Titanium alloy material for high-temperature oxidation-resistant titanium welded pipe

Abstract

The application relates to the technical field of alloy materials, and discloses a titanium alloy material for high-temperature oxidation-resistant titanium welded pipes, which comprises a titanium alloy base and a reinforcing phase, wherein the titanium alloy base is composed of Sn, Nb, Zr, Al, Si, Cr, Mo, Mn, O, C, N, H, and the balance is Ti and inevitable impurities; and the reinforcing phase comprises silicon carbide. Through the technical scheme, the problem that the high-temperature oxidation resistance of the titanium alloy material in related technologies sharply decreases during service at 600 DEG C or above is solved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of alloy materials, in particular to a titanium alloy material for high-temperature oxidation-resistant titanium welded pipes. BACKGROUND

[0002] Compared with other metals, titanium has better corrosion resistance and is widely used in the fields of chemical industry, petroleum industry, power stations and seawater desalination. At present, titanium welded pipes are widely used, the titanium welded pipe is a pipe made of titanium alloy plate or titanium alloy strip after bending or spinning and then welding, has the characteristics of light weight, high strength and excellent mechanical properties, and is widely used in heat exchange equipment, coil type heat exchanger, serpentine type heat exchanger, condenser, evaporator and conveying pipeline.

[0003] With the continuous progress of science and technology, the titanium welded pipe cannot meet the needs in some aspects. For example, due to the sharp decline of the high-temperature oxidation resistance of the titanium alloy material during service above 600 DEG C, the titanium welded pipe prepared has poor high-temperature oxidation resistance. SUMMARY

[0004] The application provides a titanium alloy material for high-temperature oxidation-resistant titanium welded pipes, and solves the problem of the sharp decline of the high-temperature oxidation resistance of the titanium alloy material during service above 600 DEG C in the related art.

[0005] The technical scheme of the application is as follows:

[0006] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes, comprising a titanium alloy base body and a reinforcing phase, wherein the titanium alloy base body is composed of the following components in mass percentage: Sn: 1.6% to 3.3%, Nb: 0.36% to 1.8%, Zr: 3.2% to 4.7%, Al: 4.1% to 6.5%, Si: 0.1% to 0.25%, Cr: 0.02% to 0.25%, Mo: 1.8% to 3.2%, Mn: 0.03% to 0.2%, O: ≤0.1%, C: ≤0.05%, N: ≤0.05%, H: ≤0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase comprises silicon carbide.

[0007] As a further technical scheme, 0.1 <= (6Cr-0.7Mn) / (Mo+0.15Cr) <= 0.25 in mass percentage.

[0008] In the application, the content of Cr, Mo and Mn is optimized to satisfy 0.1 <= (6Cr-0.7Mn) / (Mo+0.15Cr) <= 0.25 in mass percentage, and the high-temperature oxidation resistance of the titanium alloy material is further improved.

[0009] In the present application, the amount of the reinforcing phase can be any conventional amount in the art, and preferably, the mass ratio of the titanium alloy matrix and the reinforcing phase is 100:1-4, for example, it can be 100:1, 100:1.5, 100:2, 100:2.5, 100:3, 100:3.5 or 100:4, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0010] As a further technical solution, the silicon carbide includes pre-processed silicon carbide, and the pre-processed silicon carbide is aluminum oxide composite silicon carbide.

[0011] In the present application, the aluminum oxide composite silicon carbide is used as the reinforcing phase, and after the silicon carbide is compounded with the aluminum oxide, the wettability of the reinforcing phase and the titanium alloy matrix is improved, and the thermal expansion coefficients of the aluminum oxide and the titanium alloy matrix are similar, thereby reducing the thermal stress of the titanium alloy matrix and the reinforcing phase due to the mismatch of the thermal expansion coefficients, stabilizing the interface bonding of the two, and achieving the effect of improving the tensile strength of the titanium alloy material.

[0012] As a further technical solution, the raw materials of the aluminum oxide composite silicon carbide include aluminum oxide and silicon carbide with a mass ratio of 1-5:100.

[0013] As a further technical solution, the particle size of the aluminum oxide is nanoscale, and the particle size of the silicon carbide is micrometer scale.

[0014] In the present application, the aluminum oxide can be any one or more conventional nanoscale aluminum oxides in the art, and preferably, the particle size of the aluminum oxide is 20-500 nm, for example, it can be 20 nm, 30 nm, 50 nm, 100 nm, 150 nm, 200 nm, 300 nm or 500 nm, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0015] In the present application, the silicon carbide can be any one or more conventional micrometer-scale silicon carbides in the art, and preferably, the particle size of the silicon carbide is 1-10 μm, for example, it can be 1 μm, 2 μm, 3 μm, 5 μm, 8 μm or 10 μm, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0016] As a further technical solution, the preparation method of the aluminum oxide composite silicon carbide includes the following steps: mixing the aluminum oxide and the silicon carbide, and then performing ball milling to obtain the aluminum oxide composite silicon carbide.

[0017] In the present application, after mixing alumina and silicon carbide, nanoscale alumina can be coated on the surface of micron-sized silicon carbide by ball milling, which improves the wettability of the reinforcing phase and the titanium alloy matrix when used as a reinforcing phase, allowing the reinforcing phase to fully function and thus improving the tensile strength of the titanium alloy material. In addition, ball milling can use any conventional process parameters in the art, preferably a ball milling speed of 300-700 rpm, such as 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm or 700 rpm, but not limited to the listed values, other values not listed in this range are also applicable. The ball milling time is 3-5 h, for example, it can be 3 h, 3.5 h, 4 h, 4.5 h or 5 h, but not limited to the listed values, other values not listed in this range are also applicable.

[0018] As a further technical solution, the silicon carbide is titanium carbide composite pretreated silicon carbide.

[0019] In the present application, the use of titanium carbide composite pretreated silicon carbide as a reinforcing phase improves the stability of the reinforcing phase in the titanium alloy matrix, further improving the tensile strength of the titanium alloy material.

[0020] As a further technical solution, the raw materials of the titanium carbide composite pretreated silicon carbide include alumina, titanium carbide and silicon carbide in a mass ratio of 1-2:3-4:100.

[0021] As a further technical solution, the particle size of the titanium carbide is nanoscale.

[0022] In the present application, the titanium carbide can be any one or more conventional nanoscale titanium carbide in the art, preferably titanium carbide with a particle size of 40-800 nm, such as 40 nm, 50 nm, 80 nm, 500 nm or 800 nm, but not limited to the listed values, other values not listed in this range are also applicable.

[0023] As a further technical solution, the preparation method of the titanium carbide composite pretreated silicon carbide comprises the following steps: mixing alumina and silicon carbide, then ball milling; adding titanium carbide and continuing ball milling to obtain titanium carbide composite pretreated silicon carbide.

[0024] In the present application, firstly, the alumina and silicon carbide are mixed, then the nanoscale alumina is coated on the micron-scale silicon carbide surface through ball milling, and then titanium carbide is further added and ball milled to further coat the nanoscale titanium carbide on the outermost layer. When used as a reinforcing phase, the thermal expansion coefficients of the reinforcing phase and the titanium alloy matrix are similar, and the stability of the reinforcing phase in the titanium alloy matrix is also ensured, so that the reinforcing phase can fully play a role, thereby further improving the tensile strength of the titanium alloy material. In addition, the ball milling can use any conventional process parameters in the art, preferably the ball milling speed is 300-700 rpm, for example, it can be 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm or 700 rpm, but not limited to the listed values, other values not listed in this range are also applicable, the ball milling time is 3-5 h, for example, it can be 3 h, 3.5 h, 4 h, 4.5 h or 5 h, but not limited to the listed values, other values not listed in this range are also applicable.

[0025] The working principle and beneficial effects of the present application are as follows:

[0026] In the present application, a titanium alloy material for high-temperature oxidation-resistant titanium welded pipe is provided, which comprises a titanium alloy matrix and a reinforcing phase. The titanium alloy matrix is composed of Sn, Nb, Zr, Al, Si, Cr, Mo, Mn, O, C, N, H, Ti and inevitable impurities. By adding Cr, Mo and Mn and optimizing the content of each component, the high-temperature oxidation resistance of the titanium alloy material is improved. In addition, the reinforcing phase comprises silicon carbide, which has high strength, high hardness, excellent thermal stability and oxidation resistance, and further improves the high-temperature oxidation resistance of the titanium alloy material as a reinforcing phase. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0028] The parameters of the raw materials in the following examples and comparative examples are as follows:

[0029] The particle size of the alumina is 30 nm, and the specific surface area is 50 m 2 / g;

[0030] The particle size of the titanium carbide is 40 nm, and the specific surface area is 65 m 2 / g;

[0031] The particle size of the silicon carbide is 8 μm, and the specific surface area is 8 m 2 / g.

[0032] The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes in the following examples and comparative examples is prepared by the following method:

[0033] S1, after the components of the titanium alloy matrix are proportioned, they are mixed uniformly, the electrode is pressed, vacuum welding of the electrode is performed, the vacuum consumable arc furnace is used to melt at 1700℃ for 45 min, the reinforcing phase is added, and casting is performed to obtain a titanium alloy cast blank;

[0034] S2, the titanium alloy cast blank is forged, and after heat treatment, the titanium alloy material for high-temperature oxidation-resistant titanium welded pipes is obtained.

[0035] Example 1

[0036] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes includes a titanium alloy matrix and a reinforcing phase in a mass ratio of 100:1, the titanium alloy matrix is composed of the following components in mass percentage: Sn: 1.6%, Nb: 0.36%, Zr: 3.2%, Al: 4.1%, Si: 0.1%, Cr: 0.02%, Mo: 1.8%, Mn: 0.03%, O: 0.05%, C: 0.02%, N: 0.01%, H: 0.003%, and the balance is Ti and inevitable impurities; the reinforcing phase is silicon carbide.

[0037] Example 2

[0038] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes includes a titanium alloy matrix and a reinforcing phase in a mass ratio of 100:3, the titanium alloy matrix is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.1%, Mo: 2.7%, Mn: 0.13%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; the reinforcing phase is silicon carbide.

[0039] Example 3

[0040] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes includes a titanium alloy matrix and a reinforcing phase in a mass ratio of 100:5, the titanium alloy matrix is composed of the following components in mass percentage: Sn: 3.3%, Nb: 1.8%, Zr: 4.7%, Al: 6.5%, Si: 0.25%, Cr: 0.25%, Mo: 3.2%, Mn: 0.2%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; the reinforcing phase is silicon carbide.

[0041] Example 4

[0042] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.05%, Mo: 2.5725%, Mn: 0.06%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0043] Example 5

[0044] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.14%, Mo: 2.835%, Mn: 0.18%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0045] Example 6

[0046] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.03%, Mo: 3%, Mn: 0.17%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0047] Example 7

[0048] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.25%, Mo: 1.8%, Mn: 0.05%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0049] Example 8

[0050] The difference from Example 2 is that the reinforcing phase is alumina composite silicon carbide.

[0051] The preparation method of the alumina composite silicon carbide is that alumina and silicon carbide are mixed in a mass ratio of 1:20, then ball-milled at 300 rpm for 5 h to obtain the alumina composite silicon carbide.

[0052] Example 9

[0053] The difference from Example 2 is that the reinforcing phase is alumina composite silicon carbide;

[0054] The preparation method of the alumina composite silicon carbide is that alumina and silicon carbide are mixed in a mass ratio of 1:100, then ball-milled at 700 rpm for 3 h to obtain the alumina composite silicon carbide.

[0055] Example 10

[0056] The difference from Example 8 is that the alumina is replaced by an equal amount of alumina and titanium carbide in a mass ratio of 1:4.

[0057] Example 11

[0058] The difference from Example 8 is that the alumina is replaced by an equal amount of alumina and titanium carbide in a mass ratio of 2:3.

[0059] Example 12

[0060] The difference from Example 11 is that the reinforcing phase is titanium carbide composite pretreated silicon carbide;

[0061] The preparation method of the titanium carbide composite pretreated silicon carbide is that alumina and silicon carbide are mixed, then ball-milled at 300 rpm for 3 h; titanium carbide is added and ball-milled for another 2 h to obtain the titanium carbide composite pretreated silicon carbide, and the mass ratio of alumina, titanium carbide and silicon carbide is 2:3:100.

[0062] Example 13

[0063] The difference from Example 11 is that the reinforcing phase is titanium carbide composite pretreated silicon carbide;

[0064] The preparation method of the titanium carbide composite pretreated silicon carbide is that titanium carbide and silicon carbide are mixed, then ball-milled at 300 rpm for 3 h; alumina is added and ball-milled for another 2 h to obtain the titanium carbide composite pretreated silicon carbide, and the mass ratio of alumina, titanium carbide and silicon carbide is 2:3:100.

[0065] Comparative Example 1

[0066] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Mo: 2.85%, Mn: 0.18%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0067] Comparative Example 2

[0068] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 1.45%, Mn: 1.48%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0069] Comparative Example 3

[0070] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes comprises a titanium alloy base and a reinforcing phase in a mass ratio of 100:3, the titanium alloy base is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.165%, Mo: 2.765%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities; and the reinforcing phase is silicon carbide.

[0071] Comparative Example 4

[0072] A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes is composed of the following components in mass percentage: Sn: 2.1%, Nb: 0.95%, Zr: 3.8%, Al: 5.4%, Si: 0.17%, Cr: 0.1%, Mo: 2.7%, Mn: 0.13%, O: 0.1%, C: 0.05%, N: 0.05%, H: 0.01%, and the balance is Ti and inevitable impurities.

[0073] Performance test:

[0074] (1) High-temperature oxidation resistance: the titanium alloy material is heat treated at 750 DEG C for 1000h, and the weight is measured by a precision electronic balance every 200h during the period, and the test results are recorded in Table 1.

[0075] (2) Tensile strength: the titanium alloy material was tested for room temperature tensile strength according to the method in GB / T 228.1-2021, and the test results are recorded in Table 2.

[0076] Table 1 High temperature oxidation resistance test results

[0077]

[0078] As can be seen from Table 1, the titanium alloy materials obtained in Examples 1-7 have lower oxidation weight gain after heat treatment at 750℃ for 1000h than Comparative Examples 1-4, indicating that the addition of Cr, Mo and Mn, and the optimization of the content of each component, and the use of silicon carbide as a reinforcing phase, improve the high temperature oxidation resistance of the titanium alloy material. In addition, the titanium alloy materials obtained in Examples 2 and 4-5 have lower oxidation weight gain after heat treatment at 750℃ for 1000h than Examples 6-7, indicating that the content of Cr, Mo and Mn satisfies 0.1≤(6Cr-0.7Mn) / (Mo+0.15Cr)≤0.25, further improving the high temperature oxidation resistance of the titanium alloy material.

[0079] Table 2 Tensile strength test results

[0080]

[0081] As can be seen from Table 2, the titanium alloy materials obtained in Examples 8-13 have higher tensile strength than Example 2, indicating that the use of aluminum oxide composite silicon carbide as a reinforcing phase improves the tensile strength of the titanium alloy material. In addition, the titanium alloy materials obtained in Examples 10-13 have higher tensile strength than Examples 8-9, indicating that the use of titanium carbide composite pretreated silicon carbide as a reinforcing phase further improves the tensile strength of the titanium alloy material.

[0082] The above is only a preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A titanium alloy material for high-temperature oxidation-resistant titanium welded pipes, characterized by comprising, in mass %, The titanium alloy base consists of the following components in mass percentage: Sn: 1.6%-3.3%, Nb: 0.36%-1.8%, Zr: 3.2%-4.7%, Al: 4.1%-6.5%, Si: 0.1%-0.25%, Cr: 0.02%-0.25%, Mo: 1.8%-3.2%, Mn: 0.03%-0.2%, O: ≤0.1%, C: ≤0.05%, N: ≤0.05%, H: ≤0.01%, and the balance of Ti and inevitable impurities; the reinforcing phase comprises silicon carbide; the silicon carbide comprises pretreated silicon carbide, which is alumina composite silicon carbide; the particle size of alumina in the alumina composite silicon carbide is nanoscale; and the particle size of silicon carbide in the alumina composite silicon carbide is micrometer scale.

2. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 1, characterized by 0.1≤(6Cr-0.7Mn) / (Mo+0.15Cr)≤0.25 in mass percentage.

3. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 1, characterized by The raw material of the alumina composite silicon carbide comprises alumina and silicon carbide in a mass ratio of 1-5:

100.

4. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 1, characterized by The preparation method of the alumina composite silicon carbide comprises the following steps: mixing alumina and silicon carbide, and then performing ball milling to obtain the alumina composite silicon carbide.

5. The high temperature oxidation resistant titanium alloy material for a titanium welded tube according to claim 1, wherein The silicon carbide is titanium carbide composite pretreated silicon carbide.

6. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 5, characterized by The raw material of the titanium carbide composite pretreated silicon carbide comprises alumina, titanium carbide and silicon carbide in a mass ratio of 1-2:3-4:

100.

7. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 6, characterized by The particle size of the titanium carbide is nanoscale.

8. The titanium alloy material for high-temperature oxidation-resistant titanium welded pipes according to claim 7, characterized by The preparation method of the titanium carbide composite pretreated silicon carbide comprises the following steps: mixing alumina and silicon carbide, and then performing ball milling; adding titanium carbide and continuing the ball milling to obtain the titanium carbide composite pretreated silicon carbide.

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