CN113718314A - Preparation method of lead alloy surface anticorrosive composite coating - Google Patents
Preparation method of lead alloy surface anticorrosive composite coating Download PDFInfo
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- 229910000978 Pb alloy Inorganic materials 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004070 electrodeposition Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- OKJMLYFJRFYBPS-UHFFFAOYSA-J tetraazanium;cerium(4+);tetrasulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKJMLYFJRFYBPS-UHFFFAOYSA-J 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229940075397 calomel Drugs 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 18
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polyethylene chain Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a preparation method of a lead alloy surface anticorrosive composite coating, which comprises the following steps: degreasing and acidifying a lead alloy matrix, and forming a compact composite coating on the surface of the lead alloy by adopting an electrochemical deposition method; the electrolyte for electrochemical deposition comprises 5-30 mmol/L of cerium ammonium sulfate, 1-5 g/L of polyvinylpyrrolidone and 1-8 mol/L of sulfuric acid; the process conditions of the electrochemical deposition are as follows: the temperature is 25-60 ℃, the scanning cycle times are 50-300, the potential range is-0.9-2V, and the deposition time is 10-50 min. The main component of the passive film formed on the surface of the lead alloy by the method is lead sulfate, and the passive film contains a small amount of cerium and organic matters, so that the passive film is flat and compact, and the corrosion resistance of the lead alloy is effectively enhanced; the method has simple process and short time consumption.
Description
Technical Field
The invention belongs to the technical field of preparation of anticorrosive coatings, and particularly relates to a preparation method of a lead alloy surface anticorrosive composite coating.
Background
Lead alloy has low melting point, high density, good mechanical strength and casting performance, and is popular with the materials of initiating explosive devices such as cutting cables. However, lead alloy is affected by temperature, humidity, atmospheric composition and other factors during storage and long-distance transportation, and is easily affected by moisture to cause surface corrosion and generate white rust. The existence of white rust on the surface of the lead alloy seriously affects the service performance of the lead alloy, in particular to products with higher requirements on the mechanical performance and the corrosion resistance of the lead. The corrosion resistance of the lead alloy not only affects the production cost, but also affects the product quality, so the corrosion resistance is a key factor for evaluating the quality of the lead alloy.
At present, a passivation film generated on the surface of a lead alloy by an electrochemical method for preparing a corrosion-resistant coating is thin, so that the bonding strength with a lead alloy matrix is weak, and an oxidation film is not compact, so that a lead alloy member has weak corrosion resistance. Secondly, the rare earth cerium (Ce) can refine grains, so that the stability of the generated composite film is enhanced, but most of the rare earth elements are doped into the lead alloy by a heat treatment process, and the process is complex and consumes long time.
Therefore, the development of a lead alloy coating material with industrial development potential, corrosion resistance and simple process is urgently needed, so that the application of the lead alloy coating material in aerospace military is promoted.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a preparation method of a lead alloy surface anticorrosive composite coating, which generates PbSO on the surface of a lead alloy through an electrochemical method4The lead alloy is an organic composite coating mainly containing trace rare earth elements, has high density and can effectively improve the corrosion resistance of the lead alloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a lead alloy surface anticorrosive composite coating, which comprises the following steps: degreasing and acidifying a lead alloy matrix, and forming a compact composite coating on the surface of the lead alloy by adopting an electrochemical deposition method;
the electrolyte for electrochemical deposition comprises 5-30 mmol/L of cerium ammonium sulfate, 1-5 g/L of polyvinylpyrrolidone and 1-8 mol/L of sulfuric acid;
the process conditions of the electrochemical deposition are as follows: the temperature is 25-60 ℃, the scanning cycle times are 50-300, the potential range is-0.9-2V, and the deposition time is 10-50 min.
The main component of the passive film formed on the surface of the lead alloy is lead sulfate (PbSO)4) And the composite film layer contains a small amount of cerium and organic matters, so that the corrosion resistance of the lead alloy is effectively enhanced.
As the electrodeposition process proceeds, a part of Ce3+Filling holes of the lead sulfate oxide film to enhance the compactness of the oxide film layer; as the deposition time is prolonged, PbSO is gradually formed4A composite coating which is mainly composed of rare earth elements and contains a small amount of rare earth elements.
The longer the deposition time is, the larger the film thickness is, but the later-stage acceleration rate is slowed down, and further, the deposition time is 10-50 min.
Further, the degreasing treatment comprises the following steps: and (3) placing the polished lead alloy matrix in an acetone solution, and removing oil at room temperature for 3-15 min.
Further, the treatment liquid for acidification treatment is sulfuric acid with the concentration of 3-10 ml/L.
Further, the acidification treatment method comprises the following steps: and (3) placing the degreased lead alloy in a sulfuric acid solution, and standing at room temperature for 3-6 min to remove the oxide and rust layer on the surface of the substrate.
When the lead alloy is placed in a natural environment, the surface of the lead alloy can be oxidized to attach oxides, so that the subsequent composite coating process is influenced, and the oxide layer on the surface of the lead alloy substrate can be removed through degreasing and acidification.
Further, in the electrochemical deposition method, lead alloy is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and the working surface area is 0.5-2 cm2。
Furthermore, the electrolyte for electrochemical deposition comprises 5-30 mmol/L of ammonium ceric sulfate, 1-5 g/L of polyvinylpyrrolidone and 1-8 mol/L of sulfuric acid.
Further, the polyvinylpyrrolidone is selected from PVPK15、PVPK17、PVPK25、PVPK30、PVPK90Is further one of PVPK30。
Furthermore, the scanning cycle number of the electrochemical deposition is 50-300.
Further, the potential range of the electrochemical deposition is-0.9-1.5V.
Further, the electrochemical deposition time is 10-50 min.
The invention has the following beneficial effects:
the composite coating prepared by the invention is uniform, the surface of the film has few microscopic defects, the bonding force with a substrate is good, and the corrosion resistance is excellent.
Secondly, the electrolytic solution has simple components and almost no toxicity, and NH in the waste gas discharged during electrolysis3The concentration is lower, can directly reach emission standard through ordinary exhaust treatment device, has saved the cost, has maintained the production personnel healthy.
The method has the advantages of simple operation process, no deformation of the lead alloy matrix, easy control, stable process and saving of a large amount of time and production cost.
Drawings
FIG. 1 is an SEM topography of a composite coating prepared in example 1, comparative example 1 and a phosphate coating prepared in comparative example 2;
FIG. 2 is a Fourier transform infrared spectrum of the composite coating prepared in example 1;
FIG. 3 is an XRD pattern of the composite coating prepared in example 2;
fig. 4 is a graph showing polarization curves of the composite coating prepared in example 2 and comparative example 1, the phosphate coating prepared in comparative example 2, and the lead substrate in a saturated carbonic acid solution.
In fig. 1, fig. 1 a: composite coating prepared in example 1, fig. 1 b: composite coating prepared in comparative example 1, fig. 1 c: phosphate coating prepared in comparative example 2.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The sample is lead alloy, and the specific operation steps are as follows:
(1) acetone degreasing: and (3) placing the polished lead alloy matrix in an acetone solution to remove oil, and standing at room temperature for 3 min.
(2) Acidifying: and (3) placing the polished sample in a 5ml/L sulfuric acid solution, and removing the oxide and rust layer on the surface of the sample at room temperature for 3 min.
(3) And (3) electrodeposition of a composite coating: the lead alloy after acid cleaning is used as a working electrode, a platinum sheet is used as a counter electrode, and a calomel electrode is used as a reference electrode.
Electrodeposition aqueous solution: 10mmol/L cerium ammonium sulfate ((NH)4)4Ce(SO4)4) 2g/L polyvinylpyrrolidone (PVP)K30) 4mol/L sulfuric acid H2SO4The mixed solution of (1).
Temperature of the electrolyte: and (4) room temperature.
Electrodeposition parameters: the scanning cycle time is 200, the potential range is-0.5-1.2V, the deposition time is 10min, the PbSO is obtained after taking out and drying4Is a composite coating mainly composed of the components.
Example 2
The sample is lead alloy, and the specific operation steps are as follows:
(1) degreasing with acetone; and (3) placing the polished lead alloy matrix in an acetone solution to remove oil, and standing at room temperature for 5 min.
(2) Acidifying: and (3) placing the polished sample in 8ml/L sulfuric acid solution for soaking for 5min, and removing the oxide and rust layer on the surface of the sample.
(3) And (3) electrodeposition of a composite coating: the lead alloy after acid cleaning is used as a working electrode, a platinum sheet is used as a counter electrode, and a calomel electrode is used as a reference electrode.
Electrodeposition aqueous solution: 10mmol/L cerium ammonium sulfate ((NH)4)4Ce(SO4)4) 2g/L polyvinylpyrrolidone (PVP)K30) 5mol/L sulfuric acid H2SO4The mixed solution of (1).
Temperature of the electrolyte: at 30 ℃.
Electrodeposition parameters: the scanning cycle time is 250, the potential range is-0.9-1.5V, the deposition time is 20min, the PbSO is obtained after taking out and drying4Is a composite coating mainly composed of the components.
Comparative example 1
The sample is lead alloy, and the specific operation steps are as follows:
(1) degreasing with acetone; and (3) placing the polished lead alloy matrix in an acetone solution to remove oil, and standing at room temperature for 3 min.
(2) Acidifying: and (3) soaking the polished sample in 8ml/L sulfuric acid solution at room temperature for 5min to remove the oxide and rust layer on the surface of the sample.
(3) And (3) electrodeposition of a composite coating: the lead alloy after acid cleaning is used as a working electrode, a platinum sheet is used as a counter electrode, and a calomel electrode is used as a reference electrode.
Electrodeposition aqueous solution: 10mmol/L cerium ammonium sulfate ((NH)4)4Ce(SO4)4) 2g/L polyvinylpyrrolidone (PVP)K30) 5mol/L sulfuric acid H2SO4The mixed solution of (1).
Temperature of the electrolyte: at 30 ℃.
Electrodeposition parameters: scanning cycle times are 80, the potential range is-0.9-1.5V, the deposition time is 6min, and the composite coating is obtained after taking out and drying.
Comparative example 2
The sample is lead alloy, and the specific operation steps are as follows:
(1) degreasing with acetone; and (3) placing the polished lead alloy matrix in an acetone solution, removing oil stains and other impurities, and keeping the room temperature for 5 min.
(2) Acidifying: the sanded sample was immersed in 1: 4, acidifying in hydrochloric acid, soaking at room temperature for 8min, and washing with distilled water.
(3) And (3) electrodeposition of a composite coating: the lead alloy after acid cleaning is used as a working electrode, a carbon rod is used as a counter electrode, and a calomel electrode is used as a reference electrode.
Electrodeposition aqueous solution: the phosphating solution is mainly prepared from 25ml/L of phosphoric acid, 2.5g/L of zinc oxide, 3.0g/L of calcium chloride and 8.0-12.0 g/L of sodium hydroxide.
Temperature of the electrolyte: and 65 ℃.
Electrodeposition parameters: the scanning cycle number is 200, the potential range is-0.75-1.2V, the deposition time is 8min, the film is taken out and dried, wherein the main film forming substances are zinc ions and calcium ions generated by the reaction of zinc oxide, calcium chloride and phosphoric acid, and metal ions and phosphate ions from a matrix.
The coatings prepared in examples 1 and 2 and comparative examples 1 and 2 were subjected to performance analysis, and the results are shown in fig. 1 to 4.
The surface morphology of the film prepared in example 1 is shown in fig. 1(a), and it can be seen that the bottom layer of the film is a very dense film completely covering the lead substrate, and the upper surface layer is uniformly distributed with white fine particles; the appearance of the composite film formed in the comparative example 1 is shown in fig. 1b, when the deposition time is too short and is only 6min, the formed composite film is very thin, the particles are fine and compact, but partial pores exist, the corrosion resistance of the film is poor compared with that of the film obtained in the example 1, and the protective effect on a lead alloy matrix is limited; in comparative example 2, as shown in the SEM image of fig. 1c, the particles of the film layer generated when the above-mentioned phosphating solution was used as the electrolyte solution were not uniformly distributed, the film layer was thick but loose, and the density was not as good as the composite film layer generated when the mixed solution of cerium ammonium sulfate, polyvinylpyrrolidone and sulfuric acid was used as the electrolyte solution.
The composite coating generated on the surface of the lead alloy in example 1 was characterized by Fourier infrared spectroscopy, as shown in FIG. 2, by infrared spectroscopy of 400-4000 cm-1Obtaining PbSO in the lead alloy sample within the range4Chemical bond characteristics with organic PVP; at 630.70cm-1And 1178.47cm-1The peaks at the left and right are similar to the frequency range of lead sulfate; at 2933.58cm-1The peaks at the left and right are due to stretching of the C-H bond, indicating that the side chain is a polyethylene chain; 1433.07cm-1And 1465.86cm-1The peak at (a), due to C-N stretching of the PVP ring; the PVP obviously improves the uniformity of the coating generated on the surface of the lead alloy, and the crystal grains are arranged regularly and orderly and are in a flat, smooth and compact structure because the long-chain structure of the PVP has a steric hindrance effect to inhibitThe agglomeration of the crystal grains is realized, so that a flat and compact structure can be obtained.
The XRD results of the composite coating in example 2 are shown in FIG. 3, which shows that the main component of the composite film is PbSO4The peak of Pb comes from the matrix and cannot be detected due to the low content of organic substances and cerium compounds, but Ce element can be detected in the energy spectrum test.
From the polarization curve of FIG. 4, the self-corrosion potential of the composite coating obtained in example 2 and the lead substrate is-0.47V, -0.49V in sequence, and the open-circuit potential is slightly increased; the corrosion current densities of the two samples were 4.03. mu.A/cm2，12.5μA/cm2The corrosion speed is reduced by two times, the anodic polarization curve of the sample with the composite coating has obvious passivation tendency, and the Victorial current density is 13.3 mu A/cm2The corrosion resistance of the lead alloy is improved to a certain extent, and the composite coating mainly containing lead sulfate plays a good role in protecting a lead alloy matrix.
From the polarization curve of fig. 4, the anodic corrosion rate of the composite film formed in comparative example 1 is significantly higher than that of the film formed in example 1, which shows that when the deposition time is too short, the film is too thin and has a limited protective effect on the lead alloy substrate; the corrosion resistance of the film formed in comparative example 2 using the phosphating solution as the electrolyte was also inferior to that of the composite coating prepared in example 1 using the mixed solution of ammonium cerium sulfate, polyvinylpyrrolidone and sulfuric acid.
According to the invention, the pretreated lead alloy is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and a specific electrolyte and electrolysis conditions are adopted, so that the obtained anticorrosive oxide film layer has good compactness and excellent corrosion resistance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the lead alloy surface anticorrosive composite coating is characterized by comprising the following steps of:
degreasing and acidifying a lead alloy matrix, and forming a compact composite coating on the surface of the lead alloy by adopting an electrochemical deposition method;
the electrolyte for electrochemical deposition comprises 5-30 mmol/L of cerium ammonium sulfate, 1-5 g/L of polyvinylpyrrolidone and 1-8 mol/L of sulfuric acid;
the process conditions of the electrochemical deposition are as follows: the temperature is 25-60 ℃, the scanning cycle times are 50-300, the potential range is-0.9-2V, and the deposition time is 10-50 min.
2. The method according to claim 1, wherein the degreasing treatment is: and (3) placing the polished lead alloy matrix in an acetone solution, and removing oil at room temperature for 3-15 min.
3. The method according to claim 1, wherein the treatment solution for the acidification treatment is sulfuric acid having a concentration of 3 to 10 ml/L.
4. The preparation method according to claim 1, wherein the acidification treatment method comprises the following steps: and (4) placing the degreased lead alloy in a sulfuric acid solution, and placing for 3-6 min at room temperature.
5. The preparation method according to claim 1, wherein in the electrochemical deposition method, lead alloy is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and the working surface area is 0.5-2 cm2。
6. The method according to claim 1, wherein the composition of the electrolyte for electrochemical deposition comprises 5 to 30mmol/L cerium ammonium sulfate, 1 to 5g/L polyvinylpyrrolidone, and 1 to 8mol/L sulfuric acid.
7. The method according to claim 6, wherein the polyvinylpyrrolidone is selected from the group consisting of PVPK15、PVPK17、PVPK25、PVPK30、PVPK90Is further one of PVPK30。
8. The method according to claim 1, wherein the number of scanning cycles of the electrochemical deposition is 50 to 300.
9. The method according to claim 1, wherein the potential of the electrochemical deposition is in the range of-0.9 to 1.5V.
10. The method according to claim 1, wherein the electrochemical deposition time is 10-50 min.
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| CN114807675A (en) * | 2022-04-25 | 2022-07-29 | 安吉绿金金属材料有限公司 | Special pressure-resistant anti-corrosion lead material for submarine cable |
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| US20030235763A1 (en) * | 2002-06-21 | 2003-12-25 | Gonzalez Jose E. | Grid coating process for lead acid batteries |
| CN107190303A (en) * | 2017-03-27 | 2017-09-22 | 天能电池集团有限公司 | A kind of lead accumulator grid with composite coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030235763A1 (en) * | 2002-06-21 | 2003-12-25 | Gonzalez Jose E. | Grid coating process for lead acid batteries |
| CN107190303A (en) * | 2017-03-27 | 2017-09-22 | 天能电池集团有限公司 | A kind of lead accumulator grid with composite coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114807675A (en) * | 2022-04-25 | 2022-07-29 | 安吉绿金金属材料有限公司 | Special pressure-resistant anti-corrosion lead material for submarine cable |
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