CN111926357A - Preparation method of magnesium alloy composite structure layer material - Google Patents
Preparation method of magnesium alloy composite structure layer material Download PDFInfo
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- CN111926357A CN111926357A CN202010835877.8A CN202010835877A CN111926357A CN 111926357 A CN111926357 A CN 111926357A CN 202010835877 A CN202010835877 A CN 202010835877A CN 111926357 A CN111926357 A CN 111926357A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000009830 intercalation Methods 0.000 claims abstract description 16
- 230000002687 intercalation Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 94
- 239000002585 base Substances 0.000 claims description 91
- 239000007788 liquid Substances 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 claims description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 16
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 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 claims description 16
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 16
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 16
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- BLCKKNLGFULNRC-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;nickel(2+) Chemical compound [Ni+2].CN(C)C([S-])=S.CN(C)C([S-])=S BLCKKNLGFULNRC-UHFFFAOYSA-L 0.000 claims description 16
- 239000001632 sodium acetate Substances 0.000 claims description 16
- 235000017281 sodium acetate Nutrition 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 229940026189 antimony potassium tartrate Drugs 0.000 claims description 12
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 14
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 94
- 230000000052 comparative effect Effects 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910002059 quaternary alloy Inorganic materials 0.000 description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035939 shock Effects 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a preparation method of a magnesium alloy composite structure layer material, which comprises the following steps: step [1]Synthesizing magnesium alloy MgBe LDH; step [2]MnO of magnesium alloy MgBe LDH base layer4 ‑Anion intercalation assembly; step [3]Magnesium alloy MgBe-MnO4 ‑And (3) carrying out NiMoCeEr electrodeposition on the LDH base layer. The composite structure layer magnesium alloy prepared by the method has good corrosion resistance and wear resistance, and has wide application prospect in the fields of automobiles, war industry and aviation.
Description
Technical Field
The invention relates to the technical field of magnesium alloy surface treatment, in particular to a preparation method of a magnesium alloy composite structure layer material which can be used in the fields of automobiles, war industry and aviation.
Background
The magnesium alloy has high specific strength, high ratio, low density, shock absorption and electromagnetic shielding performance, so that the magnesium alloy has wide application prospect in the fields of traffic industry, electronic products, energy and aerospace. However, magnesium alloys have strong electrochemical activity and low mechanical wear resistance, which also limits their application in a wide range of fields.
Conventional magnesium alloy surface treatment techniques include a chemical conversion process and an anodic oxidation process. The chemical conversion process is to form a layer of insoluble chemical reactant on the surface of the magnesium alloy by a chemical reaction method so as to achieve the purpose of improving the corrosion resistance of the magnesium alloy, however, the magnesium alloy chemical conversion film has low compactness and poor strength and hardness and is difficult to be used as the final corrosion-resistant and wear-resistant film layer of the magnesium alloy. The anodic oxidation process can obviously improve the wear resistance of the magnesium alloy by forming an oxidation product on the surface of the magnesium alloy, however, an anodic oxidation film has larger brittleness, and the corrosion resistance is difficult to obviously improve.
Obviously, the corrosion resistance and wear resistance of the surface film layer of the magnesium alloy prepared by the prior art are still not ideal, which becomes a bottleneck restricting the large-scale application of the magnesium alloy in various fields.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a magnesium alloy composite structure layer material, and the magnesium alloy with the composite structure layer prepared by the method has good corrosion resistance and wear resistance, and has wide application prospects in the fields of automobiles, war industry and aviation.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a magnesium alloy composite structure layer material comprises the following steps:
step [1] synthesis of magnesium alloy MgBe LDH;
step [2]MnO of magnesium alloy MgBe LDH base layer4 -Anion intercalation assembly;
step [3]Magnesium alloy MgBe-MnO4 -And (3) carrying out NiMoCeEr electrodeposition on the LDH base layer.
Preferably, the step [1] specifically comprises the following operations:
beryllium nitrate, lithium bis (trimethylsilyl) amide, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, the synthetic liquid is added into a reaction kettle, magnesium alloy is immersed into the synthetic liquid, the reaction temperature is kept at 105 ℃ and 130 ℃ under a closed condition, the reaction lasts for 9-13 hours, then the magnesium alloy is washed for five times by using deionized water and dried in the air at room temperature for 4-6 hours, and the synthesis of the magnesium alloy MgBe LDH base layer is completed.
Preferably, the synthetic liquid has a beryllium nitrate concentration of 150-170g/L, a lithium bis-trimethylsilyl amide concentration of 20-35g/L, a pyridine concentration of 4-12g/L and an ammonium bicarbonate concentration of 210-225 g/L.
Preferably, the step [2] specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and potassium antimony tartrate into deionized water, mixing uniformly to form an assembly solution, immersing the obtained magnesium alloy MgBe LDH base layer into the assembly solution, immersing at 35-55 ℃ for 4-7 hours, taking out, washing twice with deionized water, drying in the air at room temperature for 2-3.5 hours to complete MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Preferably, the concentration of potassium permanganate in the assembly liquid is 45-60g/L, the concentration of citraconic anhydride is 5-12g/L, and the concentration of antimony potassium tartrate is 25-40 g/L.
Preferably, the step [3] specifically comprises the following operations:
adding nickel dimethyldithiocarbamate and molybdenum hexacarbonyl into diglyme to form organic nickel-molybdenum solution; adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a basic solution; adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 4-7: 3-6, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 50-65 deg.C with current density of 80-200mA/cm2The deposition time is 25-40 minutes, so as to obtain MgBe-MnO in the magnesium alloy4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
Preferably, the concentration of the nickel dimethyldithiocarbamate in the organic nickel-molybdenum solution is 130g/L, and the concentration of the molybdenum hexacarbonyl is 85-100 g/L.
Preferably, the concentration of ceric sulfate in the base liquid is 160g/L, the concentration of erbium nitrate is 60-80g/L and the concentration of sodium acetate is 10-20 g/L.
The invention has the following positive effects: the magnesium alloy composite structure layer material prepared by the method has a structure of MgBe-MnO on the surface of magnesium alloy4 -Layered bimetal hydroxideA composite structure consisting of a substance (LDH) base layer and a NiMoCeEr quaternary alloy surface layer tightly combined with the substance (LDH), wherein MgBe-MnO is arranged in the composite structure4 -The main layer plate of the LDH layer is made of Mg2+And Be2+With OH-Formed while inserting MnO between the body laminates4 -An anion; the MgBe-MnO4 -The LDH base layer and the NiMoCeEr quaternary alloy surface layer form a non-metal/alloy composite structure layer. Due to MgBe-MnO4 -Intercalation MnO of LDH base layer4 -Anions can capture corrosive ions in a corrosive environment through ion exchange, so that the NiMoCeEr quaternary alloy can be promoted to be applied to MgBe-MnO4 -Growing the LDH base layer to form a non-metal/alloy composite structure layer; the NiMoCeEr quaternary alloy layer not only has good corrosion resistance, but also has good wear resistance. In a word, the magnesium alloy composite structure layer material prepared by the invention has excellent corrosion resistance and wear resistance, and has wide application prospect in the fields of automobiles, war industry and aviation.
Drawings
FIG. 1 is a schematic view of a process for preparing a magnesium alloy composite structural layer material according to the present invention;
FIG. 2 is a graph showing corrosion current densities of comparative example, example 1 and example 2 in a sodium chloride solution having a mass concentration of 3.5%;
figure 3 is the 500 round-trip abrasion weight loss results for comparative example, example 1 and example 2.
Detailed Description
Referring to fig. 1, the invention provides a preparation method of a magnesium alloy composite structure layer material, comprising the following steps:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, lithium bis (trimethylsilyl) amide, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate is 170g/L, the concentration of the lithium bis (trimethylsilyl) amide is 20-35g/L, the concentration of the pyridine is 4-12g/L, and the concentration of the ammonium bicarbonate is 210-225 g/L;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 105 ℃ and 130 ℃ under a closed condition, reacting for 9-13 hours to form the MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using deionized water, and drying for 4-6 hours in the air at room temperature, thus completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2]MnO of magnesium alloy MgBe LDH base layer4 -The anion intercalation assembly specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and antimony potassium tartrate into deionized water, and uniformly mixing to form an assembly liquid, wherein the concentration of the potassium permanganate in the assembly liquid is 45-60g/L, the concentration of the citraconic anhydride in the assembly liquid is 5-12g/L, and the concentration of the antimony potassium tartrate in the assembly liquid is 25-40 g/L;
immersing the obtained magnesium alloy MgBe LDH base layer into the assembly liquid, immersing for 4-7 hours at 35-55 ℃, taking out, washing twice with deionized water, drying for 2-3.5 hours in the air at room temperature to finish MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Step [3]Magnesium alloy MgBe-MnO4 -The method comprises the following steps of performing NiMoCeEr electrodeposition on an LDH base layer, wherein the NiMoCeEr electrodeposition specifically comprises the following operations:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 130g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 85-100 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a basic solution, wherein the concentration of ceric sulfate in the basic solution is 160g/L, the concentration of erbium nitrate in the basic solution is 60-80g/L and the concentration of sodium acetate in the basic solution is 10-20 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 4-7: 3-6, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 50-65 deg.C with current density of 80-200mA/cm2The deposition time is 25-40 minutes, so as toMagnesium alloy MgBe-MnO4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
The following illustrates preferred embodiments of the invention.
Example 1
The preferred embodiment 1 of the present invention provides a method for preparing a magnesium alloy composite structural layer material, comprising the steps of:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, bis-trimethylsilyl amino lithium, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate, the concentration of the bis-trimethylsilyl amino lithium, the concentration of the pyridine and the concentration of the ammonium bicarbonate are 155g/L, 25g/L, 6g/L and 215g/L respectively;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 110 ℃ under a closed condition, reacting for 10 hours to form a MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using the deionized water, and drying for 4.5 hours in the air at room temperature, thereby completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2]MnO of magnesium alloy MgBe LDH base layer4 -The anion intercalation assembly specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and antimony potassium tartrate into deionized water, and uniformly mixing to form an assembly liquid, wherein the concentration of the potassium permanganate in the assembly liquid is 50g/L, the concentration of the citraconic anhydride in the assembly liquid is 7g/L, and the concentration of the antimony potassium tartrate in the assembly liquid is 30 g/L;
immersing the obtained magnesium alloy MgBe LDH base layer into the assembly liquid, immersing for 5 hours at 40 ℃, taking out, washing twice with deionized water, and drying for 2.5 hours in the air at room temperature to finish MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Step [3]Magnesium alloy MgBe-MnO4 -The method comprises the following steps of performing NiMoCeEr electrodeposition on an LDH base layer, wherein the NiMoCeEr electrodeposition specifically comprises the following operations:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 110g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 90 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a base solution, wherein the ceric sulfate concentration, the erbium nitrate concentration and the sodium acetate concentration are respectively 145g/L, 65g/L and 12 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 5:5, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 55 deg.C with current density of 100mA/cm2The deposition time is 30 minutes, so as to obtain MgBe-MnO in the magnesium alloy4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
Example 2
The embodiment 2 of the invention provides a preparation method of a magnesium alloy composite structure layer material, which comprises the following steps:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, bis-trimethylsilyl amino lithium, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate in the synthetic liquid is 160g/L, the concentration of the bis-trimethylsilyl amino lithium is 30g/L, the concentration of the pyridine in the synthetic liquid is 8g/L, and the concentration of the ammonium bicarbonate in the synthetic liquid is 220 g/L;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 120 ℃ under a closed condition, reacting for 12 hours to form a MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using the deionized water, and drying for 5 hours in the air at room temperature, thereby completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2]MnO of magnesium alloy MgBe LDH base layer4 -The anion intercalation assembly specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and antimony potassium tartrate into deionized water, and uniformly mixing to form an assembly liquid, wherein the concentration of the potassium permanganate in the assembly liquid is 55g/L, the concentration of the citraconic anhydride in the assembly liquid is 10g/L, and the concentration of the antimony potassium tartrate in the assembly liquid is 35 g/L;
immersing the obtained magnesium alloy MgBe LDH base layer into the assembly liquid, immersing for 6 hours at 50 ℃, taking out, washing twice with deionized water, drying for 3 hours in the air at room temperature to finish MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Step [3]Magnesium alloy MgBe-MnO4 -The method comprises the following steps of performing NiMoCeEr electrodeposition on an LDH base layer, wherein the NiMoCeEr electrodeposition specifically comprises the following operations:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 120g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 95 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a base solution, wherein the ceric sulfate concentration, the erbium nitrate concentration and the sodium acetate concentration are respectively 150g/L, 70g/L and 15 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 6:4, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 60 deg.C with current density of 150mA/cm2Deposition time of 35 minutes to obtain MgBe-MnO in magnesium alloy4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
Comparative example
The comparative example provides a preparation method of a magnesium alloy composite layer material, which comprises the following steps:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, bis-trimethylsilyl amino lithium, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate, the concentration of the bis-trimethylsilyl amino lithium, the concentration of the pyridine and the concentration of the ammonium bicarbonate are 155g/L, 25g/L, 6g/L and 215g/L respectively;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 110 ℃ under a closed condition, reacting for 10 hours to form a MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using the deionized water, and drying for 4.5 hours in the air at room temperature, thereby completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2] NiMoCeEr electrodeposition on the magnesium alloy MgB LDH base layer, which comprises the following steps:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 110g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 90 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a base solution, wherein the ceric sulfate concentration, the erbium nitrate concentration and the sodium acetate concentration are respectively 145g/L, 65g/L and 12 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 5:5, and uniformly mixing to form an electrodeposition solution;
taking the magnesium alloy MgBe LDH base layer as a cathode and a metal nickel plate as an anode, and carrying out constant-current electrodeposition at the temperature of 55 ℃, wherein the current density is 100mA/cm2And the deposition time is 30 minutes, so that a NiMoCeEr electrodeposition layer is formed on the surface of the magnesium alloy MgBe LDH base layer, and the preparation of the magnesium alloy composite layer material (the magnesium alloy MgBe LDH/NiMoCeEr composite layer) is completed.
To comparatively study the corrosion resistance of comparative example, example 1 and example 2, potentiodynamic polarization curves of comparative example, example 1 and example 2 in a sodium chloride solution having a mass concentration of 3.5% were measured using comparative example, example 1 and example 2 as working electrodes, platinum as auxiliary electrodes, and a saturated calomel electrode as a reference electrode, respectively, and corrosion current densities of comparative example, example 1 and example 2 in a sodium chloride solution having a concentration of 3.5% were calculated by Tafel extrapolation. In addition, the abrasion resistance of the surface layers of comparative example, example 1 and example 2 was measured using a wheel type abrasive wear tester, in which the test pressure was 30N, and the abrasive was 200-mesh SiC abrasive paper, which was reciprocated at a speed of 50 cycles per minute.
Results of corrosion current densities in 3.5% sodium chloride solution of comparative example, example 1 and example 2 are shown in FIG. 2, and the corrosion current densities in 3.5% sodium chloride solution of example 1 and example 2 are 4.31X 10-7A·cm-2And 4.29X 10-7A·cm-2Corrosion current density 15.7X 10, significantly lower than that of comparative example-7A·cm-2。
The results of 500 double abrasion weight loss for comparative example, example 1 and example 2 are shown in fig. 3, and the 500 double abrasion weight loss for example 1 and example 2 are 24.3mg and 23.9mg, respectively, which are significantly lower than 198.7mg for comparative example.
The above results show that: magnesium alloy MgBe-MnO prepared according to the invention4 -The LDH/NiMoCeEr composite structure layer material has excellent corrosion resistance and wear resistance and has wide application prospect in the fields of automobiles, war industry and aviation.
For further detailed illustration, two additional examples are provided below.
Example 3
The preferred embodiment 3 of the present invention provides a method for preparing a magnesium alloy composite structural layer material, comprising the following steps:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, bis-trimethylsilyl amino lithium, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate in the synthetic liquid is 150g/L, the concentration of the bis-trimethylsilyl amino lithium is 20g/L, the concentration of the pyridine in the synthetic liquid is 11g/L, and the concentration of the ammonium bicarbonate in the synthetic liquid is 225 g/L;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 105 ℃ under a closed condition, reacting for 13 hours to form a MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using the deionized water, and drying for 4 hours in the air at room temperature, thereby completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2]MnO of magnesium alloy MgBe LDH base layer4 -The anion intercalation assembly specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and antimony potassium tartrate into deionized water, and uniformly mixing to form an assembly liquid, wherein the concentration of the potassium permanganate in the assembly liquid is 46g/L, the concentration of the citraconic anhydride in the assembly liquid is 12g/L, and the concentration of the antimony potassium tartrate in the assembly liquid is 26 g/L;
immersing the obtained magnesium alloy MgBe LDH base layer into the assembly liquid, immersing for 7 hours at 35 ℃, taking out, cleaning twice with deionized water, and drying for 3.5 hours in the air at room temperature to finish MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Step [3]Magnesium alloy MgBe-MnO4 -The method comprises the following steps of performing NiMoCeEr electrodeposition on an LDH base layer, wherein the NiMoCeEr electrodeposition specifically comprises the following operations:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 105g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 100 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a base solution, wherein the ceric sulfate concentration in the base solution is 140g/L, the erbium nitrate concentration in the base solution is 80g/L and the sodium acetate concentration in the base solution is 12 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 4:3, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 65 deg.C with current density of 80mA/cm2The deposition time is 40 minutes, so as to obtain MgBe-MnO in the magnesium alloy4 -Forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the magnesium alloy composite structural layer materialAnd (4) preparing.
Example 4
The preferred embodiment 4 of the present invention provides a method for preparing a magnesium alloy composite structure layer material, comprising the following steps:
step [1] synthesis of magnesium alloy MgBe LDH, which comprises the following steps:
beryllium nitrate, bis-trimethylsilyl amino lithium, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, wherein the concentration of the beryllium nitrate in the synthetic liquid is 170g/L, the concentration of the bis-trimethylsilyl amino lithium is 35g/L, the concentration of the pyridine in the synthetic liquid is 4.2g/L, and the concentration of the ammonium bicarbonate in the synthetic liquid is 211 g/L;
adding the synthetic solution into a reaction kettle, immersing the magnesium alloy into the synthetic solution, keeping the reaction temperature at 130 ℃ under a closed condition, reacting for 9 hours to form a MgBe LDH base layer on the surface of the magnesium alloy, then washing for five times by using the deionized water, and drying for 6 hours in the air at room temperature, thereby completing the synthesis of the MgBe LDH base layer of the magnesium alloy.
Step [2]MnO of magnesium alloy MgBe LDH base layer4 -The anion intercalation assembly specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and antimony potassium tartrate into deionized water, and uniformly mixing to form an assembly liquid, wherein the concentration of the potassium permanganate in the assembly liquid is 60g/L, the concentration of the citraconic anhydride in the assembly liquid is 5g/L, and the concentration of the antimony potassium tartrate in the assembly liquid is 39 g/L;
immersing the obtained magnesium alloy MgBe LDH base layer into the assembly liquid, immersing for 4 hours at 55 ℃, taking out, washing twice with deionized water, and drying for 2 hours in the air at room temperature to finish the MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
Step [3]Magnesium alloy MgBe-MnO4 -The method comprises the following steps of performing NiMoCeEr electrodeposition on an LDH base layer, wherein the NiMoCeEr electrodeposition specifically comprises the following operations:
adding nickel dimethyl dithiocarbamate and molybdenum hexacarbonyl into diglyme to form an organic nickel-molybdenum solution, wherein the concentration of nickel dimethyl dithiocarbamate in the organic nickel-molybdenum solution is 130g/L, and the concentration of molybdenum hexacarbonyl in the organic nickel-molybdenum solution is 85 g/L;
adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a base solution, wherein the ceric sulfate concentration in the base solution is 160g/L, the erbium nitrate concentration in the base solution is 60g/L and the sodium acetate concentration in the base solution is 19 g/L;
adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 5:6, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 50 deg.C with current density of 200mA/cm2The deposition time is 25 minutes, so as to obtain MgBe-MnO in the magnesium alloy4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
The above embodiments are only preferred embodiments of the present invention, and it should be understood that the above embodiments are only for assisting understanding of the method and the core idea of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The preparation method of the magnesium alloy composite structure layer material is characterized by comprising the following steps of:
step [1] synthesis of magnesium alloy MgBe LDH;
step [2]MnO of magnesium alloy MgBe LDH base layer4 -Anion intercalation assembly;
step [3]Magnesium alloy MgBe-MnO4 -And (3) carrying out NiMoCeEr electrodeposition on the LDH base layer.
2. The method for preparing the magnesium alloy composite structure layer material according to the claim 1, wherein the step [1] specifically comprises the following operations:
beryllium nitrate, lithium bis (trimethylsilyl) amide, pyridine and ammonium bicarbonate are added into deionized water and uniformly mixed to form synthetic liquid, the synthetic liquid is added into a reaction kettle, magnesium alloy is immersed into the synthetic liquid, the reaction temperature is kept at 105 ℃ and 130 ℃ under a closed condition, the reaction lasts for 9-13 hours, then the magnesium alloy is washed for five times by using deionized water and dried in the air at room temperature for 4-6 hours, and the synthesis of the magnesium alloy MgBe LDH base layer is completed.
3. The method for preparing a magnesium alloy composite structural layer material according to claim 2, wherein: the concentration of beryllium nitrate in the synthetic liquid is 150-170g/L, the concentration of lithium bis (trimethylsilyl) amide in the synthetic liquid is 20-35g/L, the concentration of pyridine is 4-12g/L, and the concentration of ammonium bicarbonate is 210-225 g/L.
4. The method for preparing a magnesium alloy composite structural layer material according to claim 1, wherein the step [2] specifically comprises the following operations:
adding potassium permanganate, citraconic anhydride and potassium antimony tartrate into deionized water, mixing uniformly to form an assembly solution, immersing the obtained magnesium alloy MgBe LDH base layer into the assembly solution, immersing at 35-55 ℃ for 4-7 hours, taking out, washing twice with deionized water, drying in the air at room temperature for 2-3.5 hours to complete MnO of the magnesium alloy MgBe LDH base layer4 -Intercalation assembly of anions to form magnesium alloy MgBe-MnO4 -LDH substrate.
5. The method for preparing a magnesium alloy composite structural layer material according to claim 4, wherein the method comprises the following steps: the concentration of potassium permanganate in the assembly liquid is 45-60g/L, the concentration of citraconic anhydride is 5-12g/L, and the concentration of antimony potassium tartrate is 25-40 g/L.
6. The method for preparing a magnesium alloy composite structural layer material according to claim 1, wherein the step [3] specifically comprises the following operations:
adding nickel dimethyldithiocarbamate and molybdenum hexacarbonyl into diglyme to form organic nickel-molybdenum solution; adding ceric sulfate, erbium nitrate and sodium acetate into deionized water to form a basic solution; adding an organic nickel-molybdenum solution into the base solution, wherein the volume ratio of the organic nickel-molybdenum solution to the base solution is 4-7: 3-6, and uniformly mixing to form an electrodeposition solution;
with said magnesium alloy MgBe-MnO4 -LDH base layer as cathode and metal nickel plate as anode, and performing constant current electrodeposition at 50-65 deg.C with current density of 80-200mA/cm2The deposition time is 25-40 minutes, so as to obtain MgBe-MnO in the magnesium alloy4 -And forming a NiMoCeEr electrodeposition layer on the surface of the LDH base layer to finish the preparation of the magnesium alloy composite structure layer material.
7. The method for preparing a magnesium alloy composite structural layer material according to claim 6, wherein: the concentration of the nickel dimethyldithiocarbamate in the organic nickel-molybdenum solution is 130g/L, and the concentration of the molybdenum hexacarbonyl is 85-100 g/L.
8. The method for preparing a magnesium alloy composite structural layer material according to claim 6, wherein: the concentration of ceric sulfate in the basic solution is 160g/L, the concentration of erbium nitrate is 60-80g/L and the concentration of sodium acetate is 10-20 g/L.
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