CN105385988B - A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer - Google Patents
A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer Download PDFInfo
- Publication number
- CN105385988B CN105385988B CN201510762634.5A CN201510762634A CN105385988B CN 105385988 B CN105385988 B CN 105385988B CN 201510762634 A CN201510762634 A CN 201510762634A CN 105385988 B CN105385988 B CN 105385988B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- binary
- rare earth
- molybdenum alloy
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides the preparation method of a kind of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer, wherein, salt melting system is pre-processed first before electrochemistry binary permeation is carried out, and described preprocessing process is：Tank is oozed into salt melting system addition sealing, the pressure heat-preserving in tank is oozed, moulding pressure is 0.3~0.7MPa, and holding temperature is 100 DEG C~300 DEG C, and pressing time is 0.5~1h.The molybdenum with binary co-penetration layer or molybdenum alloy high-temperature oxidation resistance prepared by the method for the present invention is good, can resist high temperature oxidation and corrosion；La B binary co-penetration layers prepared by this method are good with the compatibility of molybdenum or molybdenum alloy matrix, are not likely to produce crackle, difficult for drop-off.The temperature in use of molybdenum or molybdenum alloy after surface binary permeation processing can reach 1500 DEG C.
Description
Technical field
The invention belongs to molybdenum or molybdenum alloy field, it is related to binary co-penetration layer, and in particular to a kind of molybdenum or molybdenum alloy surface are dilute
The preparation method of earth metal-boron binary co-penetration layer.
Background technology
Molybdenum is the silver gray refractory metal that a kind of fusing point is up to 2625 DEG C, having excellent high-temperature strength, and electrical and thermal conductivity is good, heat
The coefficient of expansion low (6.7 × 10-6/ DEG C, 1200K), high temperature creep resistance is excellent, while to liquid metal potassium, sodium, magnesium, caesium, bismuth etc.
There is good corrosion stability, one of rare metal as its own strategic significance of new generation, be widely used in metallurgical, stone
The numerous areas such as oil, machinery, chemical industry, Aero-Space, nuclear industry.Using molybdenum as matrix material, add appropriate Ti, Zr, W, Re,
The elements such as Si, Hf, C or rare earth oxide, just obtain molybdenum-base alloy, and it has excellent mechanical behavior under high temperature, low thermal expansion
Coefficient and high conductive and heat-conductive coefficient, it is a kind of refractory metal material for having very much application prospect.
Molybdenum or molybdenum alloy is oxidizable in high temperature aerobic environment limits its application in aerospace field.Correlation analysis is ground
Study carefully and point out, temperature is very slow less than 400 DEG C of molybdenum alloy oxidations rate, and alloy surface generates not volatile MoO2；Temperature 400~
750 DEG C of oxidation weight gains are accelerated rapidly, and alloy surface generates volatile MoO3；Temperature is higher than 750 DEG C, MoO3Volatilization makes weightening anxious
Play declines, and mass loss is serious, limits its possibility as heat resistant structure materials application.On the other hand, current molybdenum-base alloy antioxygen
Change method mainly has two kinds：Develop the molybdenum alloy of high-temperature oxidation resistant and formed by other means in alloy surface anti-oxidant
Layer.But molybdenum can alloying level it is smaller, add improve antioxygenic property alloying element it is more when, alloy processing characteristics become
Difference, high-temperature behavior, such as elevated temperature strength, impact resistance, resistance to heat shocks and creep resistance are severely impacted, therefore with alloying
Method can not fundamentally change the oxidation resistance of molybdenum alloy.Current comparatively ideal solution method is to form height in alloy surface
Warm anti oxidation layer, not only improve alloy antioxygenic property and temperature in use, at the same alloy surface crystal grain refinement, alloy mechanical property
Can enhancing.
Admire the influence that east describes tissue and high-temperature oxidation resistance after the non ferrous metal and their alloy boronising such as Ti, Ni, Co.
Because refractory metal and its alloy etc. with unique physical and mechanical properties such as its high-melting-point, high rigidity, high intensity make its extensive
Applied to fields such as defence and military, Aero-Space, electronic information, nuclear industry and low-temperature superconductings, occupy in national economy important
Status so that boronising research of the Abroad in Recent Years scholar to refractory metal is concentrated mainly on Cr, Mo, Nb, W.In analysis boronising
Emphasis mentions refractory metal and its alloy existing deficiency and the weight studied from now in terms of boronising during the problem of research is present
The heart.
Yang Shuan utilizes praseodymium gas permeation method, different types of rare earth molybdenum carbide is prepared under different penetration enhancers, to preparation
Structure, heat endurance, chemical composition and the surface valence state of rare earth molybdenum carbide are tested research.As a result show：Rare earth is carbonized
The inoxidizability of molybdenum is higher than the molybdenum carbide industrially produced at present；Neodymium and samarium element in penetration enhancer can be penetrated into molybdenum carbide, table
The neodymium element in face exists in the form of trivalent.
Sun Xuanhua etc. is studied rare-earth-boron Bath Multiple Permeation, and emphasis discusses permeation and urging for rare earth is oozed
Mechanism, it is indicated that (1) rare earth atom is during expansion is oozed, and because atomic radius is variable, reactivity is very strong, enhance rare earth atom and
Permeation atom accelerates the process of thermo-chemical treatment in the absorption and diffusion of workpiece surface；(2) rare earth atom is in diffusion process
In, have the function that improve balance vacancy concentration, more room " bivacancy " and " atom vacancy group " can be produced, be rare earth and
The diffusion of permeation element, there is provided good conveying channel, promote the diffusion process of permeation atom；(3) due to rare earth atom
The solid solution formed with parent metal original family belongs to dilute solid solution.It is produced between a kind of rare earth atom and its surrounding matrix atom
The polarization of raw additional polarization key is strengthened, i.e., the solid solution of remote action possessed by the atom pair parent metal atom of rare earth element
Strengthen；(4) because rare earth element is in phase transition process, the nucleation rate of cenotype can be made increase, it is suppressed that thick in phase transition process
The formation of phase morphology, it is that alloy structure is refined.Diffusion layer organization is improved, improves mechanical performance, physics and the change of infiltration layer
Learn performance.
Huang Youguo etc. have studied fused salt electrolysis process in metallic titanium surface boronising boriding medium and boriding process, the boronising on surface
Layer forms good two boronisings titanium crystal, and compound phase boride layer it is more single-phase two boronising titanium AdhesionStrengths it is good, be not easy
Come off, wherein, the layering of boride layer is also more apparent, and interface is clear, be have chosen for metal titanium or titanium alloy in boronising most preferably
Boriding medium and boriding process parameter, but its boriding medium is with Na2B4O7And B4The form of celite is present, and fails accurately to embody
The concrete content of borax, therefore, the bad control of salt melting system of preparation.The boronizing process simply have studied boriding medium and boronising work
The optimal parameter of skill, but the corrosion resistance, wearability and high temperature oxidation resistance of Titanium are not tested.
Yu Zhongsun etc. has carried out specific research to molten-salt electrolysis cementation of rare-earth and rare earth-boriding technology, and workpiece surface is formed
Rare earth or rare-earth-boron infiltration layer be well combined with matrix, 3~6% content of rare earth plays a part of kollag in infiltration layer,
The anti-seizing property and service life for making workpiece are improved.The process belongs to chemical heat treatment technology, by salt bath formula and heat
Handling process parameter two parts form, but lack and urge the effect of oozing to total system, and only research material is under abrasive wear conditions
Corrosive nature under service life and different medium, detailed sign but is not carried out to the antioxygenic property of material at high temperature.
Using rare earth element special architectural characteristic and chemical property, the new technology being modified to metal surface.Earliest
Study the metals such as pure 20 steel, 08 steel and carry out rare-earth penetration processing.Wherein, the rare earth element such as cerium (Ce) and lanthanum (La) is preferentially along crystal boundary
Diffusion, causes distortion of lattice around, causes the vacancy defect of metal surface to increase, turn into the active component of metal surface, dissolves
In the crystal boundary of solid metal.
In summary, its antioxygenic property is improved by boriding process in refractory metal and hard alloy and studies species slightly
Boron infiltration rate also be present in the problem of single, and boronising mode is simple, and some boride layers still suffer from high fragility, technique of the prior art
The problems such as rate is low, alloying layer thickness is thin.
The content of the invention
Based on problems of the prior art, the present invention provides a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary
The preparation method of co-penetration layer, solves in the prior art that binary permeation speed is low, the thin antioxygen for causing molybdenum or molybdenum alloy of alloying layer thickness
Change the technical problem of poor performance.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved：
A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, this method using salt melting system as
Anode, Mo substrate or molybdenum alloy matrix be negative electrode carry out electrochemistry binary permeation, described salt melting system include fused salt, borax and
Urge and ooze activator rare earth metal；
Described salt melting system is pre-processed first before electrochemistry binary permeation is carried out, described preprocessing process
For：Tank is oozed into salt melting system addition sealing, the pressure heat-preserving in tank is oozed, moulding pressure is 0.3~0.7MPa, and holding temperature is
100 DEG C~300 DEG C, pressing time is 0.5~1h.
The present invention also has following distinguishing feature：
Described fused salt includes NaCl, KCl, NaF and KBF4, fused salt is according to NaCl, KCl, NaF and KBF4Mol ratio be
1：1：3：0.5 prepares.
Described salt melting system, by weight percentage, it is made up of following raw material：Borax is 10%~20%, urges and oozes work
Agent rare earth metal is 0.9%~1.2%, and surplus is fused salt, and the percetage by weight sum of raw material is 100%.
Described electrochemistry binary permeation condition is：Using salt melting system as anode, Mo substrate or molybdenum alloy matrix are negative electrode
Electrochemistry binary permeation is carried out, salt melting system is fitted into crucible, melted, Mo substrate or molybdenum alloy matrix are immersed in salt
In bath, heated, control 700 DEG C~1100 DEG C of temperature of molten salt, 0~5mA/cm2 of cathode-current density), the binary permeation time 3
~7h.
Described Mo substrate or the preparation method of molybdenum alloy matrix are：Molybdenum or molybdenum alloy are placed in 20wt% NaOH solution
In boil alkali cleaning degreasing, be eluted with water after being cleaned with ultrasonic wave；It is subsequently placed in 30wt% HCl solution and is heated to 90 DEG C, protects
Hold 1h pickling decontaminations；It is placed in again in the 10wt% hydrofluoric acid solutions that temperature is 80 DEG C and carries out surface etch, until surface is formed
Even pitted skin, cleaned after taking-up with deionized water and alcohol, drying, molybdenum or molybdenum alloy matrix is made.
It is described to urge that to ooze activator rare earth metal be lanthanum (La), cerium (Ce), neodymium (Nd) or samarium (Sm), wherein by neodymium (Nd) and
Samarium (Sm) is used in the form of methanol solution.
Described Mo substrate or the material of molybdenum alloy matrix are pure molybdenum, Mo-Ti systems alloy, Mo-W systems alloy, the conjunction of Mo-Cu systems
The sheet material or bar of gold, Mo-Re systems alloy, TZC alloys or TZM alloys.
Compared with prior art, beneficial has the technical effect that the present invention：
(I) molybdenum with binary co-penetration layer or molybdenum alloy high-temperature oxidation resistance prepared by the method for the present invention is good, energy
Resist high temperature oxidation and corrosion；La-B binary co-penetration layer prepared by this method is good with the compatibility of molybdenum or molybdenum alloy matrix, is not easy to produce
It is raw crackle, difficult for drop-off.The temperature in use of molybdenum or molybdenum alloy after surface binary permeation processing can reach 1500 DEG C.
(II) rare earth La prepared by the method for the present invention can increase the diffusion coefficient of boron, drop diffusion activation energy
Low, the activation of boron can be reduced to by 220kJ/mol through to the pretreated 182kJ/mol of electrolyte, significantly improving boronising speed,
Greatly improve industrial production efficiency.
(III) the La-B binary co-penetration layer thickness prepared by the method for the present invention never adds the alloying layer thickness 119 of cocatalyst
480 μm of the alloying layer thickness of the present invention μm is brought up to, La-B binary co-penetration layer thickness is improved 4 times, makes the high temperature antioxygen of alloy
Change performance to be improved.
(IV) molybdenum with binary co-penetration layer or molybdenum alloy prepared by the method for the present invention is simple to operate, it is not necessary to answers
Technology and equipment is oozed in miscellaneous painting.
Brief description of the drawings
Fig. 1 is the binary permeation layer cross section SEM figures formed in embodiment 1.
Fig. 2 is the binary permeation layer cross section SEM figures formed in comparative example 1.
Fig. 3 is the binary co-penetration layer SEM organization charts formed in embodiment 1.
Fig. 4 is the binary co-penetration layer SEM organization charts formed in comparative example 1.
Fig. 5 is the rear surface SEM organization charts formed in embodiment 3.
Fig. 6 is the surface SEM organization charts that comparative example 3 is formed.
The particular content of the present invention is described in more detail below in conjunction with drawings and examples.
Embodiment
For technical problem present in background technology, principle is oozed based on permeation and urging for rare earth, in molybdenum or molybdenum alloy
Surface prepares rare earth metal-boron binary co-penetration layer, carrys out anti-oxidation and just seems very necessary.In refractory metal and hard alloy
The common boronising in surface has fluid bed boronising, pack boriding, the boronising of discharge plasma sintering, fused salt electrolysis process boronising etc.,
Wherein fused salt electrolysis process boronising is compared with other boronisings, major advantage:1) equipment requirement is simple and convenient to operate, and condition is easily-controllable
System, can handle the more complicated part of shape；2) current efficiency is high, decomposition voltage is big, and gas solubility is low, during side reaction
Influence small；3) molten-salt electrolysis exchange current density is high, and electrolytic speed is fast, and electrolysis ability is strong；4) infiltration layer obtained by pulse electrolysis boronising
Fine and close, uniform, dispersibility is strong, it is good to ooze ability deeply；5) infiltration layer is tightly combined with parent metal, and electrolysate structure is excellent, shape
Looks are good.And binary permeation, especially rare earth doped element, by permeation and the Catalyzing mechanism of rare earth element so that rare earth adds
The decomposition of fast penetration enhancer, accelerate absorption of the activated boron atoms in alloy surface, form co-penetration layer well, improve molybdenum or molybdenum alloy
Antioxygenic property.
Above-mentioned technical proposal is deferred to, specific embodiment of the invention given below is, it is necessary to which explanation is the present invention not office
It is limited to specific examples below, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.The present invention is described in further details with reference to embodiment.
Activator rare earth metal is oozed in addition to lanthanum (La) it should be noted that being urged in following embodiments, and cerium also can be selected
(Ce), neodymium (Nd) or samarium (Sm), wherein neodymium (Nd) and samarium (Sm) are used in the form of methanol solution, in view of length, no longer
Provide one by one, with lanthanum (La) for representative.
Embodiment 1：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey comprises the following steps：
Step 1, prepare Mo substrate or foundry alloy matrix：
Molybdenum or molybdenum alloy are placed in 20wt% NaOH solution and boil alkali cleaning degreasing, is washed with water after being cleaned with ultrasonic wave
Only；It is subsequently placed in 30wt% HCl solution and is heated to 90 DEG C, keeps 1h pickling decontaminations；It is 80 DEG C to be placed in temperature again
Surface etch is carried out in 10wt% hydrofluoric acid solutions, until surface forms uniform pitted skin, is washed after taking-up with deionized water and alcohol
Only, dry, molybdenum or molybdenum alloy matrix is made.
The present embodiment selects Mo substrate, and the material of Mo substrate is pure molybdenum plate matrix.
Step 2, prepare salt melting system：
Formula according to table 1 prepares salt melting system, and fused salt is according to NaCl, KCl, NaF and KBF4Mol ratio be 1：1：3：
0.5 prepares, and adds borax according still further to the formula of table 1 and urges and ooze activator rare-earth metal La, by obtained salt melting system at 100 DEG C
Under be put into it is standby in drying box.
Salt melting system is pre-processed first before electrochemistry binary permeation is carried out, and preprocessing process is：By fused salt system
Tank is oozed in system addition sealing, oozes tank heating, is incubated by oozing lid with lute, then is pressurizeed to overall, oozes tank and heats
Referring to table 1, pressing time is 0.5~1h for temperature and moulding pressure.
Step 3：Prepare binary co-penetration layer：
Using salt melting system as anode, Mo substrate or molybdenum alloy matrix are that negative electrode carries out electrochemistry binary permeation, by fused salt system
Bulk cargo enters in crucible, is melted, and Mo substrate or molybdenum alloy matrix are immersed in salt bath, heated, according to the bar in table 1
Part, electrochemistry binary permeation is carried out, Rare Earth Lanthanum-boron binary co-penetration layer is made in pure molybdenum plate matrix surface.
Comparative example 1：
This comparative example provides the preparation that the present embodiment provides a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer
Method, other technical characteristics are same as Example 1, differ only in：Do not implemented in salt melting system in this comparative example
The sealing pressing isothermal holding of example 1.
Embodiment 2：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and actual conditions is referring to table 1, and difference is that the present embodiment selects Mo substrate, and the material of Mo substrate is pure molybdenum bar
Matrix.
Comparative example 2：
This comparative example provides the preparation that the present embodiment provides a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer
Method, other technical characteristics are same as Example 1, differ only in：Do not implemented in salt melting system in this comparative example
The sealing pressing isothermal holding of example 2.
Embodiment 3：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the sheet material of Mo-Ti systems alloy.
Comparative example 3：
This comparative example provides the preparation that the present embodiment provides a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer
Method, other technical characteristics are same as Example 1, differ only in：Do not implemented in salt melting system in this comparative example
The sealing pressing isothermal holding of example 3.
Comparative example 4：
This comparative example provides the preparation that the present embodiment provides a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer
Method, other technical characteristics are same as Example 1, differ only in：Do not implemented in salt melting system in this comparative example
The sealing pressing isothermal holding of example 3, and cathode-current density is 5mA/cm in this comparative example2。
Embodiment 4：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the bar of Mo-Ti systems alloy.
Embodiment 5：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the sheet material of Mo-W systems alloy.
Embodiment 6：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the bar of Mo-W systems alloy.
Embodiment 7：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the sheet material of Mo-Cu systems alloy.
Embodiment 8：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the bar of Mo-Cu systems alloy.
Embodiment 9：
The present embodiment provides a kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, specific mistake
Journey embodiment 1 is identical, and for actual conditions referring to table 1, difference is that the present embodiment selects molybdenum alloy matrix, the material of molybdenum alloy matrix
For the sheet material of Mo-Re systems alloy.
The formula of 1 each embodiment of table and comparative example forms
Performance test：
Molybdenum plate or mother to forming binary co-penetration layer by above-described embodiment 1 to 9 and the fused salt electrolysis process of comparative example 1 to 4
Alloy sheets are cut into 10 × 10mm squares and carry out 1000 DEG C, 1200 DEG C and 1400 DEG C high-temperature oxydation experiments, measure mass loss rate, and
Compared with not forming the pure molybdenum plate oxidation quality damaed cordition of binary co-penetration layer.
The Rare Earth Lanthanum of embodiment 1-boron binary permeation layer cross section SEM figures are as shown in figure 1, the matrix surface of embodiment 1 is formed
Binary co-penetration layer SEM organization charts as shown in figure 3, the surface SEM organization charts of embodiment 3 are as shown in Figure 5.The rare earth of comparative example 1
Lanthanum-boron binary permeation layer cross section SEM figures are as shown in Fig. 2 the binary co-penetration layer SEM organization charts that the matrix surface of comparative example 1 is formed
As shown in figure 4, the surface SEM organization charts of comparative example 3 are as shown in Figure 6.
Fig. 1 shows that molten-salt electrolysis liquid pure molybdenum plate surface after pretreatment forms binary permeation layer cross section, the section permeation
Uniform and more smooth, the binary co-penetration layer thickness formed is about 480 μm；Fig. 2 shows that molten-salt electrolysis liquid is not pretreated
Pure molybdenum plate surface forms binary permeation layer cross section, and the binary co-penetration layer thickness that the section is formed is about 42.6 μm, the μ of top layer 76.4
Boride phase is formed at m, it is seen that infiltration rate is slow, and boride fails to be completely formed binary co-penetration layer；Fig. 3 shows that molten-salt electrolysis liquid passes through
The binary permeation layer surface formed after pretreatment is comparatively dense and surfacing, no hole defect；Fig. 4 shows molten-salt electrolysis liquid not
There is a small amount of cavity blemish in the binary permeation layer surface of preprocessed formation, and part of matrix has been oxidized, gone out from surface exposure
Come；Fig. 5 show pretreatment when ooze more than 200 DEG C of tank heating-up temperature, be pressurized above 0.5MPa, melt temperature is more than 1000 DEG C
Boronising sample has excellent high-temperature oxidation；Fig. 6 show the boronising sample of the not preprocessed formation of molten-salt electrolysis liquid by
Oxidation product large area is attached to matrix skin.Due to the pretreatment of salt melting system, make La elements in given temperature and pressure
It is lower to accelerate it to urge oozing effect, promote boron atom and expand and ooze and the diffusion of its own, caused activated boron atoms is passed through suction again
Echo diffusion to penetrate into alloy substrate surface and internally spread, change the chemical composition and tissue of sample top layer passivating film,
The co-penetration layer compact structure, it is good with the associativity of matrix, it is difficult for drop-off.The uninfluenced destruction of co-penetration layer after high-temperature oxydation,
Matrix is not preferable by oxygen attack, antioxidant effect.
Claims (4)
1. the preparation method of a kind of molybdenum or molybdenum alloy surface rare earth metal-boron binary co-penetration layer, this method is using salt melting system as sun
Pole, Mo substrate or molybdenum alloy matrix are that negative electrode carries out electrochemistry binary permeation, and described salt melting system includes fused salt, borax and urged
Ooze activator rare earth metal, it is characterised in that：
Described salt melting system is pre-processed first before electrochemistry binary permeation is carried out, and described preprocessing process is：
Tank is oozed by what salt melting system added sealing, the pressure heat-preserving in tank is oozed, moulding pressure is 0.3~0.7MPa, holding temperature 100
DEG C~300 DEG C, pressing time is 0.5~1h；
Described fused salt includes NaCl, KCl, NaF and KBF4, fused salt is according to NaCl, KCl, NaF and KBF4Mol ratio be 1：1：
3：0.5 prepares；
Described salt melting system, by weight percentage, it is made up of following raw material：Borax is 10%~20%, urges and oozes activator
Rare earth metal is 0.9%~1.2%, and surplus is fused salt, and the percetage by weight sum of raw material is 100%；
Described electrochemistry binary permeation condition is：Using salt melting system as anode, Mo substrate or molybdenum alloy matrix are carried out for negative electrode
Electrochemistry binary permeation, salt melting system is fitted into crucible, melted, and Mo substrate or molybdenum alloy matrix are immersed in into salt bath
In, heated, control 700 DEG C~1100 DEG C of temperature of molten salt, 0~5mA/cm of cathode-current density2, the binary permeation time 3~
7h。
2. preparation method as claimed in claim 1, it is characterised in that：Described Mo substrate or the preparation method of molybdenum alloy matrix
For：Molybdenum or molybdenum alloy are placed in 20wt% NaOH solution and boil alkali cleaning degreasing, is eluted with water after being cleaned with ultrasonic wave；Then
It is placed in 30wt% HCl solution and is heated to 90 DEG C, keeps 1h pickling decontaminations；The 10wt% hydrofluoric acid that temperature is 80 DEG C is placed in again
Surface etch is carried out in solution, until surface forms uniform pitted skin, is cleaned, drying, is made with deionized water and alcohol after taking-up
Molybdenum or molybdenum alloy matrix.
3. preparation method as claimed in claim 1, it is characterised in that：Described urging oozes activator rare earth metal for lanthanum, cerium, neodymium
Or samarium.
4. preparation method as claimed in claim 1, it is characterised in that：Described Mo substrate or the material of molybdenum alloy matrix are pure
Molybdenum, Mo-Ti systems alloy, Mo-W systems alloy, Mo-Cu systems alloy, Mo-Re systems alloy, the sheet material or rod of TZC alloys or TZM alloys
Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510762634.5A CN105385988B (en) | 2015-11-10 | 2015-11-10 | A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510762634.5A CN105385988B (en) | 2015-11-10 | 2015-11-10 | A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105385988A CN105385988A (en) | 2016-03-09 |
| CN105385988B true CN105385988B (en) | 2018-04-03 |
Family
ID=55418753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510762634.5A Active CN105385988B (en) | 2015-11-10 | 2015-11-10 | A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105385988B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521408B (en) * | 2016-11-10 | 2018-11-27 | 洛阳科威钨钼有限公司 | A method of preparing anti-oxidant molybdenum product |
| CN107779813B (en) * | 2017-12-23 | 2020-01-31 | 北方民族大学 | Preparation process of Cr-Al-Ce-Y thermal protection coating on surface of titanium-aluminum alloy and penetrating agent thereof |
| CN113445098A (en) * | 2021-06-28 | 2021-09-28 | 西北工业大学 | Method for improving wear resistance and self-lubricating property of high-entropy alloy by using electrochemical liquid boronizing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181821A (en) * | 2011-04-15 | 2011-09-14 | 广西师范大学 | Boronizing agent for fusion electrolysis boronizing on surface of metal titanium and boronizing process |
| CN102534469A (en) * | 2011-11-25 | 2012-07-04 | 厦门虹鹭钨钼工业有限公司 | High temperature anti-oxidation coating molybdenum material and preparation method thereof |
| CN104630860A (en) * | 2015-02-02 | 2015-05-20 | 西安建筑科技大学 | Rare-earth-catalyzed titanizing melting salt pulse electrolysis boronizing method near phase transition temperature |
-
2015
- 2015-11-10 CN CN201510762634.5A patent/CN105385988B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181821A (en) * | 2011-04-15 | 2011-09-14 | 广西师范大学 | Boronizing agent for fusion electrolysis boronizing on surface of metal titanium and boronizing process |
| CN102534469A (en) * | 2011-11-25 | 2012-07-04 | 厦门虹鹭钨钼工业有限公司 | High temperature anti-oxidation coating molybdenum material and preparation method thereof |
| CN104630860A (en) * | 2015-02-02 | 2015-05-20 | 西安建筑科技大学 | Rare-earth-catalyzed titanizing melting salt pulse electrolysis boronizing method near phase transition temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105385988A (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105385988B (en) | A kind of preparation method of molybdenum or molybdenum alloy surface rare earth metal boron binary co-penetration layer | |
| CN101597739B (en) | Method for preparing borax salt bath tungstenized coating on steel matrix surface | |
| CN104164690A (en) | Method for large-area deposition of coating and surface modification by cathodic plasma electrolysis | |
| CN103225055A (en) | Surface wear-resistant strengthening treatment method for high-carbon cold work die steel | |
| CN102011144A (en) | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer | |
| Falcon et al. | Corrosion Behavior of Mg‐Al/TiC Composites in NaCl Solution | |
| CN102828218B (en) | Electrolyte used for magnesium alloy anode oxidation treatment and treatment method | |
| Liu et al. | Electro-deposition metallic tungsten coatings in a Na2WO4–WO3 melt on copper based alloy substrate | |
| CN105331926A (en) | N-C-Cr-V-RE multi-element co-diffusion material for 45 steel surface strengthening | |
| Feng et al. | Corrosion properties of ceramic coating on pure titanium by pack boronizing with Nd2O3 | |
| CN104372394A (en) | Preparation method for oxide ceramic layer | |
| CN104831333A (en) | Preparation method for magnetic micro-arc oxidation film layer on steel surface | |
| CN105385989B (en) | A kind of salt melting system, compound cocatalyst and the application of the binary permeation of molybdenum or molybdenum alloy | |
| Al Afghani et al. | Plasma electrolytic oxidation of zircaloy-4 in a mixed alkaline electrolyte | |
| CN103147112B (en) | A kind of electrolytic solution and for the preparation of the purposes of nuclear fuel rod zirconium alloy cladding micro-arc oxidation films and method | |
| CN109943872B (en) | Preparation method of composite coating for protecting Cr-containing stainless steel in molten fluoride salt | |
| CN104451810B (en) | A kind of low-temperature electrolytic boronising boriding medium and boriding process | |
| CN102002743B (en) | Preparation method for electroplating thick tungsten coating on pure copper or copper alloy substrate with molten salt | |
| CN112322938B (en) | Nickel-based composite material based on additive manufacturing, preparation method and forming method thereof | |
| CN107130242B (en) | The surface treatment method of the based high-temperature alloy containing ferrochrome and the part of based high-temperature alloy containing ferrochrome | |
| CN103469278B (en) | A kind of electrolyte of preparing for zirconium alloy cladding diaphragm and micro-arc oxidation process | |
| Shao et al. | Preparation and performance of electroless nickel on AZ91D magnesium alloy | |
| US3930060A (en) | Method for forming a carbide layer of a V-a group element of the periodic table on the surface of an iron, ferrous alloy or cemented carbide article | |
| Massot et al. | Preparation of tantalum carbide layers on carbon using the metalliding process | |
| CN109504996B (en) | Cathode micro-arc oxidation solution and method for preparing DLC composite oxide film on steel surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |