CN107083560A - 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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- CN107083560A CN107083560A CN201710286191.6A CN201710286191A CN107083560A CN 107083560 A CN107083560 A CN 107083560A CN 201710286191 A CN201710286191 A CN 201710286191A CN 107083560 A CN107083560 A CN 107083560A
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- refractory metal
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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 invention provides a kind of ultrahigh hardness refractory metal nanocrystalline deposit and preparation method thereof.First, 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 average grain size is between 4 200nm, and hardness reaches as high as 18Gpa, is more than 4 times of coarse-grain molybdenum.Refractory metal nanocrystalline deposit prepared by the present invention not only has excellent a mechanical property and heat endurance, and compared to other prepares methods of refractory metal coating and also have and prepare that cost is low, the simple advantage of preparation flow.Can be applied to copper, nickel and its alloy, and stainless steel and other metal materials wear Protection.
Description
Technical field
Prepared the present invention relates to refractory metal nano material and coating protection field, a kind of ultrahigh hardness infusibility is especially provided
Metallic nano crystal coating and preparation method thereof.
Background technology
Magnesium-yttrium-transition metal molybdenum is as a kind of refractory metal, with high fusing point (2623 DEG C), 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 electrical conductivity, number
Times many high temperature alloys, are only the half of copper thermal conductivity, and high elevated temperature strength.Molybdenum is main extensively should in the form of alloy
For military project and each field, such as solid propellant propulsion rocket part such as civilian, honeycomb part, rapid neutron breeder reactor sodium is returned
Target in road tubing, x-ray instrument etc..
Nano crystal material refers to that microstructure characteristic size is less than 100nm single-phase or multiphase crystalline material.This knot
Structure size than small three orders of magnitude of traditional polycrystalline material, the volume ratio shared by crystal boundary significantly lifts.Thus also make
Obtaining nano crystal material has the performance for being better than traditional material, such as：High intensity, high rigidity, excellent wear resistance and
Excellent fatigue behaviour.Currently, fine and close, simple metal nanometer that impurity content few of the crystallite dimension between 0-20nm how to be prepared
There is very big blank in crystalline substance.On the whole, two classes can be divided into by preparing the method for simple metal nano structural material, the first kind be by
Coarse grain in original material is crushed to the crystal grain of nanoscale, and this is referred to as the method for " (top-down) from top to bottom ".
The another kind of crystal grain that the atom or elementide of material are mainly synthesized to nanoscale by method physically or chemically, this
It is referred to as " from bottom to top " (bottom-up) method.At present, method is mainly the side using severe plastic deformation " from bottom to top "
Method, including etc. channel pressings (equal channel angular pressing, ECAP), high pressure torsion (high pressure
Torsion, HPT) and accumulation ply 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 treatment technology (Surface Mechanical Grinding Treatment, SMGT) SMAT.And this
There is the limit in a little methods refinement crystalline sizes, such as channel pressings, high pressure torsion and accumulation ply rolling can only refining grain size arrive
Ultra-fine Grained rank (100-1000nm), and be difficult further be refined to sub- nanoscale (<100nm)；Surface mechanical attrition treatment
Although the layer crystal particle size of outer metallic surface one can be refined to nanocrystalline scope by technology and surface cal rolling technology, equally
There is also certain limit, about 20nm.The presence of these saturations/limit crystallite dimension comes from the caused dislocation density of plastic deformation
Increase and the reduction of dislocation density caused by dynamic recovery reach dynamic equilibrium.Equations of The Second Kind " 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 weak point in these materials, mainly consistency is low, there is macroscopical or microcosmic sky
Hole, and prepare with high costs.
In addition, the nanocrystalline preparation method of refractory metal also has very big vacancy at present, above-mentioned severe plastic deformation method is main
Apply on the metal that crystal structure is FCC, apply and study also seldom on BCC metals especially refractory metal, Er Qie
Under same preparation technology, due to BCC metal dislocation activities than FCC metal it is weak, deformability is also poor compared with FCC metal, so
Cause BCC metal saturations crystallite dimension big, the refractory metal nanometer prepared by severe plastic deformation method reported in document
Jingjing particle size is typically larger than 40nm, and the smallest grain size that such as refractory metals tantalum is obtained by high pressure torsion is 40nm, infusibility
The smallest grain size that metal molybdenum is obtained by high pressure torsion is 75nm.Another conventional preparation method is magnetron sputtering system
Standby refractory metal film, the smallest grain size is up to 20nm.Thus, the nanocrystalline preparation of refractory metal also has many problems at present
Need to probe into.
The content of the invention
The problem of lacking for the nanocrystalline effective preparation method of current refractory metal, the present invention provides one kind and prepares cost
Nanocrystalline deposit of the simple refractory metal molybdenum of low, preparation flow and preparation method thereof, the metal molybdenum prepared using this method
Plated layer compact, and be well combined with substrate, its average grain size is in 4-200nm, and Vickers hardness is in 8-18GPa, with excellent
Mechanical property and heat endurance, can be applied to copper, nickel and its alloy, and stainless steel and other metal materials wear Protection.
To reach above-mentioned purpose, the present invention is adopted 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, high-purity hydrogen is passed through, by controlling to anneal
Temperature and time, controllable preparation goes out 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 negative electrode or electroplated substrates, with high concentration (solution reclaimed water and the mol ratio of acetate
Scope is in 1.8-3.5) acetate ion solution be electroplate liquid, electroplate out molybdenum oxygen alloy coating.
Wherein, the concrete technology step of electro-deposition method is：
1), substrate is polished, and polishing, organic solvent (such as in acetone) carries out ultrasonic activation in surface degreasing, dilute sulfuric acid；
2), plating solution is configured：Weigh sodium molybdate two water 0.2-10g/L, ammonium acetate 260-340g/L, potassium acetate 300-400g/
L, glacial acetic acid 200-230mL/L, are dissolved in filter paper after deionized water, stirring and dissolving and filter；PH value is adjusted to 6.75 ± 0.20；
3), current density and electroplating time regulation and control：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.%.
It is used as 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, use insoluble anode (such as platinum plate electrode) during plating, and place it in PEM every
In film groove, prevent molybdenum acid ion and acetate ion from may decompose or aggregate into labyrinth macromolecular in anodic oxidation dirty
Contaminate solution, influence Coating composition and pattern.
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
Atmosphere is reduced with during Amorphous Crystallization, and annealing region is 400-1200 DEG C in nitrogen atmosphere, and annealing time is in 1-36 hours
Between, it is 1-2 atmospheric pressure to be passed through stove internal pressure strong demand after hydrogen.By controlling annealing temperature and time accurately to control preparation
The crystallite dimension and hardness of the coating gone out.
As preferred technical scheme, the vacuum drying oven used is electron tubes type resistance furnace.Annealing temperature is excellent in hydrogen atmosphere
It is 500-630 DEG C to select scope, and annealing time is preferably between 10-24 hours.Crystallite dimension is 6-12nm in this preferred scope,
Vickers hardness, in 15-18GPa, is more than 4 times of coarse-grain molybdenum.
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 present invention has advantages below：
1st, the present invention combines plating, and three kinds of methods of hydrogen reducing and Amorphous Crystallization method breach conventional refractory metal nanometer
The dimension limit problem of crystal preparation method, to prepare, refractory metal is nanocrystalline to provide a kind of new thinking.
2nd, refractory metal nanocrystalline deposit prepared by the present invention has excellent mechanical property, and crystallite dimension is 11nm molybdenum
Nanocrystalline hardness be 18GPa, close to theoretical hardness, be BCC, FCC, HCP metal reported at present nanocrystalline hardness in
Highest.
3rd, preparation method of the present invention is simple, and cost is low, efficiency high, crystal grain chi that can according to demand needed for controllable preparation
It is very little.
Brief description of the drawings
Fig. 1 is coating surface morphology (b) under the cross section (a) of coating and ESEM.
Fig. 2 is the nanocrystalline XRD curves of the molybdenum of the various grain sizes obtained in nitrogen atmosphere under different annealing.
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), SEAD (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), SEAD (b), crystallite dimension statistical Butut (c).
Fig. 5 is several different simple metal hardness range block diagrams.
Embodiment
Embodiment 1
1) molybdenum oxygen alloy coating, is electroplated：
Using platinized platinum as anode, using copper as negative electrode, 1000mL plating solutions are prepared on request, solution composition is：
Sodium molybdate two water 5g/L, ammonium acetate 270g/L, potassium acetate 370g/L, glacial acetic acid 200mL/L, weigh in the balance and take the above
Medicine, in deionized water, filter paper is filtered after stirring and dissolving, then by plating solution magnetic stirrer, temperature control for dissolving
In 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, and the composition of coating is molybdenum by analysis
97.1wt.%, oxygen 2.9wt.%.The XRD curves of coating show there is an obvious 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, 10 are first evacuated to-3Pa, then be passed through high-purity
Hydrogen, stove overpressure is 1-2 atmospheric pressure, and annealing temperature selection is 630 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 3, its crystal grain is nanocrystalline for the shaft-like such as uniform, tiny, average chi
Very little is 10.7 ± 4.1nm.Electron diffraction diagram has that signal intensity is uniform, continuous diffraction ring, shows that nanocrystal has random
Crystalline orientation, and there is no obvious preferred orientation in whole sample.Coating Vickers hardness is 18GPa.
Embodiment 2
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using nickel as negative electrode, 1000mL plating solutions are prepared on request, solution composition is：
Sodium molybdate two water 10g/L, ammonium acetate 290g/L, potassium acetate 340g/L, glacial acetic acid 200mL/L, weigh in the balance take with
Upper medicine, in deionized water, filter paper is filtered after stirring and dissolving, then by plating solution magnetic stirrer, temperature control for dissolving
System is in 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 1.0A/cm2, electroplating time is 10 hours.Finally, section of coating
Face figure and surface topography are as shown in figure 1, thickness of coating is about 10 μm, and dense non-porous hole, and the composition of coating is 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, 10 are first evacuated to-3Pa, then be passed through high-purity
Hydrogen, stove overpressure is 1-2 atmospheric pressure, and annealing temperature selection is 500 DEG C, and annealing time is 24 hours.
The Coating prepared is as shown in figure 3, its crystal grain is nanocrystalline for the shaft-like such as uniform, tiny, average chi
Very little is 6.5 ± 2.1nm.Electron diffraction diagram has that signal intensity is uniform, continuous diffraction ring, shows that nanocrystal has random
There is no obvious preferred orientation in crystalline orientation, and whole sample.Coating Vickers hardness is 15GPa.
Embodiment 3
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steels as negative electrode, 1000mL plating solutions are prepared on request, solution composition is：
Sodium molybdate two water 5g/L, ammonium acetate 280g/L, potassium acetate 350g/L, glacial acetic acid 230ml/L, weigh in the balance and take the above
Medicine, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolving, then will plating
Liquid magnetic stirrer, temperature control is in 50 ± 2 DEG C, pH value 6.75 ± 0.20.Current density is 2.5A/cm2, during plating
Between be 5h.Finally, the sectional view and surface topography of coating are as shown in figure 1, thickness of coating is about 10 μm, and dense non-porous hole, plating
The composition 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, 10 are first evacuated to-3Pa, then be passed through high-purity
Hydrogen, stove overpressure is 1-2 atmospheric pressure, and annealing temperature selection is 550 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 3, its crystal grain is nanocrystalline for the shaft-like such as uniform, tiny, average chi
Very little is 7.1 ± 2.5nm.Electron diffraction diagram has that signal intensity is uniform, continuous diffraction ring, shows that nanocrystal has random
There is no obvious preferred orientation in crystalline orientation, and whole sample.Coating Vickers hardness is 15.5GPa.
Embodiment 4
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steels as negative electrode, 1000mL plating solutions are prepared on request, solution composition is：
Sodium molybdate two water 10g/L, ammonium acetate 300g/L, potassium acetate 350g/L, glacial acetic acid 200mL/L, weigh in the balance take with
Upper medicine, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolving, then will
Plating solution magnetic stirrer, temperature control is in 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 are as shown in figure 1, thickness of coating is about 10 μm, and dense non-porous
Hole, the composition of coating is molybdenum 97.5wt.%, oxygen 2.5wt.% by analysis.Coating micromechanism is converted into amorphous+receive from amorphous
Meter Jing Tuan clusters.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, 10 are first evacuated to-3Pa, then be passed through high-purity
Hydrogen, stove overpressure is 1-2 atmospheric pressure, and annealing temperature selection is 450 DEG C, and annealing time is 12 hours.
The Coating prepared is as shown in figure 4, its crystal grain is nanocrystalline for the shaft-like such as uniform, tiny, average chi
Very little is 5.6 ± 2.2nm.Electron diffraction diagram has that signal intensity is uniform, continuous diffraction ring, shows that nanocrystal has random
There is no obvious preferred orientation in crystalline orientation, and whole sample.Coating Vickers hardness is 13.5GPa.
Embodiment 5
1) molybdenum oxygen alloy coating, is electroplated
Using platinized platinum as anode, using 304L stainless steels as negative electrode, 1000mL plating solutions are prepared on request, solution composition is:
Sodium molybdate two water 10g/L, ammonium acetate 300g/L, potassium acetate 350g/L, glacial acetic acid 200mL/L, weigh in the balance take with
Upper medicine, in deionized water, then by plating solution magnetic stirrer, filter paper is filtered after stirring and dissolving for dissolving, then will
Plating solution magnetic stirrer, temperature control is in 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 are as shown in figure 1, thickness of coating is about 10 μm, and dense non-porous
Hole, the composition of coating is molybdenum 98.0wt.%, oxygen 2.0wt.% by analysis.Coating micromechanism is converted into amorphous+receive from amorphous
Meter Jing Tuan clusters.
2), nitrogen atmosphere reduction and Amorphous Crystallization
Coating is put into high vacuum water flat tube type resistance furnace together with substrate, 10 are first evacuated to-3Pa, then be passed through high-purity
Hydrogen, stove overpressure is 1-2 atmospheric pressure, and annealing temperature selection is 1000 DEG C, and annealing time is 1 hour.
The coating XRD curves prepared are 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 can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
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 alloy coating is prepared, then molybdenum oxygen alloy coating is put into vacuum drying oven, high-purity hydrogen is passed through, by controlling annealing temperature
Degree and time, prepare the pure molybdenum coating of various grain sizes and different hardness.
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 process, using copper, nickel and its alloy or steel as negative electrode or electroplated substrates.
3. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that：With highly concentrated
It is electroplate liquid to spend acetate ion solution.
4. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 1, it is characterised in that electro-deposition
The concrete technology step of method is：
1), substrate is polished, polishing, surface degreasing, ultrasonic activation in dilute sulfuric acid；
2), plating solution is configured：Weigh sodium molybdate two water 0.2-10g/L, ammonium acetate 260-340g/L, potassium acetate 300-400g/L, ice
Acetic acid 200-230mL/L, is dissolved in filter paper after deionized water, stirring and dissolving and filters；PH value is adjusted to 6.75 ± 0.20；
3), current density and electroplating time regulation and control：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.%.
5. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 4, 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.
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 400-1200 DEG C in atmosphere, and annealing time is between 1-36 hours.
7. according to the preparation method of ultrahigh hardness refractory metal nanocrystalline deposit described in claim 6, it is characterised in that：It is passed through hydrogen
Stove internal pressure strong demand is 1-2 atmospheric pressure after gas.
8. 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.
9. ultrahigh hardness refractory metal nanocrystalline deposit prepared by a kind of any methods describeds of use claim 1-8.
10. according to ultrahigh hardness refractory metal nanocrystalline deposit described in claim 9, it is characterised in that：The crystal grain of the coating
Size 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 |
|---|
| RADU BANICA ET AL.: "A comparative study of the electrochemical deposition of molybdenum oxides thin films on copper and platinum", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 刘灿: "氧化钼薄膜的制备和电化学性能调控", 《中国优秀硕士学位论文全文数据库》 * |
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