CN105386013A - Preparing method of molybdenum or molybdenum alloy surface Pd-CeO2-Co nanometer coating - Google Patents
Preparing method of molybdenum or molybdenum alloy surface Pd-CeO2-Co nanometer coating Download PDFInfo
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Abstract
The invention provides a preparing method of a molybdenum or molybdenum alloy surface Pd-CeO2-Co nanometer coating. Molybdenum or molybdenum alloy is subjected to cleaning and surface etching, an even pitted surface is formed on the surface of the molybdenum or molybdenum alloy, and a molybdenum base body or a molybdenum alloy base body is prepared through flushing and drying; Pd(NO3), CeO2 and cobaltous acetate are dissolved in anhydrous isobutanol and heated to 60 DEG C to 70 DEG C, diethanol amine and distilled water are added, after ammonium hydroxide is added, the pH value of the solution is adjusted to 7.5-8, sol is formed through constant stirring, and after evaporation and condensation are carried out in 10-24 h, stable, even and transparent precursor sol is obtained; and the molybdenum base body or the molybdenum alloy base body is coated with the precursor soil, and the molybdenum or molybdenum alloy surface Pd-CeO2-Co nanometer coating is obtained. The nanometer Pd-CeO2-Co nanometer coating prepared through a roller painting method is even and high in density, superior anti-oxidation performance is achieved, and the high-temperature oxidation corrosion can be resisted. The using temperature of the molybdenum or molybdenum alloy processed through the surface coating can reach 1,500 DEG C.
Description
Technical field
The invention belongs to molybdenum or molybdenum alloy field, relate to molybdenum or molybdenum alloy is anti-oxidant and corrosion-resistant coating, be specifically related to a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating.
Background technology
Molybdenum or 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 or molybdenum alloy.
The approach of current solution molybdenum or 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 or 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 or 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.As S.P.Chakraborty etc. adopts bag method of oozing to prepare aluminide coating on Mo substrate.At high temperature, aluminium atom and molybdenum atom inter-diffusion reaction, at aluminum substrate Surface Creation one deck chemical composition continuous print aluminium molybdenum compound.Research shows, aluminium alloy covered shows good antioxidant defense performance between 1000 ~ 1200 DEG C; But owing at high temperature there is quick mutual diffusion between atoms metal, after temperature is more than 1400 DEG C, coating life sharply shortens, and holiday increases, barrier propterty is deteriorated, and when being especially subject to high temperature thermal shocking, coating is easily peeled off.Jia Zhonghua etc. adopt slurry process to prepare silicide (Si-Cr-Fe, Si-Cr-Ti) coating at molybdenum alloy surface, coating is combined with matrix closely, epoxidation experiments is carried out between 25 ~ 1400 DEG C, its times of thermal cycle can reach 500 times, there is excellent thermal shock resistance, and coating density is high, melt surface state is good, and crackle is few; But owing to easily there is the defect such as crackle, gap in coating, the extexine of most silicide coating a lot of position V-arrangement penetration of cracks coating on molybdenum, thus cause the net thickness of coating much smaller than coating actual (real) thickness, reduce the work-ing life of molybdenum alloy.Difficulty melt oxide coating (pottery) be the molybdenum alloy oxidation protection being applicable to more than 1650 DEG C only have material, there is excellent stability at elevated temperature and high-temperature oxidation resistance; But oxide ceramic coating is often poor with matrix associativity, greatly, obtained coating is often destroyed because thermal expansion coefficient difference produces excessive internal stress for thermal expansivity and matrix difference.
Chen Zhaofeng, Wu king's equality application number be 201010123869.7 " platinum metals coating of a kind of refractory metal surfaces and preparation method thereof " patent of invention prepare the noble coatings such as platinum, rhodium, ruthenium by plasma sputtering method in refractory metal surfaces, and there is one deck transition layer between matrix and coating.It is fast that the method has sedimentation velocity, the smooth feature such as bright and clean of obtained coatingsurface, but the method complicated process of preparation, need through vacuum plasma bombardment target, therefore higher to equipment requirements, cost is higher, and obtained noble coatings and matrix conjugation not high, do not form stable composite structure, easily come off.
Summary of the invention
Based on problems of the prior art, the invention provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, solves molybdenum or molybdenum in prior art and closes anti-oxidant low with corrosion-resistant coating density, the technical problem that bonding force is not strong.
In order to solve the problems of the technologies described above, the application adopts following technical scheme to be achieved:
A kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, the method comprises the following steps:
Step one, passes through cleaning and surface etch by molybdenum or molybdenum alloy, makes molybdenum or molybdenum alloy surface form even pitted skin, rinses and dries obtained Mo substrate or molybdenum alloy matrix;
Step 2, by Pd (NO
3)
2, CeO
2dissolve in dry isobutanol with cobaltous acetate, be heated to 60 DEG C ~ 70 DEG C, add diethanolamine and distilled water, add constantly to stir behind ammoniacal liquor regulator solution pH value to 7.5 ~ 8 and form colloidal sol, stablized after 10 ~ 24h evaporation-condensation, even, transparent aqueous precursor gel;
Step 3, aqueous precursor gel step 2 obtained is coated on the obtained Mo substrate of step one or molybdenum alloy matrix, obtains molybdenum or molybdenum alloy surface Pd-CeO
2-Co nano coating.
The present invention also has and distinguishes technical characteristic as follows:
Concrete, the detailed process in described step one is: by molybdenum or molybdenum alloy surface 800 ~ 1000 order sand paperings, the NaOH solution being placed in 30 ~ 50wt% boils alkali cleaning decontamination, washes with after ultrasonic cleaning; Then being placed in temperature is that 20 ~ 30wt% hydrofluoric acid solution of 80 ~ 90 DEG C carries out surface etch, until surface forms even pitted skin, takes out rear distilled water and alcohol is clean, oven dry, obtains Mo substrate or molybdenum alloy matrix.
Concrete, in described step 2, diethanolamine, CeO in aqueous precursor gel
2, Pd (NO
3)
2be 4:(0.5 ~ 2 with cobaltous acetate mol ratio): (2 ~ 4): (0.5 ~ 2).
Concrete, the detailed process in described step 3 is: by carrying out roller coat in the nip rolls of beam two obtained aqueous precursor gels in steps on the surface of the obtained Mo substrate of step one or molybdenum alloy matrix, obtain molybdenum or molybdenum alloy surface Pd-CeO
2-Co nano coating.
Preferably, the width of described nip rolls is greater than matrix width, and nip rolls linear velocity is 2 ~ 5mm/s, and when roller coat, aqueous precursor gel continuously, homogeneous beam is on nip rolls; Dry at again the molybdenum after roller coat or molybdenum alloy being placed in 100 ~ 120 DEG C, microwave exposure 1 ~ 3h at 350 ~ 430 DEG C, repeats 5 ~ 10 times, last microwave exposure 5 ~ 10h.
Preferably, described Mo substrate or molybdenum alloy body 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.
Compared with prior art, useful technique effect is in the present invention:
(I) through nano Pd particle-CeO that rolling method is obtained
2-Co nano coating evenly and high compaction, has excellent antioxidant property, can resist high temperature oxidation and corrosion.Molybdenum after surface coated treatment or the use temperature of molybdenum alloy can reach 1500 DEG C.
(II) Pd and molybdenum similar thermal expansion coefficient, the coating obtained through coating and microwave heating treatment is spinel-like type structure PdCeCoO
4nano-complex, wherein Co
3+mix can the skeleton structure of stable spinel, greatly enhance its stability.This structured material has the features such as density is large, hardness is high, stability is strong, and has Pd and molybdenum similar thermal expansion coefficient and CeO concurrently
2the feature of stiff stability, good with the consistency of molybdenum or molybdenum alloy matrix, stable mechanical property, not easily cracks, difficult drop-off, has oxidation-resistance.
(III) use nip rolls roller coat to add pressure than conventional coating, coating and matrix are fully contacted, thus the Pt-CeO of preparation
2-Co-Pd nano coating and molybdenum or molybdenum alloy basal body binding force strong, stable performance.
(IV) the method is prepared molybdenum or molybdenum alloy oxidation resistant coating and is not needed complicated paint-on technique and equipment, simple to operate.
Accompanying drawing explanation
Fig. 1: the present invention's nip rolls schematic diagram used; In figure, the implication of each label is: 1-molybdenum or molybdenum alloy material plate, and 2-nip rolls is taken turns, 3-aqueous precursor gel funnel, 4-aqueous precursor gel accumulator tank.
Fig. 2: spinel-like type structure PdCeCoO obtained by embodiment 1
4nano coating XRD figure is composed.
Fig. 3: pure molybdenum plate oxidation resistant coating surface SEM figure in embodiment 1.
Fig. 4: in embodiment 1, pure molybdenum plate oxidation resistant coating section S EM schemes.
Fig. 5: the coating molybdenum plate surface SEM figure in embodiment 1 after 10min, 1500 DEG C of high temperature oxidations.
Fig. 6: the coating molybdenum plate surface SEM figure in embodiment 1 after 30min, 1500 DEG C of high temperature oxidations.
Fig. 7: TZM sheet alloy oxidation resistant coating surface SEM figure in embodiment 2.
Fig. 8: in embodiment 2, TZM sheet alloy oxidation resistant coating section S EM schemes.
Fig. 9: oxidation resistant coating XRD figure spectrum in comparative example 1.
Figure 10: oxidation resistant coating surface SEM figure in comparative example 1.
Figure 11: oxidation resistant coating surface SEM figure in comparative example 1.
Figure 12: oxidation resistant coating surface SEM figure in comparative example 1.
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Embodiment
Defer to technique scheme, below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the pure molybdenum board material that purity is more than 99.95%, area 100cm
2(5cm × 20cm), after 800 order sand paperings, the NaOH solution being placed in 30wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 80 DEG C of hydrofluoric acid solutions (30wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained pure molybdenum plate matrix.
Get 30gPd (NO
3)
2, 10gCeO
2mix with 15g cobaltous acetate and be dissolved in 100ml dry isobutanol solution, heating in water bath to 60 DEG C, slowly add 20g diethanolamine and 50mL distilled water, add ammoniacal liquor regulator solution pH value to 7.5, stablized after constantly stirring 24h, even, transparent aqueous precursor gel.
Obtained pure molybdenum plate matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 3mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 110 DEG C, microwave exposure 2h at 400 DEG C again, repeat 10 times, last microwave exposure 5h, pure molybdenum plate matrix obtains Pd-CeO
2-Co nano coating.
Pure molybdenum plate through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated pure molybdenum plate oxidation quality damaed cordition.
The pure molybdenum plate surface oxidation-resistant coating XRD structure iron of the present embodiment as shown in Figure 2, SEM shape appearance figure as shown in Figure 3, section S EM figure as shown in Figure 4, through 10min, coating after 1500 DEG C of high temperature oxidations pure molybdenum plate surface SEM organization chart as shown in Figure 5, Fig. 6 is through 30min, the pure molybdenum plate surface of the coating after 1500 DEG C of high temperature oxidations SEM organization chart.Fig. 2 shows that this pure molybdenum plate surface defines spinel-like type structure PdCeCoO
4nano-complex; Fig. 3 shows that this pure molybdenum plate surface defines layer protective layer, and this protective layer is comparatively fine and close, without hole; Fig. 4 shows that the protective layer thickness formed is at 0.666 μm; Fig. 5 shows through 10min, the uninfluenced destruction of coating after 1500 DEG C of high temperature oxidations, and matrix is not by oxygen attack, and antioxidant effect is better; Fig. 6 shows through 30min, and after 1500 DEG C of high temperature oxidations, top coat starts to be damaged, and occurs hole, and matrix is easy to the erosion being subject to oxygen.
Embodiment 2:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the rear earth lanthanum doping TZM sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 1000 order sand paperings, the NaOH solution being placed in 40wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 90 DEG C of hydrofluoric acid solutions (20wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained TZM sheet alloy matrix.
Get 30gPd (NO
3)
2, 5gCeO
2mix with 8g cobaltous acetate and be dissolved in 100ml dry isobutanol solution, heating in water bath to 65 DEG C, slowly add 8g diethanolamine and 50mL distilled water, add ammoniacal liquor regulator solution pH value to 7.8, stablized after constantly stirring 20h, even, transparent aqueous precursor gel.
Obtained TZM sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 120 DEG C, microwave exposure 1.5h at 430 DEG C again, repeat 8 times, last microwave exposure 6h, TZM sheet alloy matrix obtains Pd-CeO
2-Co nano coating.
TZM sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated TZM sheet alloy oxidation quality damaed cordition.
As shown in Figure 7, section S EM figure as shown in Figure 8 for the surface oxidation-resistant coating SEM organization chart of the present embodiment rear earth lanthanum doping TZM sheet alloy.
Embodiment 3:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the Mo-Re sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 800 order sand paperings, the NaOH solution being placed in 50wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 80 DEG C of hydrofluoric acid solutions (25wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained Mo-Re sheet alloy matrix.
Get 20gPd (NO
3)
2, 5gCeO
2mix with 20g cobaltous acetate and be dissolved in 150ml dry isobutanol solution, heating in water bath to 70 DEG C, slowly add 10g diethanolamine and 100mL distilled water, add ammoniacal liquor regulator solution pH value to 8, stablized after constantly stirring 18h, even, transparent aqueous precursor gel;
Obtained Mo-Re sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 5mm/s, and when roller coat, aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 100 DEG C, microwave exposure 1h at 380 DEG C again, repeat 6 times, last microwave exposure 8h, Mo-Re sheet alloy matrix obtains Pd-CeO
2-Co nano coating.
Mo-Re sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated Mo-Re sheet alloy oxidation quality damaed cordition.
Embodiment 4:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose TZC sheet alloy prepared by vacuum melting method, area 80cm
2(4cm × 20cm), after 1000 order sand paperings, the NaOH solution being placed in 35wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 90 DEG C of hydrofluoric acid solutions (20wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained TZC sheet alloy matrix.
Get 20gPd (NO
3)
2, 15gCeO
2mix with 10g cobaltous acetate and be dissolved in 150ml dry isobutanol solution, heating in water bath to 70 DEG C, slowly add 8g diethanolamine and 100mL distilled water, add ammoniacal liquor regulator solution pH value to 7.5, stablized after constantly stirring 15h, even, transparent aqueous precursor gel.
Obtained TZC sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 110 DEG C, microwave exposure 3h at 400 DEG C again, repeat 5 times, last microwave exposure 10h, TZC sheet alloy matrix obtains Pd-CeO
2-Co nano coating.
TZC sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated TZC sheet alloy oxidation quality damaed cordition.
Embodiment 5:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the Mo-Ti sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 800 order sand paperings, the NaOH solution being placed in 45wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 80 DEG C of hydrofluoric acid solutions (30wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained Mo-Ti sheet alloy matrix.
Get 20gPd (NO
3)
2, 10gCeO
2mix with 10g cobaltous acetate and be dissolved in 150ml dry isobutanol solution, heating in water bath to 70 DEG C, slowly add 6g diethanolamine and 100mL distilled water, add ammoniacal liquor regulator solution pH value to 8, stablized after constantly stirring 12h, even, transparent aqueous precursor gel.
Obtained Mo-Ti alloy sheets matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 3mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 110 DEG C, microwave exposure 3h at 350 DEG C again, repeat 6 times, last microwave exposure 8h, Mo-Re sheet alloy matrix obtains Pd-CeO
2-Co nano coating.
Mo-Ti sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated Mo-Re sheet alloy oxidation quality damaed cordition.
Embodiment 6:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the Mo-W sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 1000 order sand paperings, the NaOH solution being placed in 50wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 90 DEG C of hydrofluoric acid solutions (25wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained Mo-W sheet alloy matrix.
Get 30gPd (NO
3)
2, 2.5gCeO
2mix with 5g cobaltous acetate and be dissolved in 150ml dry isobutanol solution, heating in water bath to 70 DEG C, slowly add 15g diethanolamine and 100mL distilled water, add ammoniacal liquor regulator solution pH value to 7.8, stablized after constantly stirring 15h, even, transparent aqueous precursor gel.
Obtained Mo-W sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and when roller coat, aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 120 DEG C, microwave exposure 3h at 360 DEG C again, repeat 8 times, last microwave exposure 6h, Mo-W sheet alloy matrix obtains Pd-CeO
2-Co nano coating.
Mo-Re sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated Mo-W sheet alloy oxidation quality damaed cordition.
Comparative example 1:
The present embodiment provides the preparation method of a kind of molybdenum or molybdenum alloy surface Pd-Co nano coating, specifically comprises the following steps:
Choose the pure molybdenum board material that purity is more than 99.95%, area 100cm
2(5cm × 20cm), after 800 order sand paperings, the NaOH solution being placed in 30wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 80 DEG C of hydrofluoric acid solutions (30wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained pure molybdenum board material matrix.
Get 30gPd (NO
3)
2mix with 15g cobaltous acetate and be dissolved in 100ml dry isobutanol solution, heating in water bath to 60 DEG C, slowly add 20g diethanolamine and 50mL distilled water, add ammoniacal liquor regulator solution pH value to 7.5, stablized after constantly stirring 24h, even, transparent aqueous precursor gel.
Obtained pure molybdenum board material matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 3mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 110 DEG C, microwave exposure 2h at 400 DEG C again, repeat 10 times, last microwave exposure 5h, pure molybdenum board material matrix obtains Pd-Co coating.
Pure molybdenum board material through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and with embodiment 1 in compare through the pure molybdenum board material oxidation quality damaed cordition of surface coated treatment.
The pure molybdenum board material surface oxidation-resistant coating XRD structure iron of this comparative example as shown in Figure 9, as shown in Figure 10, XRD structure iron and SEM surface topography map all show the Pd-Co coating of this comparative example prepared by pure molybdenum surface and the Pd-CeO prepared by embodiment 1 to SEM surface topography map
2-Co nano coating is different, not the dense coating materials of spinel-like structural.Tested known by high temperature oxidation, the antioxidant property of the coating prepared of this comparative example under 1100 DEG C, 1300 DEG C and 1500 DEG C of hot conditionss is far below the Pd-CeO prepared by embodiment 1
2-Co nano coating.
Comparative example 2:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface CeO
2the preparation method of-Co nano coating, specifically comprises the following steps:
Choose the rear earth lanthanum doping TZM sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 1000 order sand paperings, the NaOH solution being placed in 50wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 90 DEG C of hydrofluoric acid solutions (20wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained TZM sheet alloy matrix.
Get 5gCeO
2mix with 8g cobaltous acetate and be dissolved in 100ml dry isobutanol solution, heating in water bath to 65 DEG C, slowly add 8g diethanolamine and 50mL distilled water, add ammoniacal liquor regulator solution pH value to 7.8, stablized after constantly stirring 20h, even, transparent aqueous precursor gel.
Obtained TZM sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and when roller coat by aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 120 DEG C, microwave exposure 1.5h at 430 DEG C again, repeat 8 times, last microwave exposure 6h, TZM sheet alloy matrix obtains CeO
2-Co coating.
TZM sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated TZM sheet alloy oxidation quality damaed cordition.
The TZM sheet alloy surface oxidation-resistant coating SEM surface topography map of this comparative example as shown in figure 11, shows the CeO of this comparative example prepared by pure molybdenum surface
2-Co coating and the Pd-CeO prepared by embodiment 2
2-Co nano coating is different, not the dense coating materials of spinel-like structural.Tested known by high temperature oxidation, the antioxidant property of the coating prepared of this comparative example under 1100 DEG C, 1300 DEG C and 1500 DEG C of hot conditionss is far below the Pd-CeO prepared by embodiment 2
2-Co nano coating.
Comparative example 3:
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of nano coating, specifically comprises the following steps:
Choose the Mo-Re sheet alloy prepared by powder metallurgical technique, area 100cm
2(5cm × 20cm), after 800 order sand paperings, the NaOH solution being placed in 20wt% is boiled, and uses ultrasonic cleaning 1h, and taking-up washes; Being placed on temperature is carry out surface etch in 50 DEG C of hydrofluoric acid solutions (25wt%), until surface forms even pitted skin, cleans, dry after taking-up with deionized water, obtained Mo-Re sheet alloy matrix.
Get 20gPd (NO
3)
2with 5gCeO
2mixing is dissolved in 150ml dry isobutanol solution, heating in water bath to 70 DEG C, slowly adds 10g diethanolamine and 100mL distilled water, adds ammoniacal liquor regulator solution pH value to 8, is stablized, even, transparent aqueous precursor gel after constantly stirring 18h;
Obtained Mo-Re sheet alloy matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 5mm/s, and when roller coat, aqueous precursor gel continuously, homogeneous beam is on nip rolls, then dry at the sheet material after roller coat being placed in 100 DEG C, microwave exposure 1h at 380 DEG C again, repeat 6 times, last microwave exposure 8h, Mo-Re sheet alloy matrix obtains Pd-CeO
2coating.
Mo-Re sheet alloy through surface coated treatment is cut into 10 × 10mm square and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C of high temperature oxidation experiments, measurement quality rate of loss, and compare with not surface treated Mo-Re sheet alloy oxidation quality damaed cordition.
The Mo-Re sheet alloy surface oxidation-resistant coating SEM surface topography map of this comparative example as shown in figure 12, shows the Pd-CeO of this comparative example prepared by pure molybdenum surface
2coating and the Pd-CeO prepared by embodiment 3
2-Co nano coating is different, not the dense coating materials of spinel-like structural.Tested known by high temperature oxidation, the antioxidant property of the coating prepared of this comparative example under 1100 DEG C, 1300 DEG C and 1500 DEG C of hot conditionss is far below the Pd-CeO prepared by embodiment 3
2-Co nano coating.
Above-described 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.
Table 1, table 2, table 3 are the various embodiments described above and comparative example material in the oxidative mass loss rate correlation data of 1100 DEG C, 1300 DEG C and 1500 DEG C respectively.As can be seen from the table, at 1100 DEG C to 1300 DEG C, be oxidized no matter 10 to 30 minutes, through the molybdenum of this invention coating process or molybdenum alloy quality all without considerable change, until 1500 DEG C be oxidized after, mass loss rate shows a rising trend; And without any surface-treated molybdenum or molybdenum alloy, 10min at 1100 DEG C is oxidized by vigorous oxidation, after oxidation 30min matrix ablation totally, and do not adopt the method for the invention to prepare the molybdenum prepared by comparative example 1 ~ 3 of oxidation resistant coating or the antioxidant property of molybdenum alloy material under 1100 DEG C, 1300 DEG C and 1500 DEG C of hot conditionss far below the Pd-CeO prepared by each embodiment
2-Co nano coating.Illustrate that this invention is highly resistant to the erosion of oxygen in oxidation resistant coating prepared by molybdenum or molybdenum alloy surface, and use temperature is up to 1500 DEG C.
The each embodiment of table 1 and the oxidative mass loss rate of comparative example material at 1100 DEG C
The each embodiment of table 2 and the oxidative mass loss rate of comparative example material at 1300 DEG C
The each embodiment of table 3 and the oxidative mass loss rate of comparative example material at 1500 DEG C
Claims (6)
1. a molybdenum or molybdenum alloy surface Pd-CeO
2the preparation method of-Co nano coating, is characterized in that: the method comprises the following steps:
Step one, passes through cleaning and surface etch by molybdenum or molybdenum alloy, makes molybdenum or molybdenum alloy surface form even pitted skin, rinses and dries obtained Mo substrate or molybdenum alloy matrix;
Step 2, by Pd (NO
3)
2, CeO
2dissolve in dry isobutanol with cobaltous acetate, be heated to 60 DEG C ~ 70 DEG C, add diethanolamine and distilled water, add constantly to stir behind ammoniacal liquor regulator solution pH value to 7.5 ~ 8 and form colloidal sol, stablized after 10 ~ 24h evaporation-condensation, even, transparent aqueous precursor gel;
Step 3, aqueous precursor gel step 2 obtained is coated on the obtained Mo substrate of step one or molybdenum alloy matrix, obtains molybdenum or molybdenum alloy surface Pd-CeO
2-Co nano coating.
2. preparation method as claimed in claim 1, it is characterized in that: the detailed process in described step one is: by molybdenum or molybdenum alloy surface 800 ~ 1000 order sand paperings, the NaOH solution being placed in 30 ~ 50wt% boils alkali cleaning decontamination, washes with after ultrasonic cleaning; Then being placed in temperature is that 20 ~ 30wt% hydrofluoric acid solution of 80 ~ 90 DEG C carries out surface etch, until surface forms even pitted skin, takes out rear distilled water and alcohol is clean, oven dry, obtains Mo substrate or molybdenum alloy matrix.
3. preparation method as claimed in claim 1, is characterized in that: in described step 2, diethanolamine, CeO in aqueous precursor gel
2, Pd (NO
3)
2be 4:(0.5 ~ 2 with cobaltous acetate mol ratio): (2 ~ 4): (0.5 ~ 2).
4. preparation method as claimed in claim 1, it is characterized in that: the detailed process in described step 3 is: by carrying out roller coat in the nip rolls of beam two obtained aqueous precursor gels in steps on the surface of the obtained Mo substrate of step one or molybdenum alloy matrix, obtain molybdenum or molybdenum alloy surface Pd-CeO
2-Co nano coating.
5. preparation method as claimed in claim 4, it is characterized in that: the width of described nip rolls is greater than matrix width, nip rolls linear velocity is 2 ~ 5mm/s, and when roller coat, aqueous precursor gel is continuously, homogeneous beam is on nip rolls; Dry at again the molybdenum after roller coat or molybdenum alloy being placed in 100 ~ 120 DEG C, microwave exposure 1 ~ 3h at 350 ~ 430 DEG C, repeats 5 ~ 10 times, last microwave exposure 5 ~ 10h.
6. preparation method as claimed in claim 1, is characterized in that: described Mo substrate or molybdenum alloy body 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.
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| CN117448837A (en) * | 2023-11-03 | 2024-01-26 | 广州齐达材料科技有限公司 | Treatment method for removing oxide on surface of high-purity molybdenum strip |
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| CN117448837B (en) * | 2023-11-03 | 2024-07-23 | 广州齐达材料科技有限公司 | Treatment method for removing oxide on surface of high-purity molybdenum strip |
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