CN108004541A - A kind of low stress gradient, the lead-based anode material preparation method of high life - Google Patents

A kind of low stress gradient, the lead-based anode material preparation method of high life Download PDF

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CN108004541A
CN108004541A CN201711341324.1A CN201711341324A CN108004541A CN 108004541 A CN108004541 A CN 108004541A CN 201711341324 A CN201711341324 A CN 201711341324A CN 108004541 A CN108004541 A CN 108004541A
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lead
alloy
pbo
based anode
anode material
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CN108004541B (en
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王运凯
李建中
田彦文
杨中东
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.

Abstract

The invention belongs to field of hydrometallurgy, more particularly to a kind of low stress gradient, the lead-based anode material preparation method of high life.Using high energy micro arc deposition technique, i.e., intensive treatment directly is carried out to workpiece surface using the electric energy with high-energy-density, alloying or dense oxide surface peening layer are formed, so that the physics on lead-based anode surface, chemistry, mechanical performance are improved.This technology is due to electric flux temporally and spatially high concentration, melt the local material in region, electrode material is transitioned into workpiece surface and diffuses into workpiece surface at a high speed, can form the alloy-layer being firmly combined with, and improves the combination power between base film or film film.The condition such as heterogeneity gas, control gas flow, voltage, discharge frequency, output power can be purged during meanwhile, and oxide-film internal stress may also obtain release to a certain extent, optimizing stress gradient under high energy, the condition of high temperature.

Description

A kind of low stress gradient, the lead-based anode material preparation method of high life
Technical field
The invention belongs to field of hydrometallurgy, more particularly to a kind of low stress gradient, the lead-based anode material system of high life Preparation Method.
Background technology
Since lead-based anode material has：(1) good electric conductivity；(2) corrosion resistance is strong；(3) mechanical strength and processing Performance is good；(4) service life is long, expense is low；(5) there is good electrocatalysis characteristic to electrode reaction, it not only exists Tin-free steel field of electroplating has an important application, and electrotinning (or zinc), lead-acid battery, electrolysis (zinc, copper, manganese etc.) and The field of hydrometallurgy such as chlorine industry also have a wide range of applications.The lead-based anode under these field of hydrometallurgy, electric field action Material is in more severe solution environmental long service, such as：Strongly acidic solution environment (sulfur-bearing acid solution), strong oxidizing solution ring Border (contains chromic acid solution), or severe corrosive solution environmental (fluoride or chloride solution), causes lead-based anode surface oxidation Corrosion.
As oxide-film relatively thin (about hundreds of nm), the oxide-film crystal growth direction identical with matrix holding；But due to length Time aoxidizes, and promotes oxide-film oriented growth excessive so that and the lattice constant of metal and oxide-film is inconsistent, is distorted, from And produce stress.With the progress of oxidation, lead compound → lead oxides will occur for the oxide-film institutional framework of metal surface Change, causes its lattice constant also can accordingly change, the stress so produced also changes therewith.It is further, since golden Belong to ion diffusion produce hole, metal structure it is uneven, high oxide, surface shape are re-formed in established oxide-film Phase structure into multilayer oxide-film, oxide changes, such as PbO → β-PbO2→α-PbO2, stress can be produced.It is thin Film internal stress acts on either in the form of tension or compression, and all can produce shearing in film-matrix or membrane-membrane interface should Power.Meanwhile the presence of membrane interface lattice mismatch, thermal expansion coefficient difference and various defects also aggravates the internal stress of oxide-film and drills Become.Under electric field action, lead-based anode material internal stress, which develops, shows as stress gradient growth, and causing oxide-film, there are high stress Gradient or micro-sized stress are concentrated, and when reaching stress characteristics transition point, are formed a kind of release of stress, are caused oxide-film fine fisssure occur Line.When shear stress between the adhesive force or membrane-membrane that can be overcome between film-basal body interface greatly to when combining power, film layer will be in height Crackle occurs at stress gradient and frills, or even comes off, and then shortens the service life of anode.
Lead anode surface film oxide is loose, porous has close relationship with metal interface combination power, stress gradient.Cause How this, improve compactness, control oxygen or the ion diffusion of lead oxide-film, how to improve and aoxidize intermembranous stress gradient, oxidation Combination power between film and metal interface becomes the key for improving anode service life.
Many researchs coat one layer of conductive coating with good electro catalytic activity on lead electrode surface, to reduce anode table The oxygen evolution potential in face, so as to improve oxide layer internal stress, achieve the purpose that to reduce energy consumption, improve anode service life.French Le P.C. with Petit M.A. et al. research in Pb, Pb-Ag substrate deposit IrO2Lead-based anode, research finds, anode tool There is good electro catalytic activity.But IrO2Slow mechanism dissolved causes electro catalytic activity to decline.Walker J.K. and Bishara J.I. RuO is studied2Lead-based anode, its distinguishing feature are that have relatively low overpotential for oxygen evolution, can reduce the energy consumption of specific yield.This Outside, the research of non-noble metal oxide coated anode also obtains certain achievement, such as coats Co3O4Electrode is considered as most to have to answer With one kind of future, it is satisfactory in the using effect of The Dow Chemical Co.'s chlor-alkali plant.Bulgarian Hussanova A. Also study electrodeposition process and prepare Pb-Co3O4The performance of composite coating anode, the results showed that, its corrosion resistance is strong, and energy consumption is low.Someone carries Go out the lead base PbO of PTFE bondings2Electrode, but PbO2The mechanical strength of catalyst layer is at a fairly low, so that anode life is very low, increases Power-up resistance.Surface pre-polarizing lead anode, i.e., carry out lead anode appropriate surface pre-polarizing in particular solution, it is possibility to have effect Ground improves its performance, such as in CoSO4Polarize in solution, its surface forms CoxOy-PbO2Mixed oxide films, can affirm Ground says, great impetus is played in this development to whole lead-based anode material, the energy-saving exhibition to electrolysis, field of electroplating Existing very important application prospect.But people focus on the effect of institutional framework, materials microstructure transformation, oxygen but have ignored Change membrane volume expansion and the coupled problem of material mechanical performance.
The content of the invention
It is more for lead-based anode species currently on the market, and its application environment complicated condition, the lead base sun of field application The problems such as pole service life is shorter, it is an object of the invention to provide a kind of low stress gradient, the lead-based anode material of high life Preparation method, using high energy micro arc deposition technique to rely on, is analyzed, the preparation with reference to detection techniques such as SEM, Raman and XRD Method is easy, quick, cost is low, and the high life lead-based anode material of preparation is economical and practical, helps to improve electrolysis, electroplating industry Involved lead-based anode service life, it is ensured that continuous production, improves cathode product quality.
The technical scheme is that：
A kind of low stress gradient, the lead-based anode material preparation method of high life, comprise the following steps：
1) using 800~1000# sand paper polishing ferritic stainless steel, afterwards with the nitric acid that concentration is 10~20wt% to it Surface activation process is carried out, then is cleaned up with acetone, and it is dry；
2) using the slicker solder silver alloy or lead-calcium alloy of 3~5mm of diameter or lead calcium strontium alloy as depositing electrode, using high energy Micro-arc cold welding machine carries out ferritic stainless steel on high energy micro arc surface and oozes slicker solder silver alloy or lead-calcium alloy or the conjunction of lead calcium strontium Gold processing, electrical parameter is middle 70~90V of voltage, middle 700~1500Hz of frequency；
3) using 20wt%~30wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, slicker solder silver is oozed to surface and is closed Ferrite stainless steel matrix Direct precipitation PbO base coatings after gold or the processing of lead-calcium alloy or lead calcium strontium alloy, electrical parameter are low Voltage 40~60V, middle 900~1700Hz of frequency；
4) in the case where 80~90% air and 10~20% water vapours press volume mixture gaseous environment, temperature control 100~ The PbO of slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy is oozed under the conditions of 150 DEG C to ferritic stainless steel matrix alloy surface Coating carries out 10~20min of oxidation processes；
5) 30wt%~40wt%Pb-PbO of hot pressed sintering is used2Composite material is as depositing electrode, to ferrite not Rust steel matrix alloy surface oozes slicker solder silver alloy or lead-calcium alloy or the PbO coatings of lead calcium strontium alloy carry out deposition PbO2Coating, Electrical parameter is 20~50V of low-voltage, 1500~2000Hz of high-frequency；
6) pressed using 50~70% air and 30~50% water vapours under volume mixture gaseous environment, temperature control is 150 Slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy are oozed under the conditions of~200 DEG C to ferritic stainless steel matrix alloy surface PbO-PbO2Coating carries out 30~50min of oxidation processes.
The low stress gradient, the lead-based anode material preparation method of high life, in step 2), deposition process uses side 10~15L/min argon gas is blown to be protected.
The low stress gradient, the lead-based anode material preparation method of high life, in step 3), deposition process uses side 5~10L/min argon gas is blown to be protected.
The low stress gradient, the lead-based anode material preparation method of high life, in step 5), deposition process is using surveying 1~5L/min argon gas is blown to be protected.
The low stress gradient, the lead-based anode material preparation method of high life, lead base sun is prepared based on this method Pole material, it is 1.0~4.1MPa to test its internal stress excursion, it is used 360 days in electrodeposited chromium or cathode copper application field Afterwards, stress decay rate 30%~45%, service life 1.5 years~2 years.
The present invention mentality of designing be：
Extending one of lead-based anode service life key issue is limitation oxide film breakdown or comes off, that is, controls oxide-film The formation and differentiation of internal stress, reduce stress gradient.The present invention utilizes high energy micro arc deposition technique, i.e., directly utilizing has Highdensity electric energy carries out intensive treatment to workpiece surface, alloying or dense oxide surface peening layer is formed, so that lead Base anode surface physics, chemistry, mechanical performance are improved.This technology is temporally and spatially highly collected due to electric flux In, melt the local material in region, electrode material is transitioned into workpiece surface and diffuses into workpiece surface at a high speed, can be formed The alloy-layer being firmly combined with, improves the combination power between matrix-film or membrane-membrane.Heterogeneity can be purged during meanwhile The condition such as gas, control gas flow, voltage, discharge frequency, output power.In addition oxide-film internal stress is in high energy, high temperature shape Release to a certain extent, optimizing stress gradient may also be obtained under state.Therefore, prepared using high energy micro arc technology Lead-based anode material, has efficiently controlled the structure, compactness and internal stress gradient of oxidation film layer, and then improves the use of anode Service life.
Advantages of the present invention and beneficial effect are：
1st, the present invention prepares low stress gradient, the lead-based anode of high service life using high energy micro arc deposition technique Material, the preparation method is simple, quick, and cost is low.
2nd, the lead-based anode material that the present invention designs, its stress value is 1.0~4.1MPa, is decayed using process stress slow, Service life reduced the financial cost produced in production because replacing anode up to 1.5~2 years.
3rd, the present invention is conducive to improve plating/electrolyte using low stress gradient, the lead-based anode material of high service life Composition, technological parameter stability control, improve the quality of electrolysis/electroplating cathode also original product.
Brief description of the drawings
Fig. 1 is the lead-based anode material surface pattern that the present invention is prepared using high energy micro arc deposition technique.
The lead-based anode material surface Raman spectrum that Fig. 2 present invention is prepared using high energy micro arc deposition technique.Wherein, Abscissa Raman Shift represent Raman shift (cm-1), peak is peak value.
The lead-based anode material XRD spectra that Fig. 3 present invention is prepared using high energy micro arc deposition technique.Wherein, a) Pb- Sn-Ag；b)Pb-Ca-Sr；C) Pb-Ca, peak are peak value.
Embodiment
In the following, the present invention is further elaborated on by embodiment and attached drawing.
In embodiment, carried out using 3E-ES types metal surface reinforcing repair machine (Metal Inst., Chinese Academy of Sciences) High energy micro arc deposits；Using the thickness of ZEISS/EVO18 type electron scannings Electronic Speculum measurement oxide-film；Drawn using micro laser Graceful spectrometer (JY Labram HR 800) and XRD (the X-ray stress test of Canadian PROTO companies LXRD) test lead base sun Pole and its internal stress of surface film oxide, using Chinese invention patent：A kind of evaluation method in lead-based anode materials'use service life (ZL201510920083.0, publication number：CN105543903A the analysis calculation method described in).
Embodiment 1
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, comprise the following steps that：
1) using 800# sand paper polishing ferritic stainless steel, surface work is carried out to it with the nitric acid that concentration is 20wt% afterwards Change is handled, then is cleaned up with acetone, and dry.
2) using the slicker solder silver alloy of diameter 4mm as depositing electrode, using high energy micro-arc cold welding machine to ferritic stainless steel Carry out high energy micro arc surface and ooze the processing of slicker solder silver alloy, electrical parameter is middle voltage 90V, middle frequency 900Hz.Deposition process is adopted Protected with side-blown 12L/min argon gas.
3) using 20wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, after the processing of slicker solder silver alloy is oozed to surface Ferrite stainless steel matrix Direct precipitation PbO base coatings, electrical parameter is low-voltage 55V, middle frequency 1000Hz.Deposition process is adopted Protected with side-blown 9L/min argon gas.
4) in the case where 80% air and 20% water vapour press volume mixture gaseous environment, temperature control is right under the conditions of 120 DEG C The PbO coatings that slicker solder silver alloy is oozed on ferritic stainless steel matrix alloy surface carry out oxidation processes 19min.
5) 40wt%Pb-PbO of hot pressed sintering is used2Composite material is as depositing electrode, to ferrite stainless steel matrix The PbO coatings that alloy surface oozes slicker solder silver alloy carry out deposition PbO2Coating, electrical parameter are low-voltage 45V, high-frequency 1700Hz. Deposition process is blown 5L/min argon gas using survey and is protected.
6) pressed using 50% air and 50% water vapour under volume mixture gaseous environment, temperature control is under the conditions of 190 DEG C The PbO-PbO of slicker solder silver alloy is oozed to ferritic stainless steel matrix alloy surface2Coating carries out oxidation processes 50min.
7) slicker solder silver alloy anode material is prepared based on the above method, its internal stress excursion is 1.9~3.9MPa, It is after simulation electrodeposited chromium use condition is on active service 360 days, stress decay rate 33%.
The live electrodeposited chromium use condition of simulation, the lead anode service life are 632 days.
Embodiment 2
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, comprise the following steps that：
1) using 900# sand paper polishing ferritic stainless steel, surface work is carried out to it with the nitric acid that concentration is 15wt% afterwards Change is handled, then is cleaned up with acetone, and dry.
2) using the lead calcium strontium alloy of diameter 4mm as depositing electrode, using high energy micro-arc cold welding machine to ferritic stainless steel Carry out high energy micro arc surface and ooze the processing of lead calcium strontium alloy, electrical parameter is middle voltage 80V, middle frequency 1100Hz.Deposition process Protected using side-blown 15L/min argon gas.
3) using 25wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, after the processing of lead calcium strontium alloy is oozed to surface Ferrite stainless steel matrix Direct precipitation PbO base coatings, electrical parameter is low-voltage 50V, middle frequency 1500Hz.Deposition process is adopted Protected with side-blown 7L/min argon gas.
4) in the case where 85% air and 15% water vapour press volume mixture gaseous environment, temperature control is right under the conditions of 140 DEG C The PbO coatings that lead calcium strontium alloy is oozed on ferritic stainless steel matrix alloy surface carry out oxidation processes 15min.
5) 35wt%Pb-PbO of hot pressed sintering is used2Composite material is as depositing electrode, to ferrite stainless steel matrix The PbO coatings that alloy surface oozes lead calcium strontium alloy carry out deposition PbO2Coating, electrical parameter are low-voltage 50V, high-frequency 1900Hz. Deposition process is blown 4L/min argon gas using survey and is protected.
6) pressed using 65% air and 35% water vapour under volume mixture gaseous environment, temperature control is under the conditions of 170 DEG C The PbO-PbO of lead calcium strontium alloy is oozed to ferritic stainless steel matrix alloy surface2Coating carries out oxidation processes 45min.
7) lead calcium strontium alloy anode material is prepared based on the above method, its internal stress excursion is 1.3~3.8MPa, It under simulating cathode copper use condition after being on active service 360 days, stress decay rate 39%.
The live cathode copper use condition of simulation, the lead anode service life are 590 days.
Embodiment 3
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, comprise the following steps that：
1) using 1000# sand paper polishing ferritic stainless steel, surface is carried out to it with the nitric acid that concentration is 10wt% afterwards Activation process, then cleaned up with acetone, and it is dry.
2) using the lead-calcium alloy of diameter 4mm as depositing electrode, using high energy micro-arc cold welding machine to ferritic stainless steel into Lead-calcium alloy processing is oozed on row high energy micro arc surface, and electrical parameter is middle voltage 70V, middle frequency 1500Hz.Deposition process uses Side-blown 13L/min argon gas is protected.
3) using 30wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, after lead-calcium alloy processing is oozed to surface Ferrite stainless steel matrix Direct precipitation PbO base coatings, electrical parameter are low-voltage 60V, middle frequency 1700Hz.Deposition process uses Side-blown 6L/min argon gas is protected.
4) in the case where 90% air and 10% water vapour press volume mixture gaseous environment, temperature control is right under the conditions of 110 DEG C The PbO coatings that lead-calcium alloy is oozed on ferritic stainless steel matrix alloy surface carry out oxidation processes 17min.
5) 30wt%Pb-PbO of hot pressed sintering is used2Composite material is as depositing electrode, to ferrite stainless steel matrix The PbO coatings that alloy surface oozes lead-calcium alloy carry out deposition PbO2Coating, electrical parameter are low-voltage 40V, high-frequency 1700Hz.It is heavy Product process is blown 5L/min argon gas using survey and is protected.
6) use under 50% air and 50% water vapor mixture body environment, temperature control is under the conditions of 180 DEG C to iron element Body stainless steel base alloy surface oozes the PbO-PbO of lead-calcium alloy2Coating carries out oxidation processes 50min.
7) lead-calcium alloy anode material is prepared based on the above method, its internal stress excursion is 1.0~4.0MPa, its After being on active service 360 days under simulating cathode copper use condition, stress decay rate 41%.
The live cathode copper use condition of simulation, the lead anode service life are 579 days.
As shown in Figure 1, the surface shape of the lead-based anode material prepared in the present invention using high energy micro arc deposition technique Looks.There is surface depositing coating high energy micro arc to deposit typical splash shape shape characteristic.Coating be by many splashes to The condensation that the molten drop of lead-based anode matrix is formed mutually overlap joint forms.Therefore, even if single condensed layer is there are the defects of hole, These defects can't be overall through coating, generally speaking still has relatively compact structure with regard to coating.
As shown in Fig. 2, the lead-based anode material surface Raman spectrum prepared using high energy micro arc deposition technique.By scheming Raman spectrum in 2, which can be seen that the lead-based anode material surface prepared using high energy micro arc deposition technique, has stabilization Component composition, suitable for different types of lead-based anode.
As shown in figure 3, the lead-based anode material XRD spectra prepared using high energy micro arc deposition technique.By in Fig. 3 The data of gained are it can be calculated that the lead-based anode prepared in the present invention using high energy micro arc deposition technique in XRD spectra The scope of the initial internal stress of material is 1.0~4.1MPa.

Claims (5)

1. a kind of low stress gradient, the lead-based anode material preparation method of high life, it is characterised in that comprise the following steps：
1) using 800~1000# sand paper polishing ferritic stainless steel, it is carried out with the nitric acid that concentration is 10~20wt% afterwards Surface activation process, then cleaned up with acetone, and it is dry；
2) using the slicker solder silver alloy or lead-calcium alloy of 3~5mm of diameter or lead calcium strontium alloy as depositing electrode, using the high energy differential of the arc Cold welding machine carries out high energy micro arc surface to ferritic stainless steel and oozes at slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy Reason, electrical parameter is middle 70~90V of voltage, middle 700~1500Hz of frequency；
3) 20wt%~30wt%Pb-PbO prepared using hot pressing sintering method as depositing electrode, surface is oozed slicker solder silver alloy or Ferrite stainless steel matrix Direct precipitation PbO base coatings after lead-calcium alloy or the processing of lead calcium strontium alloy, electrical parameter is low-voltage 40~60V, middle 900~1700Hz of frequency；
4) in the case where 80~90% air and 10~20% water vapours press volume mixture gaseous environment, temperature control is at 100~150 DEG C Under the conditions of ferritic stainless steel matrix alloy surface is oozed the PbO coatings of slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy into 10~20min of row oxidation processes；
5) 30wt%~40wt%Pb-PbO of hot pressed sintering is used2Composite material is as depositing electrode, to ferrite stainless base steel Body alloy surface oozes slicker solder silver alloy or lead-calcium alloy or the PbO coatings of lead calcium strontium alloy carry out deposition PbO2Coating, electrical parameter For 20~50V of low-voltage, 1500~2000Hz of high-frequency；
6) pressed using 50~70% air and 30~50% water vapours under volume mixture gaseous environment, temperature control is 150~200 The PbO- of slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy is oozed under the conditions of DEG C to ferritic stainless steel matrix alloy surface PbO2Coating carries out 30~50min of oxidation processes.
2. low stress gradient described in accordance with the claim 1, the lead-based anode material preparation method of high life, it is characterised in that In step 2), deposition process is protected using side-blown 10~15L/min argon gas.
3. low stress gradient described in accordance with the claim 1, the lead-based anode material preparation method of high life, it is characterised in that In step 3), deposition process is protected using side-blown 5~10L/min argon gas.
4. low stress gradient described in accordance with the claim 1, the lead-based anode material preparation method of high life, it is characterised in that In step 5), deposition process is blown 1~5L/min argon gas using survey and is protected.
5. low stress gradient described in accordance with the claim 1, the lead-based anode material preparation method of high life, it is characterised in that Lead-based anode material is prepared based on this method, it is 1.0~4.1MPa to test its internal stress excursion, it is in electrodeposited chromium or electricity After solution copper application field uses 360 days, stress decay rate 30%~45%, service life 1.5 years~2 years.
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