CN109706423B - Biphase boron-titanium composite layer - Google Patents
Biphase boron-titanium composite layer Download PDFInfo
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- CN109706423B CN109706423B CN201811569985.4A CN201811569985A CN109706423B CN 109706423 B CN109706423 B CN 109706423B CN 201811569985 A CN201811569985 A CN 201811569985A CN 109706423 B CN109706423 B CN 109706423B
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Abstract
The invention relates to a two-phase boron-titanium composite layer, which is based on a titanium alloy base material, wherein a prefabricated layer is covered on the surface layer, and the prefabricated layer comprises the following components: can grow into TiBXThe composite layer of (1); the invention not only obviously improves the wear resistance of the titanium alloy and can bear larger load, but also provides reliability for stable application of the lightweight titanium alloy under more severe conditions. The boron-titanium composite layer can be applied to high-temperature and high-speed erosion resistant materials.
Description
Technical Field
The invention relates to the field of wear-resistant infiltrated layers, in particular to a two-phase boron-titanium composite layer.
Background
Titanium alloy is widely applied to the fields of aerospace, chemical engineering, biomedicine and the like due to high specific strength, low density and good biocompatibility, and also becomes one of the first materials for light weight development, but the low hardness, poor wear resistance and rapid degradation performance at high temperature of the titanium alloy are main obstacles for limiting the titanium alloy to obtain more applications in the aspect of light weight.
Due to chemical combination formed by reaction of Ti with BThing TiBXThe titanium alloy has the characteristics of high melting point, high hardness, high strength and the like of ceramic materials, has excellent characteristics of high heat conduction and the like of metal materials, and can obviously improve the surface properties of the titanium alloy, such as wear resistance, high-temperature oxidation resistance and the like, so that the formation of titanium boride on the surface of the titanium alloy becomes one of important ways for improving the performance of the titanium alloy. The titanium alloy in-situ modification can ensure that no obvious interface exists between a surface modification layer and a matrix, specific structural components with complex structures can be processed, the modification layer is metallurgically bonded with the matrix, the bonding force can be obviously improved, in a plurality of modification methods, a boronizing method does not need special equipment, is simple and convenient to operate and easy to popularize, and a boronizing compound layer which is metallurgically bonded in situ can be obtained on the surface of the titanium alloy matrix.
Under the general condition, the boronizing time and the thickness are in a positive correlation relationship, but the higher working temperature and the longer heat preservation time can ensure that the energy consumption of the whole boronizing process is higher, and the tissue is easy to be thick due to long-time heat preservation, so that the thickness and the performance of the composite coating can be limited, and the application of the coating is further limited. If the boron-titanium composite layer with enough thickness can be obtained in a fixed short time at a low temperature, the comprehensive performance can be exerted to the maximum extent.
Disclosure of Invention
The invention aims to provide a two-phase boron-titanium composite layer, which is based on a titanium alloy matrix, wherein the surface layer of the two-phase boron-titanium composite layer is covered with a prefabricated layer, and the prefabricated layer can grow into TiBXThe composite layer of (1).
Wherein the thickness of the two-phase boron-titanium composite layer is not less than 2 μm, and the growth direction is vertical to the surface for ordered growth.
Wherein, the TiBXIs TiB and TiB2。
The biphase boron-titanium composite layer is introduced with a 'prefabricated layer' before the boronizing process, namely, a pure titanium layer with adjustable thickness, a pure titanium and titanium matrix or titanium alloy matrix is prepared in advanceThe thermal expansion coefficients are consistent, the problem of binding force can be avoided, and the solid embedding infiltration process is adopted again to synthesize the TiB required by the pure titanium layerXThe composite layer breaks through the key technologies of easy oxidation of titanium alloy, controllable tissue structure, controllable thickness, optimized growth direction and the like in non-inert atmosphere. The invention aims to provide a method for preparing a wear-resistant boron-titanium compound layer with adjustable thickness and oriented growth by a 'prefabricated layer' + boronizing method.
Specifically, the biphase boron-titanium composite layer is prepared by the following method: a pure titanium layer is deposited on the surface of a titanium alloy substrate in advance, and then a boron-titanium composite layer is grown through a boronizing method.
Wherein the thickness of the pure titanium layer is adjustable from nano-scale, micron-scale to millimeter-scale;
the porosity of the pure titanium layer is 3% -12%.
The method for depositing the pure titanium layer is one or more of a PVD method, a coating method, cold spraying or chemical plating. Preferably, a PVD method is adopted, the pores of the PVD method are combined with the high-temperature diffusion characteristic of active boron atoms during boronization, and the stable dual-phase property of the titanium alloy boronizing layer prepared under the composite condition of the two processes is developed.
The PVD method specifically comprises the following steps: in an argon atmosphere, depositing for 2-6 h on the surface layer of the titanium alloy matrix under the conditions that the titanium target current is gradually reduced from 3-5A to 0.15-0.5A, the carbon target current is gradually increased from 0A to 0.2-0.6A and the argon flow is 20-40 sccm, so as to obtain the titanium alloy matrix deposited with the pure titanium layer.
In order to avoid the influence of other impurities and factors, the titanium alloy substrate needs to be deeply cleaned in advance; the deep cleaning comprises oil removal, surface polishing, ultrasonic cleaning and plasma cleaning;
preferably, the deep cleaning is specifically as follows:
1) mixing a metal cleaner with water to prepare a solution with the concentration of 3-10%, heating to 55-60 ℃, immersing the titanium alloy substrate into the metal cleaner solution, and soaking for degreasing for 1-2 hours;
2) sequentially grinding the titanium alloy substrate by using water grinding sand paper of 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000 #;
3) ultrasonically cleaning the titanium alloy matrix for 30-60 min by using acetone as a cleaning agent, and then ultrasonically cleaning for 30-60 min by using deionized water;
4) and (3) placing the titanium alloy substrate in a PVD device, vacuumizing until the vacuum degree is 2-20 Pa, and then cleaning for 3-10 min by using plasma.
Optionally, the boronizing method specifically comprises the following steps: and (3) burying the boronizing agent on the surface of the titanium alloy matrix deposited with the pure titanium layer, and then keeping the temperature at 900-990 ℃ for 2-20 h.
Preferably, the boronizing agent is a boron supply agent and a penetration enhancer in a mass ratio of (90-98) to (10-2);
more preferably, the particle size of the boronizing agent is no greater than 50 μm.
The invention provides a preferable scheme, the two-phase boron-titanium composite layer is based on a titanium alloy base material, a prefabricated layer is covered on the surface layer, and the prefabricated layer can grow into TiBXThe composite layer of (1);
the two-phase boron-titanium composite layer is prepared by adopting the following method:
1) deeply cleaning a titanium alloy matrix, wherein the deep cleaning comprises oil removal, surface polishing, ultrasonic cleaning and plasma cleaning;
2) depositing a pure titanium layer on the titanium alloy substrate by adopting a PVD method;
3) and then burying the boronizing agent on the surface of the titanium alloy matrix deposited with the pure titanium layer, and then placing the titanium alloy matrix at the temperature of 900-990 ℃ for heat preservation for 2-20 hours to grow and obtain the boron-titanium composite layer.
The boron-titanium composite layer obtained by the preparation method can effectively control the thickness and the growth direction. The invention not only obviously improves the wear resistance of the titanium alloy and can bear larger load, but also provides reliability for stable application of the lightweight titanium alloy under more severe conditions. The boron-titanium composite layer can be applied to high-temperature and high-speed erosion resistant materials.
Preferably materials for aerospace, weaponry, oil exploration and the like.
Compared with the prior art, the method has at least the following beneficial effects:
1) the deposited pure titanium layer has certain porosity, can provide a diffusion channel for active boron atoms, can improve the deposition quality of pure titanium, and TiB formed by subsequent boronizing treatmentXThe layers have a "pinning" effect.
2) The invention can break through the defects of thin thickness, low efficiency, high energy consumption and the like of the existing solid boronizing, the boronizing thickness can be realized by adjusting the thickness of the prefabricated layer, and the thickness of the prefabricated layer can be continuously adjusted from nanometer to micron.
3) Because the 'prefabricated layer' contains micropores, a stable two-phase boride layer can be obtained at any subsequent boronizing temperature (900-990 ℃) and any heat preservation time (2-20 hours), and the subsequently grown TiB can be obtained due to the limitation of the microporesXThe layer has a characteristic of directional growth.
Drawings
FIG. 1 is a schematic representation of a boron-titanium composite layer made in comparative example 1 (without the addition of a pre-fabricated layer);
FIG. 2 is a cross-sectional profile of the boron-titanium composite layer prepared in example 1;
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The titanium alloy test piece used in the following examples was TC4 having dimensions of 20 mm. times.20 mm. times.10 mm.
Example 1
The embodiment provides a two-phase boron-titanium composite layer, which is prepared by the following steps:
step one) surface treatment of titanium alloy substrate
1) Oil removal: mixing a metal cleaner with water to prepare a solution with the concentration of 5%, heating to 58 ℃, immersing the titanium alloy substrate into the metal cleaner solution, and soaking for degreasing for 1.5 hours;
2) surface grinding: sequentially grinding the surface of the titanium alloy matrix after washing by using water grinding sand paper of 400#, 600#, 800#, 1000#, 1200#, 1500# and 2000 #;
3) ultrasonic cleaning: firstly, cleaning a titanium alloy substrate with a polished surface for 40 minutes at room temperature by using acetone as a cleaning agent and an ultrasonic cleaning machine; then, deionized water is used as a cleaning agent, and ultrasonic cleaning is carried out for 40 minutes;
4) plasma cleaning: and (3) placing the titanium alloy substrate in a PVD device, vacuumizing until the vacuum degree is 2-20 Pa, and then cleaning for 3-10 min by using plasma.
Step two) preparing a pure titanium layer by a PVD method
1) Placing a titanium alloy substrate on a rotary worktable, placing a carbon target and a titanium target on the periphery of the rotary worktable, pre-vacuumizing a cavity, and introducing argon;
2) the titanium target current is gradually reduced to 0.2A from 4A, the carbon target current is gradually increased to 0.5A from 0A, the argon flow is 30sccm, the deposition time is 5h, and a pure titanium bottom layer is deposited;
step three) preparation of boronizing agent
And (3) preparing the boron donor with the purity of 95-99% and the catalytic agent according to mass percent, and uniformly mixing to ensure that the granularity of the mixture powder is less than 50 mu m.
Step four) boriding treatment
Placing the titanium alloy matrix with the pure titanium layer deposited on the surface in the second step) into a corundum crucible, and burying the corundum crucible by using the boronizing agent prefabricated in the third step); then the crucible is sealed, placed in a high temperature furnace, heated to 960 ℃, kept for 15h, and then taken out for air cooling to room temperature.
The boronized TC4 sample is detected by a Scanning Electron Microscope (SEM), the thickness of a penetration layer is 45-60 mu m, and the penetration layer is composed of two-phase TiB and TiB2The boronized layer is compact and well wedged with the matrix, and the growth direction is vertical to the matrix.
The thickness of the biphase boron-titanium composite layer is 55um, and the outer surface layer of the sample is TiB2The phase and inner layer whisker-shaped tissues are TiB phases, and the growth direction is vertical to the matrix.
As shown in FIG. 2, the boron-titanium composite layer prepared in this example has a thick penetration and a directional growth.
Example 2
This embodiment provides a dual-phase boron-titanium composite layer, which is only specific to embodiment 1:
step four) "heating to 960 ℃ and replacing with" heating to 980 ℃.
And (3) detecting the boronized TC4 sample by a Scanning Electron Microscope (SEM), wherein the thickness of a boronized layer is 50-65 um, the boronized layer on the surface layer of the sample is compact and well wedged with the matrix, and the growth direction of the boronized layer is vertical to the matrix.
Example 3
This embodiment provides a dual-phase boron-titanium composite layer, which is only specific to embodiment 1:
depositing a pure titanium layer by replacing a PVD method with cold spraying;
the method specifically comprises the following steps: the process conditions of cold spraying the pure titanium prefabricated layer are as follows: nitrogen pressure (40-60 bar), flow (80-95 cubic meters per minute), temperature (950-1100 ℃, powder delivery amount (50-70 g/min), carrier gas pressure (5-20 bar), carrier gas flow (1-9 cubic meters per minute) and spraying distance (15-35 mm).
And (3) detecting the boronized TC4 sample by a Scanning Electron Microscope (SEM), wherein the thickness of a boronized layer is 60-80 um, the boronized layer on the surface layer of the sample is compact and well wedged with the matrix, and the growth direction of the sample is mostly vertical to the matrix.
Example 4
This embodiment provides a dual-phase boron-titanium composite layer, which is only specific to embodiment 1:
the deposition time of the prefabricated layer in step 3 is 4 h.
And (3) detecting the boronized TC4 sample by a Scanning Electron Microscope (SEM), wherein the thickness of a boronized layer is 25-35 um, the boronized layer on the surface layer of the sample is compact and well wedged with the matrix, and the growth direction of the sample is mostly vertical to the matrix. Comparative example 1
The present comparative example provides a method for preparing a two-phase boron-titanium composite layer, which is different from example 1 in that: no prefabricated layer is added. (i.e., less pure titanium layer)
As shown in FIG. 1, the boron-titanium composite layer without the prefabricated layer (i.e. depositing pure titanium layer) has thin diffusion layer and disordered growth direction.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. The double-phase boron-titanium composite layer is characterized in that a titanium alloy matrix is taken as a base, a prefabricated layer is covered on the surface layer, and the prefabricated layer can be grown into TiBXThe composite layer of (1); the thickness of the two-phase boron-titanium composite layer is not less than 2 mu m, and the growth direction is vertical to the surface for orderly growth;
the two-phase boron-titanium composite layer is prepared by the following method: depositing a pure titanium layer on the surface of a titanium alloy substrate in advance, and then growing to obtain a boron-titanium composite layer by a boronizing method; the porosity of the pure titanium layer is 3% -12%;
the method for depositing the pure titanium layer is a PVD method; the PVD method specifically comprises the following steps: in an argon atmosphere, depositing for 2-6 h on the surface layer of the titanium alloy matrix under the conditions that the titanium target current is gradually reduced from 3-5A to 0.15-0.5A, the carbon target current is gradually increased from 0A to 0.2-0.6A and the argon flow is 20-40 sccm, so as to obtain the titanium alloy matrix deposited with the pure titanium layer.
2. The dual phase boron-titanium composite layer of claim 1, wherein said TiBXIs TiB and TiB2。
3. The two-phase boron-titanium composite layer according to claim 1, wherein said titanium alloy matrix is previously subjected to a deep cleaning comprising degreasing, surface grinding, ultrasonic cleaning, plasma cleaning.
4. The dual-phase boron-titanium composite layer according to claim 1, wherein the boronizing agent is embedded in the surface of the titanium alloy substrate deposited with the pure titanium layer, and then the titanium alloy substrate is placed at 900-990 ℃ for heat preservation for 2-20 hours.
5. The dual-phase boron-titanium composite layer of claim 4, wherein the boronizing agent is a boron donor and an accelerant in a mass ratio of (90-98) to (10-2).
6. The dual phase boron-titanium composite layer of claim 5, wherein the particle size of the boronizing agent is not greater than 50 μm.
7. The dual-phase boron-titanium composite layer of claim 1, wherein the titanium alloy substrate is coated with a pre-fabricated layer that can be grown to TiBXThe composite layer of (1);
the two-phase boron-titanium composite layer is prepared by adopting the following method:
1) deeply cleaning a titanium alloy matrix, wherein the deep cleaning comprises oil removal, surface polishing, ultrasonic cleaning and plasma cleaning;
2) depositing a pure titanium layer on the titanium alloy substrate by adopting a PVD method;
3) and then burying the boronizing agent on the surface of the titanium alloy matrix deposited with the pure titanium layer, and then placing the titanium alloy matrix at the temperature of 900-990 ℃ for heat preservation for 2-20 hours to grow and obtain the boron-titanium composite layer.
8. Use of the two-phase boron-titanium composite layer according to any one of claims 1 to 7 in a high temperature and high speed erosion resistant material.
9. Use of the dual phase boron-titanium composite layer according to any one of claims 1 to 7 in aerospace, weaponry, and oil exploration materials.
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| CN104233180B (en) * | 2014-08-04 | 2016-07-27 | 东北大学 | A kind of method obtaining boride diffusion layer at titanium alloy surface |
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