CN105543903A - Evaluation method for service life of lead-based anode material - Google Patents
Evaluation method for service life of lead-based anode material Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 88
- 238000011156 evaluation Methods 0.000 title claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 230000003245 working effect Effects 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 238000004364 calculation method Methods 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000013341 scale-up Methods 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 abstract description 5
- 238000009854 hydrometallurgy Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 238000012993 chemical processing Methods 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 6
- 229910001128 Sn alloy Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000001530 Raman microscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 229910006529 α-PbO Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/25—Measuring force or stress, in general using wave or particle radiation, e.g. X-rays, microwaves, neutrons
Abstract
The invention provides an evaluation method for the service life of a lead-based anode material, and belongs to the field of hydrometallurgy. The evaluation method for the service life of the lead-based anode material comprises the following steps that 1, the lead-based anode material is processed through the methods of polishing and chemical processing, and it is ensured that the surface of the lead-based anode material is free of obvious scratches; 2, electrolytic treatment is conducted on the lead-based anode material through a solution containing CrO3, H2SO4, NaCl and NH4F; 3, the thicknesses of oxidation films within different processing time are analyzed through SEM; 4, the internal stress of the oxidation films of different thickness is determined by using a Raman spectrographic method and an XRD analysis method; 5, the relationship between the stress sigma and the oxidation film thickness X is built, that is, sigma=AX+B; and 6, the service life of the lead-based anode material is evaluated according to the stress gradient A. According to the evaluation method for the service life of the lead-based anode material, the service life of the lead-based anode material can be evaluated easily, conveniently, rapidly and accurately, the economical and practical effects are achieved, and the cost is low; it is conducive to master the using and replacing periodicity of a lead anode in the electrolysis industry and the electroplating industry, continuous production is ensured, and the quality of cathode products is improved.
Description
Technical field
The invention belongs to field of hydrometallurgy, particularly the evaluation method in a kind of lead-based anode materials'use life-span.
Background technology
Lead-based anode material has (1) good electroconductibility; (2) erosion resistance is strong; (3) physical strength and good processability; (4) long service life, expense are low; (5) to electrode reaction, there is the features such as good electrocatalysis characteristic, it not only has important application in tin-free steel field of electroplating, and also has a wide range of applications in field of hydrometallurgy such as eleetrotinplate (or zinc), lead-acid cell, electrolysis (zinc, copper, manganese etc.) and chlorine industries.In these field of hydrometallurgy, under electric field action, lead-based anode material is at comparatively severe solution environmental long service (individual month of short then 3-6, reach 24 months or longer), as strongly acidic solution environment (sulfur acid solution), strong oxidizing solution environment (containing chromic acid solution), or severe corrosive solution environmental (fluoride or chloride soln), cause lead-based anode surface oxidation, corrosion.Along with the carrying out of oxidation, will there is the change of lead compound → lead oxides in the oxide film weave construction of metallic surface, as PbO → β-PbO
2→ α-PbO
2, cause oxide film loose porous, can there is crackle and frill in local, even come off, and then shorten the work-ing life of anode.
The oxide film formed for lead-based anode surface is loose, porous; be easy to problems such as coming off; as far back as twentieth century beginning of the eighties; researchist has begun one's study the impact of current potential on lead anode surface film oxide; after this someone proposes reaction protective layer concept successively; namely generate fine and close protective oxide film at the surface oxidation of metal anode, thus make inner metallic matrix from corrosion.For the raising compactness of protective layer and the sticking power with metallic lead matrix thereof, research focuses mostly in metals such as Ag, Ca, Ba, Sr, Sn, Mn, Co, Ti, Bi, Se, Te, As and nonmetal, and it forms alloy with plumbous.But, no matter any one alloy Addition ofelements, all as alterant, its object is exactly the crystal grain of refinement lead alloy, increase physical strength and the hardness of stereotype, make stereotype form the plumbic oxide film of one deck densification on its surface, strengthen the corrosion resistance nature of alloy, be intended to the work-ing life of improving anode.Because lead anode contains at least two or three kind of alloy, and also have difference for the change alloy species of its environment for use, add the difference of lead-based anode preparation method (as teeming practice and rolling process etc.), the evaluation in antianode work-ing life is comparatively difficult, therefore about the also rare evaluation method in work-ing life of lead-based anode.No matter be in electrolysis field at present, or in field of electroplating, the work-ing life of lead anode is evaluated mainly through effect of field application.Due to the lead-based anode duration of service of some months at least, more than 1 year at most, this has had a strong impact on design and the quality evalution thereof of lead-based anode, in rig-site utilization process, lead anode erosion enters plating solution simultaneously, all there is bad impact to the composition of plating/electrolytic solution, processing parameter, even reduce the quality of cathodic reduction product.This is also one of main drawback exposed in lead-based anode application process.Therefore, propose the evaluation method in a kind of quick and easy lead-based anode work-ing life, there is important theoretical and practical significance.
Summary of the invention
For lead-based anode kind is more in the market, and its applied environment complicated condition, lead-based anode work-ing life of rig-site utilization cannot the problem such as anticipation, the invention provides a kind of is rely on electrochemistry, in conjunction with detection technique analyses such as SEM, Raman and XRD, the evaluation method in lead-based anode materials'use life-span.Present method can easy, fast, accurately evaluate lead-based anode work-ing life, economical and practical, cost is low, contributes to the use replacement cycle property grasping electrolysis, electroplating industry lead anode, guarantees continuous seepage, improve cathode product quality.
The evaluation method in lead-based anode materials'use life-span, comprises the following steps:
Step 1: to be polished in the surface of lead-based anode material, polishing and chemical treatment;
Step 2: adopt CrO
3+ H
2sO
4+ NaCl+NH
4after F mixing solutions carries out electrolysis to lead-based anode material, lead-based anode material surface generates oxide film; Wherein, the current density 20 ~ 40A/dm of electrolysis
2, electrolyte temperature 40 ~ 60 DEG C, electrolysis time is 5 ~ 30min;
Step 3: adopt the cross section of SEM to the lead-based anode material surface oxide film under different electrolysis time condition to analyze, determine lead-based anode material surface oxide thickness;
Step 4: according to the oxide thickness in step 3, analyze the internal stress change of oxide film, set up the relation between the internal stress of oxide film and oxide thickness, i.e. formula (Ι):
σ＝AX+B(Ι)
Wherein, σ is the internal stress of oxide film, MPa; A is stress gradient, MPa/ μm; X is oxide thickness, μm; B is matrix stress, MPa;
Step 5:
(1) according to formula (Ι), identified sign gradient A;
(2) under following electrolytic condition, the work-ing life of lead-based anode material is evaluated:
Electrolytic condition is (a) or (b):
During (a) electrolytic copper, H in electrolytic solution
2sO
4concentration is 150 ~ 200g/L, Cu
2+concentration is 30 ~ 50g/L, and current density is 2 ~ 5A/dm
2, electrolysis temperature is 30 ~ 50 DEG C;
During (b) electrolysis chromium, CrO in electrolytic solution
3concentration is 100 ~ 300g/L, F
-concentration is 1 ~ 5g/L, and current density is 10 ~ 50A/dm
2, electrolysis temperature is 30 ~ 50 DEG C;
Evaluation method is:
Stress gradient | during A|≤0.5, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 12 ~ 24 months;
Stress gradient 0.5 < | during A|≤0.95, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 9 ~ 12 months;
Stress gradient 0.95 < | during A|≤1.25, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 6 ~ 9 months;
Stress gradient | during A| > 1.25, lead-based anode material is less than 6 months the work-ing life under (a) or (b) electrolytic condition.
In above-mentioned lead-based anode material, mass percentage >=90% of Pb;
In above-mentioned steps 1, adopt the surface of 1000 ~ 1400# waterproof abrasive paper to lead-based anode material to polish, adopt woollen goods polishing cloth to the surface finish of lead-based anode material extremely without obvious cut; The mixing solutions of acetic acid and hydrogen peroxide is adopted to carry out chemical treatment to the surface of lead-based anode material, wherein, the volume ratio 2.5 ~ 4.5 of acetic acid and hydrogen peroxide;
In above-mentioned steps 2, CrO
3+ H
2sO
4+ NaCl+NH
4f solution, concentration is respectively: CrO
3be 100 ~ 200g/L, H
2sO
4be 10 ~ 30g/L, NH
4f is 2 ~ 6g/L, NaCl is 1 ~ 5g/L;
In above-mentioned steps 3, the electrolysis time got be spaced apart 2 ~ 7min;
In above-mentioned steps 4, when oxide thickness is less than or equal to 2 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II):
σ＝I
N×(ω
S-ω
0)(Ⅱ)
Wherein, ω
0the single order optical phonon feature peak position wave number of lead base body, cm
-1; ω
sthe single order optical phonon feature peak position wave number of lead-based anode material after step 1, step 2 process, cm
-1; σ is the internal stress of oxide film, MPa; I
nscale-up factor, MPacm;
When oxide thickness is greater than 2 μm, adopts XRD analysis method to measure its internal stress, adopt calculation formula (III):
Wherein, θ is diffraction angle, degree;
for the side rake angle of sample, degree; ν is Poisson's ratio, and dimension is 1; E is Young's modulus of elasticity, MPa.
Scale-up factor I
nrelevant with Composition of Oxide Scale, determine mainly through calculating; Its internal stress of oxide thickness one timing is certain value, adopts above two kinds of methods to survey the internal stress of same oxide film when oxide thickness is greater than 2 μm, and then calculates scale-up factor I
nvalue; Although the Composition of Oxide Scale that the present invention relates to is slightly different, more than 95% is all plumbous oxide, therefore, and the I in the present invention's three examples
nvalue is same value.
The evaluation method beneficial effect in lead-based anode materials'use life-span of the present invention:
1, the evaluation method in lead-based anode materials'use life-span, achieve easy, quick, the accurate evaluation in different lead-based anode materials'use life-span, the sample analysis cycle is less than 24 hours, simple to operate, can assess the work-ing life of different lead-based anode in different attack solution accurately;
2, the evaluation method in lead-based anode materials'use life-span of the present invention, bath composition involved in lead-based anode evaluation of material process is simple, and economical and practical, low cost, can be recycled;
3, the evaluation method in lead-based anode materials'use life-span of the present invention, for the design of lead-based anode and quality evalution thereof provide foundation, be conducive to improving composition, the processing parameter Stability Control of plating/electrolytic solution, the quality of raising electrolysis/electroplating cathode also original product simultaneously.
Accompanying drawing explanation
Fig. 1 is the micro-organization chart of lead-based anode material oxide film of electrolysis 30min after step 1, step 2 process of the embodiment of the present invention 1.
Fig. 2 is the lead-based anode material surface Raman spectrogram of the embodiment of the present invention, wherein curve 1 is the Raman spectrogram of the electrolysis time 5min in embodiment 1, curve 2 is the Raman spectrogram of embodiment 2 electrolysis time 5min, curve 3 is the Raman spectrogram of the electrolysis time 5min in embodiment 3, curve 4 is the Raman spectrogram of electrolysis 10min in embodiment 1, curve 5 is the Raman spectrogram of electrolysis 15min in embodiment 1, and curve 6 is the Raman spectrogram of the electrolysis time 5min in embodiment 4.
Embodiment
Matrix ω
0value mainly affects by the factor such as working method, anode material components; The invention process case Anodic adopts identical working method, and alloying constituent change is less, can think three example ω
0equal, its defining method is shown in example 1.
ZEISS/EVO18 type electronic scanning Electronic Speculum is all adopted to record the micro-organization chart of oxide film in embodiment; Laser-Raman microspectroscopy (JYLabramHR800) is adopted to test lead-based anode Surface Raman Spectra figure.
Embodiment 1
The evaluation method in the lead-based anode materials'use life-span of the present embodiment, comprises the following steps:
Step 1: after adopting 1000# waterproof abrasive paper to polish to Pb-0.5%Ca alloy lead base anode material, adopt woollen goods polishing cloth to the surface finish of lead-based anode material extremely without obvious cut, then adopt acetic acid and hydrogen peroxide volume ratio to be the mixing solutions of 2.5, chemical treatment is carried out to the lead-based anode material surface after polishing;
Step 2: adopt CrO
3for 110g/L, H
2sO
4for 26g/L, NH
4f is 5g/L, NaCl is that 2g/L mixing solutions carries out electrolysis to lead-based anode material, wherein, and the current density 25A/dm of electrolysis
2, electrolyte temperature 40 DEG C, electrolysis time is 5min, 10min, 15min, 20min, 25min and 30min;
Step 3: adopt the cross section of SEM to the lead-based anode material surface oxide film under different electrolysis time condition to analyze, determine that lead-based anode material surface oxide thickness is respectively 1.8 μm, 3.5 μm, 5.7 μm, 7.5 μm, 9.4 μm and 10.5 μm; Wherein, the lead-based anode surface film oxide micro-organization chart of electrolysis 30min as shown in Figure 1;
Step 4: according to oxide thickness, analyzes the internal stress change of oxide film;
During oxide thickness X=3.5 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
10min=-5.89Mpa;
During oxide thickness X=5.7 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
15min=-8.32Mpa;
During oxide thickness X=7.5 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
20min=-10.16Mpa;
During oxide thickness X=9.4 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
25min=-11.96Mpa;
During oxide thickness X=10.5 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
30min=-13.85Mpa;
During oxide thickness X=1.8 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II) σ=I
n× (ω
s-ω
0) calculate σ; According to the curve 5 in Fig. 2, curve 4, known ω
s-15min=816.48cm
-1, ω
s-10min=827.99cm
-1; Tested from XRD analysis method, the stress value σ of electrolysis 15min oxide film
15minfor-8.32Mpa, the stress value ω of electrolysis 10min oxide film
10minfor-5.89Mpa, by ω
s-15min, ω
s-10min, σ
15minand σ
10minbe brought into public formula II σ=I respectively
n× (ω
s-ω
0) in, subtract each other the known I of rear calculating
n=0.21MPacm;
As oxide thickness X=3.5 μm, XRD analysis method is adopted to measure the internal stress σ of oxide film
10min=-5.89Mpa, its value equals the stress value of the same terms Raman spectrographic determination; By σ
10minbring public formula II σ=I into
n× (ω
s-ω
0) in, can ω be calculated
s-10min-ω
0=-28.05cm
-1, can ω be obtained
0=855.92cm
-1; From Fig. 2 curve 1, ω
s-5min=837.62cm
-1, ω
s-5min-ω
0=-18.30cm
-1, calculate σ
5min=-3.84Mpa;
According to the value of above-mentioned stress σ and the value of oxide thickness X, set up the relation between stress σ and oxide thickness X, i.e. σ=-1.11X-1.90;
Step 5: according to σ=-1.11X-1.90, identified sign gradient A, | A|=1.11, namely the lead-based anode material of Pb-0.5%Ca alloy is as 6 ~ 9 months work-ing life of anode.
Simulated field electrolytic copper working conditions, at H
2sO
4concentration is 150 ~ 200g/L, Cu
2+concentration is in 30 ~ 50g/L electrolytic solution, and the current density adopting electrolysis is 2 ~ 5A/dm
2, at 30 ~ 50 DEG C, carry out electrolysis, the lead-based anode materials'use life-span of the present embodiment is 210 ~ 260 days.
Embodiment 2
The evaluation method in the lead-based anode materials'use life-span of the present embodiment, comprises the following steps:
Step 1: after adopting the lead-based anode material of 1200# waterproof abrasive paper to Pb-1%Ca-1.2%Sn alloy to polish, adopt woollen goods polishing cloth to the surface finish of Pb-1%Ca-1.2%Sn alloy extremely without obvious cut, then adopt acetic acid and hydrogen peroxide volume ratio to be the mixing solutions of 3, chemical treatment is carried out to the lead-based anode material surface after polishing;
Step 2: adopt CrO
3for 170g/L, H
2sO
4for 18g/L, NH
4f is 2g/L, NaCl is that 3g/L mixing solutions carries out electrolysis to Pb-1%Ca-1.2%Sn alloy lead base anode material, wherein, and the current density 35A/dm of electrolysis
2, electrolyte temperature 50 DEG C, electrolysis time is 5min, 10min, 15min, 20min, 25min and 30min;
Step 3: adopt the cross section of SEM to the lead-based anode material surface oxide film of the Pb-1%Ca-1.2%Sn alloy under different electrolysis time condition to analyze, determine that Pb-1%Ca-1.2%Sn alloy surface oxide thickness is respectively 1.3 μm, 2.8 μm, 4.6 μm, 6.4 μm, 8.1 μm and 9.6 μm;
Step 4: according to oxide thickness, analyzes the internal stress change of oxide film;
During oxide thickness X=1.3 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II) to calculate σ, according to Fig. 2 curve 2, known ω
s-5min=841.82cm
-1, calculate σ
5min=-2.96Mpa;
During oxide thickness X=2.8 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
10min=-4.12Mpa;
During oxide thickness X=4.6 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
15min=-5.63Mpa;
During oxide thickness X=6.4 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
20min=-7.18Mpa;
During oxide thickness X=8.1 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
25min=-8.75Mpa;
During oxide thickness X=9.6 μm, adopt XRD analysis method to measure its internal stress, adopt calculation formula (III) to calculate σ
30min=-10.36Mpa;
According to the value of above-mentioned stress σ and the value of oxide thickness X, set up the relation between stress σ and oxide thickness X, i.e. σ=-0.89X-1.66;
Step 5: according to σ=-0.89X-1.66, identified sign gradient A, stress gradient | A|=0.89, namely Pb-1%Ca-1.2%Sn alloy is as 9 ~ 12 months work-ing life of anode.
Simulated field electrolytic copper working conditions, at concentration H
2sO
4be 150 ~ 200g/L, Cu
2+concentration is in 30 ~ 50g/L electrolytic solution, and the current density adopting electrolysis is 2 ~ 5A/dm
2, at temperature 30 ~ 50 DEG C, carry out electrolysis, the lead-based anode materials'use life-span of the present embodiment is 300 ~ 330 days.
Embodiment 3
The evaluation method in the lead-based anode materials'use life-span of the present embodiment, comprises the following steps:
Step 1: after adopting the lead-based anode material of 1400# waterproof abrasive paper to Pb-1.2%Sn-0.5%Ag alloy to polish, adopt woollen goods polishing cloth to the surface finish of the lead-based anode material of Pb-1.2%Sn-0.5%Ag alloy extremely without obvious cut, then adopt acetic acid and hydrogen peroxide volume ratio to be the mixing solutions of 4, chemical treatment is carried out to the lead-based anode material surface after polishing;
Step 2: adopt CrO
3for 190g/L, H
2sO
4for 12g/L, NH
4f is 4g/L, NaCl is that 3g/L mixing solutions carries out electrolysis to Pb-1%Sn-0.3%Ag alloy lead base anode material, wherein, and the current density 40A/dm of electrolysis
2, electrolyte temperature 60 DEG C, electrolysis time is 5min, 10min, 15min, 20min, 25min and 30min;
Step 3: adopt the cross section of SEM to the lead-based anode material surface oxide film of the Pb-1.2%Sn-0.5%Ag alloy under same electrolysis time condition to analyze, determine that Pb-1.2%Sn-0.5%Ag alloy surface oxide thickness is respectively 1.5 μm, 3.1 μm, 4.6 μm, 6.3 μm, 7.9 μm and 9.5 μm;
Step 4: according to oxide thickness, analyzes the internal stress change of oxide film;
During oxide thickness X=1.5 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II) σ=I
n× (ω
s-ω
0) calculate σ, according to Fig. 2 curve 3, known ω
s-5min=840.87cm
-1, calculate σ
5min=-3.16Mpa;
During oxide thickness X=3.1 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
10min=-3.95Mpa;
During oxide thickness X=4.6 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
15min=-4.61Mpa;
During oxide thickness X=6.3 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
20min=-5.53Mpa;
During oxide thickness X=7.9 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
25min=-6.25Mpa;
During oxide thickness X=9.5 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
30min=-7.02Mpa;
According to the value of above-mentioned stress σ and the value of oxide thickness X, set up the relation between stress σ and oxide thickness X, i.e. σ=-0.48X-2.44;
Step 5: according to σ=-0.48X-2.44, identified sign gradient A, stress gradient | A|=0.48, namely Pb-1.2%Sn-0.5%Ag alloy is as 12 ~ 24 months work-ing life of anode.
Simulated field electrodeposited chromium working conditions, at CrO
3concentration is 100 ~ 300g/L, F
-concentration is in 1 ~ 5g/L electrolytic solution, and the current density adopting electrolysis is 10 ~ 50A/dm
2, at 30 ~ 50 DEG C, carry out electrolysis, the lead-based anode material of the present embodiment is 470 ~ 500 days.
Embodiment 4
The evaluation method in the lead-based anode materials'use life-span of the present embodiment, comprises the following steps:
Step 1: after adopting 1300# waterproof abrasive paper to polish to the lead-based anode material that lead content is 99.9%, woollen goods polishing cloth is adopted to be that the surface finish of the lead-based anode material of 99.9% is extremely without obvious cut to lead content, then adopt acetic acid and hydrogen peroxide volume ratio to be the mixing solutions of 3.5, chemical treatment is carried out to the lead-based anode material surface after polishing;
Step 2: adopt CrO
3for 200g/L, H
2sO
4for 15g/L, NH
4f is 3g/L, NaCl be 5g/L mixing solutions is that 99.9% lead-based anode material carries out electrolysis to lead content, wherein, and the current density 35A/dm of electrolysis
2, electrolyte temperature 55 DEG C, electrolysis time is 5min, 10min, 15min, 20min, 25min and 30min;
Step 3: employing SEM is that the cross section of the lead-based anode material surface oxide film of 99.9% is analyzed to the lead content under same electrolysis time condition, determines that lead content is that 99.9% alloy surface oxide thickness is respectively 1.9 μm, 3.7 μm, 5.9 μm, 7.7 μm, 9.5 μm and 10.7 μm;
Step 4: according to oxide thickness, analyzes the internal stress change of oxide film;
During oxide thickness X=1.9 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II) σ=I
n× (ω
s-ω
0) calculate σ, according to Fig. 2 curve 6, known ω
s-5min=843.54cm
-1, calculate σ
5min=-2.60Mpa;
During oxide thickness X=3.7 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
10min=-4.37Mpa;
During oxide thickness X=5.9 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
15min=-7.23Mpa;
During oxide thickness X=7.7 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
20min=-9.61Mpa;
During oxide thickness X=9.5 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
25min=-11.84Mpa;
During oxide thickness X=10.7 μm, adopt XRD analysis method to measure its internal stress, calculate σ according to public formula III
30min=-13.09Mpa;
According to the value of above-mentioned stress σ and the value of oxide thickness X, set up the relation between stress σ and oxide thickness X, i.e. σ=-1.26X+0.219;
Step 5: according to σ=-1.26X+0.219, identified sign gradient A, stress gradient | A|=1.26, namely lead content is 99.9% be less than 6 months work-ing life as lead-based anode.
Simulated field electrodeposited chromium working conditions, at CrO
3concentration is 100 ~ 300g/L, F
-concentration is in 1 ~ 5g/L electrolytic solution, and the current density adopting electrolysis is 10 ~ 50A/dm
2, under 30 ~ 50 DEG C of conditions, carry out electrolysis, the lead-based anode material of the present embodiment is 150 ~ 170 days.
Claims (7)
1. the evaluation method in lead-based anode materials'use life-span, is characterized in that, comprises the following steps:
Step 1: to be polished in the surface of lead-based anode material, polishing and chemical treatment;
Step 2: adopt CrO
3+ H
2sO
4+ NaCl+NH
4after F mixing solutions carries out electrolysis to lead-based anode material, lead-based anode material surface generates oxide film; Wherein, the current density 20 ~ 40A/dm of electrolysis
2, electrolyte temperature 40 ~ 60 DEG C, electrolysis time is 5 ~ 30min;
Step 3: adopt the cross section of SEM to the lead-based anode material surface oxide film under different electrolysis time condition to analyze, determine lead-based anode material surface oxide thickness;
Step 4: according to the oxide thickness in step 3, analyze the internal stress change of oxide film, set up the relation between the internal stress of oxide film and oxide thickness, i.e. formula (Ι):
σ＝AX+B(Ι)
Wherein, σ is the internal stress of oxide film, MPa; A is stress gradient, MPa/ μm; X is oxide thickness, μm; B is matrix stress, MPa;
Step 5:
(1) according to formula (Ι), identified sign gradient A;
(2) under following electrolytic condition, the work-ing life of lead-based anode material is evaluated:
Electrolytic condition is (a) or (b):
During (a) electrolytic copper, H in electrolytic solution
2sO
4concentration is 150 ~ 200g/L, Cu
2+concentration is 30 ~ 50g/L, and current density is 2 ~ 5A/dm
2, electrolysis temperature is 30 ~ 50 DEG C;
During (b) electrolysis chromium, CrO in electrolytic solution
3concentration is 100 ~ 300g/L, F
-concentration is 1 ~ 5g/L, and current density is 10 ~ 50A/dm
2, electrolysis temperature is 30 ~ 50 DEG C;
Evaluation method is:
Stress gradient | during A|≤0.5, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 12 ~ 24 months;
Stress gradient 0.5 < | during A|≤0.95, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 9 ~ 12 months;
Stress gradient 0.95 < | during A|≤1.25, the work-ing life of lead-based anode material under (a) or (b) electrolytic condition is 6 ~ 9 months;
Stress gradient | during A| > 1.25, lead-based anode material is less than 6 months the work-ing life under (a) or (b) electrolytic condition.
2. the evaluation method in lead-based anode materials'use life-span according to claim 1, is characterized in that: described lead-based anode material, mass percentage >=90% of Pb.
3. the evaluation method in lead-based anode materials'use life-span according to claim 1, it is characterized in that: in described step 1, adopt the surface of 1000 ~ 1400# waterproof abrasive paper to lead-based anode material to polish, adopt woollen goods polishing cloth to the surface finish of lead-based anode material extremely without obvious cut; The mixing solutions of acetic acid and hydrogen peroxide is adopted to carry out chemical treatment to the surface of lead-based anode material, wherein, the volume ratio 2.5 ~ 4.5 of acetic acid and hydrogen peroxide.
4. the evaluation method in lead-based anode materials'use life-span according to claim 1, is characterized in that: in described step 2, CrO
3+ H
2sO
4+ NaCl+NH
4f solution, concentration is respectively: CrO
3be 100 ~ 200g/L, H
2sO
4be 10 ~ 30g/L, NH
4f is 2 ~ 6g/L, NaCl is 1 ~ 5g/L.
5. the evaluation method in lead-based anode materials'use life-span according to claim 1, is characterized in that: in described step 3, the electrolysis time got be spaced apart 2 ~ 7min.
6. the evaluation method in lead-based anode materials'use life-span according to claim 5, is characterized in that: electrolysis time be spaced apart 5min.
7. the evaluation method in lead-based anode materials'use life-span according to claim 1, it is characterized in that: in described step 4, when oxide thickness is less than or equal to 2 μm, adopt the stress of Raman analysis of spectral method oxide film, adopt calculation formula (II):
σ＝I
N×(ω
S-ω
0)(Ⅱ)
Wherein, ω
0the single order optical phonon feature peak position wave number of lead base body, cm
-1; ω
sthe single order optical phonon feature peak position wave number of sample after step 1, step 2 process, cm
-1; σ is the internal stress of oxide film, MPa; I
nscale-up factor, MPacm;
When oxide thickness is greater than 2 μm, adopts XRD analysis method to measure its internal stress, adopt calculation formula (III):
Wherein, θ is diffraction angle, degree;
for the side rake angle of sample, degree; ν is Poisson's ratio, and dimension is 1; E is Young's modulus of elasticity, MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986005272A1 (en) * | 1985-02-27 | 1986-09-12 | Hitachi Construction Machinery Co., Ltd | Method of measuring stress in plate material with ultrasonic waves |
| CN101736369A (en) * | 2009-12-29 | 2010-06-16 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102888625A (en) * | 2012-10-10 | 2013-01-23 | 昆明理工恒达科技有限公司 | Fence type anode plate for electrodeposition of nonferrous metals |
-
2015
- 2015-12-10 CN CN201510920083.0A patent/CN105543903B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986005272A1 (en) * | 1985-02-27 | 1986-09-12 | Hitachi Construction Machinery Co., Ltd | Method of measuring stress in plate material with ultrasonic waves |
| CN101736369A (en) * | 2009-12-29 | 2010-06-16 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102888625A (en) * | 2012-10-10 | 2013-01-23 | 昆明理工恒达科技有限公司 | Fence type anode plate for electrodeposition of nonferrous metals |
Non-Patent Citations (3)
| Title |
|---|
| LI JIANZHONG: ""Internal Stress Formation and Changes in Oxide Films on a Lead Alloy Anode Surface"", 《INT.J.ELECTROCHEM.SCI.》 * |
| 曹江林等: ""PbO2阳极在硫酸溶液中的析氧失活行为"", 《物理化学学报》 * |
| 李建中等: ""电场作用下铅基阳极表面氧化膜残余内应力产生机理研究"", 《无机材料学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108004541A (en) * | 2017-12-14 | 2018-05-08 | 东北大学 | A kind of low stress gradient, the lead-based anode material preparation method of high life |
| CN108004541B (en) * | 2017-12-14 | 2019-08-16 | 东北大学 | A kind of low stress gradient, the lead-based anode material preparation method of high life |
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