CN108004541B - 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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CN108004541B
CN108004541B CN201711341324.1A CN201711341324A CN108004541B CN 108004541 B CN108004541 B CN 108004541B CN 201711341324 A CN201711341324 A CN 201711341324A CN 108004541 B CN108004541 B CN 108004541B
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pbo
based anode
anode material
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CN108004541A (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, in particular 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 be made to be improved.This technology is due to electric flux temporally and spatially high concentration, melt the local material in region, electrode material high speed is transitioned into workpiece surface and diffuses into workpiece surface, can form the alloy-layer being firmly combined, and improves the binding force between matrix-film or membrane-membrane.Meanwhile heterogeneity gas can be purged in the process, the conditions such as control gas flow, voltage, discharge frequency, output power, and oxidation 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, in particular to a kind of low stress gradient, the lead-based anode material system of high life Preparation Method.
Background technique
Since lead-based anode material includes (1) good electric conductivity；(2) corrosion resistance is strong；(3) mechanical strength and processing Performance is good；(4) long service life, expense are low；(5) have the characteristics that good electrocatalysis characteristic to electrode reaction, not only exist Tin-free steel field of electroplating has 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 (containing chromic acid solution) or strong corrosive solution environmental (fluoride or chloride solution), cause lead-based anode surface oxidation Corrosion.
As oxidation film relatively thin (about several hundred nm), oxidation film and matrix keep identical crystal growth direction；But due to length Time oxidation, promotes oxidation film oriented growth excessive, so that the lattice constant of metal and oxidation film is inconsistent, is distorted, from And generate stress.With the progress of oxidation, lead compound → lead oxides will occur for the oxidation film institutional framework of metal surface Variation, causes its lattice constant also can accordingly change, the stress generated in this way also changes therewith.Further, since golden Belong to ion diffusion generate hole, metal structure it is uneven, high oxide, surface shape are re-formed in established oxidation film It changes at the phase structure of multilayer oxidation film, oxide, such as PbO → β-PbO2→α-PbO2, stress can be generated.It is thin Film internal stress acts on either in the form of tensile stress or compression, all can generate shearing in film-matrix or membrane-membrane interface and answer Power.Meanwhile the presence of membrane interface lattice mismatch, thermal expansion coefficient difference and various defects also aggravates the internal stress of oxidation film and drills Become.Under electric field action, the differentiation of lead-based anode material internal stress shows as stress gradient growth, and causing oxidation film, there are high stresses Gradient or micro-sized stress are concentrated, and when reaching stress characteristics transition point, form a kind of release of stress, oxidation film is caused fine fisssure occur Line.When shear stress arrives greatly binding force between the adhesive force between capable of overcoming film-basal body interface or membrane-membrane, film layer will be in height Crackle occurs at stress gradient and frills, or even falls off, and then shorten the service life of anode.
Lead anode surface film oxide is loose, porous and metal interface binding force, stress gradient have close relationship.Cause How this, improve compactness, control oxygen or the ion diffusion of lead oxidation film, how to improve the stress gradient between oxidation film, aoxidize Binding force 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, achievees the purpose that reduce energy consumption, raising anode service life.French Le P.C. IrO is deposited on Pb, Pb-Ag matrix with Petit M.A. et al. research2Lead-based anode, the study found that the anode have There is good electro catalytic activity.But IrO2Being slowly dissolved causes electro catalytic activity to decline.Walker J.K. and Bishara J.I. RuO is studied2Lead-based anode, distinguishing feature are that have lower 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 answering It is satisfactory in the using effect of The Dow Chemical Co.'s chlor-alkali plant with one kind of future.Bulgarian Hussanova A. Also research electrodeposition process prepares Pb-Co3O4The performance of composite coating anode, the results showed that, corrosion resistance is strong, and low energy consumption.Someone mentions The lead base PbO of PTFE bonding out2Electrode, but PbO2The mechanical strength of catalyst layer is at a fairly low, thus make anode life it is very low, increase Power-up resistance.Surface pre-polarizing lead anode carries out surface pre-polarizing appropriate to lead anode in particular solution, can also be effective Ground improves its service performance, such as in CoSO4It polarizes in solution, surface forms CoxOy-PbO2Mixed oxide films can be affirmed Ground says that this plays great impetus to the development of entire 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, but have ignored materials microstructure transformation, oxygen Change the coupled problem of membrane volume expansion and material mechanical performance.
Summary of the invention
It is more for lead-based anode type 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, the purpose of the present invention is to provide a kind of low stress gradients, the lead-based anode material of high life Preparation method is to rely on high energy micro arc deposition technique, analyzes in conjunction with detection techniques such as SEM, Raman and XRD, the preparation Method is easy, quick, at low cost, and the high life lead-based anode material of preparation is economical and practical, helps to improve electrolysis, electroplating industry Related 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, comprising the following steps:
1) using 800~1000# sand paper polishing ferritic stainless steel, later with the nitric acid that concentration is 10~20wt% to it Surface activation process is carried out, then is cleaned up with acetone, and 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 high energy micro arc surface to ferritic stainless steel and seeps slicker solder silver alloy or lead-calcium alloy or the conjunction of lead calcium strontium Gold processing, electrical parameter are 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 seeped to surface and is closed Gold or lead-calcium alloy or lead calcium strontium alloy treated ferrite stainless steel matrix Direct precipitation PbO base coating, 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 are by volume mixture gaseous environment, temperature control 100~ The PbO of slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy is seeped 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, not to ferrite Rust steel matrix alloy surface seeps slicker solder silver alloy or lead-calcium alloy or the PbO coating of lead calcium strontium alloy carries out deposition PbO2Coating, Electrical parameter is 20~50V of low-voltage, 1500~2000Hz of high-frequency；
6) using 50~70% air and 30~50% water vapours by under volume mixture gaseous environment, temperature is controlled 150 Slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy are seeped to ferritic stainless steel matrix alloy surface under the conditions of~200 DEG C PbO-PbO2Coating carries out 30~50min of oxidation processes.
The lead-based anode material preparation method of the low stress gradient, high life, in step 2), deposition process uses side 10~15L/min argon gas is blown to be protected.
The lead-based anode material preparation method of the low stress gradient, high life, in step 3), deposition process uses side 5~10L/min argon gas is blown to be protected.
The lead-based anode material preparation method of the low stress gradient, high life, in step 5), deposition process is using surveying 1~5L/min argon gas is blown to be protected.
The lead-based anode material preparation method of the low stress gradient, high life prepares lead base sun based on this method Pole material, testing its internal stress variation range is 1.0~4.1MPa, 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.
Mentality of designing of the invention is:
Extend lead-based anode service life critical issue first is that limitation or falls off at oxide film breakdown, i.e. control oxidation 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, to make 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 high speed is transitioned into workpiece surface and diffuses into workpiece surface, can be formed The alloy-layer being firmly combined improves the binding force between matrix-film or membrane-membrane.Meanwhile heterogeneity can be purged in the process Gas, the conditions such as control gas flow, voltage, discharge frequency, output power.Furthermore oxidation 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, it is 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 has improved the use of anode Service life.
The invention has the advantages and beneficial effects that:
1, the present invention prepares the lead-based anode of low stress gradient, high service life using high energy micro arc deposition technique Material, the preparation method is simple, quick, at low cost.
2, the lead-based anode material that the present invention designs, stress value are 1.0~4.1MPa, and use process stress decay is slow, Service life reduced the economic cost generated in production because replacing anode up to 1.5~2 years.
3, the present invention is conducive to improve plating/electrolyte using the lead-based anode material of low stress gradient, high service life Composition, technological parameter stability control, improve the quality of electrolysis/electroplating cathode also original product.
Detailed description of the invention
Fig. 1 is lead-based anode material surface pattern of the present invention using the preparation of high energy micro arc deposition technique.
Fig. 2 present invention uses the lead-based anode material surface Raman spectrum of high energy micro arc deposition technique preparation.Wherein, Abscissa Raman Shift represents Raman shift (cm-1), peak is peak value.
Fig. 3 present invention uses the lead-based anode material XRD spectra of high energy micro arc deposition technique preparation.Wherein, a) Pb- Sn-Ag；b)Pb-Ca-Sr；C) Pb-Ca, peak are peak value.
Specific embodiment
In the following, being further elaborated on by embodiment and attached drawing to the present invention.
In embodiment, carried out using 3E-ES type metal surface reinforcing repair machine (Metal Inst., Chinese Academy of Sciences) High energy micro arc deposition；Using the thickness of ZEISS/EVO18 type electron scanning Electronic Speculum measurement oxidation film；It is drawn using micro laser Graceful spectrometer (JY Labram HR 800) and XRD (the X-ray stress test of Canadian PROTO company LXRD) test lead base sun The internal stress of pole and its surface film oxide, using Chinese invention patent: a kind of evaluation method in lead-based anode materials'use service life The analysis calculation method recorded in (ZL201510920083.0, publication number: CN105543903A).
Embodiment 1
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, the specific steps are as follows:
1) using 800# sand paper polishing ferritic stainless steel, it is living that the nitric acid for being later 20wt% with concentration carries out surface to it Change processing, then 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 It carries out high energy micro arc surface and seeps the processing of slicker solder silver alloy, electrical parameter is middle voltage 90V, middle frequency 900Hz.Deposition process is adopted It is protected with side-blown 12L/min argon gas.
3) using 20wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, after seeping the processing of slicker solder silver alloy to surface Ferrite stainless steel matrix Direct precipitation PbO base coating, electrical parameter be low-voltage 55V, middle frequency 1000Hz.Deposition process is adopted It is protected with side-blown 9L/min argon gas.
4) in the case where 80% air and 20% water vapour are by volume mixture gaseous environment, temperature control is right under the conditions of 120 DEG C The PbO coating that slicker solder silver alloy is seeped on ferritic stainless steel matrix alloy surface carries 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 coating that alloy surface seeps slicker solder silver alloy carries 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) using 50% air and 50% water vapour by under volume mixture gaseous environment, temperature is controlled under the conditions of 190 DEG C The PbO-PbO of slicker solder silver alloy is seeped 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, internal stress variation range is 1.9~3.9MPa, It is after simulation electrodeposited chromium use condition is on active service 360 days, stress decay rate 33%.
Live electrodeposited chromium use condition is simulated, which is 632 days.
Embodiment 2
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, the specific steps are as follows:
1) using 900# sand paper polishing ferritic stainless steel, it is living that the nitric acid for being later 15wt% with concentration carries out surface to it Change processing, then 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 It carries out high energy micro arc surface and seeps the processing of lead calcium strontium alloy, electrical parameter is middle voltage 80V, middle frequency 1100Hz.Deposition process It is protected using side-blown 15L/min argon gas.
3) using 25wt%Pb-PbO prepared by hot pressing sintering method as depositing electrode, after seeping the processing of lead calcium strontium alloy to surface Ferrite stainless steel matrix Direct precipitation PbO base coating, electrical parameter be low-voltage 50V, middle frequency 1500Hz.Deposition process is adopted It is protected with side-blown 7L/min argon gas.
4) in the case where 85% air and 15% water vapour are by volume mixture gaseous environment, temperature control is right under the conditions of 140 DEG C The PbO coating that lead calcium strontium alloy is seeped on ferritic stainless steel matrix alloy surface carries 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 coating that alloy surface seeps lead calcium strontium alloy carries 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) using 65% air and 35% water vapour by under volume mixture gaseous environment, temperature is controlled under the conditions of 170 DEG C The PbO-PbO of lead calcium strontium alloy is seeped 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, internal stress variation range is 1.3~3.8MPa, After it is on active service 360 days in the case where simulating cathode copper use condition, stress decay rate 39%.
Live cathode copper use condition is simulated, which is 590 days.
Embodiment 3
In the present embodiment, low stress gradient, the lead-based anode material preparation method of high life, the specific steps are as follows:
1) using 1000# sand paper polishing ferritic stainless steel, surface is carried out to it with the nitric acid that concentration is 10wt% later It is activated, then is cleaned up with acetone, and 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 seeped 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, seeping lead-calcium alloy to surface, treated Ferrite stainless steel matrix Direct precipitation PbO base coating, 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 are by volume mixture gaseous environment, temperature control is right under the conditions of 110 DEG C The PbO coating that lead-calcium alloy is seeped on ferritic stainless steel matrix alloy surface carries 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 coating that alloy surface seeps lead-calcium alloy carries 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) using under 50% air and 50% water vapor mixture body environment, temperature control is under the conditions of 180 DEG C to iron element The PbO-PbO of body stainless steel base alloy surface infiltration lead-calcium alloy2Coating carries out oxidation processes 50min.
7) lead-calcium alloy anode material is prepared based on the above method, internal stress variation range is 1.0~4.0MPa, After being on active service 360 days in the case where simulating cathode copper use condition, stress decay rate 41%.
Live cathode copper use condition is simulated, which is 579 days.
As shown in Figure 1, using the surface shape of the lead-based anode material of high energy micro arc deposition technique preparation in the present invention Looks.There is surface depositing coating high energy micro arc to deposit typical splash shape shape characteristic.Coating be by many splashes to What the condensation that the molten drop of lead-based anode matrix is formed mutually was formed by overlapping.Therefore, even if single condensed layer the defects of there are holes, Generally speaking these defects can't still have relatively compact structure with regard to coating through coating entirety.
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 have using the lead-based anode material surface of high energy micro arc deposition technique preparation, to be stablized At being grouped as, be 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 Data obtained in XRD spectra are it can be calculated that using the lead-based anode of high energy micro arc deposition technique preparation in the present invention The range of the initial internal stress of material is 1.0~4.1MPa.

Claims (5)

1. the lead-based anode material preparation method of a kind of low stress gradient, high life, which comprises 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% later Surface activation process, then cleaned up with acetone, and 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 seeps at slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy Reason, electrical parameter are middle 70~90V of voltage, middle 700~1500Hz of frequency；
3) using hot pressing sintering method prepare 20wt%~30wt%Pb-PbO be used as depositing electrode, to surface infiltration slicker solder silver alloy or Lead-calcium alloy or lead calcium strontium alloy treated ferrite stainless steel matrix Direct precipitation PbO base coating, 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 are by volume mixture gaseous environment, temperature is controlled at 100~150 DEG C Under the conditions of to ferritic stainless steel matrix alloy surface seep the PbO coating 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 seeps slicker solder silver alloy or lead-calcium alloy or the PbO coating of lead calcium strontium alloy carries out deposition PbO2Coating, electrical parameter For 20~50V of low-voltage, 1500~2000Hz of high-frequency；
6) using 50~70% air and 30~50% water vapours by under volume mixture gaseous environment, temperature is controlled 150~200 The PbO- of slicker solder silver alloy or lead-calcium alloy or lead calcium strontium alloy is seeped under the conditions of DEG C to ferritic stainless steel matrix alloy surface PbO2Coating carries out 30~50min of oxidation processes.
2. the lead-based anode material preparation method of low stress gradient described in accordance with the claim 1, high life, which is characterized in that In step 2), deposition process is protected using side-blown 10~15L/min argon gas.
3. the lead-based anode material preparation method of low stress gradient described in accordance with the claim 1, high life, which is characterized in that In step 3), deposition process is protected using side-blown 5~10L/min argon gas.
4. the lead-based anode material preparation method of low stress gradient described in accordance with the claim 1, high life, which is characterized in that In step 5), deposition process is protected using side-blown 1~5L/min argon gas.
5. the lead-based anode material preparation method of low stress gradient described in accordance with the claim 1, high life, which is characterized in that Lead-based anode material is prepared based on this method, testing its internal stress variation range is 1.0~4.1MPa, 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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