CN105386013B - A kind of molybdenum or molybdenum alloy surface Pd CeO2The preparation method of Co nano coatings - Google Patents
A kind of molybdenum or molybdenum alloy surface Pd CeO2The preparation method of Co nano coatings Download PDFInfo
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Abstract
The invention provides a kind of molybdenum or molybdenum alloy surface Pd CeO2The preparation method of Co nano coatings, by molybdenum or molybdenum alloy through over cleaning and surface etch so that molybdenum or molybdenum alloy surface form uniform pitted skin, rinse drying and Mo substrate or molybdenum alloy matrix is made；By Pd (NO3)2、CeO2Dissolved in cobalt acetate in dry isobutanol, it is heated to 60 DEG C~70 DEG C, diethanol amine and distilled water are added, is stirred continuously to form colloidal sol after addition ammoniacal liquor regulation solution ph to 7.5~8, stabilization, uniform, transparent aqueous precursor gel is obtained after 10~24h evaporation-condensations；By aqueous precursor gel coated on Mo substrate or molybdenum alloy matrix, molybdenum or molybdenum alloy surface Pd CeO are obtained2Co nano coatings.Through nano Pd particle CeO made from rolling method2Co nano coatings uniformly and high compaction, there is excellent antioxygenic property, high temperature oxidation and corrosion can be resisted.The temperature in use of molybdenum or molybdenum alloy after surface coated treatment can reach 1500 DEG C.
Description
Technical field
The invention belongs to molybdenum or molybdenum alloy field, it is related to molybdenum or molybdenum alloy is anti-oxidant and corrosion-resistant coating, and in particular to one
Kind molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings.
Background technology
Molybdenum or molybdenum alloy are a kind of important high-temperature alloy materials, because it has excellent conduction, thermal conductivity, and fusing point
Height, intensity is big, linear expansion coefficient is small, corrosion stability is strong and mechanical behavior under high temperature is good, thus is widely used in Aero-Space, hair
The fields such as electricity, nuclear reactor, war industry, chemical industry and glass work.But because molybdenum is at about 300 DEG C
When oxidation can occur form MoO2, secondary oxidation can occur when temperature rise is to 600 DEG C or so, generate MoO3, in 725 DEG C or so MoO3
Volatilize and liquid phase occur, can not be from although the molybdenum base material high-temperature oxidation resistance by alloying is improved
Fundamentally solves the defects of it is easily oxidized.So oxidation and volatilization phenomena impair its mechanical behavior under high temperature of molybdenum, are limited
The application of molybdenum or molybdenum alloy.
Solving molybdenum or the approach of molybdenum alloy oxidisability at present has two, first, the molybdenum alloy of high-temperature oxidation resistant is developed, second,
Applying surface antioxidant coating.But molybdenum can alloying level very little, when improve antioxygenic property alloy adding
When slightly more, the poor processability of alloy, not even with temperature-room type plasticity, so can not fundamentally be changed with the method for alloying
Become the oxidation resistance of molybdenum or molybdenum alloy, and also affect its many high-temperature behaviors, such as elevated temperature strength, impact resistance
Property, resistance to heat shocks and creep resistance etc..So the surface prepares coating in molybdenum or molybdenum alloy carrys out anti-oxidation and just seemed very must
Will.
Common high-temperature oxidation resistant coating has coat of aluminide, silicide coating, heat-resisting alloy coating etc., but deposits mostly
In coating and the shortcomings of substrate combinating strength is high, poor compatibility, bad acid-alkali-corrosive-resisting effect.Such as S.P.Chakraborty
Coat of aluminide is prepared on Mo substrate Deng method is oozed using bag.At high temperature, aluminium atom and molybdenum atom inter-diffusion reaction, in aluminium
Matrix surface generates the continuous aluminium molybdenum compound of one layer of chemical composition.Research shows, aluminium alloy covered 1000~1200 DEG C it
Between show good antioxidant defense performance；But due to quick counterdiffusion occurs between metallic atom at high temperature, work as temperature
After degree is more than 1400 DEG C, coating life drastically shortens, and holiday increases, and barrier propterty is deteriorated, and is especially rushed by high warm
When hitting, coating easily peels off.Jia Zhonghua etc. prepares silicide (Si-Cr-Fe, Si-Cr-Ti) in molybdenum alloy surface using slurry process and applied
Layer, coating is tightly combined with matrix, and epoxidation experiments are carried out between 25~1400 DEG C, its times of thermal cycle up to 500 times,
With excellent thermal shock resistance, and coating consistency is high, and melt surface state is good, and crackle is few；But due to easy in coating
The defects of cracked, gap, the extexine of most many position V-arrangement penetration of cracks coatings of silicide coating on molybdenum, so as to lead
Cause the effective thickness of coating to be much smaller than coating actual (real) thickness, reduce the service life of molybdenum alloy.Difficulty melts oxide coating (pottery
Porcelain) apply to more than 1650 DEG C molybdenum alloy oxidation protection only material, there is excellent stability at elevated temperature and height
Warm oxidation resistance；But oxide ceramic coating is often poor with matrix associativity, thermal coefficient of expansion and matrix difference are big, made
The coating obtained often destroys because thermal expansion coefficient difference produces excessive internal stress.
Chen Zhaofeng, Wu king's equality Application No. 201010123869.7 a kind of " the platinum group metal painting of refractory metal surfaces
Layer and preparation method thereof " patent of invention prepares the noble metals such as platinum, rhodium, ruthenium in refractory metal surfaces by plasma sputtering method and applied
Layer, and there is one layer of transition zone between matrix and coating.This method has that deposition velocity is fast, and obtained coating surface is smooth
The features such as bright and clean, but this method preparation technology is complicated, need to through vacuum plasma bombardment target, therefore to equipment requirement compared with
Height, cost is higher, and obtained noble coatings are not high with matrix conjugation, does not form stable composite construction, easily de-
Fall.
The content of the invention
Based on problems of the prior art, the present invention provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2- Co nanometers
The preparation method of coating, solves molybdenum in the prior art or molybdenum conjunction is anti-oxidant low with corrosion-resistant coating consistency, and adhesion is not strong
Technical problem.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved：
A kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, this method comprise the following steps：
Step 1, by molybdenum or molybdenum alloy through over cleaning and surface etch so that molybdenum or molybdenum alloy surface form uniform pitted skin,
Rinse drying and Mo substrate or molybdenum alloy matrix is made；
Step 2, by Pd (NO3)2、CeO2Dissolved in cobalt acetate in dry isobutanol, be heated to 60 DEG C~70 DEG C, added
Diethanol amine and distilled water, add ammoniacal liquor and adjust solution ph to being stirred continuously to form colloidal sol after 7.5~8, steamed by 10~24h
Stabilization, uniform, transparent aqueous precursor gel are obtained after hair cohesion；
Step 3, aqueous precursor gel made from step 2 is coated on Mo substrate made from step 1 or molybdenum alloy matrix
On, obtain molybdenum or molybdenum alloy surface Pd-CeO2- Co nano coatings.
The present invention also has following distinguishing feature：
Specifically, the detailed process in described step one is：By 800~1000 mesh sand paper of molybdenum or molybdenum alloy surface
Polishing, is placed in 30~50wt% NaOH solution and boils alkali cleaning decontamination, be eluted with water after being cleaned with ultrasonic wave；It is subsequently placed in temperature
Spend in 20~30wt% hydrofluoric acid solutions for 80~90 DEG C and carry out surface etch, until surface forms uniform pitted skin, after taking-up
Cleaned with distilled water and alcohol, drying, Mo substrate or molybdenum alloy matrix is made.
Specifically, in described step two, diethanol amine, CeO in aqueous precursor gel2、Pd(NO3)2Rubbed with cobalt acetate
You are than being 4:(0.5~2):(2~4):(0.5~2).
Specifically, the detailed process in described step three is：In Mo substrate made from step 1 or molybdenum alloy matrix
Have on surface by beam in the nip rolls of aqueous precursor gel made from step 2 and carry out roller coat, obtain molybdenum or molybdenum alloy surface Pd-
CeO2- Co nano coatings.
Preferably, the width of the nip rolls is more than matrix width, and nip rolls linear velocity is 2~5mm/s, and in roller coat
Aqueous precursor gel is continuous, on homogeneous beam to nip rolls；The molybdenum after roller coat or molybdenum alloy are placed at 100~120 DEG C again and dried,
1~3h of microwave irradiation at 350~430 DEG C, repeat 5~10 times, 5~10h of last time microwave irradiation.
Preferably, described Mo substrate or molybdenum alloy matrix material are pure molybdenum, Mo-Ti systems alloy, Mo-W systems alloy, Mo-
Cu systems alloy, Mo-Re systems alloy, the sheet material or bar of TZC alloys or TZM alloys.
Compared with prior art, beneficial has the technical effect that the present invention：
(I) through nano Pd particle-CeO made from rolling method2- Co nano coatings uniformly and high compaction, there is excellent antioxygen
Change performance, high temperature oxidation and corrosion can be resisted.The temperature in use of molybdenum or molybdenum alloy after surface coated treatment can reach
1500℃。
(II) Pd and molybdenum similar thermal expansion coefficient, are spinel-like type by the coating coated and microwave heating treatment obtains
Structure PdCeCoO4Nano-complex, wherein Co3+Incorporation can stable spinel skeleton structure, it is stable greatly to enhance its
Property.The structural material has the characteristics that density is big, hardness is high, stability is strong, and have concurrently Pd and molybdenum similar thermal expansion coefficient and
CeO2It is the characteristics of stiff stability, good with the compatibility of molybdenum or molybdenum alloy matrix, stable mechanical property, it is not likely to produce crackle, is not easy
Come off, great inoxidizability.
(III) pressure is added than conventional coating using nip rolls roller coat so that coating fully contacts with matrix, so as to prepare
Pd-CeO2- Co nano coatings and molybdenum or molybdenum alloy basal body binding force are strong, stable performance.
(IV) this method prepares molybdenum or molybdenum alloy antioxidant coating does not need complicated paint-on technique and equipment, operation letter
It is single.
Brief description of the drawings
Fig. 1：Nip rolls schematic diagram used in the present invention；The implication of each label is in figure：1- molybdenums or molybdenum alloy material plate, 2-
Nip rolls wheel, 3- aqueous precursor gel funnels, 4- aqueous precursor gel accumulator tanks.
Fig. 2：Spinel-like type structure PdCeCoO obtained by embodiment 14Nano coating XRD spectrum.
Fig. 3：Pure molybdenum plate antioxidant coating surface SEM figures in embodiment 1.
Fig. 4：Pure molybdenum plate antioxidant coating section SEM figures in embodiment 1.
Fig. 5：Coating molybdenum plate surface SEM figures in embodiment 1 after 10min, 1500 DEG C of high-temperature oxydations.
Fig. 6：Coating molybdenum plate surface SEM figures in embodiment 1 after 30min, 1500 DEG C of high-temperature oxydations.
Fig. 7：TZM sheet alloys antioxidant coating surface SEM schemes in embodiment 2.
Fig. 8：TZM sheet alloys antioxidant coating section SEM schemes in embodiment 2.
Fig. 9：Antioxidant coating XRD spectrum in comparative example 1.
Figure 10：Antioxidant coating surface SEM schemes in comparative example 1.
Figure 11：Antioxidant coating surface SEM schemes in comparative example 1.
Figure 12：Antioxidant coating surface SEM schemes in comparative example 1.
The particular content of the present invention is described in more detail below in conjunction with drawings and examples.
Embodiment
Above-mentioned technical proposal is deferred to, specific embodiment of the invention given below is, it is necessary to which explanation is the present invention not office
It is limited to specific examples below, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.The present invention is described in further details with reference to embodiment.
Embodiment 1：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose the pure molybdenum board material that purity is more than 99.95%, area 100cm2(5cm × 20cm), beaten with 800 mesh sand paper
After mill, it is placed in 30wt% NaOH solution and boils, cleans 1h with ultrasonic wave, taking-up is eluted with water；Temperature is placed on as 80
Surface etch is carried out in DEG C hydrofluoric acid solution (30wt%), until surface forms uniform pitted skin, be washed with deionized water after taking-up it is net,
Drying, pure molybdenum plate matrix is made.
Take 30g Pd (NO3)2、10g CeO2Mixed with 15g cobalt acetates and be dissolved in 100ml dry isobutanol solution, heating water bath
To 60 DEG C, 20g diethanol amine and 50mL distilled water are slowly added to, ammoniacal liquor is added and adjusts solution ph to 7.5, be stirred continuously 24h
Stabilization, uniform, transparent aqueous precursor gel are obtained afterwards.
Obtained pure molybdenum plate matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 3mm/s, and in roller coat
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 110 DEG C and dried, then at 400 DEG C
Lower microwave irradiation 2h, is repeated 10 times, and last time microwave irradiation 5h, Pd-CeO is obtained on pure molybdenum plate matrix2- Co nanometers apply
Layer.
Pure molybdenum plate by surface coated treatment is cut into 10 × 10mm squares and carries out 1100 DEG C, 1300 DEG C and 1500 DEG C height
Warm oxidation experiment, mass loss rate is measured, and compared with not surface treated pure molybdenum plate oxidation quality damaed cordition.
The pure molybdenum plate surface oxidation-resistant coating XRD structure charts of the present embodiment as shown in Fig. 2 SEM shape appearance figures as shown in figure 3,
Section SEM is schemed as shown in figure 4, by 10min, coating pure molybdenum plate surface SEM organization charts such as Fig. 5 institutes after 1500 DEG C of high-temperature oxydations
Show, Fig. 6 is the pure molybdenum plate surface SEM organization charts of coating after 1500 DEG C of high-temperature oxydations by 30min.Fig. 2 shows the pure molybdenum plate table
Face forms spinel-like type structure PdCeCoO4Nano-complex；Fig. 3 shows that the pure molybdenum plate surface forms layer protective layer,
And the protective layer is comparatively dense, no hole；Fig. 4 shows the protective layer thickness to be formed at 0.666 μm；Fig. 5 show by
10min, the uninfluenced destruction of coating after 1500 DEG C of high-temperature oxydations, matrix be not preferable by oxygen attack, antioxidant effect；Fig. 6 tables
Bright to pass through 30min, after 1500 DEG C of high-temperature oxydations, face coat starts to be destroyed, and hole occurs, and matrix is susceptible to invading for oxygen
Erosion.
Embodiment 2：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose the rear earth lanthanum doping TZM sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm),
After being polished with 1000 mesh sand paper, it is placed in 40wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；Will
It is placed in temperature to carry out surface etch in 90 DEG C of hydrofluoric acid solutions (20wt%), until surface forms uniform pitted skin, after taking-up
Net, drying, obtained TZM sheet alloy matrixes is washed with deionized water.
Take 30g Pd (NO3)2、5g CeO2Mixed with 8g cobalt acetates and be dissolved in 100ml dry isobutanol solution, heating water bath is extremely
65 DEG C, 8g diethanol amine and 50mL distilled water are slowly added to, ammoniacal liquor is added and adjusts solution ph to 7.8, obtained after being stirred continuously 20h
To stable, uniform, transparent aqueous precursor gel.
Obtained TZM sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 120 DEG C and dried during roller coat, then
Microwave irradiation 1.5h, is repeated 8 times at 430 DEG C, last time microwave irradiation 6h, Pd- is obtained on TZM sheet alloy matrixes
CeO2- Co nano coatings.
By by surface coated treatment TZM sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated TZM sheet alloys oxidation quality
Situation is compared.
The surface oxidation-resistant coating SEM organization charts of the present embodiment rear earth lanthanum doping TZM sheet alloys are as shown in fig. 7, section
SEM figures are as shown in Figure 8.
Embodiment 3：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose the Mo-Re sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm), with 800 mesh
After sand paper polishing, it is placed in 50wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；It is placed on temperature
Spend to carry out surface etch in 80 DEG C of hydrofluoric acid solutions (25wt%), until surface forms uniform pitted skin, deionization is used after taking-up
Water is cleaned, and drying, Mo-Re sheet alloy matrixes is made.
Take 20g Pd (NO3)2、5g CeO2Mixed with 20g cobalt acetates and be dissolved in 150ml dry isobutanol solution, heating water bath
To 70 DEG C, 10g diethanol amine and 100mL distilled water, addition ammoniacal liquor regulation solution ph to 8, after being stirred continuously 18h are slowly added to
Obtain stabilization, uniform, transparent aqueous precursor gel；
Obtained Mo-Re sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 5mm/s, and
In roller coat, aqueous precursor gel is continuous, on homogeneous beam to nip rolls, and then the sheet material after roller coat is placed at 100 DEG C and dried, then
Microwave irradiation 1h, is repeated 6 times at 380 DEG C, last time microwave irradiation 8h, Pd- is obtained on Mo-Re sheet alloy matrixes
CeO2- Co nano coatings.
By by surface coated treatment Mo-Re sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated Mo-Re sheet alloys oxidation quality
Situation is compared.
Embodiment 4：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose TZC sheet alloys prepared by vacuum melting method, area 80cm2(4cm × 20cm), polished with 1000 mesh sand paper
Afterwards, it is placed in 35wt% NaOH solution and boils, cleans 1h with ultrasonic wave, taking-up is eluted with water；Temperature is placed on as 90 DEG C
Surface etch is carried out in hydrofluoric acid solution (20wt%), until surface forms uniform pitted skin, net, baking is washed with deionized water after taking-up
It is dry, TZC sheet alloy matrixes are made.
Take 20g Pd (NO3)2、15g CeO2Mixed with 10g cobalt acetates and be dissolved in 150ml dry isobutanol solution, heating water bath
To 70 DEG C, 8g diethanol amine and 100mL distilled water are slowly added to, ammoniacal liquor is added and adjusts solution ph to 7.5, be stirred continuously 15h
Stabilization, uniform, transparent aqueous precursor gel are obtained afterwards.
Obtained TZC sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 110 DEG C and dried during roller coat, then
Microwave irradiation 3h, is repeated 5 times at 400 DEG C, last time microwave irradiation 10h, Pd- is obtained on TZC sheet alloy matrixes
CeO2- Co nano coatings.
By by surface coated treatment TZC sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated TZC sheet alloys oxidation quality
Situation is compared.
Embodiment 5：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose the Mo-Ti sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm), with 800 mesh
After sand paper polishing, it is placed in 45wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；It is placed on temperature
Spend to carry out surface etch in 80 DEG C of hydrofluoric acid solutions (30wt%), until surface forms uniform pitted skin, deionization is used after taking-up
Water is cleaned, and drying, Mo-Ti sheet alloy matrixes is made.
Take 20g Pd (NO3)2、10g CeO2Mixed with 10g cobalt acetates and be dissolved in 150ml dry isobutanol solution, heating water bath
To 70 DEG C, 6g diethanol amine and 100mL distilled water, addition ammoniacal liquor regulation solution ph to 8, after being stirred continuously 12h are slowly added to
Obtain stabilization, uniform, 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 3 mm/s, and
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 110 DEG C and dried during roller coat, then
Microwave irradiation 3h, is repeated 6 times at 350 DEG C, last time microwave irradiation 8h, Pd- is obtained on Mo-Re sheet alloy matrixes
CeO2- Co nano coatings.
By by surface coated treatment Mo-Ti sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated Mo-Re sheet alloys oxidation quality
Situation is compared.
Embodiment 6：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, specifically include with
Lower step：
Choose the Mo-W sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm), with 1000 mesh
After sand paper polishing, it is placed in 50wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；It is placed on temperature
Spend to carry out surface etch in 90 DEG C of hydrofluoric acid solutions (25wt%), until surface forms uniform pitted skin, deionization is used after taking-up
Water is cleaned, and drying, Mo-W sheet alloy matrixes is made.
Take 30g Pd (NO3)2、2.5g CeO2Mixed with 5g cobalt acetates and be dissolved in 150ml dry isobutanol solution, heating water bath
To 70 DEG C, 15g diethanol amine and 100mL distilled water are slowly added to, ammoniacal liquor is added and adjusts solution ph to 7.8, be stirred continuously 15h
Stabilization, uniform, transparent aqueous precursor gel are obtained afterwards.
Obtained Mo-W sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and
Aqueous precursor gel is continuous during roller coat, on homogeneous beam to nip rolls, and then the sheet material after roller coat is placed at 120 DEG C and dried, then
Microwave irradiation 3h, is repeated 8 times at 360 DEG C, last time microwave irradiation 6h, Pd-CeO is obtained on Mo-W sheet alloy matrixes2-
Co nano coatings.
By by surface coated treatment Mo-Re sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated Mo-W sheet alloys oxidation quality
Situation is compared.
Comparative example 1：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface Pd-Co nano coatings, specifically includes following step
Suddenly：
Choose the pure molybdenum board material that purity is more than 99.95%, area 100cm2(5cm × 20cm), beaten with 800 mesh sand paper
After mill, it is placed in 30wt% NaOH solution and boils, cleans 1h with ultrasonic wave, taking-up is eluted with water；Temperature is placed on as 80
Surface etch is carried out in DEG C hydrofluoric acid solution (30wt%), until surface forms uniform pitted skin, be washed with deionized water after taking-up it is net,
Drying, pure molybdenum board material matrix is made.
Take 30g Pd (NO3)2Mixed with 15g cobalt acetates and be dissolved in 100ml dry isobutanol solution, heating water bath delays to 60 DEG C
It is slow to add 20g diethanol amine and 50mL distilled water, add ammoniacal liquor and adjust solution pH value to 7.5, obtained surely after being stirred continuously 24h
Fixed, uniform, 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 in roller
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 110 DEG C and dried during painting, then
Microwave irradiation 2h, is repeated 10 times at 400 DEG C, last time microwave irradiation 5h, Pd-Co coatings is obtained on pure molybdenum board material matrix.
Pure molybdenum board material by surface coated treatment is cut into 10 × 10mm squares and carries out 1100 DEG C, 1300 DEG C and 1500
The experiment of DEG C high-temperature oxydation, mass loss rate is measured, and with passing through the pure molybdenum board material oxidation quality of surface coated treatment in embodiment 1
Damaed cordition is compared.
The pure molybdenum board material surface oxidation-resistant coating XRD structure charts of this comparative example are as shown in figure 9, SEM surface topography maps such as figure
Shown in 10, XRD structure charts show this comparative example in the Pd-Co coatings and reality prepared by pure molybdenum surface with SEM surface topography maps
Apply the Pd-CeO prepared by example 12- Co nano coatings are different, not the dense coating materials of spinel-like structural.Pass through height
Warm oxidation experiment understands, inoxidizability of the coating under 1100 DEG C, 1300 DEG C and 1500 DEG C hot conditions prepared by this comparative example
Can be far below the Pd-CeO prepared by embodiment 12- Co nano coatings.
Comparative example 2：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface CeO2The preparation method of-Co nano coatings, specifically include following
Step：
Choose the rear earth lanthanum doping TZM sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm),
After being polished with 1000 mesh sand paper, it is placed in 50wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；Will
It is placed in temperature to carry out surface etch in 90 DEG C of hydrofluoric acid solutions (20wt%), until surface forms uniform pitted skin, after taking-up
Net, drying, obtained TZM sheet alloy matrixes is washed with deionized water.
Take 5g CeO2Mixed with 8g cobalt acetates and be dissolved in 100ml dry isobutanol solution, heating water bath slowly adds to 65 DEG C
Enter 8g diethanol amine and 50mL distilled water, add ammoniacal liquor and adjust solution ph to 7.8, obtained stably, after being stirred continuously 20h
Even, transparent aqueous precursor gel.
Obtained TZM sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 4mm/s, and
By aqueous precursor gel is continuous, on homogeneous beam to nip rolls, then the sheet material after roller coat is placed at 120 DEG C and dried during roller coat, then
Microwave irradiation 1.5h, is repeated 8 times at 430 DEG C, last time microwave irradiation 6h, CeO is obtained on TZM sheet alloy matrixes2-
Co coatings.
By by surface coated treatment TZM sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated TZM sheet alloys oxidation quality
Situation is compared.
The TZM sheet alloy surface oxidation-resistant coating SEM surface topography maps of this comparative example are as shown in figure 11, show this contrast
Example is in the CeO prepared by pure molybdenum surface2- Co coatings and the Pd-CeO prepared by embodiment 22- Co nano coatings are different, and
The dense coating materials of non-spinel-like structural.By high-temperature oxydation test, this comparative example preparation coating 1100 DEG C,
Antioxygenic property under 1300 DEG C and 1500 DEG C of hot conditions is far below the Pd-CeO prepared by embodiment 22- Co nano coatings.
Comparative example 3：
The present embodiment provides a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of nano coating, specifically include following
Step：
Choose the Mo-Re sheet alloys prepared by powder metallurgical technique, area 100cm2(5cm × 20cm), with 800 mesh
After sand paper polishing, it is placed in 20wt% NaOH solution and boils, clean 1h with ultrasonic wave, taking-up is eluted with water；It is placed on temperature
Spend to carry out surface etch in 50 DEG C of hydrofluoric acid solutions (25wt%), until surface forms uniform pitted skin, deionization is used after taking-up
Water is cleaned, and drying, Mo-Re sheet alloy matrixes is made.
Take 20g Pd (NO3)2With 5g CeO2Mixing is dissolved in 150ml dry isobutanol solution, and heating water bath is to 70 DEG C, slowly
Add 10g diethanol amine and 100mL distilled water, add ammoniacal liquor and adjust solution pH value to 8, be stirred continuously after 18h obtain stabilization,
Uniformly, transparent aqueous precursor gel；
Obtained Mo-Re sheet alloys matrix is placed in nip rolls and carries out roller coat, nip rolls linear velocity is 5mm/s, and
In roller coat, aqueous precursor gel is continuous, on homogeneous beam to nip rolls, and then the sheet material after roller coat is placed at 100 DEG C and dried, then
Microwave irradiation 1h, is repeated 6 times at 380 DEG C, last time microwave irradiation 8h, Pd- is obtained on Mo-Re sheet alloy matrixes
CeO2Coating.
By by surface coated treatment Mo-Re sheet alloys be cut into 10 × 10mm squares carry out 1100 DEG C, 1300 DEG C and
1500 DEG C of high-temperature oxydation experiments, mass loss rate is measured, and lost with not surface treated Mo-Re sheet alloys oxidation quality
Situation is compared.
The Mo-Re sheet alloy surface oxidation-resistant coating SEM surface topography maps of this comparative example show this as shown in Figure 12
Comparative example is in the Pd-CeO prepared by pure molybdenum surface2Coating and the Pd-CeO prepared by embodiment 32- Co nano coatings are not
Together, not dense coating materials of spinel-like structural.Tested by high-temperature oxydation, coating prepared by this comparative example exists
Antioxygenic property under 1100 DEG C, 1300 DEG C and 1500 DEG C hot conditions is far below the Pd-CeO prepared by embodiment 32- Co receives
Rice coating.
Above-described embodiment is the present invention preferably example, is merely to illustrate the present invention, the invention is not restricted to above-described embodiment,
The addition for the technical characteristic that every technical scheme according to the technology of the present invention is made, equivalent transformation, belong to the technology of the present invention side
The protection domain of case.
Table 1, table 2, table 3 are the oxygen of the various embodiments described above and comparative example material at 1100 DEG C, 1300 DEG C and 1500 DEG C respectively
Change mass loss rate correction data.As can be seen from the table, aoxidized at 1100 DEG C to 1300 DEG C no matter 10 to 30 minutes, pass through
The molybdenum or molybdenum alloy quality of the invention coating treatment are all without significant change, until after 1500 DEG C of oxidations, mass loss rate is in growth
Trend；And the 10min oxidations at 1100 DEG C of the molybdenum or molybdenum alloy without any surface treatment by vigorous oxidation, aoxidize
After 30min matrix ablation totally, and using the method for the invention prepare antioxidant coating comparative example 1~3 prepared by
Antioxygenic property under 1100 DEG C, 1300 DEG C and 1500 DEG C hot conditions of molybdenum or molybdenum alloy material be far below each embodiment institute
The Pd-CeO of preparation2- Co nano coatings.Illustrate that the invention is highly resistant in antioxidant coating prepared by molybdenum or molybdenum alloy surface
The erosion of oxygen, and temperature in use is up to 1500 DEG C.
The oxidative mass loss rate of 1 each embodiment of table and comparative example material at 1100 DEG C
The oxidative mass loss rate of 2 each embodiment of table and comparative example material at 1300 DEG C
The oxidative mass loss rate of 3 each embodiment of table and comparative example material at 1500 DEG C
Claims (3)
1. a kind of molybdenum or molybdenum alloy surface Pd-CeO2The preparation method of-Co nano coatings, it is characterised in that：This method includes following
Step：
Step 1, by molybdenum or molybdenum alloy through over cleaning and surface etch so that molybdenum or molybdenum alloy surface form uniform pitted skin, rinse
Mo substrate or molybdenum alloy matrix is made in drying；
Step 2, by Pd (NO3)2、CeO2Dissolved in cobalt acetate in dry isobutanol, be heated to 60 DEG C~70 DEG C, add diethanol
Amine and distilled water, add ammoniacal liquor and adjust solution ph to being stirred continuously to form colloidal sol after 7.5~8, by 10~24h evaporation-condensations
Stabilization, uniform, transparent aqueous precursor gel are obtained afterwards；
In described step two, diethanol amine, CeO in aqueous precursor gel2、Pd(NO3)2It is 4 with cobalt acetate mol ratio:
(0.5~2):(2~4):(0.5~2)；
Step 3, by aqueous precursor gel made from step 2 coated on Mo substrate made from step 1 or molybdenum alloy matrix, obtain
To molybdenum or molybdenum alloy surface Pd-CeO2- Co nano coatings；
Detailed process in described step three is：Pass through note on the surface of Mo substrate made from step 1 or molybdenum alloy matrix
Stream, which has in the nip rolls of aqueous precursor gel made from step 2, carries out roller coat, obtains molybdenum or molybdenum alloy surface Pd-CeO2- Co nanometers apply
Layer；
The width of the nip rolls is more than matrix width, and nip rolls linear velocity is 2~5mm/s, and the aqueous precursor gel in roller coat
Continuously, on homogeneous beam to nip rolls；The molybdenum after roller coat or molybdenum alloy are placed at 100~120 DEG C again and dried, at 350~430 DEG C
1~3h of lower microwave irradiation, repeat 5~10 times, 5~10h of last time microwave irradiation.
2. preparation method as claimed in claim 1, it is characterised in that：Detailed process in described step one is：By molybdenum or
Molybdenum alloy surface is polished with 800~1000 mesh sand paper, is placed in 30~50wt% NaOH solution and is boiled alkali cleaning decontamination, with ultrasound
It is eluted with water after ripple cleaning；It is subsequently placed in 20~30wt% hydrofluoric acid solutions that temperature is 80~90 DEG C and carries out surface etch,
Until surface forms uniform pitted skin, cleaned after taking-up with distilled water and alcohol, drying, Mo substrate or molybdenum alloy matrix is made.
3. preparation method as claimed in claim 1, it is characterised in that：Described Mo substrate or molybdenum alloy matrix material is pure
Molybdenum, Mo-Ti systems alloy, Mo-W systems alloy, Mo-Cu systems alloy, Mo-Re systems alloy, the sheet material or rod of TZC alloys or TZM alloys
Material.
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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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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
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| TZM合金抗氧化性研究进展;康轩齐等;《热加工工艺》;20130228;第42卷(第4期);全文 * |
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