CN103938190B - The preparation method of a kind of molybdenum and molybdenum alloy surface oxidation resistant coating - Google Patents
The preparation method of a kind of molybdenum and molybdenum alloy surface oxidation resistant coating Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of molybdenum and molybdenum alloy surface oxidation resistant coating, the method adopts substep squeegee process to prepare Hf-Y mixed oxide coatings at molybdenum and molybdenum alloy surface, its step is as follows: first carry out alkali cleaning degreasing and pickling decontamination to molybdenum and molybdenum alloy surface, hydrofluoric acid surface etching treatment is carried out, obtained matrix after washing; Prepare the n-propyl alcohol solution of oxychlorination hafnium and Yttrium trichloride more by a certain percentage, obtained required masking liquid; Masking liquid is evenly painted on molybdenum and molybdenum alloy matrix surface, roasting after first drying after each brushing, repeat 15 ~ 30 times, last roasting 1 ~ 2h, namely obtains Hf-Y mixed oxide coatings at molybdenum and molybdenum alloy surface.Coating prepared by this method has excellent high-temperature oxidation resistance, and coated material is fine and close, and good with the consistency of matrix, difficult drop-off, greatly expands the use range of molybdenum and molybdenum alloy.
Description
Technical field
The present invention relates to the preparation method of a kind of molybdenum and molybdenum alloy surface oxidation resistant coating, particularly the preparation method of a kind of molybdenum and molybdenum alloy surface Hf-Y mixed oxide oxidation resistant coating.
Technical background
Molybdenum and molybdenum alloy are a kind of important high temperature alloys, because it has excellent conduction, thermal conductivity, and fusing point is high, intensity is large, linear expansivity is little, corrosion stability is strong and mechanical behavior under high temperature good, is thus widely used in the fields such as aerospace, generating, nuclear reactor, war industry, chemical industry and glass work.But, form MoO because oxidation can occur about 300 DEG C time molybdenum
2, can secondary oxidation be there is time about temperature rise to 600 DEG C, generate MoO
3, at about 725 DEG C MoO
3volatilize and occur liquid phase, although be improved through the molybdenum base material high-temperature oxidation resistance of alloying, fundamentally can not solve its easily oxidized defect.So the oxidation of molybdenum and its mechanical behavior under high temperature of phenomena impair of volatilizing, limit the range of application of molybdenum and molybdenum alloy.
The approach of current solution molybdenum and molybdenum alloy oxidisability has two, and one is the molybdenum alloy developing high-temperature oxidation resistant, and two is applying surface oxidation resistant coating.But molybdenum can alloying level very little, when the alloy adding improving antioxidant property is slightly many, the poor processability of alloy, even not there is temperature-room type plasticity, so fundamentally cannot change the resistance of oxidation of molybdenum and molybdenum alloy by the method for alloying, but also its many high-temperature behaviors can be had influence on, as hot strength, shock-resistance, resistance to heat shocks and creep resistance etc.So, prepare coating on the surface of molybdenum and molybdenum alloy and carry out anti-oxidation and just seem very necessary.Common high-temperature oxidation resistant coating has aluminide coating, silicide coating, refractory alloy coating etc., but mostly there is coating and the shortcoming such as substrate combinating strength is not high, poor compatibility, acid-alkali-corrosive-resisting effect are bad.
Summary of the invention
The defect existed for existing anti-oxidation tech or deficiency, the object of the invention is to, and proposes the preparation method of a kind of molybdenum and molybdenum alloy surface oxidation resistant coating.
To achieve these goals, the present invention takes following technical solution:
A preparation method for molybdenum and molybdenum alloy surface oxidation resistant coating, is characterized in that, follows these steps to:
(1) NaOH solution molybdenum and molybdenum alloy being placed in 10 ~ 30wt% boils alkali cleaning degreasing, washes with after ultrasonic cleaning; Then the HCl solution being placed in 20 ~ 40wt% is heated to 70 DEG C ~ 90 DEG C, keeps 0.5 ~ 1.5h pickling decontamination; Being placed in temperature is again that the hydrofluoric acid solution (5 ~ 20wt%) of 60 ~ 80 DEG C carries out surface etch, until surface forms even pitted skin, takes out rear deionized water and alcohol is clean, oven dry, obtains molybdenum and molybdenum alloy matrix;
(2) oxychlorination hafnium and Yttrium trichloride are mixed with appropriate ratio be dissolved in n-propyl alcohol solution, masking liquid needed for obtained coating;
(3) masking liquid is evenly painted on surface treated matrix pitted skin, brushes 15 ~ 30 times, dry 15min ~ 20min after each brushing, drying temperature is 100 DEG C ~ 150 DEG C; After drying, then be placed in retort furnace roasting 20min ~ 30min, maturing temperature 350 DEG C ~ 450 DEG C, after last brushing drying, roasting 1 ~ 2h under above-mentioned identical maturing temperature, namely obtains Hf-Y mixed oxide coatings at molybdenum and molybdenum alloy surface.
The material of above-mentioned molybdenum and molybdenum alloy can be sheet material or the bar of pure molybdenum, Mo-Ti system alloy, Mo-W system alloy, Mo-Cu system alloy, Mo-Re system alloy, TZC alloy or TZM alloy.
In above-mentioned coating solution, the ratio of oxychlorination hafnium and Yttrium trichloride is that 1:2 ~ 4:1 prepares according to the mol ratio of Hf and Y.
Described drying adopts loft drier or infrared lamp.
Detect through high temperature oxidation experiment, use temperature≤1400 DEG C of above-mentioned Hf-Y mixed oxide coatings.
The preparation of molybdenum of the present invention and molybdenum alloy surface oxidation resistant coating, prepares Hf-Y mixed oxide coatings by molybdenum and molybdenum alloy surface, can prevent molybdenum and molybdenum alloy oxidation, compared with prior art have the following advantages:
1. the Hf-Y mixed oxide coatings that obtains at molybdenum and molybdenum alloy surface of the method, high-temperature oxidation resistance is good, can resist high temperature oxidation and corrosion;
2. the consistency of the Hf-Y mixed oxide coatings prepared of the method and molybdenum and molybdenum alloy matrix is good, and thermal expansivity is similar, not easily cracks, difficult drop-off.
3. the method is simple to operate, does not need complicated paint-on technique and equipment.
Accompanying drawing explanation
Fig. 1: in embodiment 1, oxidation resistant coating section S EM schemes;
Fig. 2: the surperficial SEM figure of pure molybdenum plate after coating process in embodiment 1;
Fig. 3: embodiment 1 through 15min, coating molybdenum plate after 1000 DEG C of high temperature oxidations surface SEM organization chart.
Embodiment
Be described further of the present invention below in conjunction with drawings and Examples.It should be noted that; following embodiment is the present invention's preferably example, only for illustration of the present invention, the invention is not restricted to above-described embodiment; the interpolation of every technical characteristic done according to the technical scheme of the technology of the present invention, equivalent transformation, all belong to the protection domain of technical solution of the present invention.
Embodiment 1:
Step 1: choose the pure molybdenum board material that purity is more than 99.95%, area 100cm
2, the NaOH solution being placed in 30wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Be placed in the HCl solution of 10wt% and be heated to 90 DEG C, keep 1.5h; Being placed in temperature is again that 80 DEG C of hydrofluoric acid solutions (5wt%) carry out surface etch, until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained pure molybdenum plate matrix.
Step 2: get 5g oxychlorination hafnium and mix with 4g Yttrium trichloride and be dissolved in 50ml n-propyl alcohol solution, obtained required masking liquid.
Step 3: again the masking liquid of step 2 is evenly painted on surface treated matrix pitted skin, brush 20 times, each brushing is placed on loft drier and dries 10min, bake out temperature is 120 DEG C, be placed in retort furnace roasting 20min again, maturing temperature is 380 DEG C, after last brushing is dried, roasting 2h under above-mentioned identical maturing temperature, obtained final coating.
Step 4: 10 × 10mm square is cut into the molybdenum plate through surface coated treatment and carries out 1000 DEG C, 1200 DEG C and 1400 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated molybdenum plate oxidation quality damaed cordition.
The oxidation resistant coating section S EM of the present embodiment schemes as shown in Figure 1, and as shown in Figure 2, through 15min, the coating molybdenum plate surface SEM organization chart after 1000 DEG C of high temperature oxidations as shown in Figure 3 for sealer SEM organization chart.Fig. 1 shows that this pure molybdenum plate surface defines one deck Hf-Y mixed oxide coatings, and thickness is at 3.8 ~ 6.4 μm; Fig. 2 shows that the Hf-Y mixed oxide coatings formed is comparatively fine and close, without hole; Fig. 3 shows through 15min, the uninfluenced destruction of coating after 1000 DEG C of high temperature oxidations, and matrix is not by oxygen attack, and antioxidant effect is better.
Embodiment 2:
Step 1: choose the pure molybdenum bar material that purity is more than 99.95%, long 100mm, diameter 15mm, the NaOH solution being placed in 20wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Be placed in the HCl solution of 20wt% and be heated to 80 DEG C, keep 1.5h; Being placed in temperature is again that 80 DEG C of hydrofluoric acid solutions (10wt%) carry out surface etch, until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained pure molybdenum bar matrix.
Step 2: get 8g oxychlorination hafnium and mix with 4g Yttrium trichloride and be dissolved in 50ml n-propyl alcohol solution, obtained required masking liquid.
Step 3: again the masking liquid of step 2 is evenly painted on surface treated matrix pitted skin, brush 20 times, each brushing dries 10min under being placed on infrared lamp, bake out temperature is 130 DEG C, be placed in retort furnace roasting 15min again, maturing temperature is 400 DEG C, after last brushing is dried, roasting 1.5h under above-mentioned identical maturing temperature, obtained final coating.
Step 4: 1000 DEG C, 1200 DEG C and 1400 DEG C of high temperature oxidation experiments are carried out to the molybdenum bar through surface coated treatment, measurement quality rate of loss, and compare with not surface treated molybdenum bar oxidation quality damaed cordition.
Embodiment 3:
Step 1: choose the rear earth lanthanum doping TZM sheet alloy prepared by powder metallurgical technique, area 80cm
2, the NaOH solution being placed in 10wt% is boiled, and uses ultrasonic cleaning 1.5h, and taking-up washes; Be placed in the HCl solution of 30wt% and be heated to 80 DEG C, keep 1h; Being placed in temperature is again that 70 DEG C of hydrofluoric acid solutions (15wt%) carry out surface etch, until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained TZM alloy sheets matrix.
Step 2: get 15g oxychlorination hafnium and mix with 4g Yttrium trichloride and be dissolved in 80ml n-propyl alcohol solution, obtained required masking liquid.
Step 3: again the masking liquid of step 2 is coated with and evenly brushes in surface treated matrix pitted skin, brush 30 times, each brushing is placed on loft drier and dries 15min, bake out temperature is 140 DEG C, be placed in retort furnace roasting 20min again, maturing temperature is 420 DEG C, after last brushing is dried, roasting 1h under above-mentioned identical maturing temperature, obtained final coating.
Step 4: 10 × 10mm square is cut into the rear earth lanthanum doping TZM sheet alloy through surface coated treatment and carries out 1000 DEG C, 1200 DEG C and 1400 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated molybdenum bar oxidation quality damaed cordition.
Embodiment 4:
Step 1: choose TZC sheet alloy prepared by vacuum melting method, area 60cm
2, the NaOH solution being placed in 20wt% is boiled, and uses ultrasonic cleaning 1.5h, and taking-up washes; Be placed in the HCl solution of 20wt% and be heated to 80 DEG C, keep 1h; Being placed in temperature is again that 60 DEG C of hydrofluoric acid solutions (20wt%) carry out surface etch, until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained TZC alloy sheets matrix.
Step 2: get 10g oxychlorination hafnium and mix with 4g Yttrium trichloride and be dissolved in 60ml n-propyl alcohol solution, obtained required masking liquid.
Step 3: again the masking liquid of step 2 is evenly painted on surface treated matrix pitted skin, brush 25 times, each brushing is placed on loft drier and dries 12min, bake out temperature is 150 DEG C, be placed in retort furnace roasting 15min again, maturing temperature is 450 DEG C, after last brushing is dried, roasting 1h under above-mentioned identical maturing temperature, obtained final coating.
Step 4: 10 × 10mm square is cut into the TZM sheet alloy through surface coated treatment and carries out 1000 DEG C, 1200 DEG C and 1400 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated molybdenum bar oxidation quality damaed cordition.
Table 1, table 2, table 3 are the various embodiments described above materials in the oxidative mass loss rate correlation data of 1000 DEG C, 1200 DEG C and 1400 DEG C respectively.As can be seen from the table, at 1000 DEG C to 1200 DEG C, be oxidized no matter 10min to 30min, through the molybdenum of this invention coating process and molybdenum alloy quality all without considerable change, until 1400 DEG C be oxidized after, mass loss rate is remarkable rising tendency; And without any surface-treated molybdenum and molybdenum alloy at 1000 DEG C 10min oxidation by vigorous oxidation, after oxidation 30min matrix ablation totally, the oxidation resistant coating prepared by explanation is highly resistant to the erosion of oxygen, and use temperature is up to 1400 DEG C.
Table 1:
Table 2:
Table 3:
Claims (4)
1. a preparation method for molybdenum and molybdenum alloy surface oxidation resistant coating, is characterized in that, follows these steps to:
(1) NaOH solution molybdenum and molybdenum alloy being placed in 10 ~ 30wt% boils alkali cleaning degreasing, washes with after ultrasonic cleaning; Then the HCl solution being placed in 20 ~ 40wt% is heated to 70 DEG C ~ 90 DEG C, keeps 0.5 ~ 1.5h pickling decontamination; Being placed in temperature is again that the hydrofluoric acid solution of the 5wt% ~ 20wt% of 60 ~ 80 DEG C carries out surface etch, until surface forms even pitted skin, takes out rear deionized water and alcohol is clean, oven dry, obtains molybdenum and molybdenum alloy matrix;
(2) oxychlorination hafnium and Yttrium trichloride are mixed with appropriate ratio be dissolved in n-propyl alcohol solution, masking liquid needed for obtained coating;
(3) masking liquid is evenly painted on surface treated matrix pitted skin, brushes 15 ~ 30 times, dry 15min ~ 20min after each brushing, drying temperature is 100 DEG C ~ 150 DEG C; After drying, be placed in retort furnace roasting 20min ~ 30min again, maturing temperature 350 DEG C ~ 450 DEG C, after last brushing drying, roasting 1 ~ 2h at above-mentioned identical maturing temperature 350 DEG C ~ 450 DEG C, namely obtains Hf-Y mixed oxide coatings at molybdenum and molybdenum alloy surface;
Oxychlorination hafnium in described masking liquid and the ratio of Yttrium trichloride are that 1:2 ~ 4:1 prepares according to the mol ratio of Hf and Y.
2. the method for claim 1, is characterized in that, described molybdenum and molybdenum alloy material are sheet material or the bar of pure molybdenum, Mo-Ti system alloy, Mo-W system alloy, Mo-Cu system alloy, Mo-Re system alloy, TZC alloy or TZM alloy.
3. the method for claim 1, is characterized in that, described drying adopts loft drier or infrared lamp.
4. the method for claim 1, is characterized in that, use temperature≤1400 DEG C of described Hf-Y mixed oxide coatings.
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| CN108754409B (en) * | 2018-06-13 | 2019-12-17 | 西南科技大学 | Method for preparing antioxidant coating on molybdenum metal surface based on activated carbon powder protection |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534617A (en) * | 2012-02-21 | 2012-07-04 | 西安建筑科技大学 | Method for preventing molybdenum and molybdenum alloys from being oxidized |
| CN102534469A (en) * | 2011-11-25 | 2012-07-04 | 厦门虹鹭钨钼工业有限公司 | High temperature anti-oxidation coating molybdenum material and preparation method thereof |
| CN103614713A (en) * | 2013-12-05 | 2014-03-05 | 广西大学 | Method for preparing high-temperature composite coating on niobium-based surface by utilizing sol-gel method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534469A (en) * | 2011-11-25 | 2012-07-04 | 厦门虹鹭钨钼工业有限公司 | High temperature anti-oxidation coating molybdenum material and preparation method thereof |
| CN102534617A (en) * | 2012-02-21 | 2012-07-04 | 西安建筑科技大学 | Method for preventing molybdenum and molybdenum alloys from being oxidized |
| CN103614713A (en) * | 2013-12-05 | 2014-03-05 | 广西大学 | Method for preparing high-temperature composite coating on niobium-based surface by utilizing sol-gel method |
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