CN103060881B - Titanium alloy surface black high temperature coatings preparation method - Google Patents
Titanium alloy surface black high temperature coatings preparation method Download PDFInfo
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- CN103060881B CN103060881B CN201310029887.2A CN201310029887A CN103060881B CN 103060881 B CN103060881 B CN 103060881B CN 201310029887 A CN201310029887 A CN 201310029887A CN 103060881 B CN103060881 B CN 103060881B
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Abstract
<b> titanium alloy surface black high temperature coatings preparation method </b> of the present invention, in particular to the integrated technology that differential arc oxidation and silane-modified powder combine, this </b> of <b> invention agent object is titanium alloy, adopt phosphoric acid salt, aluminate, silicate, meta-aluminate or sulfate solution or its two kinds of mixing salts are as the electrolytic solution of differential arc oxidation, add the pH value that weak acid regulates electrolytic solution, add the powder containing aluminium in the electrolytic solution, or basis above adds rare earth powder again, it is made to be dispersed in electrolytic solution, electrolytic solution keeps in alkalescence, after chemical reaction, electrochemical reaction and isoionic effect, formed on the surface less or imporous compound coating at titanium alloy substrate, this coating presents black, there is excellent resistance to high temperature oxidation characteristic and radiation characteristic, also have wear-resisting preferably simultaneously, corrosion resisting property.This coating production also has environmental protection, the feature that the process time is short.
Description
Technical field
The present invention relates to the technology of preparing of titanium alloy surface complex function coating, particularly the integrated technology that combines of differential arc oxidation and silane-modified powder.
Background technology
Titanium alloy is a kind of alloy in lightweight, due to the characteristic that it has high specific tenacity and excellent anti-chlorine ion corrosion, obtains great application in fields such as aerospace, weaponry, chemical industry.But the use temperature of titanium alloy is not high, mainly the solubleness of oxygen in titanium is high, be easy to form oxide film, easily there is oxidation film layer in common alloy of titanium its surface of life-time service at higher than 400 DEG C, even if the current use temperature of special heat-resistant titanium alloy is also difficult to more than 600 DEG C, this oxidation film layer along with the rising of temperature and the prolongation of time can progressive additive, cause coating and matrix to occur peeling off due to the difference of thermal expansivity.Therefore often need to prepare one deck coating by the method for top coat at titanium alloy surface, intercept or delay the speed of extraneous oxygen to matrix internal diffusion.In addition black coating has disguise, and has high radiation characteristic, the high heat of self can be delivered to the external world rapidly, therefore the black oxidation resistant coating of the titanium alloy surface efficacy effect that has it special.
The preparation method of current titanium alloy surface black rete is mainly prepared by the method for vacuum PVD, by surface deposition titanium carbide rete as decorating film, this film thickness is thinner, titanium carbide hardness is large, also can have certain wear resistance as hard films, but not there is anti-oxidation characteristics.
It is by being first oxidized by titanium alloy surface that patent (CN101177773A) is reported in the method that titanium alloy surface prepares black rete, and then process obtains in the Temperature Vacuum non-oxidizing atmosphere of 200-1000 DEG C, this method will pass through two steps, vacuum-treat will have great restriction to big scale workpiece, simultaneously in comparatively high temps thermal treatment, workpiece is easily made to produce distortion.
Summary of the invention
The object of this invention is to provide a kind of electrolytic solution of the aqueous solution as differential arc oxidation adopting phosphoric acid salt or aluminate, add the powder containing aluminium in the electrolytic solution, can be pure aluminium powder, Al alloy powder or alumina powder jointed, it is made to be dispersed in electrolytic solution, after chemical reaction, electrochemical reaction and isoionic acting in conjunction, form one deck few imporous black anti-oxidation composite coating on the surface at titanium alloy substrate
titanium alloy surface black high temperature coatings preparation method.
Technical scheme of the present invention is: titanium alloy surface black high temperature coatings preparation method, specifically comprises the following steps:
1) configure electrolytic solution: get a certain amount of solute and join in deionized water, obtaining concentration is 5-20g/L salt-containing solution, adding concentration is that 0.3-1g/L weak acid regulates the pH value of saline solns to be 7-12; Wherein, described solute is one or more mixing salts of phosphoric acid salt, silicate, meta-aluminate or vitriol;
2) by particle diameter be less than 50 microns containing after aluminium powder body and the mixing of a certain amount of rare earth powder by silane by above-mentioned powder-modified or directly add step 1 and prepare in electrolytic solution, stir; Wherein, described is add 5-30 gram in 1 liter of electrolytic solution containing aluminium powder body add-on, and described rare earth powder add-on adds to be less than 15 grams in 1 liter of electrolytic solution; Described powder is one or more mixing of pure aluminium powder, Al alloy powder or aluminum oxide powder;
3) electrolytic solution containing aluminium powder body step 2 prepared is inserted in electrolyzer, using titanium matrix as anode, graphite, stainless steel or platinum are as negative electrode, by high-voltage power-supply unit, adopt the pulse power, pass into the voltage that can make the titanium alloy surface starting the arc, voltage range is 300-600V, the time of passing into is 5-30 minute, and make its Surface Creation a layer thickness then wash away electrolytic solution with water in the coating of 2-300 micron black even, room temperature is dried or dried.
Beneficial effect of the present invention is: the coating adopting aforesaid method to obtain has the fundamental characteristics that differential arc oxidization technique prepares coating, surface presentation black, its porosity is low more than common differential arc oxidation coating, surfaceness is also low, there is fabulous anti-oxidation characteristics, coating has electrochemical corrosion resistant, the characteristic such as wear-resisting concurrently, and coat-thickness is at 2-300 micron.This method technique is simple, and easy to operate, the time is short, therefore will be with a wide range of applications.
Accompanying drawing explanation
The titanium alloy surface black oxidation resistant coating that Fig. 1 the present invention obtains compares schematic diagram with the surface color of common differential arc oxidation coating.
Fig. 2 is that the black oxidation resistant coating that the present invention obtains compares schematic diagram with common differential arc oxidation coating surface porosity factor.
The curve synoptic diagram of the titanium alloy surface coating that Fig. 3 the present invention obtains and naked titanium alloy increasing weight of oxidation (anti-oxidation characteristics) over time at 750 DEG C.
be described further below in conjunction with specific embodiment to technical scheme of the present invention.
Embodiment 1: the compound coating preparation adding pure aluminium powder
The sodium metaaluminate electrolytic solution of preparation 5g/L, adding the pure aluminium powder of 25g/L in the electrolytic solution, is then negative electrode with graphite cake, titanium alloy print is anode, with the pulse power, carry out differential arc oxidation process in the electrolytic solution, parameter is constant voltage 300V, time 5min, dutycycle 60%, frequency 2000, turns off power supply and is taken out by print after the time, rinse with water, then naturally dry.
Embodiment 2: the compound coating preparation adding aluminum oxide powder
The sodium phosphate of preparation 12g/L and magnesium sulfate mixed electrolytic solution, adding the aluminum oxide powder of 5g/L in the electrolytic solution, is then negative electrode with stainless steel plate, titanium alloy print is anode, with the pulse power, carry out differential arc oxidation process in the electrolytic solution, parameter is constant voltage 480V, time 20min, dutycycle 60%, frequency 2000, turns off power supply and is taken out by print after the time, rinse with water, then naturally dry.
Embodiment 3: the compound coating preparation adding mixed powder
Prepare the mixed electrolytic solution of the water glass of 20g/L, sodium metaaluminate and sodium phosphate, add the Al alloy powder of 10g/L and the mixed powder (powder quality is than 1:1) of aluminum oxide powder in the electrolytic solution, then with platinum sheet for negative electrode, titanium alloy print is anode, carry out differential arc oxidation in the electrolytic solution, parameter is constant voltage 400V, time 10min, dutycycle 60%, frequency 2000, after the time, turn off power supply print is taken out, rinse with water, then naturally dry.
Embodiment 4: the compound coating preparation adding rare earth mixed powder
Preparation 20g/L sodium phosphate electrolytic solution, add the Al alloy powder of 30g/L and the mixed powder (powder quality is than 1:1:1) of aluminum oxide powder and cerium oxide in the electrolytic solution, then with platinum sheet for negative electrode, titanium alloy print is anode, carry out differential arc oxidation process in the electrolytic solution, the pulse power, parameter is constant voltage 600V, time 8min, dutycycle 50%, frequency 2000, turns off power supply and is taken out by print after the time, rinse with water, then naturally dry.
The surface color of titanium alloy surface black oxidation resistant coating obtained from the present invention shown in Fig. 1 and comparing of common differential arc oxidation coating, find out that the compound coating of gained of the present invention is black (as shown in Figure 1A), and common arc differential oxide ceramic coating gray (as shown in Figure 1B).
From the present invention shown in Fig. 2 obtain titanium alloy surface black oxidation resistant coating the comparing of surface topography (as shown in Figure 2 A) and common differential arc oxidation coating (as shown in Figure 2 B, find out the compound coating surface pore diameter that the present invention obtains and porosity little compared with common arc differential oxide ceramic coating.
From the present invention shown in Fig. 3 obtain titanium alloy surface coating and naked titanium alloy anti-oxidation characteristics at 750 DEG C compare, find out obtained black anti-oxidation composite coating, under 750 DEG C of conditions, more uncoated titanium alloy oxidation weight gain is slow, after 50 hours, the weightening finish of naked titanium alloy is 1.5% than (/ original weight of gaining in weight), and after differential arc oxidation process, the weightening finish ratio of sample is 0.59%.Common differential arc oxidation coating just peels off for 10 hours under 750 DEG C of conditions later simultaneously, and the coating that therefore prepared by explanation the present invention improves the resistance to high temperature oxidation characteristic under 750 DEG C of conditions of titanium alloy.
Claims (3)
1. titanium alloy surface black high temperature coatings preparation method, is characterized in that, specifically comprise the following steps:
The sodium phosphate of preparation 12g/L and magnesium sulfate mixed electrolytic solution, adding the aluminum oxide powder of 5g/L in the electrolytic solution, is then negative electrode with stainless steel plate, titanium alloy print is anode, with the pulse power, carry out differential arc oxidation process in the electrolytic solution, parameter is constant voltage 480V, time 20min, dutycycle 60%, frequency 2000, turns off power supply and is taken out by print after the time, rinse with water, then naturally dry.
2. titanium alloy surface black high temperature coatings preparation method, is characterized in that, specifically comprise the following steps:
Prepare the mixed electrolytic solution of the water glass of 20g/L, sodium metaaluminate and sodium phosphate, add the Al alloy powder of 10g/L and the mixed powder of aluminum oxide powder in the electrolytic solution, powder quality compares 1:1, then with platinum sheet for negative electrode, titanium alloy print is anode, carries out differential arc oxidation in the electrolytic solution, and parameter is constant voltage 400V, time 10min, dutycycle 60%, frequency 2000, turns off power supply and is taken out by print after the time, rinse with water, then naturally dry.
3. titanium alloy surface black high temperature coatings preparation method, is characterized in that, specifically comprise the following steps:
The sodium phosphate electrolytic solution of preparation 20g/L, add the Al alloy powder of 30g/L and the mixed powder of aluminum oxide powder and cerium oxide in the electrolytic solution, powder quality compares 1:1:1, then with platinum sheet for negative electrode, titanium alloy print is anode, carries out differential arc oxidation process in the electrolytic solution, the pulse power, parameter is constant voltage 600V, time 8min, dutycycle 50%, frequency 2000, after the time, turn off power supply print is taken out, rinse with water, then naturally dry.
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| WO2015122901A1 (en) | 2014-02-14 | 2015-08-20 | Hewlett-Packard Development Company, L.P. | Substrate with insulating layer |
| RU2570869C1 (en) * | 2014-09-10 | 2015-12-10 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing of black wear-resistant anti-corrosion coating on aluminium and aluminium based alloys by method of microarc oxydation |
| CN104790010A (en) * | 2015-05-05 | 2015-07-22 | 贵州大学 | Micro-arc oxidation electrolyte new energy-saving mixed additive and application thereof |
| CN105603495B (en) * | 2015-12-31 | 2017-12-29 | 浙江大学 | A kind of preparation technology of titanium-base alloy high temperature coatings |
| CN106362718A (en) * | 2016-08-17 | 2017-02-01 | 华南理工大学 | ZrO2/TiO2 composite photocatalyst and its preparation method and use |
| CN108486631A (en) * | 2018-03-13 | 2018-09-04 | 浙江工业大学 | A method of improving titanium-base alloy resistance to high temperature oxidation |
| CN108823626B (en) * | 2018-05-27 | 2020-11-03 | 中南大学 | Al (aluminum)2O3Al/Mg layered density gradient material and preparation method and application thereof |
| CN114807825B (en) * | 2022-04-13 | 2023-04-07 | 四川大学 | Preparation method of MCrAlY high-temperature-resistant coating |
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