Preparation method of fiber reinforced titanium matrix composite with adjustable matrix structure

Abstract

The application discloses a preparation method of a fiber reinforced titanium matrix composite material with adjustable matrix structure, and comprises the following steps: S1, winding SiC fibers with a protective coating on a rotating wheel of a magnetron sputtering device, and placing TC4 and TC17 titanium alloy targets on the inner and outer sides of the SiC fibers; S2, introducing pure argon and argon / oxygen mixed gas into the sputtering chamber, starting all the targets to perform sputtering deposition when the pressure in the sputtering chamber reaches 0.5-2 Pa, and stopping the argon / oxygen mixed gas when the deposition thickness reaches 2-5 microns; S3, continuously introducing pure argon, and again depositing 2-10 microns thick; S4, repeating S2 and S3 until the titanium alloy deposition layer thickness reaches 20-45 microns, stopping, taking out the titanium alloy precursor wire, cutting the wire into bundles, and then performing hot isostatic pressing forming on the sealed blank. The preparation method can obtain titanium matrix composite materials with equiaxed structure, lamellar structure and bimodal structure matrix, and can realize the strengthening effect.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a titanium-based composite material, in particular to a preparation method of a fiber-reinforced titanium-based composite material with adjustable matrix structure, and belongs to the field of metal matrix composite material preparation. BACKGROUND

[0002] Continuous SiC fiber-reinforced titanium matrix (SiC f / Ti) composite material has the advantages of low density, high specific strength and specific stiffness, high temperature resistance, creep resistance and fatigue resistance, and has important application prospects in the field of aerospace, such as aero-engine turbine shaft and integral blade ring.

[0003] At present, SiC f / Ti composite materials are mainly prepared by foil pressing method and fiber coating method. The foil pressing method is to alternately place SiC fibers and titanium alloy foils in a desired thickness, and then to form a value by hot pressing. The foil pressing method is suitable for forming plate-shaped composite material components, but the fibers often move during hot pressing, which is easy to produce defects. The fiber coating method is to first deposit a layer of titanium alloy coating on the SiC fiber by magnetron sputtering to prepare a composite precursor, and then to densify and form the precursor by hot isostatic pressing. The fiber coating method is more widely used because the fiber arrangement form in the composite material structure is easy to control and the fiber structure defect is less. It is suitable for forming shaft and ring components.

[0004] It should be emphasized that the titanium alloy matrix structure can have an important influence on the mechanical properties of SiC f / Ti composite material. Conventional titanium alloy materials have different properties with different structures, such as equiaxed structure, lamellar structure and duplex structure. The equiaxed structure can be obtained by hot working in the (alpha + beta) phase region, and the alloy has good plasticity and strength matching. The lamellar structure can be obtained by hot working in the beta phase region, and the alloy has high fracture toughness and strong crack propagation resistance, which is suitable for scenes requiring high damage tolerance.

[0005] According to different application requirements, the same titanium alloy can obtain different structures by adjusting the hot working process and heat treatment process. SiC f / Ti composite material is formed by hot pressing or hot isostatic pressing, and the forming temperature needs to consider the deformation capacity of the titanium alloy matrix and the interface reaction degree. The forming temperature control range is extremely limited, and the deformation amount in the composite material forming is also small. Therefore, the preparation of SiC f / Ti composite material faces two problems. First, the regulation of the titanium alloy matrix structure is very difficult. A titanium alloy matrix can usually only obtain one structure, which cannot meet the diversified application scenarios of the material. Second, the strength of the titanium alloy matrix is insufficient, and the existing strengthening methods will affect the plasticity of the material. SUMMARY

[0006] In view of the problems of the prior art, the present application aims to provide a preparation method of fiber-reinforced titanium matrix composite with adjustable matrix structure, so as to solve the problems of difficulty in regulating the matrix structure, single structure, inability to meet different application scenarios such as high plasticity and high damage tolerance, and lack of suitable strengthening methods during the preparation of the composite.

[0007] To achieve the above object, the technical scheme adopted by the present application is:

[0008] The preparation method of the fiber-reinforced titanium matrix composite with adjustable matrix structure comprises the following steps:

[0009] S1: winding SiC fibers with a protective coating onto the rotating wheel of a magnetron sputtering device, placing one or more pairs of (α+β) type titanium alloy target materials on the inner and outer sides of the SiC fibers in parallel, and vacuumizing the magnetron sputtering device to a pressure lower than 1x10 ~ 3 Pa;

[0010] S2: introducing pure argon gas and argon / oxygen mixed gas into the sputtering chamber, adjusting the oxygen partial pressure to argon partial pressure ratio to the range of 0.002~0.02, and starting all the target materials for sputtering deposition when the pressure in the sputtering chamber reaches 0.5~2Pa, and closing the argon / oxygen mixed gas when the deposition thickness reaches 2~5μm;

[0011] S3: continuing to introduce pure argon gas, completely discharging the argon / oxygen mixed gas, and maintaining the pressure in the sputtering chamber within the range of 0.5~2Pa, and continuing to perform sputtering deposition, and again depositing a thickness of 2~10μm;

[0012] S4: repeatedly repeating S2 and S3 until the titanium alloy deposition layer thickness reaches 20-45 μm, stopping all target sputtering, and cooling under a pure argon protective atmosphere, when the sputtering chamber temperature is lower than 100℃, taking out the titanium alloy precursor wire and cutting into bundles, placing the prepared titanium alloy precursor wire into a titanium alloy sheath, vacuum sealing, and then hot isostatic pressing the sealed blank; when the deposition thickness ratio of step S2 and step S3 is 0.2-0.4, the oxygen partial pressure to argon partial pressure ratio of step S2 is in the range of 0.002-0.006, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a lamellar structure; when the deposition thickness ratio of step S2 and step S3 is 0.5-1.1, the oxygen partial pressure to argon partial pressure ratio of step S2 is in the range of 0.007-0.01, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a duplex structure; when the deposition thickness ratio of step S2 and step S3 is 1.2-1.5, the oxygen partial pressure to argon partial pressure ratio of step S2 is in the range of 0.011-0.02, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is an equiaxed structure.

[0013] Preferably, the (α+β) type titanium alloy in step S1 is TC4 titanium alloy or TC17 titanium alloy.

[0014] Preferably, the volume fraction of oxygen in the argon / oxygen mixed gas in step S2 is 0.5%-5%.

[0015] Preferably, the sputtering temperature in steps S2 and S3 is 450-550℃, and the sputtering bias is -350--750V.

[0016] The beneficial effects of the preparation method of the application are:

[0017] (1) For the same titanium alloy matrix, the application can obtain titanium matrix composites with equiaxed structure, lamellar structure and duplex structure matrix, different structures correspond to different mechanical properties, which expands the application range of SiC f / Ti composite materials.

[0018] (2) The application uniformly adds a small amount of oxygen element to the titanium alloy matrix, which can achieve strengthening effect and basically does not damage the plasticity of the composite material, and improves the mechanical properties of SiC f / Ti composite materials. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The scanning electron microscope image of the SiC f / Ti composite material prepared in Example 1 of the application;

[0020] Figure 2 The scanning electron microscope image of the SiC fScanning electron microscope image of titanium alloy substrate in / Ti composite material;

[0021] Figure 3 SiC prepared for example 2 of the present application f Scanning electron microscope image of / Ti composite material;

[0022] Figure 4 SiC prepared for example 2 of the present application f Scanning electron microscope image of titanium alloy substrate in / Ti composite material.

[0023] Figure 5 SiC prepared for example 3 of the present application f Scanning electron microscope image of / Ti composite material;

[0024] Figure 6 SiC prepared for example 3 of the present application f Scanning electron microscope image of titanium alloy substrate in / Ti composite material. DETAILED DESCRIPTION

[0025] The application will be further described in detail below with reference to the accompanying drawings. EMBODIMENT

[0026] A method for preparing a fiber-reinforced titanium-based composite material with adjustable substrate structure, in which a precursor wire of the composite material with different oxygen contents is prepared by magnetron sputtering under an alternating atmosphere of argon / oxygen mixed gas and pure argon, and the precursor wire is formed into a continuous SiC fiber-reinforced titanium-based composite material by hot isostatic pressing, and the method specifically comprises the following steps:

[0027] S1: winding SiC fibers with a protective coating onto a rotating wheel of a magnetron sputtering device, and placing one or more pairs of TC17 type titanium alloy targets parallel on the inner and outer sides of the SiC fibers, and vacuumizing the magnetron sputtering device to a pressure lower than 1x10 ~3 Pa;

[0028] S2: introducing pure argon and argon / oxygen mixed gas into the sputtering chamber, wherein the oxygen in the argon / oxygen mixed gas accounts for 2.5% by volume, and as a preferred scheme in this embodiment, the ratio of oxygen partial pressure to argon partial pressure is adjusted to 0.012, and when the pressure in the sputtering chamber reaches 0.5~2 Pa, all the targets are turned on for sputtering deposition, and when the deposition thickness reaches 7 μm, the argon / oxygen mixed gas is turned off;

[0029] S3: continuing to introduce pure argon, completely discharging the argon / oxygen mixed gas, and maintaining the pressure in the sputtering chamber within the range of 0.5~2 Pa, and continuing the sputtering deposition, and again depositing a thickness of 5 μm, and the sputtering temperature in S2 and S3 is 450~550 ℃, and the sputtering bias is ~350~~750 V;

[0030] S4: repeat S2 and S3 until the titanium alloy deposition layer thickness reaches 24 μm, stop all target sputtering, and cool under a pure argon protective atmosphere; when the sputtering chamber temperature is lower than 100℃, take out the titanium alloy precursor wire and cut it into a bundle, place the prepared titanium alloy precursor wire into a titanium alloy sheath, vacuum seal, and then perform hot isostatic pressing forming on the sealed blank. Figure 1 and 2 As shown, the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is an equiaxed structure, and the content of the α phase is about 60%.

[0031] The ratio of the deposition thicknesses of step S2 and step S3 is about 1.4, and the oxygen content of the titanium alloy matrix of the obtained SiC / Ti composite material in this embodiment is 0.36% (wt. %) by using an oxygen-nitrogen-hydrogen analyzer. f In order to obtain an equiaxed titanium alloy matrix, the deposition thicknesses of S2 and S3 are 7 μm and 5 μm, respectively, which is mainly considered from the amount of oxygen absorbed by the structure. If the oxygen content in S2 is too low, the oxygen-containing structure content is low, which will lead to insufficient strength of the titanium alloy matrix, and if the oxygen content in S2 is too high, the plasticity of the material itself will be reduced. At the same time, the appropriate oxygen content adjusts the structure of the alloy and also improves the strength of the alloy matrix. Although the oxygen partial pressure is different during the deposition of S2 and S3, the oxygen element in the matrix effectively diffuses and uniformly distributes during the hot isostatic pressing process. Embodiment

[0032] A method for preparing a fiber reinforced titanium matrix composite material with adjustable matrix structure, which comprises the following steps:

[0033] Step S1: wind SiC fibers with a protective coating on a rotating wheel of a magnetron sputtering device, and place one or more pairs of TC4 type titanium alloy targets on the inner and outer sides of the SiC fibers in parallel, and vacuumize the magnetron sputtering device to a pressure lower than 1x10 -3 Pa;

[0034] Step S2: introduce pure argon and argon / oxygen mixture into the sputtering chamber, the oxygen content in the argon / oxygen mixture is 1%, and the ratio of oxygen partial pressure to argon partial pressure is adjusted to the range of 0.005; when the pressure in the sputtering chamber reaches 0.5~2 Pa, start all the targets for sputtering deposition; when the deposition thickness reaches 2 μm, stop the argon / oxygen mixture;

[0035] Step S3: continue to pass pure argon, completely discharge the argon / oxygen mixed gas, and maintain the pressure in the sputtering chamber at 0.5-2 Pa, continue to perform sputtering deposition, and again deposit 6 μm in thickness, the sputtering temperature of S2 and S3 is 450-550 °C, and the sputtering bias is -350 ~ -750 V;

[0036] Step S4: repeatedly repeat S2 and S3 until the titanium alloy deposition layer thickness reaches 24 μm, stop all target sputtering, and cool under a pure argon protective atmosphere, when the sputtering chamber temperature is lower than 100 °C, take out the titanium alloy precursor wire and cut it into a bundle, place the prepared titanium alloy precursor wire into a titanium alloy sheath, vacuum seal, and then perform hot isostatic pressing forming on the sealed blank. As shown in Figure 3 and 4 The titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a lamellar structure, and the α phase content is about 53%.

[0037] The ratio of the deposition thickness of step S2 to step S3 is about 0.33, and the oxygen, nitrogen and hydrogen analyzer is used to obtain the oxygen content of the titanium alloy matrix of the obtained SiC f / Ti composite material in this embodiment is 0.11% (wt%). In this embodiment, the deposition thickness of S2 and S3 is 2 μm and 6 μm respectively, and the selection of this deposition thickness ratio can obtain a lamellar structure of the titanium alloy matrix. By controlling the partial pressure of pure argon and argon / oxygen mixed gas and the ratio of the deposition thickness to control the oxygen intake of the structure, the entire structure is a single lamellar structure. Embodiment

[0038] A method for preparing a fiber reinforced titanium matrix composite material with adjustable matrix structure, in which different oxygen content composite precursor wires are prepared by magnetron sputtering under the alternating atmosphere of argon / oxygen mixed gas and pure argon, and the precursor wires are formed into continuous SiC fiber reinforced titanium matrix composite materials by hot isostatic pressing, which specifically includes the following steps:

[0039] Step S1: wind the SiC fiber with a protective coating onto the rotating wheel of the magnetron sputtering device, and place one or more pairs of TC17 type titanium alloy targets on the inner and outer sides of the SiC fiber in parallel, and vacuumize the magnetron sputtering device to a pressure lower than 1´10 -3 Pa;

[0040] Step S2: pass pure argon and argon / oxygen mixed gas into the sputtering chamber, the oxygen volume percentage in the argon / oxygen mixed gas is 2%, adjust the oxygen partial pressure to argon partial pressure ratio to 0.008, when the pressure in the sputtering chamber reaches 0.5-2 Pa, start all the targets for sputtering deposition, and when the deposition thickness reaches 6 μm, stop the argon / oxygen mixed gas;

[0041] Step S3: continue to pass pure argon, completely discharge the argon / oxygen mixed gas, and maintain the pressure in the sputtering chamber at 0.5-2 Pa, continue to perform sputtering deposition, and again deposit 7 μm in thickness, the sputtering temperature of S2 and S3 is 450-550 ℃, and the sputtering bias is -350--750 V;

[0042] Step S4: repeatedly repeat S2 and S3 until the titanium alloy deposition layer thickness reaches 26 μm, stop all target sputtering, and cool under a pure argon protective atmosphere, when the sputtering chamber temperature is lower than 100 ℃, take out the titanium alloy precursor wire and cut it into a bundle, place the prepared titanium alloy precursor wire into a titanium alloy sheath, vacuum seal, and then perform hot isostatic pressing forming on the sealed blank. As shown in Figure 5 and 6 The titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a bimodal structure, and the α phase content is about 57%.

[0043] The ratio of the deposition thickness of step S2 to step S3 is about 0.86, and the oxygen content of the titanium alloy matrix of the obtained SiC f / Ti composite material in this embodiment is 0.24% (wt%). In this embodiment, the deposition thickness of S2 and S3 is 6 μm and 7 μm respectively, and the ratio of oxygen partial pressure to argon partial pressure is 0.008. This deposition thickness and oxygen partial pressure can obtain a bimodal structure of the titanium alloy matrix, as shown in Figure 5 , 6 .

[0044] The present application limits the flow of pure argon and argon / oxygen mixed gas in the sputtering chamber, controls the deposition thickness of steps S2 and S3, thereby limits the amount of oxygen elements dissolved in the titanium alloy matrix, and achieves the function of controlling the structure. When the ratio of the deposition thickness of step S2 to step S3 is 0.2-0.4, the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a lamellar structure, the alloy has higher fracture toughness and stronger crack propagation resistance; when the ratio of the deposition thickness of step S2 to step S3 is 0.5-1.1, the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a bimodal structure; when the ratio of the deposition thickness of step S2 to step S3 is 1.2-1.5, the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is an equiaxed structure, and the alloy has good plasticity and strength matching. At the same time, unlike the traditional method of strengthening the titanium alloy by adding oxides, the present application directly dissolves a small amount of oxygen elements to strengthen the matrix without forming oxides, which reduces the influence of oxides on the uniformity of the matrix composition, further simplifies the preparation process, and achieves more excellent results.

Claims

1. A method for producing a fiber-reinforced titanium matrix composite material with adjustable matrix structure, characterized by The application discloses a method for preparing a continuous SiC fiber reinforced titanium matrix composite material. S1: winding SiC fiber with protective coating onto the rotating wheel of a magnetron sputtering device, one or more pairs of (α+β) type titanium alloy target materials are placed parallel on the inner and outer sides of the SiC fiber, the magnetron sputtering device is vacuumed to a pressure lower than 1x10 ~3 Pa; S2: pure argon gas and argon / oxygen mixed gas are introduced into a sputtering chamber, and the oxygen partial pressure to argon partial pressure ratio is adjusted to be in a range of 0.002-0.02; when the pressure in the sputtering chamber reaches 0.5-2 Pa, all the target materials are started to perform sputtering deposition; when the deposition thickness reaches 2-5 microns, the argon / oxygen mixed gas is turned off; S3: pure argon gas is continuously introduced, the argon / oxygen mixed gas is completely discharged, and the pressure in the sputtering chamber is maintained in a range of 0.5-2 Pa, and the sputtering deposition is continuously performed, and the thickness of the second deposition is 2-10 microns; S4: S2 and S3 are repeatedly repeated until the titanium alloy deposition layer thickness reaches 20-45 microns, the sputtering of all the target materials is stopped, and cooling is performed under a pure argon gas protection atmosphere; when the temperature of the sputtering chamber is lower than 100 DEG C, the titanium alloy precursor wire is taken out and cut into bundles, the prepared titanium alloy precursor wire is placed into a titanium alloy sheath, vacuum sealing is performed, and hot isostatic pressing is performed on the sealed blank; when the deposition thickness ratio of step S2 to step S3 is 0.2-0.4, the oxygen partial pressure to argon partial pressure ratio of step S2 is in a range of 0.002-0.006, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a lamellar structure; when the deposition thickness ratio of step S2 to step S3 is 0.5-1.1, the oxygen partial pressure to argon partial pressure ratio of step S2 is in a range of 0.007-0.01, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is a dual-state structure; when the deposition thickness ratio of step S2 to step S3 is 1.2-1.5, the oxygen partial pressure to argon partial pressure ratio of step S2 is in a range of 0.011-0.02, and the titanium alloy matrix of the obtained continuous SiC fiber reinforced titanium matrix composite material is an equiaxed structure.

2. The method of claim 1, wherein the fiber reinforced titanium matrix composite material having a controllable microstructure is prepared by the steps of: In step S1, the (alpha+beta) type titanium alloy is TC4 titanium alloy or TC17 titanium alloy.

3. The method for preparing a fiber-reinforced titanium matrix composite material with adjustable matrix structure according to claim 1, characterized in that, In step S2, the oxygen accounts for 0.5%-5% of the volume fraction in the argon / oxygen mixed gas.

4. The method of claim 1, wherein the fiber reinforced titanium matrix composite material having a controllable microstructure is prepared by the steps of: In steps S2 and S3, the sputtering temperature is 450-550 DEG C, and the sputtering bias voltage is-350--750 V.

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