CN109320267B - Temporary protective coating for titanium alloy heat treatment process and preparation method thereof - Google Patents

Temporary protective coating for titanium alloy heat treatment process and preparation method thereof Download PDF

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CN109320267B
CN109320267B CN201811227387.9A CN201811227387A CN109320267B CN 109320267 B CN109320267 B CN 109320267B CN 201811227387 A CN201811227387 A CN 201811227387A CN 109320267 B CN109320267 B CN 109320267B
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coating
enamel
heat treatment
temporary protective
titanium alloy
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CN109320267A (en
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陈明辉
喻政
王群昌
周文
王福会
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Northeastern University China
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Abstract

The invention relates to an inorganic protective coating technology, and particularly provides a temporary protective coating used in a titanium alloy heat treatment process and a preparation method thereof. The coating is an enamel coating system consisting of enamel glaze, quartz, clay and other fillers, wherein the enamel glaze accounts for 65-85%, the quartz accounts for 10-20%, and the kaolin accounts for 5-15%. The formula of the enamel glaze comprises: 50-55% of silicon dioxide, 2-5% of aluminum oxide, 2-5% of boron trioxide, 4-8% of chromium trioxide, 22-28% of barium oxide, 2-8% of strontium oxide, 2-5% of zirconium dioxide and 2-5% of calcium oxide. According to the invention, the quartz particles with high temperature stability and the kaolin with good suspension performance and low cost are selected as fillers, and the prepared enamel coating has the advantages of compact structure, good high-temperature stability, adjustable softening point and thermal expansion coefficient and wide sintering temperature range. The coating is coated on the surfaces of titanium and titanium alloy, so that the oxidation atmosphere can be isolated, the oxidation loss in the alloy heat treatment process can be reduced, and the coating can be removed by simple sand blasting after the heat treatment.

Description

Temporary protective coating for titanium alloy heat treatment process and preparation method thereof
Technical Field
The invention relates to an inorganic protective coating technology, and particularly provides a temporary protective coating used in a titanium alloy heat treatment process and a preparation method thereof.
Background
Titanium is abundant in the earth, and is an important structural metal material developed in the 50 s of the 20 th century. Because of its high specific strength, good corrosion resistance, high heat resistance, etc., titanium alloys are receiving attention from material researchers all over the world, and their applications in the industrial field are increasing. However, more than 70% of titanium is currently used in the aerospace or defense military fields, and the application in the civil industry field is obviously less. The reasons for this are that titanium alloys are poor in processing properties, difficult to cut, and very easy to absorb impurities such as oxygen, hydrogen, nitrogen, and carbon during hot working, and have large intermediate loss. As a result, the price of titanium alloys is made very expensive. Therefore, the reduction of material loss in the hot working process of the titanium alloy and the improvement of the qualified rate of workpieces play a vital role in the development of the whole titanium alloy manufacturing industry.
The titanium alloy has high oxidation speed when being exposed to the air with the temperature of over 600 ℃, and can quickly absorb oxygen to generate a layer of porous fragile flake oxide skin and a layer of hard and fragile oxygen-enriched oxygen on the surfaceAnd (3) a layer. Generally, the hot working temperature of titanium alloys is far above 600 ℃ (up to 1200 ℃), and the oxidation rate is increased by orders of magnitude compared with 600 ℃. The existence of an oxide layer and a pollution layer greatly reduces the mechanical property of the titanium alloy, and the surface damage layer can not be completely removed by sand blasting after the hot working is finished, so HF + HNO is required to be used again3And (3) pickling for a long time. This results in a loss of about 2.2% of the titanium and additional processing costs, and in the case of severe oxidation, even part scrap. In addition, the scale produced during forging, rolling, and extrusion of titanium alloys damages the die, further increasing the cost. In order to ensure the safety and stability of the spacecraft, the heat treatment of most titanium parts is forced to choose under a high-cost vacuum or inert gas atmosphere. Even so, high heat workpieces can still oxidize during transfer. Since titanium has a high affinity for oxygen, the generation of a surface contamination layer cannot be completely prevented even with vacuum or inert gas shielding.
As early as the seventies of the last century, hot-working temporary protective coatings have been used in both mesu and two countries for lubrication and oxidation resistance in hot-working of various metals, but these formulations have been kept strictly secret from the outside. Although some coatings are developed by China, the high-temperature service time is short and generally not more than five hours. When a part of titanium parts needs long-time heat treatment, the protective effect of the temporary protective coating is limited. Therefore, the research on the temporary protective coating for the titanium alloy, which has long service life at high temperature and can be removed in a simple mode after the hot working is finished, has very important significance for reducing the processing loss of titanium and the processing cost of the titanium alloy.
The invention content is as follows:
the invention aims to provide a temporary protective coating for a titanium alloy heat treatment process and a preparation method thereof, which are manufactured by only using raw materials directly available in the market, have simple preparation process and low cost, can be used for high-temperature protection of the titanium alloy heat treatment process at 1200 ℃, reduce the heat treatment loss of the titanium alloy, and remove the coating through simple sand blasting after the alloy heat treatment is finished.
The technical scheme of the invention is as follows:
a temporary protective coating used in the heat treatment process of titanium alloy is a self-stripping enamel-based composite coating and consists of enamel glaze, quartz and kaolin fillers; according to the mass percentage, the enamel glaze accounts for 65-85%, the quartz accounts for 10-20%, and the kaolin accounts for 5-15%.
The temporary protective coating for the titanium alloy heat treatment process comprises the following components in percentage by mass: 50-55% of silicon dioxide, 2-5% of aluminum oxide, 2-5% of boron trioxide, 4-8% of chromium trioxide, 22-28% of barium oxide, 2-8% of strontium oxide, 2-5% of zirconium dioxide and 2-5% of calcium oxide.
The temporary protective coating used for the titanium alloy heat treatment process has the particle size range of 1-10 mu m.
The preparation method of the temporary protective coating for the titanium alloy heat treatment process comprises the following steps: (1) preparing enamel glaze; (2) preparing slurry; (3) coating slurry; (4) drying the coating and feeding into a furnace; (5) and (6) cooling the air.
The preparation method of the temporary protective coating for the titanium alloy heat treatment process comprises the following steps of: (1) preparing raw material powder according to a formula, and mixing for 1-3 hours in a planetary ball mill; (2) the mixed powder is melted at a high temperature of 1600-1700 ℃ for 0.5-2 hours and then water quenched into glass glaze blocks; (3) putting the glass glaze blocks into an agate tank, and ball-milling for 100-200 hours by adopting a planetary ball mill; (4) and (4) sieving the glass glaze powder obtained after ball milling with a 200-mesh sieve.
The preparation method of the temporary protective coating for the titanium alloy heat treatment process comprises the following preparation processes of slurry: mixing the enamel glaze, quartz and kaolin, and uniformly mixing the solid particle substances by adopting a high-speed stirring dispersion machine or other mechanical methods to obtain mixed powder; mixing the mixed powder and purified water according to the mass ratio of (1.5-2.5) to 1, fully stirring, and standing until bubbles escape to form slurry.
The preparation method of the temporary protective coating for the titanium alloy heat treatment process comprises the steps of spraying, brushing or dip-coating slurry at normal temperature in the atmosphere, wherein the spraying pressure of the normal temperature in the atmosphere spraying is 0.3-0.5 MPa, and the thickness of the coating is not more than 300 mu m.
According to the preparation method of the temporary protective coating for the titanium alloy heat treatment process, the thickness of the coating is preferably 150-250 micrometers.
According to the preparation method of the temporary protective coating for the titanium alloy heat treatment process, the coating is dried in a windless environment, the drying speed is not too high, the coating is dried at 50-70 ℃ for 0.5-1 hour, and the drying speed and the temperature are adjusted until the coating does not crack obviously.
In the invention, the performance indexes of the high-temperature enamel coating are as follows:
for titanium and titanium alloy materials such as TC4, Ti80, pure titanium and the like, after the surfaces of the titanium and titanium alloy materials are coated by a high-temperature enamel coating, when the titanium and titanium alloy materials are subjected to heat treatment at 1000-1200 ℃, the loss speed of the titanium and titanium alloy materials is less than 10 mu m/h, and the high-temperature service life can reach 20 h; after the titanium alloy is subjected to heat treatment, the affected area of the titanium alloy is smaller than 100 microns, the interface area of the enamel coating and the titanium alloy coating is loose, and the coating can be removed through simple sand blasting.
The design idea of the invention is as follows:
the components and contents of the porcelain glaze network forming agent component and the cosolvent component in the porcelain glaze coating are reasonably designed, the high-temperature fluidity of the porcelain glaze is improved as much as possible while the high-temperature strength of the porcelain glaze is ensured, and the sintering density of the coating is improved; alkaline earth metal oxides (such as barium oxide and strontium oxide) are used as ceramic glaze cosolvent components instead of alkali metal oxides (such as sodium oxide and potassium oxide) to improve the high-temperature strength and high-temperature stability of the coating; quartz particles and kaolin fillers are adopted, and the softening point of the porcelain glaze is improved in situ through the interface reaction between the fillers and the porcelain glaze, so that the service temperature of the porcelain enamel coating is improved to 1000-1200 ℃, and the high-temperature service life is at least 20 hours; meanwhile, the kaolin can also improve the suspension property of slurry so as to improve the spraying property. Finally, the prepared high-temperature enamel coating is coated on the surface of titanium or titanium alloy, plays a role in temporary protection when the alloy is subjected to heat treatment at 1000-1200 ℃, the protection time can reach 20 hours, and the coating can be completely removed through simple sand blasting after the heat treatment is finished.
The invention has the advantages and effects that:
1. the coating developed by the invention is compact and can completely isolate the high-temperature reaction between the high-temperature furnace gas and the metal matrix.
2. The enamel coating developed by the invention has a glaze formula with a wider sintering temperature and sintering time range, and can be suitable for different heating temperatures and time intervals by adjusting the proportion of grinding and feeding.
3. The coating and the titanium alloy interface layer are loose, and the coating can be removed through simple sand blasting after heat treatment, so that the working hour and the economic loss of subsequent treatment are reduced.
4. The invention is suitable for temporary protection of titanium, titanium alloy and other metal material parts during heat treatment at the temperature range of 1000-1200 ℃.
Description of the drawings:
FIG. 1 is a macroscopic picture of the original (non-heat treated) enamel coating on the surface of TC4 alloy.
FIG. 2 shows the macroscopic morphology and the spalling fragments of the enamel coating on the surface of the TC4 alloy after heat treatment for 5 hours at 1200 ℃.
FIG. 3 shows the macroscopic morphology of cracking failure and spalling fragments of the enamel coating on the surface of the TC4 alloy after heat treatment for 5 hours at 1200 ℃.
FIG. 4 is a macro morphology picture of the enamel coating on the surface of Ti60 alloy after heat treatment for 10h at 1200 ℃.
FIG. 5 is a cross-sectional back-scattered electron photograph of the TC4 alloy coated with the enamel coating after heat treatment at 1200 ℃ for 5 hours.
FIG. 6 is a photograph of the macro-topography of the TC4 alloy surface after cracking of the original (non-heat treated) enamel coating.
FIG. 7 is a cross-sectional backscattered electron photograph of a Ti80 alloy coated with an enamel coating after a heat treatment at 1200 ℃ for 15 h.
Fig. 8 is a cross-sectional back-scattered electron photograph of the TC4 alloy coated with the enamel coating after heat treatment at 1200 ℃ for 20 h.
FIG. 9 is a metallographic micrograph of a TC4 alloy coated with an enamel coating after heat treatment at 1200 ℃ for 20 hours.
FIG. 10 is a graph of the microhardness of TC4 alloy coated with an enamel coating after heat treatment at 1200 ℃ for 5 hours and 20 hours; where the ordinate hardness (HV0.1) is the alloy vickers hardness value and the abscissa depth is the depth (μm) of the measurement point from the alloy/coating interface.
The specific implementation mode is as follows:
in the specific implementation process, the temporary protection self-peeling enamel coating used for the titanium alloy heat treatment process consists of enamel glaze and fillers such as quartz, kaolin and the like. Wherein, the mass percentage of the enamel glaze is 65-85%, the mass percentage of the quartz particles is 10-20%, and the mass percentage of the kaolin is 5-15%; the formula of the enamel glaze comprises the following components in percentage by mass: 50-55% of silicon dioxide, 2-5% of aluminum oxide, 2-5% of boron trioxide, 4-8% of chromium trioxide, 22-28% of barium oxide, 2-8% of strontium oxide, 2-5% of zirconium dioxide and 2-5% of calcium oxide. According to the invention, through the formula design of the enamel glaze, the refractory quartz particles and the kaolin are filled, the strength and the temperature resistance of the enamel glaze are improved, the high-temperature fluidity of the coating and the suspension property of slurry are improved, the prepared high-temperature enamel coating has a compact structure, is matched with a titanium alloy, has moderate strength, and can be used for a temporary protective coating in the long-time (5-20 hours) heat treatment process of the titanium alloy at the temperature of 1000-1200 ℃. After the heat treatment is finished, the compressive stress generated by cooling the alloy is large, the interface layer is loose, and the coating can be completely removed through simple sand blasting treatment.
The following examples are intended to illustrate the invention in further detail, with the understanding that these are only intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
In this embodiment, the TC4 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 52% of silicon dioxide, 3% of aluminum oxide, 3% of boron trioxide, 6% of chromium trioxide, 25% of barium oxide, 5% of strontium oxide, 3% of zirconium dioxide and 3% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed for 1 hour at the temperature of 1000 ℃→ 1650 ℃;
keeping the temperature at 1650 ℃ for 1 hour, and then quenching with water to obtain the enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of enamel micro powder to quartz particles to kaolin of 75: 15: 10 preparing composite enamel powder according to the proportion of 2g composite enamel powder: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) And coating the enamel slurry on the surface of the TC4 titanium alloy sample subjected to sand blasting by adopting a dip-coating method, and then drying the sample in a drying oven at 50 ℃ for 1 hour without wind to obtain the temporary protective coating. As shown in figure 1, the dried coating has uniform and complete surface and completely covers the alloy matrix.
The TC4 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 5 hours and then taken out for air cooling. As shown in figure 2, the surface coating of the alloy is basically stripped, the stripping occurs in the air cooling stage of taking out the coating, the stripping area is about 80-90%, and the residual enamel coating can be completely removed through subsequent sand blasting. The alloy in the stripping area is not subjected to secondary oxidation, the stripping product is mainly an enamel coating, and no obvious alloy oxidation product is found in the coating, namely the alloy matrix is well protected in the heat treatment process.
Comparative example 1
The difference from the embodiment 1 is that the formula of the enamel glaze is changed into the following formula according to the mass percentage: 58% of silicon dioxide, 5% of aluminum oxide, 3% of boron trioxide, 6% of chromium trioxide, 20% of barium oxide, 3% of strontium oxide, 3% of zirconium dioxide and 2% of calcium oxide. The prepared coating surface is still uniform and complete, and is similar to the figure 1.
The TC4 alloy coated with the coating is put into a muffle furnace at 1200 ℃ for heat treatment for 5 hours, and then taken out for air cooling. As shown in FIG. 3, the surface of the alloy was heavily oxidized in some areas, and the coating showed cracking. The results show that the network forming agent component silicon dioxide content in the enamel glaze is too high, and the cosolvent component barium oxide content is low, so that the coating has poor fluidity, the coating is difficult to fire, the surface is cracked, the protective performance is reduced, and the alloy matrix is locally oxidized in the heat treatment process.
Comparative example 2
The difference from the embodiment 1 is that the weight ratio of the enamel micro powder to the quartz particles to the kaolin in the enamel coating is 60: 25: 15. the prepared coating surface is still uniform and complete, and is similar to the figure 1.
The TC4 alloy coated with the coating is put into a muffle furnace at 1200 ℃ for heat treatment for 5 hours, and then taken out for air cooling. Similar to fig. 3, severe oxidation occurred in a partial region of the alloy surface, and the coating showed signs of cracking. The results show that the interface reaction between the quartz particles and the enamel reduces the fluidity of the coating, the coating is difficult to fire, the surface is cracked, and the alloy matrix is locally oxidized during the heat treatment process because the added amount of the quartz particles is too high.
Comparative example 3
The difference from example 1 is that the heat treatment temperature of the titanium alloy coated with the coating layer was changed to 1000 ℃. The TC4 alloy coated with the temporary protective coating is put into a muffle furnace at 1000 ℃ for heat treatment for 5 hours and then taken out for air cooling. The results were similar to fig. 2, with the alloy surface coating flaking in bulk, with a flaking area of about 50%. The residual enamel coating can be completely removed by sand blasting, the alloy in the stripping area is not subjected to secondary oxidation, the stripping product is mainly the enamel coating, and no obvious alloy oxidation product is found in the coating, namely the alloy matrix is well protected in the heat treatment process.
Example 2
In this embodiment, the Ti60 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 55% of silicon dioxide, 2% of aluminum oxide, 3% of boron trioxide, 4% of chromium trioxide, 25% of barium oxide, 5% of strontium oxide, 3% of zirconium dioxide and 3% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed for 1 hour at the temperature of 1000 ℃→ 1650 ℃;
keeping the temperature at 1650 ℃ for 1.5 hours, and then water quenching to obtain the enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of the enamel micro powder to quartz particles to kaolin of 85: 10: preparing composite enamel powder according to the proportion of 2.5g composite enamel powder: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) The enamel slurry is coated on the surface of the Ti60 titanium alloy sample subjected to sand blasting by adopting a spraying method, and the spraying pressure is 0.4 MPa. Then drying for 1h in a drying oven at 60 ℃ without air to obtain the temporary protective coating. The coating bake profile is similar to that of fig. 1. The dried coating surface is uniform and complete, and the alloy matrix is completely covered.
The Ti60 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 10 hours and then taken out for air cooling. As shown in fig. 4, the alloy surface coating is not peeled off, but the natural color (green) of the enamel coating is presented, and the alloy matrix is well protected during the heat treatment.
Example 3
In this embodiment, the TC4 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 50% of silicon dioxide, 5% of aluminum oxide, 4% of boron trioxide, 8% of chromium trioxide, 22% of barium oxide, 5% of strontium oxide, 4% of zirconium dioxide and 2% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed of 1000 ℃→ 1600 ℃ for 1 hour;
keeping the temperature of 1600 ℃ for 1.5 hours, and then performing water quenching to obtain enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of the enamel micro powder to the quartz particles to the kaolin of 65: 20: 15 preparing composite enamel powder, wherein the weight ratio of the composite enamel powder to the enamel powder is 2 g: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) The enamel slurry was applied to the surface of the grit blasted TC4 alloy sample by a brush coating process. Then drying for 1h in a drying oven at 60 ℃ without air to obtain the temporary protective coating. The coating bake profile is similar to that of fig. 1. The dried coating surface is uniform and complete, and the alloy matrix is completely covered.
The TC4 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 5 hours and then taken out for air cooling. Similar to fig. 4, the alloy surface coating did not peel off, but showed the natural color (green) of the enamel coating, and the alloy matrix was well protected during the heat treatment. The cross section of the coating after the heat treatment was analyzed, and the thickness of the coating was 180 μm as shown in FIG. 5. An interface layer with the thickness of 15-20 microns is formed at the interface of the coating and the alloy, and the interface layer is loose and porous, so that the enamel coating can be easily removed in the subsequent sand blasting process. Under the interface layer, the microstructure of the alloy matrix is not obviously influenced, and further shows that the temporary coating has excellent high-temperature protection effect on the alloy matrix.
Comparative example 4
The difference from the embodiment 3 is that when the composite enamel slurry is prepared, the ratio of the composite enamel powder to the deionized water is 3 mg: 1 ml. Before the heat treatment, the macroscopic morphology of the enamel temporary protective coating is shown in FIG. 6, and a through type main crack exists on the enamel surface. The main reason is that the spraying slurry has too high concentration, and the coating has large internal stress during drying, so that the coating is cracked.
Comparative example 5
The difference from the embodiment 3 is that when the composite enamel slurry is prepared, the ratio of the composite enamel powder to the deionized water is 1 mg: 1 ml. Before the heat treatment, the enamel temporarily protects the uneven surface thickness. The main reason is that the enamel slurry is too thin, and the slurry is easy to flow and is gathered at the bottom end of a suspended sample during spraying, so that the top end of the coating is thin and the bottom is thick, and the protective effect is influenced by uneven thickness.
Example 4
In this embodiment, the Ti80 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 53% of silicon dioxide, 4% of aluminum oxide, 2% of boron trioxide, 4% of chromium trioxide, 25% of barium oxide, 5% of strontium oxide, 2% of zirconium dioxide and 5% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed for 1 hour at the temperature of 1000 ℃→ 1650 ℃;
keeping the temperature at 1650 ℃ for 2 hours, and then quenching with water to obtain the enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of enamel micro powder to quartz particles to kaolin of 75: 10: 15 preparing composite enamel powder, wherein the weight ratio of the composite enamel powder to the enamel powder is 2 g: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) The enamel slurry was applied to the surface of a grit blasted Ti80 alloy sample using a dip coating process. Then drying for 1h in a drying oven at 60 ℃ without air to obtain the temporary protective coating. The coating bake profile is similar to that of fig. 1. The dried coating surface is uniform and complete, and the alloy matrix is completely covered.
The Ti80 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 15 hours and then taken out for air cooling. The cross section of the coating after the heat treatment was analyzed, and as shown in FIG. 7, the thickness of the coating was 210. mu.m. An interface layer with the thickness of about 15 mu m is formed at the interface of the coating and the alloy, and the interface layer is loose and porous, so that the enamel coating can be easily removed in the subsequent sand blasting process. Under the interface layer, the organization structure of the alloy matrix is not obviously influenced, which shows that the temporary coating has excellent high-temperature protection effect on the alloy matrix.
Comparative example 6
The difference from example 4 is that the alloy heat treatment temperature is 1000 ℃. After 15h of heat treatment, the cross-sectional morphology of the coating is similar to that of the coating in FIG. 7, the alloy matrix is only slightly damaged at the interface, and the lower part of the interface is not obviously affected.
Comparative example 7
The difference from example 4 is that the alloy heat treatment temperature is 1100 ℃. After 15h of heat treatment, the cross-sectional morphology of the coating is similar to that of the coating in FIG. 7, the alloy matrix is only slightly damaged at the interface, and the lower part of the interface is not obviously affected.
Example 5
The difference from example 4 is that the selected alloy matrix is commercially pure titanium and an enamel-based temporary protective coating is prepared. After the alloy is subjected to heat treatment at 1200 ℃ for 15h, the cross-sectional morphology of the coating is similar to that in FIG. 7, the alloy matrix is only slightly damaged at the interface, and the lower part of the interface is not obviously affected.
Example 6
In this embodiment, the TC4 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 54% of silicon dioxide, 4% of aluminum oxide, 4% of boron trioxide, 7% of chromium trioxide, 22% of barium oxide, 4% of strontium oxide, 3% of zirconium dioxide and 2% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed of 1000 ℃→ 1700 ℃ for 1 hour;
keeping the temperature of 1700 ℃ for 1.5 hours, and then performing water quenching to obtain enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of the enamel micro powder to the quartz particles to the kaolin of 65: 20: 15 preparing composite enamel powder, wherein the weight ratio of the composite enamel powder to the enamel powder is 2 g: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) The enamel slurry was applied to the surface of the grit blasted TC4 alloy sample by dip coating. Then drying for 1h in a drying oven at 60 ℃ without air to obtain the temporary protective coating. The coating bake profile is similar to that of fig. 1. The dried coating surface is uniform and complete, and the alloy matrix is completely covered.
The TC4 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 20 hours and then taken out for air cooling. Similar to fig. 4, the alloy surface coating is not peeled off, and the alloy matrix is well protected during the heat treatment. The cross section of the coating after heat treatment was analyzed, and the coating thickness was 240 μm as shown in FIG. 8. An interface layer with the thickness of about 15 mu m is formed at the interface of the coating and the alloy, and the interface layer is loose and porous, so that the enamel coating can be easily removed in the subsequent sand blasting process. Under the interface layer, the microstructure of the alloy matrix is not obviously influenced, and further shows that the temporary coating has excellent high-temperature protection effect on the alloy matrix.
Example 7
In this embodiment, the TC4 alloy is used as a substrate to prepare the enamel-based temporary protective coating, and the preparation process thereof is as follows:
(1) smelting enamel glaze:
the formula of the enamel glaze comprises the following components in percentage by mass: 51% of silicon dioxide, 4% of aluminum oxide, 4% of boron trioxide, 7% of chromium trioxide, 25% of barium oxide, 4% of strontium oxide, 3% of zirconium dioxide and 2% of calcium oxide.
Ball-milling and mixing the oxides, rotating at 320 r/min for 2 hours, uniformly mixing, and then heating and smelting, wherein the smelting process is as follows:
RT (room temperature) → 500 ℃, and uniform heating for 1 hour;
uniformly heating for 30 minutes at the speed of 500 ℃→ 1000 ℃;
heating at the uniform speed for 1 hour at the temperature of 1000 ℃→ 1650 ℃;
keeping the temperature at 1650 ℃ for 1.5 hours, and then water quenching to obtain the enamel glaze particles.
(2) Preparing enamel micro powder: and (3) carrying out planetary ball milling (rotating speed of 320 r/min, time of 100 hours) on the enamel glaze obtained after water quenching to prepare enamel micro powder with the particle size of less than 10 mu m.
(3) According to the weight ratio of the enamel micro powder to the quartz particles to the kaolin of 65: 20: 15 preparing composite enamel powder, wherein the weight ratio of the composite enamel powder to the enamel powder is 2 g: 1ml of deionized water is prepared into the composite enamel slurry and fully stirred.
(4) And coating the enamel slurry on the surface of the TC4 alloy sample subjected to sand blasting by adopting a spraying method, wherein the spraying pressure is 0.5 MPa. Then drying for 1h in a drying oven at 70 ℃ without air to obtain the temporary protective coating. The coating bake profile is similar to that of fig. 1. The dried coating surface is uniform and complete, and the alloy matrix is completely covered.
The TC4 alloy coated with the temporary protective coating is put into a muffle furnace at 1200 ℃ for heat treatment for 20 hours and then taken out for air cooling. Similar to fig. 4, the alloy surface coating did not peel off, the alloy matrix was well protected during the heat treatment, and the metallographic analysis was performed on the cross section of the coating after the heat treatment. As shown in FIG. 9, the surface structure of the substrate was a standard air-cooled structure, indicating that the protective effect of the enamel coating was excellent.
And testing the hardness value of the matrix alloy below the coating after heat treatment. As shown in fig. 10, the hardness values of the alloys under the coating were substantially the same at heat treatment temperatures of 5h and 20 h. And as the test point moves from the coating/alloy interface to the deep part of the alloy, the hardness value is basically maintained, which indicates that the alloy surface layer is not obviously oxidized and affected in the heat treatment process, and the surface has no oxygen pollution layer, further indicates the excellent protection effect of the enamel-based temporary protective coating.
Limited by the size of the specimen, where the specimen has defects such as: the manual chamfering and the hole hanging part are oxidized, and an oxide film at the defect part can grow rapidly and damage the integrity of the coating, but the two defects can be overcome by simple procedures.
The results of the embodiment and the comparative example show that the invention selects the quartz particles with high temperature stability and the kaolin with good suspension performance and low cost as the filler, and the prepared enamel coating has compact structure, good high temperature stability, adjustable softening point and thermal expansion coefficient and wide sintering temperature range. The coating is coated on the surfaces of titanium and titanium alloy, can isolate oxidizing atmosphere, reduces the oxidation loss in the alloy heat treatment process, and can be removed by simple sand blasting after the heat treatment.
In addition, the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the present invention, and the temporary protective coating for heat treatment of metals can also be applied to the protection of other types of materials, such as stainless steel parts. Therefore, other changes and modifications can be made according to the technical scheme and the technical idea of the invention, and the changes and modifications still fall within the protection scope covered by the invention.

Claims (8)

1. A temporary protective coating used in the heat treatment process of titanium alloy is characterized in that the temporary protective coating is a self-stripping enamel-based composite coating and consists of enamel glaze, quartz and kaolin fillers; according to the mass percentage, the enamel glaze accounts for 65-85%, the quartz accounts for 10-20%, and the kaolin accounts for 5-15%;
the formula of the enamel glaze comprises the following components in percentage by mass: 50-55% of silicon dioxide, 2-5% of aluminum oxide, 2-5% of boron trioxide, 4-8% of chromium trioxide, 22-28% of barium oxide, 2-8% of strontium oxide, 2-5% of zirconium dioxide and 2-5% of calcium oxide.
2. A temporary protective coating for use in a titanium alloy heat treatment process according to claim 1, wherein the quartz particles have a particle size in the range of 1 to 10 μm.
3. A method for preparing a temporary protective coating for a titanium alloy heat treatment process according to any one of claims 1 to 2, wherein the preparation process of the coating comprises: (1) preparing enamel glaze; (2) preparing slurry; (3) coating slurry; (4) drying the coating and feeding into a furnace; (5) and (6) cooling the air.
4. A process for the preparation of a temporary protective coating for titanium alloy heat treatment processes according to claim 3, characterized in that the enamel is prepared as follows: (1) preparing raw material powder according to a formula, and mixing for 1-3 hours in a planetary ball mill; (2) the mixed powder is melted at a high temperature of 1600-1700 ℃ for 0.5-2 hours and then water quenched into glass glaze blocks; (3) putting the glass glaze blocks into an agate tank, and ball-milling for 100-200 hours by adopting a planetary ball mill; (4) and (4) sieving the glass glaze powder obtained after ball milling with a 200-mesh sieve.
5. A method of preparing a temporary protective coating for a titanium alloy heat treatment process according to claim 3, wherein the slurry is prepared by: mixing the enamel glaze, quartz and kaolin, and uniformly mixing the solid particle substances by adopting a high-speed stirring dispersion machine or other mechanical methods to obtain mixed powder; mixing the mixed powder and purified water according to the mass ratio of (1.5-2.5) to 1, fully stirring, and standing until bubbles escape to form slurry.
6. The method for preparing the temporary protective coating for the titanium alloy heat treatment process according to claim 3, wherein the slurry coating method is normal-temperature atmospheric spraying, brush coating or dip coating, the spraying pressure of the normal-temperature atmospheric spraying is 0.3-0.5 MPa, and the thickness of the coating is not more than 300 μm.
7. The method for preparing a temporary protective coating for a titanium alloy heat treatment process according to claim 6, wherein the thickness of the coating is preferably 150 to 250 μm.
8. The method for preparing a temporary protective coating for a titanium alloy heat treatment process according to claim 3, wherein the coating is dried in a windless environment, the drying speed is not too fast, the coating is dried at 50-70 ℃ for 0.5-1 hour, and the drying speed and temperature are adjusted until the coating does not crack obviously.
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