阅读说明：本技术 一种高温诱导钛锆基合金表面耐蚀氧化层的制备方法 (Preparation method of high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer ) 是由 钟华 马明臻 刘日平 刘罡 胡恩柱 胡坤宏 于 2020-06-24 设计创作，主要内容包括：本发明属于合金材料表面氧化层的制备技术领域,具体的说是一种高温诱导钛锆基合金表面耐蚀氧化层的制备方法；该制备方法采用的加热炉包括加热室、冷却室、底座、动力装置和冷却装置；所述动力装置安装在冷却室内,动力装置包括气缸、推杆和固定板；所述气缸安装在冷却室底端侧壁上；冷却装置包括冷气箱和一号喷气口；所述冷气箱对称安装在冷却室内侧壁上,冷气箱内装填有冷气；所述一号喷气口安装在冷气箱外侧壁上,且与冷气箱内部连通,实现了对坯料的降温效果,从而提高了坯料的冷却速率,避免坯料随炉冷却的速率较慢,影响生产效率。(The invention belongs to the technical field of preparation of surface oxide layers of alloy materials, and particularly relates to a preparation method of a high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer; the heating furnace adopted by the preparation method comprises a heating chamber, a cooling chamber, a base, a power device and a cooling device; the power device is arranged in the cooling chamber and comprises an air cylinder, a push rod and a fixing plate; the cylinder is arranged on the side wall of the bottom end of the cooling chamber; the cooling device comprises a cold air box and a first air jet; the cold air boxes are symmetrically arranged on the inner side wall of the cooling chamber, and cold air is filled in the cold air boxes; a gas jet is installed on the cold air box lateral wall, and with the inside intercommunication of cold air box, has realized the cooling effect to the blank to improve the cooling rate of blank, avoided the blank to be slower along with the speed of stove cooling, influence production efficiency.)

1. A preparation method of a high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer is characterized by comprising the following steps: the preparation method comprises the following steps:

s1: pressing high-purity metals of titanium, zirconium and aluminum with the purity of 99.5 percent and the intermediate alloy 50Al50V into short rod-shaped lump materials to obtain basic raw materials, manufacturing the basic raw materials into electrodes, and then carrying out smelting treatment through a vacuum consumable arc furnace to obtain alloy ingots;

s2: carrying out three-pier three-pull turning on the alloy ingot in the S1 to obtain a titanium-zirconium-based alloy bar, cutting a square sample with the shape of 10mm multiplied by 30mm from the bar by using a wire electric discharge machine, and polishing the titanium-zirconium-based alloy square sample by using SiC abrasive paper to ensure that the surface roughness of the titanium-zirconium-based alloy square sample is 0.3-0.4 mu m;

s3: cleaning the titanium-zirconium-based alloy square sample in the step S2 in an ultrasonic cleaning machine to remove impurity particles on the surface of the titanium-zirconium-based alloy square sample, and drying the surface of the titanium-zirconium-based alloy square sample by using a hot air blower; wherein the heating temperature of the hot air blower is controlled at 50-60 ℃, and the titanium-zirconium-based alloy square sample is placed into a vacuum drying oven for later use after the surface of the titanium-zirconium-based alloy square sample is dried;

s4: carrying out thermal oxidation treatment on the titanium-zirconium-based alloy square sample in the S3 by a heating furnace, wherein the heating temperature is 650-800 ℃, and the heat preservation time is 10 h; after the heat preservation is finished, cooling the titanium-zirconium-based alloy square sample by a refrigerating device at the bottom end of the heating furnace, and finishing the preparation of the high-temperature induced corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy.

2. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 1, wherein the method comprises the following steps: when the basic raw material is smelted through a vacuum consumable electrode arc furnace, firstly, the smelting current is set to be 160-190A, and the basic raw material is continuously smelted until the basic raw material is melted into a liquid state; at the moment, the smelting current is increased to 200-240A, and the liquid basic raw material is continuously smelted for 2-3 min; finally, the smelting current is increased to 280-300A, and the single smelting treatment is completed after the basic raw materials are continuously smelted for 3-5 min; in order to ensure the uniformity of the components of the alloy ingot, repeated smelting treatment is required for 2-3 times.

3. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 1, wherein the method comprises the following steps: when the titanium-zirconium-based alloy square sample is cleaned by an ultrasonic cleaning machine, the titanium-zirconium-based alloy square sample is firstly placed in an acetone solution for cleaning, and the cleaning time is 10-15 min; then putting the titanium-zirconium-based alloy square sample into an alcohol solution for cleaning for 10-15 min; and finally, putting the titanium-zirconium-based alloy square sample into deionized water for cleaning for 10-15 min.

4. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 1, wherein the method comprises the following steps: when the square sample surface of titanium zirconium base alloy weathers through the air heater, with the directional square sample surface of titanium zirconium base alloy of the air outlet department slope of air heater for contained angle between it is 45 degrees, because the tensile force on the square sample surface of titanium zirconium base alloy is great, strong to the adsorption efficiency of liquid, consequently hot-blast through the slope produces thrust to liquid for the drying rate on the square sample surface of titanium zirconium base alloy.

5. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 1, wherein the method comprises the following steps: the heating furnace comprises a heating chamber (1), a cooling chamber (2), a base (3), a power device (4) and a cooling device (5); the heating chamber (1) is arranged on the side wall of the top end of the cooling chamber (2); the cooling chamber (2) is arranged on the base (3), and an opening (21) is formed in the side wall of the top end of the cooling chamber (2) and communicated with the heating chamber (1); a support frame (31) is arranged at the bottom end of the base (3); the power device (4) is arranged in the cooling chamber (2), and the power device (4) comprises a cylinder (41), a push rod (42) and a fixing plate (43); the cylinder (41) is arranged on the side wall of the bottom end of the cooling chamber (2); the push rod (42) is arranged at the output end of the air cylinder (41); the fixing plate (43) is connected in the opening (21) in a sliding manner, and the bottom end of the fixing plate (43) is installed at the end part of the push rod (42); the cooling device (5) is arranged on the inner side wall of the cooling chamber (2), and the cooling device (5) comprises a cold air box (51) and a first air jet (52); the cold air boxes (51) are symmetrically arranged on the inner side wall of the cooling chamber (2), and cold air is filled in the cold air boxes (51); the first air jet port (52) is arranged on the outer side wall of the cold air box (51) and is communicated with the interior of the cold air box (51).

6. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 5, wherein the method comprises the following steps: a plurality of first sliding grooves (511) are formed in the side wall of the cold air box (51); a first plate (512) is connected in the first sliding groove (511) in a sliding manner, and a second air jet (513) is arranged on the side wall of the first sliding groove (511) and communicated with the cold air box (51); a second plate (514) is arranged at the top end of the first plate (512), so that the second plate (514) can shield the second air jet port (513), and a plurality of clamping columns (515) are arranged at the bottom end of the first plate (512); the clamping column (515) is made of gallium-zinc alloy materials, and the closer the clamping column (515) is to the bottom end of the cooling chamber (2), the larger the volume of the clamping column (515) is.

7. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 5, wherein the method comprises the following steps: a second sliding groove (211) is formed in the inner side wall of the opening (21); a baffle (212) is connected in the second sliding groove (211) in a sliding manner through a spring, and a hinge rod (213) is hinged to the side wall of the second sliding groove (211) close to the opening (21) through a torsion spring; one end of the hinge rod (213) extends into the second sliding groove (211) and is in contact with the end part of the hinge rod (213), and the other end of the hinge rod extends to the inner side wall of the opening (21).

8. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 7, wherein the method comprises the following steps: a third sliding groove (214) is formed in the baffle plate (212); a fixture block (215) is connected in the third sliding groove (214) in a sliding manner, and an air bag (216) is arranged between the fixture block (215) and the inner side wall of the third sliding groove (214); the side wall of the fixture block (215) close to the opening (21) is provided with a rubber tube (217), so that the rubber tube (217) is communicated with the air bag (216); and a fixing block (218) is arranged at the end part of the rubber pipe (217).

9. The method for preparing the corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy by high-temperature induction according to claim 8, wherein the method comprises the following steps: the end part of the fixed block (218) is provided with a gear shaping (219); the gear shaping (219) is serrated.

Technical Field

The invention belongs to the technical field of preparation of surface oxide layers of alloy materials, and particularly relates to a preparation method of a high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer.

Background

The titanium alloy has the excellent characteristics of low density, high strength, good corrosion resistance and the like, and is an important structural material of an aerospace aircraft. The tensile strength of the Ti6Al4V titanium alloy which is widely used at present is 900-1100 MPa, and the failure elongation is 8-12%. The TiZrAlV alloy is a novel alloy material developed on the basis of Ti6Al4V alloy, and the introduction of zirconium element effectively improves the strength and hardness of the material, so that the TiZrAlV alloy becomes a candidate material of a very potential aerospace craft.

Disclosure of Invention

The invention provides a preparation method of a high-temperature induced corrosion-resistant oxide layer on the surface of a titanium-zirconium-based alloy, aiming at improving the corrosion resistance of the titanium-zirconium-based alloy, prolonging the service life of the titanium-zirconium-based alloy and ensuring the reliability and stability of the titanium-zirconium-based alloy in the service process.

The technical scheme adopted by the invention for solving the technical problems is as follows: the invention relates to a preparation method of a high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer, which comprises the following steps:

s1: pressing high-purity metals of titanium, zirconium and aluminum with the purity of 99.5 percent and the intermediate alloy 50Al50V into short rod-shaped lump materials to obtain basic raw materials, manufacturing the basic raw materials into electrodes, and then carrying out smelting treatment through a vacuum consumable arc furnace to obtain alloy ingots;

s2: carrying out three-pier three-pull turning on the alloy ingot in the S1 to obtain a titanium-zirconium-based alloy bar, cutting a square sample with the shape of 10mm multiplied by 30mm from the bar by using a wire electric discharge machine, and polishing the titanium-zirconium-based alloy square sample by using SiC abrasive paper to ensure that the surface roughness of the titanium-zirconium-based alloy square sample is 0.3-0.4 mu m;

s3: cleaning the titanium-zirconium-based alloy square sample in the step S2 in an ultrasonic cleaning machine to remove impurity particles on the surface of the titanium-zirconium-based alloy square sample, and drying the surface of the titanium-zirconium-based alloy square sample by using a hot air blower; wherein the heating temperature of the hot air blower is controlled at 50-60 ℃, and the titanium-zirconium-based alloy square sample is placed into a vacuum drying oven for later use after the surface of the titanium-zirconium-based alloy square sample is dried;

s4: carrying out thermal oxidation treatment on the titanium-zirconium-based alloy square sample in the S3 by a heating furnace, wherein the heating temperature is 650-800 ℃, and the heat preservation time is 10 h; after the heat preservation is finished, cooling the titanium-zirconium-based alloy square sample by a refrigerating device at the bottom end of the heating furnace, and finishing the preparation of the high-temperature induced corrosion-resistant oxide layer on the surface of the titanium-zirconium-based alloy.

Preferably, when the base raw material is smelted in the vacuum consumable electrode arc furnace, the smelting current is set to 160-190A, and the base raw material is continuously smelted until the base raw material is melted into a liquid state; at the moment, the smelting current is increased to 200-240A, and the liquid basic raw material is continuously smelted for 2-3 min; finally, the smelting current is increased to 280-300A, and the single smelting treatment is completed after the basic raw materials are continuously smelted for 3-5 min; in order to ensure the uniformity of the components of the alloy ingot, repeated smelting treatment is required for 2-3 times.

Preferably, when the titanium-zirconium-based alloy square sample is cleaned by an ultrasonic cleaning machine, the titanium-zirconium-based alloy square sample is firstly placed in an acetone solution for cleaning, and the cleaning time is 10-15 min; then putting the titanium-zirconium-based alloy square sample into an alcohol solution for cleaning for 10-15 min; and finally, putting the titanium-zirconium-based alloy bar into ionized water for cleaning for 10-15 min.

Preferably, when the square sample surface of titanium zirconium base alloy weathers through the air heater, with the square sample surface of titanium zirconium base alloy of the air outlet slope directional of air heater for contained angle between it is 45 degrees, because the tensile force on the square sample surface of titanium zirconium base alloy is great, strong to the adsorption efficiency of liquid, consequently through the hot-blast thrust that produces of slope to liquid for the drying rate on the square sample surface of titanium zirconium base alloy.

Preferably, the heating furnace comprises a heating chamber, a cooling chamber, a base, a power device and a cooling device; the heating chamber is arranged on the side wall of the top end of the cooling chamber; the cooling chamber is arranged on the base, and an opening is formed in the side wall of the top end of the cooling chamber and communicated with the heating chamber; the bottom end of the base is provided with a support frame; the power device is arranged in the cooling chamber and comprises an air cylinder, a push rod and a fixing plate; the cylinder is arranged on the side wall of the bottom end of the cooling chamber; the push rod is arranged at the output end of the air cylinder; the fixed plate is connected in the opening in a sliding manner, and the bottom end of the fixed plate is arranged at the end part of the push rod; the cooling device is arranged on the inner side wall of the cooling chamber and comprises a cold air box and a first air jet; the cold air boxes are symmetrically arranged on the inner side wall of the cooling chamber, and cold air is filled in the cold air boxes; the first air jet is arranged on the outer side wall of the air cooling box and is communicated with the interior of the air cooling box; during operation, place the blank on the fixed plate earlier, aerify the cylinder again, make the cylinder do the extension motion, thereby promote the fixed plate and get into in the heating chamber, carry out heat treatment through the heating chamber to the blank, after accomplishing the heating and the heat preservation to the blank, control cylinder drives the push rod and contracts, thereby move the blank to in the cooling chamber, the air conditioning in the cold air box spouts through a gas jet, the realization is to the cooling effect of blank this moment, thereby the cooling rate of blank has been improved, it is slower to avoid the blank to cool down along with the stove, influence production efficiency, also avoided taking out the blank to take out the method of cooling outside the stove simultaneously, thereby the blank surface oxygen content has been guaranteed, the quality of reinforcing blank surface oxide layer.

Preferably, a plurality of first sliding grooves are formed in the side wall of the cold air box; a first plate is connected in the first sliding groove in a sliding manner, and a second air jet is arranged on the side wall of the first sliding groove and communicated with the cold air box; the top end of the first plate is provided with a second plate, so that the second plate can shield the second air jet, and the bottom end of the first plate is provided with a plurality of clamping columns; the clamping column is made of gallium-zinc alloy materials, and the volume of the clamping column is larger the closer the clamping column is to the bottom end of the cooling chamber; when the cooling device works, after the blank is insulated and needs to be cooled, the air cylinder is contracted, so that the fixing plate is driven to descend to the cooling chamber, at the moment, cold air is sprayed out through the first air nozzle, the cooling effect on the blank is realized, in the cooling process of the blank, the cooling rate of the blank is gradually reduced along with the reduction of the temperature of the blank, and at the moment, after the cooling rate of the blank is reduced due to the different thermal expansion rates of the inner surface layer and the outer oxidation layer of the blank, the surface of the material is easy to crack, so the uniformity of the cooling rate of the blank is required to be ensured, when the blank enters the cooling chamber, the heat of the blank is transferred to the clamping column, the clamping column is melted after being heated, so that the first plate slides towards the bottom end of the first sliding groove, and the second plate slides along with the first sliding groove, the second plate does not block the second air jet, and the second air jet can spray cold air to cool the blank; and when the blank is continuously transmitted heat to the clamping column through the air, the clamping column with smaller volume is firstly melted, and the clamping column with larger volume is also melted, so that the cooling strength of the blank is increased in stages, namely, along with the reduction of the temperature of the blank, in order to ensure the uniform cooling rate of the blank, the cooling strength of the blank is gradually increased, the synchronous shrinkage of the inner surface layer and the outer oxidation layer of the blank is further ensured, and the integrity and the oxidation quality of the surface of the blank are ensured.

Preferably, a second sliding groove is formed in the inner side wall of the opening; a baffle is connected in the second sliding groove in a sliding manner through a spring, and a hinge rod is hinged on the side wall of the second sliding groove close to the opening through a torsion spring; one end of the hinge rod extends into the second sliding groove to be contacted with the end part of the hinge rod, and the other end of the hinge rod extends to the inner side wall of the opening; the during operation, when needs cool off the blank, make the cylinder take place to contract, thereby it slides to the direction of cooling chamber to drive the fixed plate, slide in-process at the fixed plate and produce the extrusion to the hinge bar, make the hinge bar take place to rotate, the hinge bar no longer produces the extrusion to the baffle this moment, then the baffle is from No. two spout roll-offs under the spring action of spring, realized carrying out isolated effect between heating chamber and the cooling chamber, avoid thermal mutual transmission between heating chamber and the cooling chamber, influence the cooling rate to the blank, thereby the whole result of use of heating furnace has further been guaranteed.

Preferably, a third sliding groove is formed in the baffle; a clamping block is connected in the third sliding groove in a sliding mode, and an air bag is arranged between the clamping block and the inner side wall of the third sliding groove; the side wall of the clamping block close to the opening is provided with a rubber tube, so that the rubber tube is communicated with the air bag; the end part of the rubber tube is provided with a fixed block; the during operation, at the in-process of baffle roll-off from No. two spouts, the hinge bar can produce the fixture block and block for the fixture block takes place to slide in No. three spouts, thereby produce the extrusion to the gasbag, the gasbag pressurized receives its inside gas transmission to the rubber tube in, makes the rubber tube take place the expansion deformation of extension, thereby releases the fixed block, further strengthens the seal effect between the baffle through the fixed block, avoids the slag in the heating furnace to fall behind and causes the damage to the blank surface.

Preferably, the end part of the fixed block is provided with gear shaping; the gear shaping is in a sawtooth shape; during operation, when the fixed blocks contact each other under the thrust action of the rubber tube, the tightness of the contact position between the fixed blocks is further ensured through the gear shaping, so that the transmission of heat between the heating chamber and the cooling chamber is effectively avoided, meanwhile, the falling of slag generated by the blank when the blank is heated from the gap between the fixed blocks is avoided, and the effective cooling effect and the heat preservation effect on the blank are realized.

The invention has the following beneficial effects:

1. according to the preparation method of the high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer, the cooling rate of the blank is improved through the cooperation of the heating chamber, the cooling chamber, the base, the power device and the cooling device, the problem that the production efficiency is influenced due to the fact that the blank is cooled at a low rate along with the furnace is avoided, and meanwhile, the problem that the blank is taken out of the furnace to be cooled is avoided, so that the oxygen content of the blank surface is guaranteed, and the quality of the blank surface oxide layer is improved.

2. According to the preparation method of the high-temperature induced titanium-zirconium-based alloy surface corrosion-resistant oxide layer, the blank is gradually increased in cooling strength along with the reduction of the temperature of the blank in order to ensure the uniform cooling rate of the blank, so that the synchronous shrinkage of the inner surface layer and the outer oxide layer of the blank is further ensured, and the integrity and the oxidation quality of the surface of the blank are ensured.

Drawings

The invention will be further explained with reference to the drawings.

FIG. 1 is a process flow diagram of the present invention;

FIG. 2 is a perspective view of a heating furnace used in the present invention;

FIG. 3 is a sectional view of a heating furnace used in the present invention;

FIG. 4 is an enlarged view of a portion of FIG. 3 at A;

FIG. 5 is a partial enlarged view at B in FIG. 3;

FIG. 6 is a surface X-ray diffraction pattern of examples 1-4 of the present invention;

in the figure: the air conditioner comprises a heating chamber 1, a cooling chamber 2, an opening 21, a second sliding groove 211, a baffle 212, a hinge rod 213, a third sliding groove 214, a clamping block 215, an air bag 216, a rubber tube 217, a fixing plate 218, a gear shaping 219, a base 3, a support frame 31, a power device 4, an air cylinder 41, a push rod 42, a fixing plate 43, a cooling device 5, an air cooling box 51, a first sliding groove 511, a first plate 512, a second air jet 513, a second plate 514, a clamping column 515 and a first air jet 52.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.