CN110205610A - A method of in cenosphere surface coated copper nickel protection layer - Google Patents
A method of in cenosphere surface coated copper nickel protection layer Download PDFInfo
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- CN110205610A CN110205610A CN201910607862.3A CN201910607862A CN110205610A CN 110205610 A CN110205610 A CN 110205610A CN 201910607862 A CN201910607862 A CN 201910607862A CN 110205610 A CN110205610 A CN 110205610A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/101—Pretreatment of the non-metallic additives by coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- General Chemical & Material Sciences (AREA)
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- Other Surface Treatments For Metallic Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention provides a kind of methods in cenosphere surface coated copper nickel protection layer, alkali cleaning and surface roughening treatment are carried out to cenosphere first, then by Ni (NO3)2·6H2O and Cu (NO3)2·3H2O is dissolved in ethyl alcohol and the mixed solution of deionized water; the cenosphere of roughening treatment is immersed in above-mentioned mixed solution; it is stirred under 50 DEG C of water bath conditions to viscous pasty state; it is placed in air dry oven; it is sufficiently dry under the conditions of 100 DEG C; solid mixture after drying is placed in tube furnace in argon atmosphere and is roasted, the cenosphere of CuO/NiO cladding is obtained, finally obtains the cenosphere of Cu-Ni protective layer cladding with hydrogen reducing under the conditions of 700 DEG C.This method simple process, obtained Cu-Ni clad structural integrity, thickness are uniform; it is well combined with cenosphere surface; it can shield in cenosphere/composite material of magnesium alloy preparation process, reduce or prevent the generation of mechanical damage and interfacial reaction, cenosphere is made to keep complete.
Description
Technical field
The invention belongs to powder surface modification fields, are related to a kind of side in cenosphere surface coated copper nickel protection layer
Method, more particularly in floating bead or the method for hollow glass micropearl surface coated copper nickel protection layer, cenosphere wall is enable to strengthen
And protection, it is ensured that cenosphere keeps complete, do not rupture during preparing cenosphere/magnesium alloy light composite material.
Background technique
Ceramic particle or fiber reinforced magnesium base composite material are because its density is low, specific stiffness and specific strength are high, damping is strong, size
The features such as stability is good, in fields such as aerospace, rail traffic, derived energy chemicals by favor.In recent years, cenosphere enhances
Magnesium-based composite material is applied and is developed, and cenosphere is a kind of hollow thin-wall sphere that size is small, and partial size is in 10-
Between 250 μm, main component is SiO2And Al2O3, have the characteristics that density is low, intensity is high, thermal stability is good, source is main
It is the floating bead extracted in the byproduct flyash of Hazards in Power Plant and made hollow glass micropearl.Cenosphere is made
It is added in magnesium alloy for reinforcement, cenosphere is made to keep complete hollow state in material preparation process, it is compound to reduce
The density of material, is the new methods for preparing lightweight magnesium-based composite material, and preparation method mainly has powder metallurgic method, pressure casting
Make method and stirring casting method.But in the preparation process of cenosphere magnesium-based composite material, due to mechanical damage and and liquid
Interfacial reaction, which occurs, for magnesium alloy frequently can lead to the broken of cenosphere wall, cause to be filled inside floating bead by magnesium alloy substrate, multiple
The density of condensation material goes up not down.Liu Enyang etc. is prepared for using using floating bead is added in stirring casting normal direction magnesium alloy fused mass
Floating bead/AZ91D composite material, the results showed that, in composite material preparation process, interfacial reaction occurs for floating bead and magnesium alloy fused mass
Generate Mg2Si and MgO, floating bead occur rupture is filled by matrix alloy so that composite density it is high than expected (Liu Enyang,
Full of beard is flourish, Zhao Yan, waits floating bead/AZ91D composite material microstructure and performance [J] Rare Metals Materials and engineering, and 2017,46
(11):3298-3304).Rohatgi P K etc. is prepared for floating bead/AZ91D composite material by casting die, the study found that compound
Floating bead in material equally exists in the form of broken microballoon, fills (Rohatgi P K, Daoud by basis material inside floating bead
A,Schultz B F,et al.Microstructure and mechanical behavior of die casting
AZ91D-Fly ash cenosphere composites[J].Applied Science and Manufacturing,
2009,40(7):883-896).Cause composite density than pre- for the rupture of cenosphere wall, internal filled by matrix alloy
This problem of the raising of meter, researchers propose some solutions, wherein coating protective layer on cenosphere surface, are used to
Strengthen cenosphere and prevent cenosphere and magnesium alloy fused mass in material preparation process that interfacial reaction occurs, to keep hollow
The integrality of microballon in the composite is proved to be a kind of effective scheme.Braszczy ń ska M etc. is using chemistry
Plating method has coated layer of Ni-P protective layer on fly ash float surface, and it is multiple to be prepared for floating bead/AZ91 magnesium alloy with stirring casting method
Condensation material, the results showed that, Ni-P layers effectively prevent floating bead wall to react with matrix magnesium alloy, and floating bead integrality is good, not
Rupture, effectively reduces density (Braszczy ń ska M, Katarzyna N, the Kamieniak J.Analysis of composite material
of interface between components in AZ91magnesium alloy foam composite with
Ni-P coated fly ash cenospheres[J].Journal of Alloys and Compounds,2017,720:
352-359).But it needs to use AgNO when coating Ni-P protective layer using electroless plating method3、PdCl2Equal precious metal salts make activator,
The cost of raw material is increased, and the preparation step of chemical deposit is cumbersome, chemical plating fluid complicated component, while chemical plating generates
A large amount of devil liquor recoveries it is difficult, easily cause environmental pollution.Therefore, it finds a kind of cost-effective in cenosphere surface cladding guarantor
The method of sheath, the research and development and application of comprehensive utilization and lightweight magnesium alloy composite material to cenosphere all have important meaning
Justice.
Summary of the invention
It is an object of the invention to solve to prepare cenosphere/composite material of magnesium alloy using cenosphere as reinforcement
When, in material preparation process cenosphere because mechanical collision act on and occur interfacial reaction due to rupture the problem of, specially mention
For a kind of method in cenosphere surface cladding Cu-Ni protective layer, this method can be to fly ash float and hollow glass micropearl
Carry out surface cladding.
Specific step is as follows in cenosphere surface cladding Cu-Ni protective layer by the present invention:
(1) cenosphere is surface-treated, including alkali cleaning and roughening.A certain amount of cenosphere is put into 0.5- first
In the NaOH solution of 1mol/L, with mechanical agitator stirring and washing 30-60min at room temperature, on the one hand remove hollow micro-
On the other hand the greasy dirt and impurity of bead surface reduce cenosphere by alkali cleaning and reunite, increase its dispersibility in the medium, so
It filters and is rinsed repeatedly with deionized water to pH=7 afterwards.Cenosphere after alkali cleaning is added to the ammonium fluoride solution of 30g/L
In, 20-50min is stirred under 50 DEG C of water bath conditions, hydrolyzes the hydrofluoric acid of generation in the hot water using ammonium fluoride to SiO2Quarter
Erosion acts on (its mechanism is shown in reaction equation (1) and reaction equation (2)), forms many small pits and groove on cenosphere surface,
Increase its surface area, is conducive to metal ion in the absorption on its surface and clad in the fixation on its surface, in addition in this step
Occur leading to cenosphere table because of overreact when carrying out roughening treatment using ammonium fluoride and can avoid directly being roughened using hydrofluoric acid
The problem of face perforation, rupture, is finally rinsed with deionized water repeatedly until pH=7, filters drying.It is empty after alkali cleaning, roughening treatment
The surface topography of heart microballon is as shown in Figure 1.
SiO2+4HF═SiF4↑+2H2O (2)
(2) by a certain amount of Ni (NO3)2·6H2O and Cu (NO3)2·3H2O is dissolved in ethyl alcohol and the mixing of deionized water is molten
In liquid (volume ratio of ethyl alcohol and deionized water is 1:1), the metal ion total concentration in mixed solution is made to be maintained at 0.3-
0.5mol/L, wherein Ni2+With Cu2+Ratio be 1:0.2-1:5；Then cenosphere alkali cleaning in step (1) being roughened immerses
In above-mentioned mixed solution, the solid-to-liquid ratio of cenosphere and mixed solution is 1:25-1:40, then under 50 DEG C of condition of water bath heating
It is stirred to mixed liquor with the speed of 100-300r/min in viscous pasty state, is placed in air dry oven 100 with mechanical agitator
Sufficiently dry 10-20h obtains solid mixture under the conditions of DEG C, then puts it into tube furnace, logical with the flow of 50mL/min
Enter high-purity argon, tube furnace is rapidly heated to 400-600 DEG C, furnace temperature starts timing after stablizing, after roasting 3-5h, take out in air
Middle cooling obtains the cenosphere of CuO/NiO cladding, reacts as follows:
(3) the CuO/NiO cenosphere coated is lightly ground after breaing up in mortar and is put into tube furnace, using hydrogen
With high-purity argon mixture gas as also Primordial Qi, passes first into high-purity argon and the air in tube furnace is discharged, then with 30-60mL/
The flow of min is passed through hydrogen and high-purity argon mixture gas, and wherein the volume ratio of hydrogen and high-purity argon is 1:9-2:3, then will pipe
Formula furnace is warming up to 700 DEG C with the speed of 10 DEG C/min, after continuing ventilation reductase 12-4h under the conditions of 700 DEG C, closes hydrogen, with
The flow of 50mL/min leads to high-purity argon, prevents the cupro-nickel protective layer of cladding from aoxidizing under the high temperature conditions, last furnace cooling
To room temperature, the cenosphere of cladding Cu-Ni protective layer is obtained.It reacts such as following formula:
The present invention overcomes that electroless plating step is cumbersome, raw material in the method for cenosphere surface coated copper nickel protection layer
The disadvantages of at high cost.Obtained Cu-Ni protective layer structure is complete, and thickness is uniform, and preparation process is simple, can mention to cenosphere
For good protective effect, and the machinery that cenosphere can be reduced in cenosphere/composite material of magnesium alloy preparation process is broken
Generation that is bad, reducing or prevent interfacial reaction, makes cenosphere keep complete, is finally reached the mesh for reducing composite density
, and Cu-Ni layers have better wellability between magnesium alloy substrate, can preferably be combined with magnesium alloy substrate.
Detailed description of the invention
Fig. 1 is the fly ash float surface topography map after roughening；
Fig. 2 is the surface topography map for coating the fly ash float of Cu-Ni protective layer；
Fig. 3 is the EDS map for coating the fly ash float of Cu-Ni protective layer；
Fig. 4 is the surface topography map for coating the hollow glass micropearl of Cu-Ni protective layer.
Specific embodiment
Embodiment 1:
20g fly ash float is put into the NaOH solution that 500mL concentration is 0.5mol/L, with mechanical agitator in room temperature
Under the conditions of stirring and washing 60min, filter simultaneously rinsed repeatedly with deionized water to pH=7；Then alkali cleaning floating bead is added to
In the ammonium fluoride solution of 500mL30g/L, 20min is stirred under 50 DEG C of water bath conditions, is rinsed repeatedly with deionized water until pH=
7, filter drying.By 53g Ni (NO3)2·6H2O and 15g Cu (NO3)2·3H2O is dissolved in 600mL ethyl alcohol and deionized water
In mixed solution (volume ratio of ethyl alcohol and deionized water is 1:1), cenosphere after roughening is immersed in above-mentioned mixed solution,
Stirring 8h to mixed liquor with the speed of 100r/min with mechanical agitator under 50 DEG C of water bath conditions is in viscous pasty state, is then set
12h is dried under the conditions of 100 DEG C in air dry oven.Solid mixture after drying is put into tube furnace, with 50mL/
The flow of min is passed through high-purity argon, and tube furnace is rapidly heated to 500 DEG C, takes out after roasting 3h, cools down, then exist in air
It is lightly ground in mortar and breaks up solid mixture, be placed again into tube furnace, high-purity argon 5min is led to the flow of 100mL/min,
Then hydrogen and high-purity argon are passed through with the flow of 15mL/min and 35mL/min respectively, by tube furnace with the speed liter of 10 DEG C/min
Temperature is to 700 DEG C, and Continuous aeration keeps the temperature 3h after furnace temperature is stablized, and finally closes hydrogen, leads to high-purity argon with the flow of 50mL/min, with furnace
It is taken out after being cooled to room temperature, obtains the floating bead of surface cladding Cu-Ni protective layer.Its surface topography as shown in fig. 2, it can be seen that
Fine particle of uniform size is closely coated on floating bead surface, forms one layer of complete fine and close, clad in homogeneous thickness, EDS
Map as shown in figure 3, main peak be Ni and Cu, illustrate successfully to have coated Ni-Cu protective layer on floating bead surface.
Embodiment 2:
25g hollow glass micropearl is put into the NaOH solution that 500mL concentration is 0.7mol/L, with mechanical agitator in room
Stirring and washing 30min under the conditions of temperature is filtered and is rinsed repeatedly with deionized water to pH=7；Alkali cleaning hollow glass micropearl is added
Into the ammonium fluoride solution of 30g/L, 50min is stirred under 50 DEG C of water bath conditions, is rinsed repeatedly with deionized water up to pH=7,
Filter drying.By 50g Ni (NO3)2·6H2O and 40g Cu (NO3)2·3H2O is dissolved in the mixed of 800mL ethyl alcohol and deionized water
(volume ratio of ethyl alcohol and deionized water is 1:1) is closed in solution, the hollow glass micropearl after roughening is immersed into above-mentioned mixed solution
In, with mechanical agitator in viscous pasty state, then 6h is stirred to mixed liquor with the speed of 300r/min under 50 DEG C of water bath conditions
Dry 15h under the conditions of 100 DEG C is placed in air dry oven.Solid mixture after drying is placed in tube furnace, with
The flow of 50mL/min is passed through high-purity argon, and tube furnace is rapidly heated to 600 DEG C, takes out, cools down in air, so after roasting 4h
It is lightly ground in mortar afterwards and breaks up solid mixture, be placed again into tube furnace, high-purity argon is led to the flow of 100mL/min
Then 5min is passed through hydrogen and high-purity argon respectively with the flow of 10mL/min and 40mL/min, by tube furnace with 10 DEG C/min's
Speed is warming up to 700 DEG C, and Continuous aeration keeps the temperature 4h after furnace temperature is stablized, and finally closes hydrogen, is led to the flow of 50mL/min high-purity
Argon takes out after cooling to room temperature with the furnace, obtains the hollow glass micropearl of surface cladding Cu-Ni protective layer.Its surface topography such as Fig. 4
Shown, fine particle of uniform size is coated on hollow glass micropearl surface.
Embodiment 3:
25g fly ash float is put into the NaOH solution that 700mL concentration is 1mol/L, with mechanical agitator in room temperature item
Stirring and washing 40min under part is filtered and is rinsed repeatedly with deionized water to pH=7；Alkali cleaning hollow glass micropearl is added to
In the ammonium fluoride solution of 30g/L, 30min is stirred under 50 DEG C of water bath conditions, is rinsed repeatedly with deionized water until pH=7, takes out
It is filtered dry dry.By 51g Ni (NO3)2·6H2O and 43g Cu (NO3)2·3H2O is dissolved in the mixing of 700mL ethyl alcohol and deionized water
In solution (volume ratio of ethyl alcohol and deionized water is 1:1), fly ash float is immersed in above-mentioned mixed solution, in 50 DEG C of water-baths
Under the conditions of to stir 6h to mixed liquor with the speed of 200r/min with mechanical agitator be in viscous pasty state, be subsequently placed in air dry oven
In under the conditions of 100 DEG C dry 20h.Mixture after drying is placed in tube furnace, height is passed through with the flow of 50mL/min
Tube furnace is rapidly heated to 400 DEG C by straight argon, roast 5h after take out, cool down in air, be then lightly ground in mortar by
Solid mixture is broken up, and is placed again into tube furnace, leads to high-purity argon 5min with the flow of 100mL/min, then respectively with 20mL/
The flow of min and 40mL/min is passed through hydrogen and high-purity argon, tube furnace is warming up to 700 DEG C with the speed of 10 DEG C/min, furnace temperature
Continuous aeration keeps the temperature 2h after stabilization, finally closes hydrogen, leads to high-purity argon with the flow of 50mL/min, takes after cooling to room temperature with the furnace
Out.Embodiment 3 has been similarly obtained compact structure Cu-Ni protective layer in homogeneous thickness.
Claims (1)
1. a kind of method in cenosphere surface coated copper nickel protection layer, can be to fly ash float and hollow glass micropearl surface
Carry out cupro-nickel protective layer cladding, which is characterized in that the copper-nickel protective layer is prepared using following steps:
(1) cenosphere is put into the NaOH solution of 0.5-1mol/L by cenosphere surface roughening treatment first, in room temperature item
Stirring and washing 30-60min removes the greasy dirt and impurity on its surface under part, then carry out filter and rinsed repeatedly with deionized water to
PH=7；Then filtered cenosphere is put into the ammonium fluoride solution of 30g/L and stirs 20- under 50 DEG C of water bath conditions
50min performs etching roughening to its surface, to enhance the binding force on cenosphere surface and clad, is finally filtered
And it is rinsed repeatedly with deionized water until pH=7, drying are spare；
(2) by Ni (NO3)2·6H2O and Cu (NO3)2·3H2O be dissolved in ethyl alcohol and the mixed solution of deionized water (ethyl alcohol with
The volume ratio of deionized water is 1:1), holding metal ion total concentration is 0.3-0.5mol/L, wherein Ni2+With Cu2+Ratio be
1:0.2-1:5, the cenosphere that alkali cleaning in step (1) is roughened immerse in above-mentioned mixed solution, cenosphere and mixed solution
Solid-to-liquid ratio be 1:25-1:40, make to mix with the stirring of the speed of 100-300r/min with mechanical agitator under 50 DEG C of water bath conditions
Deionized water and ethanol evaporation to mixed solution in conjunction solution is in viscous pasty state, is then placed in air dry oven
Sufficiently dry 10-20h, is put into tube furnace for the solid mixture after drying under the conditions of 100 DEG C, with the logical height of the flow of 50mL/min
Straight argon roasts 3-5h under conditions of 400-600 DEG C, cools down in air after taking-up, obtains the hollow micro- of CuO/NiO cladding
Pearl；
(3) cenosphere coated of CuO/NiO obtained in step (2) is placed in tube furnace, is first passed through high-purity argon for tubular type
In furnace air discharge, hydrogen and high-purity argon mixture gas are then passed through with the flow of 30-60mL/min, wherein hydrogen with it is high-purity
The volume ratio of argon is 1:9-2:3, and tube furnace is then warming up to 700 DEG C with the speed of 10 DEG C/min, continues to lead at such a temperature
Gas reductase 12-4h, last furnace cooling to room temperature obtain the cenosphere of cladding Cu-Ni protective layer, with 50mL/ in cooling procedure
The flow of min, which leads to high-purity argon, prevents clad from aoxidizing.
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