CN115652267A - Preparation method of TiCrAlNbSi alloy high-temperature oxidation resistant coating - Google Patents
Preparation method of TiCrAlNbSi alloy high-temperature oxidation resistant coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating, which relates to the technical field of high-temperature oxidation resistance of metal materials, and the technical scheme is as follows: selecting a substrate; polishing the substrate by using abrasive paper; for the polished substrate, al is adopted 2 O 3 Polishing the solution until the surface is bright; then, respectively ultrasonically cleaning the mixture in acetone, absolute ethyl alcohol and deionized water in sequence, and finally drying the mixture by using nitrogen; putting the dried substrate into a sputtering chamber of a high-vacuum magnetron sputtering instrument; and respectively carrying out TiCrAlNbSi alloy coating deposition on the substrate subjected to sputtering air pressure fixation under different Si target radio frequency power supplies to prepare the TiCrAlNbSi alloy high-temperature oxidation resistant coating with optimal oxidation resistance. Has the effects of preventing the oxidation of oxygen on the substrate and minimizing the oxidation weight gain in a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of high-temperature oxidation resistance of metal materials, in particular to a preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating.
Background
Titanium alloy represented by TC4 is a key material for aerospace, is frequently applied to hot end parts of power systems of airplanes and spacecrafts, has a typical working condition of a medium-high temperature environment, and has a high-temperature oxidation resistance as a key index for safety of the hot end parts due to the oxophilicity of the titanium alloy. In order to prolong the service life of the titanium alloy part in a high-temperature environment, a necessary means is to prepare a thermal barrier coating with higher temperature resistance on the part. The traditional development of thermal barrier coatings aiming at titanium alloys tends to adopt simple components added with a small amount of other high-temperature resistant elements or composite coatings and the like, and the purposes are cost and controllability except for technical reasons, the improvement of the performance of the high-temperature resistant materials basically reaches the bottleneck, however, the service life of aviation hot-end parts in China has a huge gap compared with the international advanced level, and the gap is one of important technical pain points in related fields in China.
In recent years, china breaks through the new material system in the aspect of research, so that the preparation of the coating with complex components is mature gradually, the coating material can inhibit the diffusion of oxygen elements in the coating by utilizing the effects of high entropy, delayed diffusion and the like of the material based on the component control and preparation optimization of a five-element system, and inhibit the displacement of the oxygen elements and the atoms of the coating components by utilizing the combination space occupying effect among the elements, thereby improving the high-temperature oxidation resistance effect of the coating.
Disclosure of Invention
The invention aims to provide a preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating, which adopts a high vacuum magnetron sputtering instrument (Kurt J. Lesker Labline) to prepare the TiCrAlNbSi alloy coating, wherein a substrate is a Ti6Al4V titanium alloy sheet (30 mm multiplied by 1 mm), and a TiCrAlNb alloy target (direct current power supply) and a Si target (radio frequency power supply) are co-sputtered to prepare the TiCrAlNbSi alloy coating.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating comprises the following steps:
s1: selecting a substrate; selecting a titanium alloy sheet with the specification of 30mm multiplied by 1mm as a substrate;
s2: polishing; sequentially using 500#, 1000#, 1500#, 2000#, 3000# and 5000# sandpaper to polish the substrate;
s3: cleaning; for the base plate polished in the step S2, al with 0.1-0.5 μm is adopted 2 O 3 Polishing the solution until the surface is bright; then ultrasonic cleaning is carried out in acetone, absolute ethyl alcohol and deionized water respectively for 10-20min in sequence, and finally nitrogen is used for blow drying;
s4: sputtering air pressure is fixed; putting the substrate dried in the step S3 into a vacuum degree of 5 multiplied by 10 at the background -8 Sputtering chamber of Torr high vacuum magnetron sputtering apparatusThe jet pressure is fixed to be 3mTorr, the power of a TiCrAlNb alloy target power supply is 80W, and the sputtering temperature is room temperature;
s5: depositing a coating; and respectively depositing the TiCrAlNbSi alloy coating on the substrate subjected to sputtering air pressure fixation for 2 hours under the condition that the power of a Si target radio-frequency power supply is 30W, 40W and 50W, so as to obtain the TiCrAlNbSi alloy high-temperature oxidation resistant coating.
The invention is further configured to: in the step S4, the sputtering working gas during sputtering is high-purity argon gas, and the purity of the argon gas reaches 99.99%.
In conclusion, the invention has the following beneficial effects:
1. the optimal and stable oxidation resistance performance taking the oxidation rate increase as a measurement index can be obtained through the control of the co-sputtering power combined process.
2. The obtained coating with the novel component of the amorphous structure and the crystal structure of the TiCrAlNbSi can play a role in physical isolation and heat shielding on TC 4.
3. The overall oxidation resistance of the material after sputtering coating is obviously improved in a high-temperature environment of 600 ℃.
Drawings
FIG. 1 is an XRD diffraction pattern of a TiCrAlNbSi (80W + 50W) high-entropy alloy coating in an embodiment of the invention;
FIG. 2 is SEM representation of the surface morphology of the TiCrAlNbSi alloy coating at the sputtering power of 80W+30W in the embodiment of the invention;
FIG. 3 is an SEM representation of the surface morphology of a TiCrAlNbSi alloy coating at the sputtering power of 80W+40W in the embodiment of the invention;
FIG. 4 is SEM representation of the surface morphology of the coating of the TiCrAlNbSi alloy at the sputtering power of 80W +50W in the embodiment of the invention;
FIG. 5 is a graph showing the oxidation kinetics of TiCrAlNbSi high-entropy alloy coatings prepared at different powers according to the example of the present invention;
FIG. 6 is an SEM representation of the surface morphology of a TiCrAlNbSi alloy film after heat treatment at a sputtering power of 80W +30W in the embodiment of the invention;
FIG. 7 is an SEM representation of the surface morphology of an 80W +40WTiCrAlNbSi alloy film after heat treatment of the sputtering power in the embodiment of the invention;
FIG. 8 is an SEM representation of the surface morphology of a TiCrAlNbSi alloy film after heat treatment at the sputtering power of 80W +50W in the embodiment of the invention;
FIG. 9 is an XRD diffraction pattern of the TiCrAlNbSi high-entropy alloy coating after heat treatment in the embodiment of the invention.
Detailed Description
The present invention is described in further detail below with reference to FIGS. 1-9.
The embodiment is as follows: a preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating is disclosed, and shown in figures 1-9, a high-vacuum magnetron sputtering instrument (Kurt J. Lesker Labline) is adopted to prepare the TiCrAlNbSi alloy coating, a substrate is a Ti6Al4V titanium alloy sheet (30 mm multiplied by 1 mm), a TiCrAlNb alloy target (direct current power supply) and a Si target (radio frequency power supply) are adopted to carry out co-sputtering, and the working gas during sputtering is high-purity argon (99.99%).
Selecting a titanium alloy sheet with the specification of 30mm multiplied by 1mm as a substrate; sequentially using 500#, 1000#, 1500#, 2000#, 3000# and 5000# sandpaper to polish the substrate; after polishing until no scratch is visible, al with 0.1-0.5 μm is adopted 2 O 3 Polishing the solution until the surface is bright; then ultrasonic cleaning is carried out in acetone, absolute ethyl alcohol and deionized water respectively for 10-20min in sequence, and finally nitrogen is used for blow drying; placing the blow-dried substrate in a vacuum degree of 5 × 10 -8 In a sputtering chamber of a high-vacuum magnetron sputtering instrument of Torr, the sputtering pressure is fixed to be 3mTorr, the power of a TiCrAlNb alloy target power supply is 80W, and the sputtering temperature is room temperature; and respectively carrying out the deposition of the TiCrAlNbSi alloy coating for 2 hours under the condition that the power of a Si target radio frequency power supply is 30W, 40W and 50W to prepare the TiCrAlNbSi alloy high-temperature oxidation resistant coating, wherein the coating thickness is over 800nm.
The coating surface micro-morphology is characterized by using a field emission scanning electron microscope (FESEM, hitachi SU 8020), and the coating composition is analyzed by combining an energy spectrometer (EDS). The crystal structure of the resulting samples was analyzed using a grazing incidence X-ray diffractometer (Bruker D8 ADVANCE, germany) using a coating light path with an incidence angle of 2 °. A muffle furnace (middle ring SX-B07123 in Tianjin) is adopted to carry out high-temperature heat treatment on a Ti6Al4V substrate and a TiCrAlNb alloy coating sample at the temperature of 600 ℃ for 50h, and a precision electronic balance is adopted to carry out weighing measurement every 10h, so that the high-temperature oxidation resistance of the sample is analyzed.
Firstly, the components of the TiCrAlNbSi alloy coating obtained under different Si sputtering powers are analyzed. As the Ti6Al4V substrate can interfere with the EDS test result, the TiCrAlNbSi alloy coating is deposited on the ITO substrate by adopting the same process. The EDS test results are shown in table 1, with three random points for each sample. The Si content in the coating increases along with the increase of the Si target power, and when the Si target power reaches 50W, the Si in the coating has a similar atomic ratio with Al and Ti elements.
TABLE 1 analysis of EDS composition of TiCrAlNbSi alloy coating
FIG. 1 is an XRD diffraction pattern of a TiCrAlNbSi alloy film with different sputtering powers. As can be seen from the figure, when the sputtering power of the silicon target is 30W, the high-entropy alloy film has a wider diffraction peak bottom, which indicates that the high-entropy alloy film under the sputtering parameters has an amorphous structure; with the increase of sputtering power, the crystal crystallization capability of the TiCrAlNbSi high-entropy alloy film is continuously enhanced, and when the power of a silicon target is 40W, the film starts to gradually change from an amorphous structure to a BCC solid solution structure; when the silicon target power is 50W, a significant BCC phase diffraction peak appears around 2 θ =40 ℃, which may be caused by that when the magnetron sputtering power is small, the energy of sputtered atoms is small, so that the atomic diffusion migration on the surface of the film is reduced, and thus the atoms adsorbed on the surface can only gather near the position where the initial sputtered atoms hit the substrate, and the arrangement of atoms shows a random distribution state, thereby obtaining an amorphous film. As the sputtering power is increased, the film deposition rate is increased and the crystallization ability is increased.
FIGS. 2-4 are SEM characterization results of the surface morphology of the TiCrAlNbSi alloy coating with different sputtering powers. From SEM picture, it can be seen that when the sputtering power of the silicon target is 30W, small particles with irregular shapes exist on the surface of the film, and the surface is uneven; when the sputtering power of the silicon target is 40W, large crystal grains which are large in size and are densely distributed are formed on the surface of the film; when the sputtering power of the silicon target is 50W, the surface of the coating has no obvious defects such as pores, cracks or particles and the like, and the surface is smooth and compact. In combination with the above XRD and SEM analyses, the crystal structure transformation of the thin film occurs mainly for two reasons: the sputtering rate of each element of the target is influenced by experimental parameters, so that the components of the film are changed along with the adjustment of the experimental parameters, and the small change of chemical components can cause lattice distortion, thereby promoting the formation of another crystal structure; secondly, as the sputtering power is increased, the deposition rate and the crystallization capacity of the film are also increased.
The three samples were subjected to a high temperature oxidation test and the samples were weighed 1 time every 10h, with the results shown in table 2.
TABLE 2 quality of TC4 substrate and TiCrAlNbSi alloy films of different sputtering powers before and after heat treatment
The oxidation kinetics curve was calculated according to equation (1) and is shown in fig. 5. The formula is as follows:
V＝ΔG/S (1)
( V: an isothermal oxidation rate; Δ G: oxidation weight gain of the sample; s: sample surface area )
From fig. 5 it can be seen that: in the first 20h, the isothermal oxidation weight gain rates of the titanium alloy and the high-entropy alloy coating with the Si target power of 30W and 40W are not greatly different and are respectively 0.9 mg-cm -2 、0.85mg·cm -2 、0.75mg·cm -2 (ii) a When the oxidation time is 20-50h, the oxidation weight gain of the TC4 titanium alloy is linearly increased at a faster rate, the oxidation rate of the coating is slowly increased and finally tends to be stable, and a parabolic oxidation kinetic curve is presented, wherein the oxidation weight gain of the TiCrAlNbSi (80W + 50W) high-entropy alloy coating is minimum, and the final oxidation weight gain rate is 0.4 mg-cm -2 The final oxidation weight gain rate of TC4 is 1.6mg cm -2 The oxidation resistance is improved by 4 times.
The microstructure and the X-ray diffraction pattern of the heat-treated TiCrAlNbSi high-entropy alloy coating are characterized6-8 are the micro-morphology of the TiCrAlNbSi high-entropy alloy film after heat treatment at 600 ℃ for 50h under different sputtering powers, and FIG. 9 is the X-ray diffraction pattern of the TiCrAlNbSi high-entropy alloy film after heat treatment at 600 ℃ for 50h under different sputtering powers. As can be seen from FIG. 4, when the silicon target power is 30W, irregular particle oxides with small size and uniform distribution exist on the surface of the heat-treated TiCrAlNbSi high-entropy alloy coating, and the diffraction peak of the original phase can be found by combining the XRD diffraction pattern in FIG. 5, which indicates that the thickness of the oxide film is thin. With the increase of sputtering power, surface oxide with irregular shape and uneven distribution grows along the surface parallel to the TC4 substrate, when the silicon target power is 50W, the oxide layer of the TiAlCrNbSi high-entropy alloy coating is more compact, the TiAlCrNbSi high-entropy alloy coating is tightly combined with a substrate, the shedding phenomenon does not occur, and the surface oxide is mainly Al according to the XRD diffraction pattern 2 O 3 、Cr 2 O 3 、SiO 2 Most Nb elements do not participate in oxidation reaction, but widely exist among oxides as simple substance elements; the generation of the compact oxide film prevents the further diffusion of oxygen element to the substrate, and the enrichment of Nb element between oxides can also be used as a layer of diffusion barrier to enhance the high-temperature oxidation resistance, which is consistent with the conclusion of an oxidation kinetics curve, and the high-temperature oxidation resistance of the TiAlCrNbSi high-entropy alloy coating is more excellent when the silicon target power is 50W.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as required after reading the present specification, but all of them are protected by patent law within the scope of the present invention.
Claims (2)
1. A preparation method of a TiCrAlNbSi alloy high-temperature oxidation resistant coating is characterized by comprising the following steps:
s1: selecting a substrate; selecting a titanium alloy sheet with the specification of 30mm multiplied by 1mm as a substrate;
s2: polishing; sequentially using 500#, 1000#, 1500#, 2000#, 3000#, 5000# sandpaper to polish the substrate;
s3: cleaning; to pairS2, polishing the substrate by using Al with the thickness of 0.1-0.5 mu m 2 O 3 Polishing the solution until the surface is bright; then ultrasonic cleaning is carried out in acetone, absolute ethyl alcohol and deionized water respectively for 10-20min in sequence, and finally nitrogen is used for blow drying;
s4: sputtering air pressure is fixed; putting the substrate dried in the step S3 into a vacuum chamber with the background vacuum degree of 5 multiplied by 10 -8 In a sputtering chamber of a high-vacuum magnetron sputtering instrument of Torr, the sputtering pressure is fixed to be 3mTorr, the power of a TiCrAlNb alloy target power supply is 80W, and the sputtering temperature is room temperature;
s5: depositing a coating; and respectively carrying out TiCrAlNbSi alloy coating deposition on the substrate subjected to sputtering air pressure fixation for 2 hours under the condition that the power of a Si target radio frequency power supply is 30W, 40W and 50W, so as to obtain the TiCrAlNbSi alloy high-temperature oxidation resistant coating.
2. The method for preparing the TiCrAlNbSi alloy high-temperature oxidation resistant coating according to claim 1, which is characterized by comprising the following steps of: in the step S4, the sputtering working gas during the sputtering work is high-purity argon gas, and the purity of the argon gas reaches 99.99%.
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| CN116121707A (en) * | 2023-02-24 | 2023-05-16 | 广东省科学院中乌焊接研究所 | TiCrAlSiX coating on titanium alloy surface and preparation method thereof |
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| CN116121707A (en) * | 2023-02-24 | 2023-05-16 | 广东省科学院中乌焊接研究所 | TiCrAlSiX coating on titanium alloy surface and preparation method thereof |
| CN116121707B (en) * | 2023-02-24 | 2024-03-19 | 广东省科学院中乌焊接研究所 | TiCrAlSiX coating on titanium alloy surface and preparation method thereof |
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