CN107460502A - A kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy - Google Patents
A kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy Download PDFInfo
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- CN107460502A CN107460502A CN201710857443.6A CN201710857443A CN107460502A CN 107460502 A CN107460502 A CN 107460502A CN 201710857443 A CN201710857443 A CN 201710857443A CN 107460502 A CN107460502 A CN 107460502A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
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Abstract
The invention discloses a kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy.Using fused salt impulse electrodeposition technology, solid phase particle is added in molten salt system, wherein metal to be deposited is anode, matrix is negative electrode, and molten salt system provides source metal.Under temperature field and electric field action, grown up by metal ion in the forming core of minus plate and metal solid phase particle alloy material has been made in diffusion.Solid phase particle is 50 μm of high melting compounds of size 5nm.Molten salt system is the oxide system containing metal to be deposited, halogenation objects system or oxyhalogenation objects system.Solid phase particle addition is 0.1% the 20.0% of molten salt system gross mass.Electrodeposition temperature is higher than 0 500 DEG C of fused salt fusion temperature, and electrodeposition time is more than 10min, dutycycle 5% 100%, the 360mA/cm of current density 102.Present device is simple to operation, and constituent element raw material is easy to get, and cost is low, less energy consumption；Production procedure is short, and state modulator scope is wide, easily realizes.This method can obtain metal solid phase particle alloy material, have broad application prospects.
Description
Technical field
The present invention relates to a kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy material, belong to surface treatment
Technical field.
Background technology
It is conventional material modification method that the second phase solid phase particle is mixed in material matrix to improve material property.At present
Mixing the common method of solid phase particle includes powder metallurgic method, vapour deposition process, hot spray process and electroless plating method etc., but these sides
All there is the shortcomings that each different in method, such as consume energy height, equipment complex and expensive, material bond strength are low.Fused salt electrodeposition process is
It is a kind of to prepare the conventional method of material, have the advantages that low, the simple low cost of equipment of power consumption and material bond strength are higher, but this
Kind method, which is not yet realized, to be introduced into solid phase particle in deposited metal.The present invention is on the basis of conventional fused salt electro-deposition method
Upper carry out substantial improvements, the method by adding solid phase particle in molten salt system, realize straight in fused salt electrodeposited material
Connect incorporation solid phase particle.This method had both remained the advantage of fused salt electro-deposition method, realized the doping vario-property of solid phase particle again.
The content of the invention
It is an object of the invention to provide a kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy material.
The present invention uses fused salt electro-deposition techniques, and solid phase particle is mixed into molten salt system, wherein metal to be deposited is sun
Pole, matrix are negative electrode, and molten salt system is source metal.Under temperature field and electric field action, by metal ion minus plate shape
Core is grown up and metal-solid phase particle alloy material has been made in diffusion.
A kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy, it is characterised in that comprise the following steps：
Step 1：Molten salt system need to dry or/and dewater treatment；Yin, yang pole plate is successively through oil removing, polishing and polishing；
Step 2：The molten salt system of predetermined amount and solid phase particle is taken to be well mixed and be heated to fused salt fusion temperature, heating rate
5-15 DEG C/min, 1-3h is incubated, that is, the fused salt electro-deposition system of the melting containing solid phase particle is obtained, afterwards again with identical liter
Warm speed raises 0-500 DEG C again, is incubated 1-5h；The addition quality of wherein solid phase particle is the 0.1%- of molten salt system gross mass
20.0%；
Step 3：Yin, yang pole plate after processing is placed in molten salt system；Electro-deposition process parameter is adjusted, electrodeposition temperature is high
It is more than 10min, current density 10-360mA/cm in 0-500 DEG C of fused salt fusion temperature, electrodeposition time2It is with dutycycle
5%-100%；Turn on the power switch beginning sedimentation experiment；
Step 4：After electro-deposition terminates, the minus plate containing metal-solid phase particle alloy material is taken out, is put into corresponding clear
In dilution, it is cleaned by ultrasonic 1-30min, to remove the fused salt remained on minus plate；And then minus plate is put into deionization
In water, it is cleaned by ultrasonic 1-30min, to remove the cleaning solution remained on minus plate；Finally, then by minus plate it is put into anhydrous second
1-30min is cleaned in alcohol.
Molten salt system includes halogenation objects system, oxide system or oxyhalide system；Solid phase particle is 5nm-50 μm
Carbide, oxide or nitride.
According to the alloy prepared by described method.
Fused salt and solid phase particle in the present invention will pass through drying process or dewater treatment.
The quality of the solid phase particle added in the present invention is the 0.1%-20.0% of molten salt system gross mass.
The method that a kind of fused salt electro-deposition of addition solid phase particle in the present invention prepares alloy material, enters according to the following steps
OK：First, solid phase particle and fused salt are respectively put into crucible and are placed in heating furnace, heated up 200-400 DEG C, be incubated 5-12h.2nd,
Fused salt is weighed by preset quality and solid phase particle is put into crucible, is placed in electric furnace and is warming up to fused salt fusion temperature, is incubated 1-3h,
Improve 0-500 DEG C again afterwards, be incubated 1-5h.3rd, cathode and anode is put into molten salt system, by adjusting electro-deposition parameter (duty
Than, electrodeposition temperature, electrodeposition time and current density) etc. prepare high pure metal-solid phase particle alloy material.4th, by step
After three obtained metals-solid phase particle alloy material takes out, cleaned solution, deionized water and absolute ethyl alcohol are cleaned by ultrasonic successively
1-30min。
Compared with prior art, the present invention has following clear advantage：
The present invention is using fused salt as medium, under temperature field and electric field action, by the fused salt compound of metal to be deposited and solid
Phase particulate prepares metal-solid phase particle alloy material, while the solid phase particle added can provide the equiax crystal of metal ion
Be advantageous to the adventitious deposit of metal ion, and metal to be deposited is spread in metallic matrix, strengthen solid phase particle/treat
Adhesion between deposited metal and parent metal, actually obtain the metal based alloys containing metal-solid phase particle alloy material
Material.
Specific technical scheme is as follows：A kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy, including such as
Lower step：In molten salt system, using substrate as negative electrode, metal to be deposited is anode, and molten salt system is source metal, filling with inert gas
Protection, electro-deposition mode is pulse electrodeposition, it is a feature of the present invention that：Solid phase particle is mixed in molten salt system, size
For 5nm-50um, particle type includes oxide, carbide, nitride and other Melting Substances etc., solid phase particle addition matter
Amount is the 0.1-20.0% of molten salt system gross mass, micro- by controlling electro-deposition process parameter to generate metal-solid phase on substrate
Grain alloy material.
The inventive method working mechanism is as follows：Molten salt system provides source metal to be deposited, with the progress of electro-deposition, in fused salt
Metal ion to be deposited gradually decreases, anode metallic plate to be deposited provide part metal to be deposited needed for electrodeposition process from
Son, so as to ensure being smoothed out for electrodeposition process；Meanwhile it is partially depositing in the metal on substrate and can expands to cathode base inside
Dissipate；Due to temperature field and electric field, the concentration gradient change and the effect of solid phase particle of tenor to be deposited, accelerate to be deposited
Metal ion is in the deposition of matrix surface and the diffusion into matrix.So as to form following phase transformation law：Top layer is that solid phase is micro-
Grain/metal level to be deposited；Transition zone is solid phase particle/metal to be deposited and metallic matrix mixed layer；Internal layer is simple metal matrix.
Using above-mentioned electrodeposition technology, there is provided solid phase particle is present in the approach of metal material intra-die.
Beneficial effects of the present invention：
The inventive method is using fused salt as medium, under temperature field and electric field action, by metal to be deposited molten salt system and
Solid phase particle prepares metal-solid phase particle alloy material；The solid phase particle of addition can provide the forming core matter of metal ion simultaneously
Point promotes metal forming core, and metal to be deposited is spread in metallic matrix, strengthen solid phase particle/metal to be deposited with
Adhesion between parent metal, actually obtain the metal based alloys material containing metal-solid phase particle alloy material.
Brief description of the drawings
Fig. 1 .ZrC nano particles are present in a. intra-dies in electrodeposit metals tungsten；B. grain boundaries
Fig. 2 energy spectrum analysis metal-solid phase particle is free of other impurity elements
Embodiment
The substantive distinguishing features and remarkable advantage of the present invention are elucidated further below, the present invention is limited only to by no means what is stated
Embodiment.It is all that the scope of the present invention is belonged to based on the technology that present invention is realized.Inert protective gas can with but not office
It is limited to argon gas.
Embodiment 1：
(1) by the oxide molten salt system Na after dried/dewatered2WO4-WO3(3:1mol) weigh, add by preset ratio
It is the 10nm ZrC solid phase particles of molten salt system gross mass 1%, is well mixed and loads crucible, be put into full of inert protective gas
Electric furnace is warming up to 200 DEG C, is incubated 8h drying process.Yin, yang pole plate is successively through oil removing, polishing (600-2000#) and polishing (W5-
W1) handle.
(2) this system is heated to 700 DEG C with 15 DEG C/min heating rates again, is incubated 1h, rise to 950 DEG C afterwards, insulation
1h。
(3) cathode and anode is put into molten salt system, the electro-deposition process parameter (dutycycle under deployed impulse electric field
45%th, 950 DEG C of electrodeposition temperature, electrodeposition time 1h and current density 10mA/cm2), turn on the power carry out electro-deposition.
(4) deposition takes out negative electrode after terminating, and is first cleaned by ultrasonic 30min with NaOH solution, to remove fused salt attachment, then according to
It is secondary to rinse 5mim with deionized water and EtOH Sonicate, you can to obtain the metal-solid phase particle alloy material.
The present embodiment resulting materials are through GDA750 glow discharge spectrometries and sem analysis, it is known that material both side surface is solid
Phase particulate/metal material to be deposited, intermediate layer are parent metal, and alloy material gradually rises for tenor to be deposited from inside to outside
Up to 100%, parent metal content is gradually decrease to 0%, and contains a small amount of solid phase particle in sedimentary.
Embodiment 2：
(1) by dried oxygen-halide molten salt system NaCl-KCl-NaF-WO3(0.3385:0.3385:0.25:
0.073mol) weighed by preset ratio, addition is 50 μm of ZrN solid phase particles of molten salt system gross mass 10%, is well mixed dress
Enter crucible, be put into the electric furnace full of inert protective gas and be warming up to 200 DEG C, be incubated 10h drying process.By yin, yang pole plate successively
Through oil removing, polishing (600-2000#) and polishing (W5-W1) processing.
(2) this system is heated to 650 DEG C with 10 DEG C/min heating rates again, is incubated 2h, be warming up to 700 DEG C afterwards, protected
Warm 2h.
(3) cathode and anode is put into molten salt system, the electro-deposition process parameter (dutycycle under deployed impulse electric field
5%th, 700 DEG C of electrodeposition temperature, electrodeposition time 3h and current density 180mA/cm2), turn on the power carry out electro-deposition.
(4) deposition takes out negative electrode after terminating, and is first cleaned by ultrasonic 5min with NaOH solution, to remove fused salt attachment, then according to
It is secondary to rinse 15mim with deionized water and EtOH Sonicate, you can to obtain the metal-solid phase particle alloy material.
The present embodiment resulting materials are through GDA750 glow discharge spectrometries and sem analysis, it is known that material both side surface is solid
Phase particulate/metal material to be deposited, intermediate layer are parent metal, and alloy material gradually rises for tenor to be deposited from inside to outside
Up to 100%, parent metal content is gradually decrease to 0%, and contains a small amount of solid phase particle in sedimentary.
Embodiment 3：
(1) by dried halide molten salt system ZnCl2-KCl-NaCl-WCl4(0.56:0.19:0.19:0.06mol)
Weighed by preset ratio, addition is 1 μm of Al of molten salt system gross mass 20%2O3Solid phase particle, it is well mixed and loads crucible, put
Enter the electric furnace full of inert protective gas and be warming up to 100 DEG C, be incubated 12h drying process.By yin, yang pole plate successively through oil removing, mill
Light (600-2000#) and polishing (W5-W1) processing.
(2) this system is heated to 250 DEG C with 5 DEG C/min heating rates again, is incubated 3h.
(3) cathode and anode is put into molten salt system, the electro-deposition process parameter (dutycycle under deployed impulse electric field
100%th, 250 DEG C of electrodeposition temperature, electrodeposition time 5h and current density 360mA/cm2), turn on the power carry out electro-deposition.
(4) deposition takes out negative electrode after terminating, and is first cleaned by ultrasonic 15min with NaOH solution, to remove fused salt attachment, then according to
It is secondary to rinse 30mim with deionized water and EtOH Sonicate, you can to obtain the metal-solid phase particle alloy material.
The present embodiment resulting materials are through GDA750 glow discharge spectrometries and sem analysis, it is known that material both side surface is solid
Phase particulate/metal material to be deposited, intermediate layer are parent metal, and alloy material gradually rises for tenor to be deposited from inside to outside
Up to 100%, parent metal content is gradually decrease to 0%, and contains a small amount of solid phase particle in sedimentary.
Claims (3)
1. a kind of method that fused salt electro-deposition for adding solid phase particle prepares alloy, it is characterised in that comprise the following steps：
Step 1：Molten salt system need to dry or/and dewater treatment；Yin, yang pole plate is successively through oil removing, polishing and polishing；
Step 2：The molten salt system of predetermined amount and solid phase particle is taken to be well mixed and be heated to fused salt fusion temperature, heating rate 5-15
DEG C/min, 1-3h is incubated, that is, obtains the fused salt electro-deposition system of the melting containing solid phase particle, afterwards again with identical heating speed
Rate raises 0-500 DEG C again, is incubated 1-5h；The addition quality of wherein solid phase particle is the 0.1%- of molten salt system gross mass
20.0%；
Step 3：Yin, yang pole plate after processing is placed in molten salt system；Electro-deposition process parameter is adjusted, electrodeposition temperature is higher than molten
0-500 DEG C of salt fusion temperature, electrodeposition time are more than 10min, current density 10-360mA/cm2It is 5%- with dutycycle
100%；Turn on the power switch beginning sedimentation experiment；
Step 4：After electro-deposition terminates, take out the minus plate containing metal-solid phase particle alloy material, be put into clean accordingly it is molten
In liquid, it is cleaned by ultrasonic 1-30min, to remove the fused salt remained on minus plate；And then minus plate is put into deionized water
In, it is cleaned by ultrasonic 1-30min, to remove the cleaning solution remained on minus plate；Finally, then by minus plate it is put into absolute ethyl alcohol
Middle cleaning 1-30min.
2. the method that a kind of fused salt electro-deposition for adding solid phase particle as claimed in claim 1 prepares alloy, it is characterised in that
Molten salt system includes halogenation objects system, oxide system or oxyhalide system；Carbide, the oxygen that solid phase particle is 5nm-50 μm
Compound or nitride.
3. according to the alloy prepared by the method described in claim 1 or 2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110528033A (en) * | 2019-08-19 | 2019-12-03 | 北京工业大学 | The method that a kind of electro-deposition of fused salt original position prepares tungsten coating |
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| CN110528033A (en) * | 2019-08-19 | 2019-12-03 | 北京工业大学 | The method that a kind of electro-deposition of fused salt original position prepares tungsten coating |
| CN110528033B (en) * | 2019-08-19 | 2020-11-10 | 北京工业大学 | Method for preparing tungsten coating by fused salt in-situ electrodeposition |
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Application publication date: 20171212 |