CN110743765B - Titanium alloy ingot surface glass coating and preparation method thereof - Google Patents
Titanium alloy ingot surface glass coating and preparation method thereof Download PDFInfo
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- CN110743765B CN110743765B CN201911031991.9A CN201911031991A CN110743765B CN 110743765 B CN110743765 B CN 110743765B CN 201911031991 A CN201911031991 A CN 201911031991A CN 110743765 B CN110743765 B CN 110743765B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
- B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti
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Abstract
The invention discloses a surface glass of a titanium alloy ingotThe glass coating is prepared from the following raw materials in percentage by mass: 65-95% of glass matrix, 5-35% of binder and 0-30% of additive; the glass substrate is prepared from the following raw materials in percentage by mass: b is2O3 5％～12％，Al2O3 4％～20％，ZrO23 to 8 percent of NiO and/or Cr2O33 to 9 percent of CaO and/or BaO 3 to 11 percent of compound N5 to 15 percent of compound and the balance of SiO2(ii) a The invention also discloses a preparation method of the glass coating on the surface of the titanium alloy ingot, which comprises the steps of mixing the raw materials uniformly, pre-arranging the mixture on the surface of the titanium alloy ingot, and carrying out heat treatment to form the glass coating. The invention regulates and controls the composition of the glass substrate, so that the glass coating has excellent high-temperature protection performance; the method has simple process and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of titanium alloy high-temperature protection and hot working, and particularly relates to a glass coating on the surface of a titanium alloy ingot and a preparation method thereof.
Background
In order to change the casting structure of a titanium alloy ingot and obtain a billet of a necessary size, the ingot is generally cogging by a forging method. However, the titanium alloy ingot has the problem of high-temperature oxidation resistance in the hot working process. In the hot working process, firstly, the cast ingot is heated to 950 ℃ to 1100 ℃ and is kept warm for more than 5 hours. Because titanium has high affinity with oxygen and high oxygen solubility (the atomic fraction can reach 34 percent), under the high-temperature oxidation condition, the titanium alloy can not avoid the problems of brittleness caused by dissolved oxygen and surface oxidation, so loose oxide skin is generated on the surface of the cast ingot, and a hard and brittle oxygen absorption layer is formed below the oxide film. The hard and brittle oxygen-absorbing layer has poor plasticity and is easy to crack in the forging process. The cracks can seriously affect the forging forming of the titanium alloy ingot, even lead the whole ingot to crack and be scrapped, and can reduce the forging yield by more than 10 percent when the cracks are serious, and the damage to the titanium alloy ingot is more serious than the oxidation. The removal of the oxide layer on the surface of the titanium alloy ingot is not only labor-consuming and time-consuming, but also causes the loss of the titanium alloy accounting for more than 2.2 percent of the material input amount, and causes huge economic loss. In addition, the formation of the hard and brittle oxygen absorption layer on the surface of the titanium alloy ingot increases the friction force between the ingot and the die, so that the forging is difficult to form, the die is not easy to demould, and the service life of the die is shortened.
In order to reduce the oxidation consumption of the titanium alloy ingot during the heating process and prolong the service life of the die, the application of a protective and lubricating coating to the ingot is an effective method. The glass coating has very high chemical and high-temperature stability, does not have short-circuit diffusion channels such as crystal boundary and the like, and has strong barrier effect on oxygen; meanwhile, the glass coating is simple in preparation process and convenient to coat. The glass coating is used as a high-temperature protective coating of the titanium alloy ingot, so that the problem of high-temperature oxidation in the heating process of the titanium ingot can be solved, and the problem of lubrication in the forging process of the titanium alloy ingot can also be solved; in addition, the glass coating can also play a role in heat preservation and heat insulation due to the lower heat conductivity coefficient, so that the titanium alloy is ensured to have lower deformation resistance in the forging process, and the problems of surface oxidation resistance and forging cracking of the titanium cast ingot are well solved. In conclusion, the glass protective lubricating coating is the most suitable titanium alloy ingot heating protection and forging lubricating coating.
However, with the development of the hot processing technology of the titanium alloy ingot, the heat treatment temperature of part of the titanium alloy is up to 1200 ℃, and the heat treatment time is up to more than 50h, so that the existing high-temperature protective glass coating system of the titanium alloy is difficult to meet the requirement in terms of oxidation resistance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a glass coating on the surface of a titanium alloy ingot aiming at the defects of the prior art. The glass coating improves the viscosity and softening temperature of a glass substrate through design regulation and control of the components and the compositions of the raw material glass substrate, further improves the service temperature and high-temperature stability of the glass coating and the bonding performance of the glass coating and a titanium alloy ingot, forms a continuous, complete and smooth glass coating with excellent high-temperature protection performance on the surface of the titanium alloy ingot, and solves the problems of surface oxidation resistance and forging cracking of the titanium alloy ingot.
In order to solve the technical problems, the invention adopts the technical scheme that: the glass coating on the surface of the titanium alloy ingot is characterized by being prepared from the following raw materials in percentage by mass: 65-95% of glass matrix, 5-35% of binder and 0-30% of additive; the glass matrix is prepared from the following raw materials in percentage by mass: b is2O3 5％～12％，Al2O3 4％～20％，ZrO23 to 8 percent of compound K, 3 to 9 percent of compound K, 3 to 11 percent of compound M, 5 to 15 percent of compound N and the balance of SiO2The compound K is NiO and/or Cr2O3The compound M is CaO and/or BaO, and the compound N is KNO3、Na2CO3And ZnO, or a mixture thereof.
The invention designs and regulates the components of the glass substrate in the glass coating by adding Al2O3And compound K, i.e. NiO and/or Cr2The content of O improves the viscosity and softening temperature of the glass matrix, thereby improving the service temperature of the glass coating; by adding ZrO2The high-temperature crystallization behavior of the glass substrate is effectively controlled, the high-temperature stability of the glass coating is improved, and the thermal expansion coefficient of the glass coating is improved, so that the glass coating and a titanium alloy ingot form good thermal expansion coefficient matching, and the bonding performance of the glass coating and the titanium alloy ingot is further improved; by adding a proper amount of alkaline earth metal oxide, namely the compound M, and an alkali metal compound, namely the compound N, the film forming property of the glass coating is improved, and the interface bonding property of the glass coating and the titanium alloy ingot is enhanced, so that a continuous, complete and smooth glass coating is formed on the surface of the titanium alloy ingot; in addition, the oxidation resistance of the glass coating is further improved by the additives in the glass coating. The glass coating on the surface of the titanium alloy ingot has excellent high-temperature protection performance, can provide oxidation resistance protection for the titanium alloy ingot at the heat treatment temperature of 1250 ℃ or below, and combines titanium at 1200 DEG CThe high-temperature protection life of the gold ingot is not less than 50 h; in addition, the glass coating on the surface of the titanium alloy ingot plays a role in lubricating the titanium alloy ingot in the forging process, so that the problems of surface oxidation resistance and forging cracking of the titanium ingot are well solved.
The glass coating on the surface of the titanium alloy ingot is characterized in that the preparation process of the glass substrate is as follows: putting all the raw materials into a ball mill, ball-milling and uniformly mixing, then smelting for 4-10 h at 1450-1600 ℃, water-quenching to obtain glass glaze slag, drying, and ball-milling by the ball mill to obtain glass powder with the granularity of less than 10 mu m. Preferably, the glass powder is prepared by smelting at high temperature and then adopting a water quenching ball milling method, which is beneficial to the uniform distribution of all components in the glass matrix and simultaneously obtains the glass powder with smaller granularity.
The titanium alloy ingot surface glass coating is characterized in that the binder is clay and/or water glass; the clay is calcined kaolin with more than three levels, and the mass percent of the clay is 5-20%; the water glass is potassium silicate water glass with the modulus not lower than 3 and the mass concentration not lower than 40%, and the mass percent of the potassium silicate water glass is 20-35%. When the heat treatment temperature of the titanium alloy ingot coated with the glass coating is higher (more than 1000 ℃), the clay is preferably adopted as the binder, so that the reduction of the viscosity of the glass matrix is avoided, and the glass coating still has good oxidation resistance at high temperature; when the heat treatment temperature of the titanium alloy ingot is relatively low (less than or equal to 1000 ℃), the water glass is preferably used as a binder, the glass substrate and the additives are effectively bound, and the glass coating is easy to prepare.
The glass coating on the surface of the titanium alloy ingot is characterized in that the additive is one or more than two of silicon oxide, aluminum oxide and mullite; the particle size of the additive is less than 10 mu m. The preferable additive can be dissolved in the glass matrix under the high-temperature condition, so that the integrity of glass grids in the glass coating is improved, and the viscosity and the oxidation resistance of the glass coating are ensured; the additive with the granularity less than 10 mu m is dissolved in the glass matrix at a higher speed under a high-temperature condition, the effect of remarkably improving the softening point of the coating can be realized under the condition of less addition amount, and meanwhile, the additive is beneficial to enhancing the strength of the glass coating, so that the thermal shock spalling resistance of the glass coating is improved.
In addition, the invention also provides a method for preparing the glass coating on the surface of the titanium alloy ingot, which is characterized by comprising the following steps:
cleaning the surface of a titanium alloy ingot to remove adhesion, floating ash and grease on the surface of the titanium alloy ingot;
step two, placing the glass substrate, the binder and the additives in a ball mill for ball milling and mixing uniformly to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the titanium alloy ingot cleaned in the step one, drying the titanium alloy ingot to form a preset layer on the surface of the titanium alloy ingot, then placing the titanium alloy ingot with the preset layer in a muffle furnace for heat treatment, and forming a glass coating on the surface of the titanium alloy ingot.
The invention ball-mills the raw materials of the glass coating and the dispersant and mixes them uniformly to form the composite slurry, then puts them on the surface of the cleaned titanium alloy ingot, and forms the glass coating on the surface of the titanium alloy ingot after drying and heat treatment. The method has simple process and easy operation, can quickly prepare the coating on the surface of the titanium alloy ingot with poor surface state (namely the surface has the defects of oxide skin, unevenness, cracks and the like), is suitable for the titanium alloy ingot with large size and is suitable for industrial production.
The method is characterized in that the surface of the cleaned titanium alloy ingot is polished, pre-oxidized or sandblasted in the step one. The interface bonding capability of the glass coating and the surface of the titanium alloy ingot can be further improved through the treatment.
The method is characterized in that in the step two, purified water is added as a dispersing agent in the ball milling and mixing process, the volume of the dispersing agent is 2-10 times of the total mass of the glass substrate, the binder and the additives, wherein the unit of the volume is mL, and the unit of the mass is g. The pure water dispersant has low price, can obviously reduce the preparation cost, and is suitable for industrial production.
The method is characterized in that the rotation speed for ball milling and mixing uniformly in the step two is 200 r/min-400 r/min, and the time for ball milling and mixing uniformly is 2 h-5 h. The high-speed ball milling is beneficial to the full and uniform mixing of the glass matrix, the binder, the additive and the dispersing agent, so that a uniform glass coating is obtained on the surface of the titanium alloy ingot, the reduction of the particle size of each material due to long-time ball milling is avoided, and the reduction of energy consumption is facilitated.
The method is characterized in that the presetting in the third step adopts a brush coating or pneumatic spraying mode, the spraying air pressure of the pneumatic spraying is 0.2 MPa-0.4 MPa, and the spraying distance is 10 cm-40 cm; the drying temperature is 20-200 ℃, and the heat treatment temperature is 800-1250 ℃. The brush coating method can quickly obtain a thicker glass coating on the surface of the large titanium alloy ingot, and is suitable for quickly brushing the large ingot; the glass coating with relatively uniform thickness can be obtained on the surface of the cast ingot by adopting a pneumatic spraying mode, and because the components in the composite slurry have density and size difference, the change of the components in the preset layer after presetting is reduced by limiting the spraying air pressure and distance of the pneumatic spraying of the composite slurry, and the composition of the glass coating is further ensured; the optimized drying temperature effectively removes the dispersing agent in the glass coating, and ensures the composition content of the glass coating.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, through design regulation and control of the components and the components of the glass matrix in the glass coating, the viscosity and the softening temperature of the glass matrix are improved, the service temperature of the glass coating is further improved, the high-temperature crystallization behavior of the glass matrix is effectively controlled, the high-temperature stability of the glass coating is improved, the thermal expansion coefficient of the glass coating is improved, the film forming property of the glass coating is improved, and the interface bonding property of the glass coating and a titanium alloy ingot is enhanced, so that a continuous, complete and smooth glass coating is formed on the surface of the titanium alloy ingot.
2. The glass coating on the surface of the titanium alloy ingot has excellent high-temperature protection performance, can provide antioxidant protection for the titanium alloy ingot at the heat treatment temperature of 1250 ℃ or below, and has the high-temperature protection service life of not less than 50h at 1200 ℃ for the titanium alloy ingot.
3. The invention forms a continuous, complete and smooth glass coating on the surface of the titanium alloy ingot, thereby playing a role in lubricating the titanium alloy ingot in the forging process and well solving the problems of oxidation resistance and forging cracking of the surface of the titanium ingot.
4. The method has simple process and easy operation, can quickly prepare the coating on the surface of the titanium alloy ingot with poor surface state, is suitable for the titanium alloy ingot with large size, and is suitable for industrial production.
5. The glass coating on the surface of the titanium alloy ingot is simple in component, safe, non-toxic, environment-friendly and convenient to remove.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is an optical photograph of a TC17 titanium alloy ingot with a pre-set layer prepared in example 1 of the present invention.
FIG. 2 is an optical photograph of a forged TC17 titanium alloy ingot having a glass coating layer formed on the surface thereof according to example 1 of the present invention.
Detailed Description
Example 1
The TC17 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 65% of glass matrix, 5% of clay and 30% of alumina and silicon oxide with the particle sizes less than 5 mu m; the clay is calcined kaolin with more than three levels;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 5％，Al2O3 4％，ZrO28％，Cr2O3 9％，CaO 11％，KNO35% and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、Cr2O3、CaO、KNO3And SiO2Placing the mixture into a ball mill, uniformly mixing the mixture through ball milling, then smelting the mixture for 4 hours at the temperature of 1450 ℃, obtaining glass glaze slag through water quenching, drying the glass glaze slag, and then performing ball milling on the glass glaze slag for 100 hours at the rotating speed of 500r/min by adopting the ball mill to obtain glass powder with the granularity of less than 10 mu m.
In this embodiment, the additive in the raw material for preparing the glass coating can also be alumina and mullite with the grain size less than 5 μm, or silica and mullite with the grain size less than 5 μm.
The preparation method of the glass coating on the surface of the TC17 titanium alloy ingot of the embodiment comprises the following steps:
cleaning the surface of a TC17 titanium alloy ingot, removing adhesion, floating ash and grease on the surface of the TC17 titanium alloy ingot, and then polishing;
placing 0.65kg of glass substrate, 0.05kg of clay, 0.30kg of alumina and silicon oxide with the particle sizes smaller than 5 mu m in total and 10kg of purified water in a ball mill, and carrying out ball milling and mixing uniformly for 5 hours under the condition that the rotating speed is 200r/min to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the cleaned TC17 titanium alloy ingot in the step one by adopting a brush coating mode, drying at 100 ℃, forming a preset layer on the surface of the TC17 titanium alloy ingot, then placing the TC17 titanium alloy ingot with the preset layer in a muffle furnace, firing at 1250 ℃, and forming a glass coating on the surface of the TC17 titanium alloy ingot.
The TC17 titanium alloy ingot with the glass coating formed on the surface is subjected to heat treatment for 50h under the condition of 1160 ℃ and then is forged.
Fig. 1 is an optical photograph of a TC17 titanium alloy ingot with a pre-layer prepared in this example, and it can be seen from fig. 1 that the surface of the glass coating pre-layer prepared on the surface of the TC17 titanium alloy by brush coating in this example is flat, and the pre-layer is well bonded to the TC17 titanium alloy ingot after air drying, and has no peeling phenomenon.
FIG. 2 is an optical photograph of a forged TC17 titanium alloy ingot having a glass coating formed on the surface thereof according to the present example, and it can be seen from FIG. 2 that the TC17 titanium alloy ingot having a glass coating formed on the surface thereof according to the present example was not cracked and had a good surface condition after being forged at 1160 ℃ for 50 hours.
Example 2
The TC4 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 65% of glass matrix and 35% of water glass; the water glass is potassium silicate water glass with the modulus of 3.5 and the mass concentration of 43 percent;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 12％，Al2O3 20％，ZrO2 8％，NiO 3％，BaO 3％，Na2CO38 percent, and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、NiO、BaO、Na2CO3And SiO2Placing the mixture into a ball mill, uniformly mixing the mixture through ball milling, then smelting the mixture for 10 hours at the temperature of 1600 ℃, obtaining glass glaze slag through water quenching, drying the glass glaze slag, and then performing ball milling on the glass glaze slag for 100 hours at the rotating speed of 500r/min by adopting the ball mill to obtain glass powder with the granularity of less than 10 mu m.
The preparation method of the glass coating on the surface of the TC4 titanium alloy ingot of the embodiment comprises the following steps:
cleaning the surface of a TC4 titanium alloy ingot, removing adhesion, floating ash and grease on the surface of the TC4 titanium alloy ingot, and then carrying out sand blasting treatment;
placing 0.65kg of glass substrate, 0.35kg of potassium silicate water glass and 2kg of purified water in a ball mill, and carrying out ball milling and mixing uniformly for 2 hours under the condition that the rotating speed is 400r/min to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the cleaned TC4 titanium alloy ingot in the step one by adopting a brush coating mode, drying at 60 ℃, forming a preset layer on the surface of the TC4 titanium alloy ingot, then placing the TC4 titanium alloy ingot with the preset layer in a muffle furnace, firing at 800 ℃, and forming a glass coating on the surface of the TC4 titanium alloy ingot.
Through detection, the surface of the preset layer formed on the surface of the TC4 titanium alloy ingot is flat, and the preset layer is well combined with the TC4 titanium alloy ingot after being dried in the air, so that the peeling phenomenon is avoided; the TC4 titanium alloy ingot with the glass coating formed on the surface still keeps the integrity of the glass coating after being subjected to heat treatment at 800 ℃ for 10 hours, and the TC4 titanium alloy ingot has no oxidation phenomenon.
Example 3
The present embodiment is different from embodiment 2 in that: and (3) presetting the composite slurry obtained in the step (II) on the surface of the cleaned TC4 titanium alloy ingot in the step (I) in a pneumatic spraying mode, wherein the spraying pressure of the pneumatic spraying is 0.4MPa, and the spraying distance is 40 cm.
Example 4
The TA7 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 80% of glass matrix and 20% of clay; the clay is calcined kaolin with more than three levels;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 12％，Al2O3 12％，ZrO2 3％，Cr2O36 percent of CaO, 6 percent of BaO 3 percent, 10 percent of ZnO and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、Cr2O3CaO, BaO, ZnO and SiO2Placing the mixture into a ball mill, uniformly mixing the mixture through ball milling, then smelting the mixture for 6 hours at the temperature of 1500 ℃, obtaining glass glaze slag through water quenching, drying the glass glaze slag, and then performing ball milling on the glass glaze slag for 100 hours at the rotating speed of 500r/min by adopting the ball mill to obtain glass powder with the granularity of less than 10 mu m.
The preparation method of the glass coating on the surface of the TA7 titanium alloy ingot of the embodiment comprises the following steps:
cleaning the surface of a TA7 titanium alloy ingot, removing adhesion, floating ash and grease on the surface of the TA7 titanium alloy ingot, and then carrying out pre-oxidation treatment for 10min at the temperature of 800 ℃;
placing 0.80kg of glass substrate, 0.20kg of clay and 5kg of purified water in a ball mill, and carrying out ball milling and mixing uniformly for 4 hours under the condition that the rotating speed is 300r/min to obtain composite slurry;
thirdly, presetting the composite slurry obtained in the second step on the surface of the cleaned TA7 titanium alloy ingot in the first step in a pneumatic spraying mode, drying at 20 ℃ to form a preset layer on the surface of the TA7 titanium alloy ingot, then placing the TA7 titanium alloy ingot with the preset layer in a muffle furnace, firing at 850 ℃ to form a glass coating on the surface of the TA7 titanium alloy ingot; the spraying air pressure of the pneumatic spraying is 0.3MPa, and the spraying distance is 30 cm.
Through detection, the surface of the preset layer formed on the surface of the TA7 titanium alloy ingot is flat, and the preset layer is well combined with the TA7 titanium alloy ingot after being dried in the air, so that the peeling phenomenon is avoided; in the embodiment, the TA7 titanium alloy ingot with the glass coating formed on the surface has no obvious peeling of the glass coating after heat treatment at 850 ℃ for 50h, and the surface state is good.
Example 5
The TC6 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 70% of glass matrix, 20% of water glass and 10% of mullite with the granularity less than 10 mu m; the water glass is potassium silicate water glass with the modulus of 3 and the mass concentration of 40 percent;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 8％，Al2O3 12％，ZrO25％，Cr2O3 4％，NiO 3％，BaO 7％，KNO3 4％、ZnO 5％、Na2CO36 percent, and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、Cr2O3、NiO、BaO、KNO3、ZnO、Na2CO3And SiO2Placing in a ball mill, ball-milling, mixing, smelting at 1500 deg.C for 8 hr, water quenching to obtain glass glaze slag, drying, ball-milling at 500r/min for 100 hr to obtain powder with particle size less than10 μm glass powder.
The preparation method of the glass coating on the surface of the TC6 titanium alloy ingot of the embodiment comprises the following steps:
cleaning the surface of a TC6 titanium alloy ingot, removing adhesion, floating ash and grease on the surface of the TC6 titanium alloy ingot, and then polishing;
placing 0.70kg of glass substrate, 0.20kg of potassium silicate water glass, 0.10kg of mullite and 8kg of purified water in total in a ball mill, and carrying out ball milling and mixing uniformly for 2.5h under the condition that the rotating speed is 350r/min to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the cleaned TC6 titanium alloy ingot in the step one by adopting a brush coating mode, drying at 20 ℃, forming a preset layer on the surface of the TC6 titanium alloy ingot, then placing the TC6 titanium alloy ingot with the preset layer in a muffle furnace, firing at 800 ℃, and forming a glass coating on the surface of the TC6 titanium alloy ingot.
Example 6
This embodiment is different from embodiment 5 in that: and (3) presetting the composite slurry obtained in the step (II) on the surface of the cleaned TC6 titanium alloy ingot in the step (I) in a pneumatic spraying mode, wherein the spraying air pressure of the pneumatic spraying is 0.2MPa, the spraying distance is 10cm, and the drying temperature is 200 ℃.
Through detection, the surface of the preset layer formed on the surface of the TC6 titanium alloy ingot is flat, and the preset layer is well combined with the TC6 titanium alloy ingot after being dried in the air, so that the peeling phenomenon is avoided; the TC6 titanium alloy ingot with the glass coating formed on the surface is subjected to heat treatment at 900 ℃ for 10 hours, the glass coating is complete, and the TC6 titanium alloy ingot has no oxidation phenomenon.
Example 7
The TC11 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 65% of glass matrix, 8% of clay, 22% of water glass, and 5% of alumina, silica and mullite with the particle sizes less than 5 μm; the clay is calcined kaolin with more than three levels, and the water glass is potassium silicate water glass with the modulus of 3 and the mass concentration of 40%;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 5％，Al2O3 4％，ZrO28％，Cr2O3 9％，CaO 11％，KNO3 2％、Na2CO33% and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、Cr2O3、CaO、KNO3、Na2CO3And SiO2Placing the mixture into a ball mill, uniformly mixing the mixture through ball milling, then smelting the mixture for 4 hours at the temperature of 1450 ℃, obtaining glass glaze slag through water quenching, drying the glass glaze slag, and then performing ball milling on the glass glaze slag for 100 hours at the rotating speed of 500r/min by adopting the ball mill to obtain glass powder with the granularity of less than 10 mu m.
Compound N in the glass matrix starting material according to this example may also be KNO3And ZnO, or Na2CO3And ZnO.
The preparation method of the glass coating on the surface of the TC11 titanium alloy ingot of the embodiment comprises the following steps:
cleaning the surface of a TC11 titanium alloy ingot, removing adhesion, floating ash and grease on the surface of the TC11 titanium alloy ingot, and then polishing;
placing 0.65kg of glass substrate, 0.08kg of clay, 0.22kg of potassium silicate water glass, 0.05kg of alumina, silicon oxide and mullite with the particle size smaller than 5 mu m and 5kg of purified water in a ball mill, and carrying out ball milling and mixing uniformly for 5 hours under the condition that the rotating speed is 200r/min to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the cleaned TC11 titanium alloy ingot in the step one by adopting a brush coating mode, drying at 20 ℃, forming a preset layer on the surface of the TC11 titanium alloy ingot, then placing the TC11 titanium alloy ingot with the preset layer in a muffle furnace, firing at 950 ℃, and forming a glass coating on the surface of the TC11 titanium alloy ingot.
Through detection, the surface of the preset layer formed on the surface of the TC11 titanium alloy ingot is flat, and the preset layer is well combined with the TC11 titanium alloy ingot after being dried in the air, so that the peeling phenomenon is avoided; the TC11 titanium alloy ingot with the glass coating formed on the surface is subjected to heat treatment at 950 ℃ for 10 hours, the glass coating is complete, and the TC11 titanium alloy ingot has no oxidation phenomenon.
Example 8
The TC18 titanium alloy ingot surface glass coating of the embodiment is prepared from the following raw materials in percentage by mass: 95% of glass matrix and 5% of clay; the clay is calcined kaolin with more than three levels;
the glass matrix is prepared by smelting the following raw materials in percentage by mass: b is2O3 12％，Al2O3 12％，ZrO2 3％，Cr2O36 percent of CaO, 6 percent of BaO 3 percent, 10 percent of ZnO and the balance of SiO2(ii) a The preparation process of the glass matrix comprises the following steps: b is to be2O3、Al2O3、ZrO2、Cr2O3CaO, BaO, ZnO and SiO2Placing the mixture into a ball mill, uniformly mixing the mixture through ball milling, then smelting the mixture for 6 hours at the temperature of 1500 ℃, obtaining glass glaze slag through water quenching, drying the glass glaze slag, and then performing ball milling on the glass glaze slag for 100 hours at the rotating speed of 500r/min by adopting the ball mill to obtain glass powder with the granularity of less than 10 mu m.
The preparation method of the glass coating on the surface of the TC18 titanium alloy ingot of the embodiment comprises the following steps:
step one, cleaning the surface of a TC18 titanium alloy ingot to remove adhesion, floating ash and grease on the surface of the TC18 titanium alloy ingot, and then carrying out pre-oxidation treatment for 10min at the temperature of 800 ℃;
placing 0.95kg of glass substrate, 0.05kg of clay and 5kg of purified water in a ball mill, and carrying out ball milling and mixing uniformly for 4 hours under the condition that the rotating speed is 300r/min to obtain composite slurry;
thirdly, presetting the composite slurry obtained in the second step on the surface of the cleaned TC18 titanium alloy ingot in the first step in a pneumatic spraying mode, drying at 20 ℃ and forming a preset layer on the surface of the TC18 titanium alloy ingot, then placing the TC18 titanium alloy ingot with the preset layer in a muffle furnace, firing at 850 ℃ and forming a glass coating on the surface of the TC18 titanium alloy ingot; the spraying air pressure of the pneumatic spraying is 0.3MPa, and the spraying distance is 30 cm.
Through detection, the surface of the preset layer formed on the surface of the TC18 titanium alloy ingot is flat, and the preset layer is well combined with the TC18 titanium alloy ingot after being dried in the air, so that the peeling phenomenon is avoided; the TC18 titanium alloy ingot with the glass coating formed on the surface in the embodiment has no obvious peeling of the glass coating after being subjected to heat treatment at 900 ℃ for 10 hours, and the surface state is good.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. The glass coating on the surface of the titanium alloy ingot is characterized by being prepared from the following raw materials in percentage by mass: 65-95% of glass matrix, 5-35% of binder and 0-30% of additive; the glass matrix is prepared from the following raw materials in percentage by mass: b is2O3 5%~12%，Al2O3 4%~20%，ZrO23% -8%, 3% -9% of compound K, 3% -11% of compound M, 5% -15% of compound N and the balance SiO2The compound K is NiO and/or Cr2O3The compound M is CaO and/or BaO, and the compound N is KNO3、Na2CO3And ZnO;
the preparation process of the glass matrix comprises the following steps: putting all the raw materials into a ball mill, performing ball milling and uniformly mixing, then smelting for 4-10 h at 1450-1600 ℃, performing water quenching to obtain glass glaze slag, drying, and performing ball milling by using the ball mill to obtain glass powder with the particle size of less than 10 mu m;
the additive is one or more than two of silicon oxide, aluminum oxide and mullite; the particle size of the additive is less than 10 mu m.
2. The titanium alloy ingot casting surface glass coating according to claim 1, wherein the binder is clay and/or water glass; the clay is calcined kaolin with more than three levels, and the mass percent of the clay is 5-20%; the water glass is potassium silicate water glass with the modulus not lower than 3 and the mass concentration not lower than 40%, and the mass percent of the potassium silicate water glass is 20-35%.
3. A method of producing a glass coating on the surface of a titanium alloy ingot as defined in claim 1 or claim 2, comprising the steps of:
cleaning the surface of a titanium alloy ingot to remove adhesion, floating ash and grease on the surface of the titanium alloy ingot;
step two, placing the glass substrate, the binder and the additives in a ball mill for ball milling and mixing uniformly to obtain composite slurry;
and step three, presetting the composite slurry obtained in the step two on the surface of the titanium alloy ingot cleaned in the step one, drying the titanium alloy ingot to form a preset layer on the surface of the titanium alloy ingot, then placing the titanium alloy ingot with the preset layer in a muffle furnace for heat treatment, and forming a glass coating on the surface of the titanium alloy ingot.
4. The method according to claim 3, wherein the surface of the cleaned titanium alloy ingot in the first step is subjected to grinding, pre-oxidation or sand blasting.
5. The method according to claim 3, wherein purified water is added as a dispersing agent during the ball milling and uniform mixing in the second step, and the volume of the dispersing agent is 2-10 times of the total mass of the glass substrate, the binder and the additives, wherein the volume is mL, and the mass is g.
6. The method according to claim 3, wherein the rotation speed for ball milling and mixing uniformly in the second step is 200r/min to 400r/min, and the time for ball milling and mixing uniformly is 2h to 5 h.
7. The method as claimed in claim 3, wherein the presetting in step three is performed by brushing or pneumatic spraying, the spraying pressure of the pneumatic spraying is 0.2 MPa-0.4 MPa, and the spraying distance is 10 cm-40 cm; the drying temperature is 20-200 ℃, and the heat treatment temperature is 800-1250 ℃.
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