CN107083560B - A kind of ultrahigh hardness refractory metal nanocrystalline deposit and preparation method thereof - Google Patents
A kind of ultrahigh hardness refractory metal nanocrystalline deposit and preparation method thereof Download PDFInfo
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- CN107083560B CN107083560B CN201710286191.6A CN201710286191A CN107083560B CN 107083560 B CN107083560 B CN 107083560B CN 201710286191 A CN201710286191 A CN 201710286191A CN 107083560 B CN107083560 B CN 107083560B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Abstract
The present invention provides a kind of ultrahigh hardness refractory metal nanocrystalline deposits and preparation method thereof.Firstly, the molybdenum oxygen alloy coating of micron order thickness is electroplated on the metallic substrate using electro-deposition techniques；Then coating is placed into reduced anneal in the hydrogen gas stream, obtains high rigidity, high thermal stability refractory metal nanocrystalline deposit.The coating has equally distributed isometric crystal structure, and for average grain size between 4-200nm, hardness reaches as high as 18Gpa, is 4 times of coarse-grain molybdenum or more.Refractory metal nanocrystalline deposit prepared by the present invention not only has excellent a mechanical property and thermal stability, but also also has compared to other methods for preparing refractory metal coating that preparation cost is low, the simple advantage of preparation flow.It can be applied to the wear Protection of copper, nickel and its alloy and stainless steel and other metal materials.
Description
Technical field
The present invention relates to the preparation of refractory metal nano material and coating protection fields, especially provide a kind of ultrahigh hardness infusibility
Metallic nano crystal coating and preparation method thereof.
Background technique
Magnesium-yttrium-transition metal molybdenum has high fusing point (2623 DEG C) as a kind of refractory metal, be only second to tantalum, tungsten, rhenium, osmium and
Light dydrocarbon kind element, low linear expansion coefficient (4.8 × 10-6/ DEG C), it is the half of most of steel, high thermal conductivity and conductivity, number
Times many high temperature alloys, are only the half and high elevated temperature strength of copper thermal conductivity.Molybdenum is mainly answered in the form of alloy extensively
For military project and each field such as civilian, such as solid propellant propulsion rocket part, honeycomb part, rapid neutron breeder reactor sodium is returned
Road tubing, the target etc. in x-ray instrument.
Nano crystal material refers to that microstructure characteristic size is less than the single-phase or multiphase crystalline material of 100nm.This knot
Small three orders of magnitude of traditional polycrystalline material of structure size ratio, volume ratio shared by crystal boundary are significantly promoted.Thus also make
Nano crystal material have better than traditional material performance, such as: high intensity, high rigidity, excellent wear resistance and
Excellent fatigue behaviour.Currently, the few pure metal nanometer of densification of the crystallite dimension between 0-20nm, impurity content how is prepared
There is very big blank in crystalline substance.On the whole, the method for preparing pure metal nano structural material can be divided into two classes, the first kind be by
Coarse grain in original material is crushed to the crystal grain of nanoscale, this is referred to as the method for " (top-down) from top to bottom ".
The another kind of crystal grain that the atom of material or elementide are mainly synthesized to by method physically or chemically nanoscale, this
The referred to as method of (bottom-up) " from bottom to top ".Currently, " from bottom to top " method is mainly to use the side of severe plastic deformation
Method, including equal channel pressings (equal channel angular pressing, ECAP), high pressure torsion (high pressure
Torsion, HPT) and accumulation pack rolling (accumulative roll bonding, ARB) and in recent years by China's material science
Family's Lu Ke et al. invention surface mechanical attrition treatment technology (Surface Mechanical Attrition Treatment,
) and surface cal rolling processing technique (Surface Mechanical Grinding Treatment, SMGT) SMAT.And this
A little methods refinement crystalline sizes there are the limit, such as channel pressings, high pressure torsion and accumulate pack rolling can only refining grain size arrive
Ultra-fine Grained rank (100-1000nm), and be difficult further to be refined to sub-nanometer scale (< 100nm)；Surface mechanical attrition treatment
It is same although one layer crystal particle size of outer metallic surface can be refined to nanocrystalline range by technology and surface cal rolling technology
There is also certain limit, about 20nm.These saturations/limit crystallite dimension presence dislocation density caused by being plastically deformed
Increase and reaches dynamic equilibrium with the reduction of dislocation density caused by dynamic recovery.Second class " from bottom to top " method mainly has indifferent gas
Body condensation method, vapour deposition process and magnetron sputtering method etc..Although these methods can prepare crystallite dimension receiving less than 100nm
Rice structural material, but all there is certain shortcoming in these materials, mainly consistency is low, there is macroscopic view or microcosmic sky
Hole, and preparation cost is high.
In addition, the nanocrystalline preparation method of refractory metal also has very big vacancy at present, above-mentioned severe plastic deformation method is main
It applies on the metal that crystal structure is FCC, applies and study also seldom, Er Qie on BCC metal especially refractory metal
Under same preparation process, since the FCC metal of BCC metal dislocation activity ratio is weak, deformability is also poor compared with FCC metal, so
Cause BCC metal saturation crystallite dimension big, the refractory metal nanometer prepared by severe plastic deformation method reported in document
Jingjing particle size is typically larger than 40nm, if refractory metals tantalum is 40nm, infusibility by the smallest grain size that high pressure torsion obtains
Metal molybdenum is 75nm by the smallest grain size that high pressure torsion obtains.Another common preparation method is magnetron sputtering system
Standby refractory metal film, the smallest grain size is up to 20nm.There are also many problems at present for the nanocrystalline preparation of refractory metal as a result,
It needs to probe into.
Summary of the invention
Aiming at the problem that the nanocrystalline effective preparation method of current refractory metal lacks, the present invention provides a kind of preparation cost
Low, nanocrystalline deposit of the simple refractory metal molybdenum of preparation flow and preparation method thereof, the metal molybdenum prepared using this method
Plated layer compact, and be well combined with substrate, average grain size has excellent in 4-200nm, Vickers hardness in 8-18GPa
Mechanical property and thermal stability, can be applied to the wear Protection of copper, nickel and its alloy and stainless steel and other metal materials.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of preparation method of ultrahigh hardness refractory metal nanocrystalline deposit, it is characterised in that: first with electro-deposition side
Method prepares molybdenum oxygen alloy coating, and then molybdenum oxygen alloy coating is put into vacuum drying oven, is passed through high-purity hydrogen, is annealed by control
Temperature and time controllably prepares the pure molybdenum coating of various grain sizes and different hardness.
The preparation method of ultrahigh hardness refractory metal nanocrystalline deposit of the present invention, it is characterised in that: the electro-deposition
In method, using copper, nickel and its alloy or steel as cathode or electroplated substrates, with the high concentration (molar ratio of water and acetate in solution
Range is in 1.8-3.5) acetate ion solution be electroplate liquid, molybdenum oxygen alloy coating is electroplated out.
Wherein, the specific process step of electro-deposition method are as follows:
1), substrate is polished, polishing, and organic solvent (such as in acetone) carries out surface degreasing, ultrasonic activation in dilute sulfuric acid；
2), plating solution configures: weighing two water 0.2-10g/L of sodium molybdate, ammonium acetate 260-340g/L, potassium acetate 300-400g/
L, glacial acetic acid 200-230mL/L are dissolved in deionized water, and filter paper filters after stirring and dissolving；PH value is adjusted to 6.75 ± 0.20；
3), current density and electroplating time regulation: according to required thickness of coating, existed using DC power control current density
0.4-3A/cm2Between change, electroplating time is 5-36 hour, and thickness of coating is 0.2-30 μm, oxygen in the molybdenum oxygen alloy prepared
Content is 1.8-5.3wt.%.
As a preferred technical scheme: sodium molybdate two water 5-10g/L, ammonium acetate 270-290g/L, potassium acetate 340-370g/
L, glacial acetic acid 200-230mL/L；Current density 1.0-2.5A/cm2, electroplating time 5-10h.
Wherein, using insoluble anode (such as platinum plate electrode) when plating, and place it in proton exchange membrane every
In film slot, prevent molybdenum acid ion and acetate ion from may decompose or aggregate into labyrinth macromolecular in anodic oxidation dirty
Solution is contaminated, Coating composition and pattern are influenced.
All reagents of the present invention are that analysis is pure, and plating solution is prepared using deionized water.
Ultrahigh hardness refractory metal nanocrystalline deposit of the present invention and preparation method thereof, it is characterised in that: in hydrogen
During atmosphere reduction and Amorphous Crystallization, annealing region is 400-1200 DEG C in nitrogen atmosphere, and annealing time is in 1-36 hour
Between, furnace internal pressure strong demand is 1-2 atmospheric pressure after being passed through hydrogen.Preparation can be accurately controlled by control annealing temperature and time
The crystallite dimension and hardness of coating out.
The vacuum drying oven used as a preferred technical solution, is electron tubes type resistance furnace.Annealing temperature is excellent in hydrogen atmosphere
Selecting range is 500-630 DEG C, and annealing time is preferably between 10-24 hours.Crystallite dimension is 6-12nm in this preferred scope,
Vickers hardness is 4 times of coarse-grain molybdenum or more in 15-18GPa.
The ultrahigh hardness refractory metal nanocrystalline deposit prepared using the method for the invention, it is characterised in that: the plating
The grain size range of layer is 4-200nm, and Vickers hardness is in 7.5-18GPa.
The invention has the following advantages that
1, the present invention combines plating, and three kinds of methods of hydrogen reducing and Amorphous Crystallization method breach previous refractory metal nanometer
The dimension limit problem of crystal preparation method, to prepare, refractory metal is nanocrystalline to provide a kind of new thinking.
2, refractory metal nanocrystalline deposit prepared by the present invention has excellent mechanical property, and crystallite dimension is the molybdenum of 11nm
Nanocrystalline hardness be 18GPa close to theoretical hardness be in the nanocrystalline hardness of BCC, FCC, HCP metal reported at present
It is highest.
3, preparation method of the present invention is simple, at low cost, high-efficient, can crystal grain ruler needed for controllable preparation according to demand
It is very little.
Detailed description of the invention
The cross section (a) and coating surface morphology (b) under scanning electron microscope that Fig. 1 is coating.
Fig. 2 is the nanocrystalline XRD curve of the molybdenum of the various grain sizes obtained under different annealing in nitrogen atmosphere.
Fig. 3 be coating in nitrogen atmosphere 630 DEG C annealing 12 hours after, the nanocrystalline transmission electron microscope picture of refractory metal molybdenum
(a), selective electron diffraction (b), crystallite dimension statistical Butut (c).
Fig. 4 be coating in nitrogen atmosphere 450 DEG C annealing 12 hours after, the nanocrystalline transmission electron microscope picture of refractory metal molybdenum
(a), selective electron diffraction (b), crystallite dimension statistical Butut (c).
Fig. 5 is several different pure metal hardness range histograms.
Specific embodiment
Embodiment 1
1) molybdenum oxygen alloy coating, is electroplated:
Using platinized platinum as anode, using copper as cathode, 1000mL plating solution, plating solution composition are prepared as required are as follows:
Sodium molybdate two water 5g/L, ammonium acetate 270g/L, potassium acetate 370g/L, glacial acetic acid 200mL/L are weighed in the balance above
Drug, in deionized water, filter paper filters after stirring and dissolving for dissolution, then by plating solution magnetic stirrer, temperature control
At 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 0.4A/cm2, electroplating time is 24 hours.Finally, the section of coating
Figure and surface topography are as shown in Figure 1, thickness of coating is about 10 μm, and dense non-porous hole, the ingredient of coating are molybdenum by analysis
97.1wt.%, oxygen 2.9wt.%.The XRD curve of coating shows there is an apparent steamed bun peak at 40 degree or so, illustrates coating
Microstructure is amorphous.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, is first evacuated to 10-3Pa, then be passed through high-purity
Hydrogen, furnace overpressure are 1-2 atmospheric pressure, and annealing temperature is selected as 630 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 3, its crystal grain is that the shaft-like such as uniform, tiny are nanocrystalline, average ruler
Very little is 10.7 ± 4.1nm.Electron diffraction diagram uniform, continuous diffraction ring with signal strength, it is random to show that nanocrystal has
Crystalline orientation, and without apparent preferred orientation in entire sample.Coating Vickers hardness is 18GPa.
Embodiment 2
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using nickel as cathode, 1000mL plating solution, plating solution composition are prepared as required are as follows:
Sodium molybdate two water 10g/L, ammonium acetate 290g/L, potassium acetate 340g/L, glacial acetic acid 200mL/L, weigh in the balance with
Upper drug, in deionized water, filter paper filters after stirring and dissolving, then by plating solution magnetic stirrer, temperature control for dissolution
System is at 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 1.0A/cm2, electroplating time is 10 hours.Finally, coating is cut
Face figure and surface topography are as shown in Figure 1, thickness of coating is about 10 μm, and dense non-porous hole, the ingredient of coating are molybdenum by analysis
97.1wt.%, oxygen 2.9wt.%.Coating micromechanism is converted into amorphous+nanocrystalline cluster from amorphous.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, is first evacuated to 10-3Pa, then be passed through high-purity
Hydrogen, furnace overpressure are 1-2 atmospheric pressure, and annealing temperature is selected as 500 DEG C, and annealing time is 24 hours.
The Coating prepared is as shown in figure 3, its crystal grain is that the shaft-like such as uniform, tiny are nanocrystalline, average ruler
Very little is 6.5 ± 2.1nm.Electron diffraction diagram uniform, continuous diffraction ring with signal strength, shows that nanocrystal has at random
Crystalline orientation, and without apparent preferred orientation in entire sample.Coating Vickers hardness is 15GPa.
Embodiment 3
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steel as cathode, 1000mL plating solution, plating solution composition are prepared as required are as follows:
Sodium molybdate two water 5g/L, ammonium acetate 280g/L, potassium acetate 350g/L, glacial acetic acid 230ml/L are weighed in the balance above
Drug, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolution, then will plating
Liquid magnetic stirrer, temperature control is at 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 2.5A/cm2, when plating
Between be 5h.Finally, the sectional view and surface topography of coating be as shown in Figure 1, thickness of coating is about 10 μm, and dense non-porous hole, plating
The ingredient of layer is molybdenum 98wt.%, oxygen 2.0wt.% by analysis.Coating micromechanism is converted into amorphous+nanometer colony from amorphous
Cluster.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, is first evacuated to 10-3Pa, then be passed through high-purity
Hydrogen, furnace overpressure are 1-2 atmospheric pressure, and annealing temperature is selected as 550 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 3, its crystal grain is that the shaft-like such as uniform, tiny are nanocrystalline, average ruler
Very little is 7.1 ± 2.5nm.Electron diffraction diagram uniform, continuous diffraction ring with signal strength, shows that nanocrystal has at random
Crystalline orientation, and without apparent preferred orientation in entire sample.Coating Vickers hardness is 15.5GPa.
Embodiment 4
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steel as cathode, 1000mL plating solution, plating solution composition are prepared as required are as follows:
Sodium molybdate two water 10g/L, ammonium acetate 300g/L, potassium acetate 350g/L, glacial acetic acid 200mL/L, weigh in the balance with
Upper drug, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolution, then will
Plating solution magnetic stirrer, temperature control is at 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 1.0A/cm2, plating
Time is 10 hours.Finally, the sectional view and surface topography of coating be as shown in Figure 1, thickness of coating is about 10 μm, and dense non-porous
Hole, the ingredient of coating are molybdenum 97.5wt.%, oxygen 2.5wt.% by analysis.Coating micromechanism is converted into amorphous+receive from amorphous
Meter Jing Tuan cluster.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, is first evacuated to 10-3Pa, then be passed through high-purity
Hydrogen, furnace overpressure are 1-2 atmospheric pressure, and annealing temperature is selected as 450 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 4, its crystal grain is that the shaft-like such as uniform, tiny are nanocrystalline, average ruler
Very little is 5.6 ± 2.2nm.Electron diffraction diagram uniform, continuous diffraction ring with signal strength, shows that nanocrystal has at random
Crystalline orientation, and without apparent preferred orientation in entire sample.Coating Vickers hardness is 13.5GPa.
Embodiment 5
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steel as cathode, 1000mL plating solution, plating solution composition are prepared as required are as follows:
Sodium molybdate two water 10g/L, ammonium acetate 300g/L, potassium acetate 350g/L, glacial acetic acid 200mL/L, weigh in the balance with
Upper drug, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolution, then will
Plating solution magnetic stirrer, temperature control is at 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 2.5A/cm2, plating
Time is 5 hours.Finally, the sectional view and surface topography of coating be as shown in Figure 1, thickness of coating is about 10 μm, and dense non-porous
Hole, the ingredient of coating are molybdenum 98.0wt.%, oxygen 2.0wt.% by analysis.Coating micromechanism is converted into amorphous+receive from amorphous
Meter Jing Tuan cluster.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, is first evacuated to 10-3Pa, then be passed through high-purity
Hydrogen, furnace overpressure are 1-2 atmospheric pressure, and annealing temperature is selected as 1000 DEG C, and annealing time is 1 hour.
The coating XRD curve prepared is as shown in Fig. 2, average grain size is 120nm.Coating Vickers hardness is
7.5GPa。
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of ultrahigh hardness refractory metal nanocrystalline deposit, it is characterised in that: first with electro-deposition method
Molybdenum oxygen amorphous alloy coating is prepared, then molybdenum oxygen amorphous alloy coating is put into vacuum drying oven, is passed through high-purity hydrogen, passes through control
Annealing temperature processed and time prepare the pure molybdenum coating of various grain sizes and different hardness；Wherein electro-deposition method is specific
Processing step are as follows:
1), substrate is polished, polishing, surface degreasing, ultrasonic activation in dilute sulfuric acid；
2), plating solution configures: weighing two water 0.2-10g/L of sodium molybdate, ammonium acetate 260-340g/L, potassium acetate 300-400g/L, ice
Acetic acid 200-230mL/L is dissolved in deionized water, and filter paper filters after stirring and dissolving；PH value is adjusted to 6.75 ± 0.20；
3), current density and electroplating time regulation: according to required thickness of coating, using DC power control current density in 0.4-
3A/cm2Between change, electroplating time is 5-36 hour, and thickness of coating is 0.2-30 μm, oxygen content in the molybdenum oxygen alloy prepared
For 1.8-5.3wt.%.
2. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that: the electricity
In deposition method, using copper, nickel and its alloy or steel as cathode.
3. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that: sodium molybdate
Two water 5-10g/L, ammonium acetate 270-290g/L, potassium acetate 340-370g/L, glacial acetic acid 200-230mL/L；Current density 1.0-
2.5A/cm2, electroplating time 5-10h.
4. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that: hydrogen gas
Annealing region is 400-1200 DEG C in atmosphere, and annealing time is between 1-36 hours.
5. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 4, it is characterised in that: be passed through hydrogen
Furnace internal pressure strong demand is 1-2 atmospheric pressure after gas.
6. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that: hydrogen gas
Annealing region is 500-630 DEG C in atmosphere, and annealing time is between 10-24 hours.
7. a kind of ultrahigh hardness refractory metal nanocrystalline deposit using any the method preparation of claim 1-6.
8. according to ultrahigh hardness refractory metal nanocrystalline deposit described in claim 7, it is characterised in that: the crystal grain ruler of the coating
Very little range is 4-200nm, and Vickers hardness is in 7.5-18GPa.
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Citations (1)
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| EP2155832A1 (en) * | 2007-05-22 | 2010-02-24 | Element Six Limited | Coated cbn |
Non-Patent Citations (2)
| Title |
|---|
| A comparative study of the electrochemical deposition of molybdenum oxides thin films on copper and platinum;Radu Banica et al.;《Journal of Alloys and Compounds》;20081216;第483卷;全文 * |
| 氧化钼薄膜的制备和电化学性能调控;刘灿;《中国优秀硕士学位论文全文数据库》;20150915(第9期);第70页 * |
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