CN103695871B - The rust inhibition anion intercalation hydrotalcite film that a kind of Mg alloy surface hydrothermal deposition legal system is standby - Google Patents
The rust inhibition anion intercalation hydrotalcite film that a kind of Mg alloy surface hydrothermal deposition legal system is standby Download PDFInfo
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- CN103695871B CN103695871B CN201310368527.5A CN201310368527A CN103695871B CN 103695871 B CN103695871 B CN 103695871B CN 201310368527 A CN201310368527 A CN 201310368527A CN 103695871 B CN103695871 B CN 103695871B
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- hydrotalcite film
- rust inhibition
- colloidal sol
- preparation
- magnesium alloy
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 39
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 39
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 39
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 36
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 31
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000008021 deposition Effects 0.000 title claims abstract description 22
- 150000001450 anions Chemical class 0.000 title claims abstract description 20
- 238000009830 intercalation Methods 0.000 title claims abstract description 13
- 230000002687 intercalation Effects 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- -1 ion sodium salt Chemical class 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 34
- 238000000034 method Methods 0.000 abstract description 14
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229940071182 stannate Drugs 0.000 description 2
- 125000005402 stannate group Chemical group 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- NKSYNYABFPVRNP-UHFFFAOYSA-N aluminium molybdate Chemical compound [Al+3].[Al+3].[O-][Mo]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O NKSYNYABFPVRNP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The present invention proposes a kind of preparation method of rust inhibition anion intercalation hydrotalcite film, which solve the problem of complicated process of preparation in prior art, hydrotalcite film coating adhesion property difference.This preparation method comprises the following steps: a) carry out pretreated step to magnesium alloy sample; B) step of layered di-hydroxyl composite metal oxidate presoma (LDHs colloidal sol) is prepared; C) magnesium alloy sample step a) pre-treatment obtained and the LDHs colloidal sol of step b) are placed in the step that hydrothermal reaction kettle carries out hydrothermal deposition.The thin film layer that the present invention prepares is fine and close, smooth, thickness is even, good with basal body binding force, because hydrotalcite film has the anion intercalated of rust inhibition, inhibition region can be formed at boundary diffusion layer, there is higher corrosion resistance nature, after testing: hydrotalcite film of the present invention soaks 12h in 3.5%NaCl solution, surface is without point corrosion pit.
Description
Technical field
The present invention relates to a kind of method preparing rust inhibition anion intercalation hydrotalcite film, be specifically related to a kind of rust inhibition anion intercalation hydrotalcite film adopting Mg alloy surface hydrothermal deposition legal system standby.
Background technology
Magnesium alloy has that quality is light, specific tenacity is high, hardness is high, good capability of electromagnetic shielding, machinability and thermoforming performance, the features such as good heat conductivility, good biocompatibility, it is the desired matrix of Development of New Generation hitech materials, therefore, magnesium alloy has important using value and wide application prospect in fields such as automobile, electronics, aerospace, defence and military, bio-medicals, is called as 21 century " green engineering material ".Along with the development of the process for processing technology of magnesium and constantly perfect, magnesium alloy materials oneself through becoming the third-largest structural metallic engineering material after iron and steel, aluminium alloy, in worldwide, obtain swift and violent development.
At present, mainly contain for the surface treatment method improving corrosion resistance of magnesium alloy energy: chemical conversion embrane method (comprises chromic salt, stannate.Phosphoric acid salt etc.), anonizing, electrochemical plating, organic coating method etc.In chromate conversion coating, hexavalent chromium has severe toxicity, causes environmental pollution; Stannate, phosphate conversion film sample pretreatment process are complicated, have pollution to water and soil; Anodic oxidation equipment requirements is high, and power consumption is large; Electrochemical plating are poisonous, and difficult treatment.
In sum, existing method ubiquity the problems such as process costs is high, complex process, coating adhesion property difference.Therefore, along with the increase day by day of magnesium alloy user demand, develop a kind of environmental protection, process for treating surface that is simple to operate, favorable anti-corrosion effect is extremely urgent.
Summary of the invention
In order to solve problems of the prior art, the present invention proposes a kind of method of the rust inhibition anion intercalation hydrotalcite film adopting Mg alloy surface hydrothermal deposition to prepare, the method technique is simple, easy and simple to handle, synthesis condition is gentle, effectively improve the corrosion resistance nature of magnesium alloy.
One of task of the present invention is the preparation method providing a kind of rust inhibition anion intercalation hydrotalcite film, and described preparation method comprises the following steps:
A) pretreated step is carried out to magnesium alloy sample;
B) step of layered di-hydroxyl composite metal oxidate presoma is prepared;
C) magnesium alloy sample step a) pre-treatment obtained and the layered di-hydroxyl composite metal oxidate presoma of step b) are placed in the step that hydrothermal reaction kettle carries out hydrothermal deposition.
Further, above-mentioned steps b) in layered di-hydroxyl composite metal oxidate presoma be LDHs colloidal sol, the preparation of LDHs colloidal sol comprises the following steps:
D) by soluble divalent metal salt AY
2with soluble trivalent metal salt BY
3be dissolved in deionized water according to the ratio 2: 1 of amount, be mixed with 0.02 ~ 0.2mol/LAY
2with 0.01 ~ 0.1mol/LBY
3mixing solutions, mixing solutions is placed in there-necked flask stir, be heated to 60 ~ 80 DEG C;
E) NaOH and the rust inhibition negatively charged ion sodium salt that take certain amount are dissolved in the deionized water of step d) equivalent, at N
2it slowly added in there-necked flask described in step d) under protection, regulate pH to be 9 ~ 10, temperature remains on 60 ~ 80 DEG C, heated and stirred 72h, ageing 12h, obtained LDHs colloidal sol.
Further, above-mentioned steps c) step of hydrothermal deposition comprises:
Magnesium alloy sample pre-treatment obtained and LDHs colloidal sol are placed in hydrothermal reaction kettle, wherein, LDHs colloidal sol compactedness is 70%, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is 120 ~ 160 DEG C, soaking time is 12 ~ 72h, obtains rust inhibition anion intercalation hydrotalcite film.
Above-mentioned soluble divalent metal salt AY
2for Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, MgCl
2, CoCl
2, NiCl
2or ZnCl
2; Described soluble trivalent metal salt BY
3for Al (NO
3)
3, Fe (NO
3)
3, Cr (NO
3)
3, Ce (NO
3)
3, Ti (NO
3)
3, AlCl
3, FeCl
3, CrCl
3, CeCl
3or TiCl
3.
Above-mentioned steps e) in NaOH amount of substance be AY
23.25 times of amount of substance; Rust inhibition negatively charged ion sodium salt amount of substance is BY
32 times of amount of substance.
The hydrotalcite film that a kind of rust inhibition that two of task of the present invention is to provide a kind of above-mentioned preparation method to obtain is anion intercalated: this hydrotalcite film chemical general formula is:
[A
1-x，B
x(OH)
2]
x+(M)
n- x/2·mH
2O，
Wherein, A is divalent-metal ion: Mg
2+, Co
2+, Ni
2+or Zn
2+in one;
B is trivalent metal ion: Al
3+, Fe
3+, Cr
3+, Ce
3+or Ti
3+in one;
(M)
n-for having the negatively charged ion of rust inhibition: vanadic acid root, molybdate, wolframate radical, chromate, phosphate radical.
Above-mentioned hydrotalcite film soaks 12h in 3.5%NaCl solution, and surface is without point corrosion pit.
The Advantageous Effects that the present invention brings:
Compared with prior art, hydrotalcite film of the present invention has the anion intercalated of rust inhibition, can form inhibition region, have higher corrosion resistance nature at boundary diffusion layer; Thin film layer is made up of hydrotalcite, it is a kind of inorganic functional material with special laminate structure, interlayer anion has interchangeability, the film of multi-functional supermolecular intercalation structure can be obtained, and make rete have self-healing characteristics, the solidity to corrosion of magnesium alloy and the combination with organic coating will be improved further.
Raw material of the present invention is easy to get, with low cost, do not use any toxic substance, whole preparation process environmental protection, and technique is simple, is suitable for suitability for industrialized production.
The rete that the present invention prepares is fine and close, smooth, thickness even, good with basal body binding force.Hydrotalcite film of the present invention soaks 12h in 3.5%NaCl solution, and surface, without point corrosion pit, has stronger erosion resistance.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and embodiment, the present invention will be further described:
Fig. 1 is MgAl-MoO in the embodiment of the present invention 1
4 2--LDHs polarization curve;
Fig. 2 is ZnAl-MoO in the embodiment of the present invention 4
4 2-the XRD of-LDHs film;
Fig. 3 is from the MgAl-MoO that magnesium parts scrape off in the embodiment of the present invention 1
4 2the FT-IR of-LDHs powder.
Embodiment
Raw materials used all the purchase by commercial channel of following the present invention obtains.
The present invention, a kind of preparation method of rust inhibition anion intercalation hydrotalcite film, it comprises the following steps:
Step 1, pre-treatment is carried out to magnesium alloy print:
First magnesium alloy plate sand papering is carried out oil removal treatment in minute surface to surperficial in alkali lye, clean with deionized water rinsing, clean 10min with ultrasonic cleaner in acetone, then be placed in deionized water for ultrasonic cleaning 10min, cold wind dries up, for subsequent use.
The preparation of step 2, LDHs colloidal sol:
(1) by soluble divalent metal salt AY
2with soluble trivalent metal salt BY
3be dissolved in deionized water according to the ratio 2: 1 of amount, be mixed with the AY of 0.02 ~ 0.2mol/L
2with 0.01 ~ 0.1mol/LBY
3mixing solutions, mixing solutions is placed in there-necked flask and stirs, be heated to 60 ~ 80 DEG C;
(2) NaOH and the rust inhibition negatively charged ion sodium salt that take certain amount are dissolved in the deionized water of above-mentioned steps (1) equivalent, at N
2it slowly added under protection in the there-necked flask of above-mentioned steps (1), regulate pH to be 9 ~ 10, temperature remains on 60 ~ 80 DEG C, heated and stirred 72h, ageing 12h, obtained LDHs colloidal sol; Above-mentioned soluble divalent metal salt AY
2for Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, MgCl
2, CoCl
2, NiCl
2or ZnCl
2; Described soluble trivalent metal salt BY
3for Al (NO
3)
3, Fe (NO
3)
3, Cr (NO
3)
3, Ce (NO
3)
3, Ti (NO
3)
3, AlCl
3, FeCl
3, CrCl
3, CeCl
3or TiCl
3.
The step of step 3, magnesium alloy sample and LDHs colloidal sol hydrothermal deposition:
Magnesium alloy sample pre-treatment obtained and LDHs colloidal sol are placed in hydrothermal reaction kettle, wherein, LDHs colloidal sol compactedness is 70%, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is 120 ~ 160 DEG C, time is 12 ~ 72h, obtains rust inhibition anion intercalation hydrotalcite film.
Below in conjunction with specific embodiment, the present invention is described in further details:
Embodiment 1:
The pre-treatment of step 1, magnesium alloy print:
Be first that 20mm × 20mm × 3mm diecast magnesium alloy AZ31 print sand papering is extremely surperficial in minute surface by specification, oil removal treatment is carried out in alkali lye, clean with deionized water rinsing, 10min is cleaned in acetone with ultrasonic cleaner, be placed in deionized water for ultrasonic cleaning 10min again, cold wind dries up, for subsequent use.
Step 2, magnalium molybdate LDHs(MgAl-MoO
4 2--LDHs) preparation of colloidal sol:
(1) 0.04molMg (NO is taken
3)
26H
2o and 0.02molAl (NO
3)
39H
2o, adding 150mL deionized water is solvent, and wiring solution-forming, is placed in there-necked flask, is heated with stirring to 80 DEG C;
(2) 0.13molNaOH and 0.04molNa is taken
2moO
42H
2o is dissolved in 150mL deionized water, mixes, at N
2slowly add in there-necked flask under protection, regulate pH to be 10, keep 80 DEG C of heating, and with agitator Keep agitation 72h, ageing 12h.
The step of step 3, magnesium alloy sample and above-mentioned LDHs colloidal sol hydrothermal deposition:
The magnesium alloy print handled well and above-mentioned 70mLLDHs colloidal sol are placed in the hydrothermal reaction kettle that specification is 100mL, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is set to 120 DEG C, takes out, obtain even compact hydrotalcite film after insulation 48h.
Shown in composition graphs 1, Fig. 1 is the present embodiment MgAl-MoO
4 2--LDHs polarization curve, the hydrotalcite film that the present embodiment prepares is weak golden, and smooth surface is fine and close, in 3.5%NaCl solution, soak 12h, and surface is without point corrosion pit.
As shown in Figure 3, Fig. 3 is from the MgAl-MoO that magnesium parts scrape off in the present embodiment
4 2the FT-IR of-LDHs powder, wherein, 832cm
-1place is the characteristic peak of molybdate.
Embodiment 2:
Step 1 is identical with embodiment 1 step 1, and difference from Example 1 is:
Step 2, magnalium wolframate radical LDHs(MgAl-WoO
4 2--LDHs) preparation of colloidal sol:
(1) Mg (NO of 0.04mol is taken
3)
26H
2al (the NO of O and 0.02mol
3)
39H
2o, adding 150mL deionized water is solvent, and wiring solution-forming, is placed in there-necked flask, is heated with stirring to 70 DEG C;
(2) 0.13molNaOH and 0.04molNa is taken
2woO
42H
2o is dissolved in 150mL deionized water, mixes, at N
2slowly add in there-necked flask under protection, regulate pH to be 9, keep 70 DEG C of heating, and with agitator Keep agitation 72h, ageing 12h.
The step of step 3, magnesium alloy sample and above-mentioned LDHs colloidal sol hydrothermal deposition:
The magnesium alloy print handled well and above-mentioned 70mLLDHs colloidal sol are placed in the hydrothermal reaction kettle that specification is 100mL, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is set to 160 DEG C, takes out, obtain even compact hydrotalcite film after insulation 12h.
The hydrotalcite film that the present embodiment prepares is canescence, and smooth surface is fine and close, in 3.5%NaCl solution, soak 12h, and surface is without point corrosion pit.
Embodiment 3:
Step 1 is identical with embodiment 1 step 1, and difference from Example 1 is:
Step 2, nickel-aluminum-molybdenum acid group LDHs(NiAl-MoO
4 2--LDHs) preparation of colloidal sol:
(1) 0.04molNi (NO is taken
3)
26H
2o and 0.02molAl (NO
3)
39H
2o, adding 150mL deionized water is solvent, and wiring solution-forming, is placed in there-necked flask, is heated with stirring to 60 DEG C;
(2) 0.13molNaOH and 0.04molNa is taken
2moO
42H
2o is dissolved in 150mL deionized water, mixes, at N
2slowly add in there-necked flask under protection, regulate pH to be 9.5, keep 60 DEG C of heating, and with agitator Keep agitation 72h, ageing 12h.
The step of step 3, magnesium alloy sample and above-mentioned LDHs colloidal sol hydrothermal deposition:
The magnesium alloy print handled well and above-mentioned 70mLLDHs colloidal sol are placed in the hydrothermal reaction kettle that specification is 100mL, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is set to 140 DEG C, takes out, obtain even compact hydrotalcite film after insulation 48h.
In the present embodiment, hydrotalcite film is weak golden, and smooth surface is fine and close, in 3.5%NaCl solution, soak 12h, and surface is without point corrosion pit.
Embodiment 4:
Step 1 is identical with embodiment 1 step 1, and difference from Example 1 is:
Step 2, zinc-aluminium molybdate LDHs(ZnAl-MoO
4 2--LDHs) preparation of colloidal sol:
(1) 0.04molZn (NO is taken
3)
26H
2o and 0.02molAl (NO
3)
39H
2o, adding 150mL deionized water is solvent, and wiring solution-forming, is placed in there-necked flask, is heated with stirring to 80 DEG C;
(2) 0.13molNaOH and 0.04molNa is taken
2moO
42H
2o is dissolved in 150mL deionized water, mixes, at N
2slowly add in there-necked flask under protection, regulate pH to be 9, keep 80 DEG C of heating, and with agitator Keep agitation 72h, ageing 12h.
The step of step 3, magnesium alloy sample and above-mentioned LDHs colloidal sol hydrothermal deposition:
The magnesium alloy print handled well and above-mentioned 70mLLDHs colloidal sol are placed in the hydrothermal reaction kettle that specification is 100mL, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is set to 125 DEG C, takes out, obtain even compact hydrotalcite film after insulation 48h.
Shown in composition graphs 2, Fig. 2 is ZnAl-MoO in the embodiment of the present invention 4
4 2-the XRD of-LDHs film.The hydrotalcite film that the present embodiment prepares is weak golden, and smooth surface is fine and close, in 3.5%NaCl solution, soak 12h, and surface is without point corrosion pit.
Embodiment 5:
Step 1 is identical with embodiment 1 step 1, and difference from Example 1 is:
Step 2, cobalt aluminium molybdate LDHs(CoAl-MoO
4 2--LDHs) preparation of colloidal sol:
(1) 0.04molCo (NO is taken
3)
26H
2o and 0.02molAl (NO
3)
39H
2o, adding 150mL deionized water is solvent, and wiring solution-forming, is placed in there-necked flask, is heated with stirring to 80 DEG C;
(2) 0.13molNaOH and 0.04molNa is taken
2moO
42H
2o is dissolved in 150mL deionized water, mixes, at N
2slowly add in there-necked flask under protection, regulate pH to be 10, keep 80 DEG C of heating, and with agitator Keep agitation 72h, ageing 12h.
The step of step 3, magnesium alloy sample and above-mentioned LDHs colloidal sol hydrothermal deposition:
The magnesium alloy print handled well and above-mentioned 70mLLDHs colloidal sol are placed in the hydrothermal reaction kettle that specification is 100mL, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is set to 125 DEG C, takes out, obtain even compact hydrotalcite film after insulation 48h.
The hydrotalcite film that the present embodiment prepares is in dark golden, and smooth surface is fine and close, in 3.5%NaCl solution, soak 12h, and surface is without point corrosion pit.
The hydrotalcite film that above-described embodiment 1,2,3,4,5 prepares, its chemical general formula is:
[A
1-x，B
x(OH)
2]
x+(M)
n- x/2·mH
2O，
Wherein, A is divalent-metal ion: Mg
2+, Co
2+, Ni
2+or Zn
2+in one;
B is trivalent metal ion: Al
3+, Fe
3+, Cr
3+, Ce
3+or Ti
3+in one;
(M)
n-for having the negatively charged ion of rust inhibition: vanadic acid root, molybdate, wolframate radical, chromate or phosphate radical.
The present invention prepares even, fine and close by hydrothermal deposition method at Mg alloy surface and has the anion intercalated hydrotalcite film of rust inhibition, because hydrotalcite film has the anion intercalated of rust inhibition, inhibition region can be formed at boundary diffusion layer, there is higher corrosion resistance nature, after testing, hydrotalcite film of the present invention soaks 12h in 3.5%NaCl solution, and surface is without point corrosion pit.
Above-described embodiment only lists the negatively charged ion of part divalent metal salt, part trivalent metal salt and part rust inhibition; but the present invention is not limited only to above-described embodiment, what those skilled in the art can obviously learn under enlightenment of the present invention all belongs within scope.
Claims (5)
1. a preparation method for rust inhibition anion intercalation hydrotalcite film, described preparation method comprises the following steps:
A) pretreated step is carried out to magnesium alloy sample;
B) prepare the step of layered di-hydroxyl composite metal oxidate presoma, layered di-hydroxyl composite metal oxidate presoma is LDHs colloidal sol, and the preparation of described LDHs colloidal sol comprises the following steps:
B
1, by soluble divalent metal salt AY
2with soluble trivalent metal salt BY
3be dissolved in deionized water according to the ratio 2:1 of amount of substance, be mixed with 0.02 ~ 0.2mol/LAY
2with 0.01 ~ 0.1mol/LBY
3mixing solutions, mixing solutions is placed in there-necked flask stir, be heated to 60 ~ 80 DEG C;
B
2, take the NaOH of certain amount of substance and rust inhibition negatively charged ion sodium salt is dissolved in the deionized water of equivalent, at N
2it slowly added in there-necked flask under protection, regulate pH to be 9 ~ 10, temperature remains on 60 ~ 80 DEG C, heated and stirred 72h, ageing 12h, obtained LDHs colloidal sol;
C) by step a) the magnesium alloy sample that obtains of pre-treatment and step b) layered di-hydroxyl composite metal oxidate presoma be placed in the step that hydrothermal reaction kettle carries out hydrothermal deposition, its concrete steps comprise: magnesium alloy sample pre-treatment obtained and LDHs colloidal sol are placed in hydrothermal reaction kettle, wherein, LDHs colloidal sol compactedness is 70%, afterwards hydrothermal reaction kettle is put into loft drier and carry out hydrothermal deposition, temperature is 120 ~ 160 DEG C, time is 12 ~ 72h, obtains rust inhibition anion intercalation hydrotalcite film.
2. preparation method according to claim 1, is characterized in that: described soluble divalent metal salt is Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Zn (NO
3)
2, MgCl
2, CoCl
2, NiCl
2or ZnCl
2; Described soluble trivalent metal salt is Al (NO
3)
3, Fe (NO
3)
3, Cr (NO
3)
3, Ce (NO
3)
3, Ti (NO
3)
3, AlCl
3, FeCl
3, CrCl
3, CeCl
3or TiCl
3.
3. preparation method according to claim 2, is characterized in that: described step b) in NaOH amount of substance be AY
23.25 times of amount of substance; Described rust inhibition negatively charged ion sodium salt amount of substance is BY
32 times of amount of substance.
4. the hydrotalcite film that a kind of rust inhibition prepared as any one of claims 1 to 3 is anion intercalated, is characterized in that: described hydrotalcite film chemical general formula is:
[A
1-x，B
x(OH)
2]
x+(M)
n- x/2·mH
2O，
Wherein, A is divalent-metal ion: Mg
2+, Co
2+, Ni
2+or Zn
2+in one;
B is trivalent metal ion: Al
3+, Fe
3+, Cr
3+, Ce
3+or Ti
3+in one;
(M)
n-for having the negatively charged ion of rust inhibition: vanadic acid root, molybdate, wolframate radical, chromate, phosphate radical.
5. the hydrotalcite film that a kind of rust inhibition according to claim 4 is anion intercalated, is characterized in that: described hydrotalcite film soaks 12h in 3.5%NaCl solution, and surface is without point corrosion pit.
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| CN106283017B (en) * | 2016-09-07 | 2018-09-25 | 南京工程学院 | Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg-Sn houghite composite membranes and preparation method thereof |
| CN106567062B (en) * | 2016-10-20 | 2019-03-19 | 中国科学院上海硅酸盐研究所 | With modified magnesium alloy materials in the surface of good corrosion and biocompatibility and its preparation method and application |
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| CN110158095B (en) * | 2019-06-28 | 2021-11-30 | 辽宁工业大学 | Preparation method of zinc-coated steel surface LDH |
| CN111348666A (en) * | 2020-03-26 | 2020-06-30 | 中国船舶重工集团公司第七二五研究所 | Preparation method of corrosion inhibitor composite anion intercalation hydrotalcite |
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| CN113549913A (en) * | 2021-07-22 | 2021-10-26 | 重庆大学 | Preparation method and application of ternary MgAlLa-LDHs film layer on surface of magnesium alloy |
| CN116535884B (en) * | 2023-05-26 | 2024-02-20 | 西安科技大学 | Compact corrosion-resistant wear-resistant SWF/LDHs composite coating on magnesium-lithium alloy surface and preparation method thereof |
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