: hot forging, the temperature of the blank is controlled at 600℃;

[0049] Step 5: Cooling, controlling the cooling rate to 10°C / min, cooling to 20°C;

[0050] Step 6: hot working, the hot working temperature is controlled at 400 ° C, the hot working is hot rolling, and the deformation is 20%;

[0051] Step 7: Heat preservation treatment at 300℃ for 5 minutes;

[0052] Step 8: After step 7, the cooling rate is controlled to 5°C / min, cooled to the hot working temperature and hot working is performed. The hot working temperature is controlled at 200°C, the hot working is hot rolling, and the deformation is 10%;

[0053] Step 9: Heat preservation treatment at 200℃ for 20 minutes;

[0054] Step 10: Cooling, controlling the cooling rate to 0.1°C / second, cooling to 20°C;

[0055] Step 11: heating at a rate of 5°C / s to 100°C below the α-phase transition temperature;

[0056] Step 12: Keep warm for 5 minutes;

[0057] Step 13: Cooling, controlling the cooling rate to 0.1°C / second, cooling to 20°C;

[0058] Step 14: Keep warm for 24 hours;

[0059] Step 15: Cool down at a rate of 3°C / min to -260°C.

[0060] Step 16: heating at a rate of 3°C / min to 80°C;

[0061] Step 17: Cool down the temperature at a rate of 10°C / min to 20°C.

[0062] Step 18: The high-strength and ultra-low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy is obtained, wherein the tensile strength is 900 MPa and the temperature coefficient of resistance is -25 to 25 ppm / K in a temperature range of -260 to 80°C.

[0063] like Figure 1 As shown, it can be seen from the modulated decomposition structure morphology that after limiting the components to only contain Ti, Nb, Zr, Sn, and O and undergoing the technical solution in this embodiment, a lamellar modulated decomposition structure is produced, which can subsequently affect the overall resistance temperature coefficient of the alloy and improve the strength of the alloy.

[0064] like Figure 2 As shown in FIG, it can be seen from the curve of the change of the temperature coefficient of resistance with temperature that the temperature coefficient of resistance is -25 to 25 ppm / K in the temperature range of -260 to 80°C.

[0065] like Figure 3 As shown in FIG, it can be seen from the tensile curve that the strength of the obtained titanium alloy material is 1350 MPa.

[0066] Example 2:

[0067] In this embodiment, a method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance is as follows:

[0068] Step 1: Regulating the alloy stability so that the mass percentage of Nb in the titanium alloy is 24.2%;

[0069] Step 2: Suppressing the formation of metastable phases in the alloy, so that the mass percentage of Zr in the titanium alloy is 4.2%, the mass fraction of Sn is 8.2%, and the mass fraction of oxygen is 0.4%;

[0070] Step 3: vacuum melting;

[0071] Step 4: hot forging, the temperature of the blank is controlled at 1200℃;

[0072] Step 5: Cooling, controlling the cooling rate to 50°C / min, cooling to 20°C;

[0073] Step 6: hot working, the hot working temperature is controlled at 800℃, the hot working is hot rolling, and the deformation is 60%;

[0074] Step 7: Heat preservation treatment at 700℃ for 15 minutes;

[0075] Step 8: After step 7, the cooling rate is controlled to 25°C / min, cooled to the hot working temperature and hot working is performed. The hot working temperature is controlled at 500°C, the hot working is hot rolling, and the deformation amount is 50%;

[0076] Step 9: Heat preservation treatment at 400℃ for 20 minutes;

[0077] Step 10: Cooling, controlling the cooling rate to 1°C / second, cooling to 20°C;

[0078] Step 11: heating at a rate of 10°C / s to 300°C below the α-phase transition temperature;

[0079] Step 12: Keep warm for 720 minutes;

[0080] Step 13: Cooling, controlling the cooling rate to 1°C / second, cooling to 20°C;

[0081] Step 14: Keep warm for 48 hours;

[0082] Step 15: Cool down at a rate of 3°C / min to -260°C.

[0083] Step 16: heating at a rate of 3°C / min to 80°C;

[0084] Step 17: Cool down the temperature at a rate of 30°C / min to 20°C.

[0085] Step 18: Obtain the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy, which has a tensile strength of 1000 MPa and a temperature coefficient of resistance of -50 to 10 ppm / K in a temperature range of -260 to 80°C.

[0086] Example 3:

[0087] In this embodiment, a method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance is as follows:

[0088] Step 1: Regulating the alloy stability so that the mass percentage of Nb in the titanium alloy is 24.0%;

[0089] Step 2: Suppressing the formation of metastable phases in the alloy, so that the mass percentage of Zr in the titanium alloy is 4.0%, the mass fraction of Sn is 8.0%, and the mass fraction of oxygen is 0.16%;

[0090] Step 3: vacuum melting;

[0091] Step 4: hot forging, the temperature of the blank is controlled at 800℃;

[0092] Step 5: Cooling, controlling the cooling rate to 30°C / min, cooling to 20°C;

[0093] Step 6: hot working, the hot working temperature is controlled at 600℃, the hot working is hot rolling, and the deformation is 40%;

[0094] Step 7: Heat preservation treatment at 600℃ for 10 minutes;

[0095] Step 8: After step 7, the cooling rate is controlled at 15°C / min, cooled to the hot working temperature and hot worked. The hot working temperature is controlled at 400°C, the hot working is hot rolling, and the deformation is 30%.

[0096] Step 9: Heat preservation treatment at 300℃ for 20 minutes;

[0097] Step 10: Cooling, controlling the cooling rate to 0.5°C / second, cooling to 20°C;

[0098] Step 11: heating at a rate of 7°C / s to 200°C below the α-phase transition temperature;

[0099] Step 12: Keep warm for 240 minutes;

[0100] Step 13: Cooling, controlling the cooling rate to 0.5°C / second, cooling to 20°C;

[0101] Step 14: Keep warm for 36 hours;

[0102] Step 15: Cool down at a rate of 3°C / min to -260°C.

[0103] Step 16: heating at a rate of 3°C / min to 80°C;

[0104] Step 17: Cool down the temperature at a rate of 20°C / min to 20°C.

[0105] Step 18: The high-strength and ultra-low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy is obtained, wherein the tensile strength is 1085 MPa and the temperature coefficient of resistance is -10 to 50 ppm / K in a temperature range of -260 to 80°C.

[0106] Implementation results show that the present invention obtains a high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy, whose tensile strength can reach 900-1350 MPa and the temperature coefficient of resistance can reach -50-50 ppm / K in the temperature range of -260-80°C.

Claims

1. A method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance, characterized in that: The composition of the titanium-niobium-zirconium-tin alloy is as follows, by mass percentage: 3.8-4.2% Zr, 23.8-24.2% Nb, 7.8-8.2% Sn, 0.05-0.4% oxygen by mass, and the balance Ti; The method for preparing the high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy is carried out in sequence by the following steps: Step 1: Regulate the alloy stability so that the mass percentage of Nb in the alloy is 23.8~24.2%; Step 2: Suppress the formation of metastable phase in the alloy, so that the mass percentage of Zr in the alloy is 3.8-4.2%, the mass fraction of Sn is 7.8-8.2%, and the mass fraction of oxygen is 0.05-0.4%; Step 3: vacuum melting; Step 4: Hot forging, the temperature of the blank is controlled at 600~1200℃; Step 5: Cooling, controlling the cooling rate to 10-50°C / min, cooling to 20°C; Step 6: Hot working, the hot working temperature is controlled at 400~800℃; Step 7: Heat preservation treatment at 300~700℃ for 5~15 minutes; Step 8: Hot working, the hot working temperature is controlled at 200~500℃; Step 9: Heat preservation treatment at 200~400℃ for 20 minutes; Step 10: Cooling, controlling the cooling rate to 0.1~1℃ / s, cooling to 20℃; Step 11: heating at a rate of 5-10°C / s to a temperature of 100-300°C below the α-phase transition temperature; Step 12: Keep warm for 5-720 minutes; Step 13: Cooling, controlling the cooling rate to 0.1~1℃ / s, cooling to 20℃; Step 14: Keep warm for 24 to 48 hours; Step 15: Cool down at a rate of 2-4°C / min to -260°C. Step 16: Heating, controlling the heating rate at 2-4°C / min, to 80°C; Step 17: Cool down, control the cooling rate at 10-30°C / min, and cool down to 20°C; Step 18: Obtain a high-strength and extremely low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy.

2. The method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance according to claim 1, characterized in that: In step 6, the hot working is hot rolling, and the deformation amount is 20-60%.

3. The method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance according to claim 1, characterized in that: In step 7, the hot working is hot rolling, and the deformation amount is 10-50%.

4. The method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance according to claim 1, characterized in that: The holding temperature in step 7 is higher than the hot working temperature in step 8. After step 7, the cooling rate is controlled to be 5-25°C / min, and the system is cooled to the hot working temperature and hot working is performed.

5. The method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance according to claim 1, characterized in that: In step 18, the resistance temperature coefficient of the high-strength and ultra-low resistance temperature coefficient titanium-niobium-zirconium-tin alloy is -50-50 ppm / K in the range of -260-80°C.

6. The method for preparing a high-strength titanium-niobium-zirconium-tin alloy with an extremely low temperature coefficient of resistance according to claim 1, characterized in that: In step 18, the tensile strength of the high-strength and ultra-low temperature coefficient of resistance titanium-niobium-zirconium-tin alloy is 900-1350 MPa.

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