CN106283017A - Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof - Google Patents
Magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof Download PDFInfo
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- CN106283017A CN106283017A CN201610809077.2A CN201610809077A CN106283017A CN 106283017 A CN106283017 A CN 106283017A CN 201610809077 A CN201610809077 A CN 201610809077A CN 106283017 A CN106283017 A CN 106283017A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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Abstract
The present invention discloses a kind of magnesium and Mg alloy surface has the Mg (OH) of intercalation configuration2/ Mg Sn houghite composite membrane and preparation method thereof, relates to magnesium and Mg alloy surface technical field, its objective is to improve magnesium and the corrosion resistance of magnesium alloy, widens the application prospect in the fields such as bio-medical.Preparation method comprises the following steps: S1, magnesium and magnesium alloy are carried out pretreatment；S2, pre-treatment, prepare Sn4+Saline solution, regulates pH to 4.0, prepares pretreatment solution, magnesium and magnesium alloy is placed in and is continually fed into CO2Pretreatment solution, it is thus achieved that precursor film；S3, post processing, be immersed in Na by the magnesium and magnesium alloy that are covered with precursor film2CO3In solution, magnesium and Mg alloy surface growth Mg (OH)2/ Mg Sn houghite composite membrane；S4, follow-up cleaning.The present invention uses two-step method not contain aluminum at magnesium and Mg alloy surface in-situ preparation, have the Mg (OH) of biological safety2/ Mg Sn houghite composite membrane, improves magnesium and the corrosion resistance of magnesium alloy, widens the application in Biological magnesium alloy surfacecti proteon of the houghite film.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of magnesium and Mg alloy surface growth in situ has intercalation
The Mg (OH) of structure2The preparation method of/Mg-Sn houghite composite membrane.
Background technology
Magnesium is the macroelement of needed by human, and its density and elastic modelling quantity are close with people's skeleton, and it is high, raw to have specific strength
Thing compatibility feature good, biodegradable, it is possible to be prevented effectively from " stress shielding " effect and second operation brings to patient
Misery and financial burden, be expected to substitute traditional bio-inert material, becomes a new generation's degradable orthopedic implanting material, is described as
" revolutionary metallic biomaterial ".Owing to magnesium and magnesium alloy chemical character are relatively active, be easily corroded in fluid environment fall
Solving, corrosion product is loose porous effectively cannot be protected magnesium and magnesium alloy；Magnesium and the premature failure of magnesium alloy implant, it will make
Bone healing failure, and then do not reach the requirement of clinical treatment.
Chemical conversion treatment is to immerse magnesium alloy to make its surface that chemical reaction occurs in certain particular solution, forms one layer
Insoluble compound film layer, film layer is not affected by Korrosionsmedium as barrier layer, protection matrix.Its essence is at magnesium and magnesium
Alloy surface reaction generates one layer of densification, uniform corrosion product barrier layer.Mg(OH)2It is magnesium and magnesium alloy typically corrodes product
Thing, cannot form height crystallization, fine and close film layer structure, and chemical conversion treatment is most of round Mg in fluid environment
(OH)2Film layer is compound, structure optimization, and then by corrosion product densification, provide effective protection to magnesium and magnesium alloy.Tradition
Chemical conversion treatment waste liquid in there is heavy metal ion, phosphate radical, fluorion etc. and pollute the material of environment, institute in conversion film layer
Health will be caused mortality to injure after entering human body by these ions carried.Therefore, use environmental friendliness and there is human body peace
Full property and good biological corrosion proof novel surface means of defence, improve corrosion resisting property and the homogeneous corrosion side of Biological magnesium alloy
Formula, is the key promoting Biological magnesium alloy clinical practice, has important theory significance and construction value.
Based on CO2Water soluble characteristic Mg alloy surface by in-situ chemical reaction formed hydrotalcite film (Layered
Double Hydroxides, LDH) preparation technology cleaning, environmental protection.Hydrotalcite intercalation structure and shepardite Mg (OH)2Structure phase
With, introducing portion+trivalent or+4 valencys ion substitution Mg (OH) in layer structure main body2Mg2+, introduce CO at interlayer3 2-To protect
Hold whole system charge balance, and then obtain constitutionally stable film layer.The kind of hydrotalcite layers anion is in relative broad range
Can modulation, corrosivity anion in environment can with interlayer anion exchange and be trapped within hydrotalcite layers, it is to avoid and base
Body directly contacts, thus plays the effect slowing down corrosion, and the characteristic such as hydrophobicity adding its surface makes it have at corrosion field
Potential application prospect.
Chinese patent literature CN 201110057831 discloses a kind of Mg alloy surface growth in situ Mg-Al hydrotalcite film
Film forming solution and application, but Mg-Al hydrotalcite film contains cytotoxicity element aluminum.Aluminum is at people's body accumulation and produces slow
Property toxicity (including neurotoxicity, skeleton toxicity etc.), has the risk causing senile dementia.Aluminum not only stops the calcium of bone simultaneously
Change, also suppress the formation of bone, produce aluminum and cause osteomalacia.Therefore, magnesium aluminum-hydrotalcite film is not suitable for the surface modification of medical magnesium alloy.
S.Velu is by Mg (NO3)3、Al(NO3)3、SnCl2、NaOH、Na2CO3Solution blending, is prepared for magnesium with co-electrodeposition method
Stannum houghite powder body [Velu S, Suzuki K, Osaki T, et al.Synthesis of new Sn incorporated
layered double hydroxides and their evolution to mixed oxides[J].Materials
Research Bulletin,1999,34(10):1707-1717.].Tin ion in human body in there is enhancing development, shadow
Ring hemoglobin function and promote effect of wound healing.Therefore, magnesium stannum houghite has good human safety, but is total to
Mg-Sn houghite powder body prepared by sedimentation is not used to magnesium alloy protection.
Based on Mg (OH)2Stable existence in fluid environment, in conjunction with intercalation configuration optimization, compound Mg-Sn houghite film
Densification, by chemical conversion treatment, at magnesium and Mg alloy surface in-situ preparation Mg (OH)2/ Mg-Sn houghite film, exploitation
There is human safety and the corrosion proof novel Mg of good biological (OH)2/ Mg-Sn houghite composite membrane, is to widen biological magnesium
The research direction of alloy promise application.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of magnesium and Mg alloy surface has intercalation configuration
Mg(OH)2The preparation method of/Mg-Sn houghite composite membrane.The present invention can improve the corrosion resistance of magnesium and magnesium alloy, and multiple
Close film elemental composition and meet biological safety principle, provide new way for houghite film in the application of Biological magnesium alloy, tool
There is the meaning of initiative.
For achieving the above object, present invention employs techniques below scheme:
A kind of magnesium and Mg alloy surface growth in situ have the Mg (OH) of intercalation configuration2/ Mg-Sn houghite composite membrane
Preparation method, comprises the steps:
S1, magnesium and magnesium alloy pretreatment: magnesium and magnesium alloy are successively carried out mechanical grinding, ethanol ultrasonic cleaning, ultrasonic goes
Ionized water cleans；
S2, magnesium and magnesium alloy sample are carried out pre-treatment: the first tin ion saline solution of preparation 0.01～0.04mol/L,
And regulate pH to 3.8～5.0, prepare pretreatment solution, magnesium and the magnesium alloy through pretreatment is placed in and is continually fed into CO2Before
Processing in solution 0.5～3h, pre-treatment temperature is 20～50 DEG C, it is thus achieved that be covered with magnesium and the magnesium alloy of precursor film；
S3, the magnesium and magnesium alloy being covered with precursor film is carried out post processing: the sample that step S2 prepares is placed in 50～80
DEG C containing CO3 2-, pH be 8.5～13 post-treatment solution in soak 12～48h, thus magnesium and Mg alloy surface have intercalation
The Mg (OH) of structure2/ Mg-Sn houghite composite membrane；
S4, follow-up cleaning: use the sample that deionized water ultrasonic cleaning step S3 processes, then sample cold wind is dried up or oneself
So air-dry.
Preferably, in step S1, described magnesium and magnesium alloy are pure magnesium or the magnesium alloy that bio-medical does not contains Al, including Mg-
Zn system, Mg-RE system, Mg-Ca system, Mg-Sn system, Mg-Mn system alloy and pure magnesium.
Preferably, in step S2, described tin ion saline solution is SnCl4Or Sn (SO4)2。
Preferably, in step S2, described tin ion saline solution by the NaOH/KOH of alkaline solution 0～2mol/L with
The Na of 0.5～1mol/L2CO3/NaHCO3/K2CO3/KHCO3Mixed solution, regulate the pH value of pretreatment solution.
Preferably, in step S3, described post-treatment solution is the Na of 0.5～1mol/L2CO3/NaHCO3/K2CO3/
KHCO3Solution or unsaturated carbonate solution, and with 0～2mol/L NaOH/KOH solution regulate pH be 8.5～13.
Preferably, in step S2 and S3, the ratio of the surface area of described sample and treatment fluid volume is all 1:20's～1:60
In the range of.
Present invention also offers the brucite composite membrane obtained according to above-mentioned preparation method, described Mg-Sn houghite
Chemical formula is Mg6Sn2(OH)16(CO3)2·yH2O, wherein Sn is+4 valencys, and y is 1,2 or 3.
The beneficial effects of the present invention is:
1) present invention prepares the Mg (OH) with intercalation configuration at magnesium and Mg alloy surface2/ Mg-Sn houghite composite membrane
Being that magnesium alloy substrate directly participates in film formation reaction and generated in-situ, in pretreatment process, precursor film introduces tin element, locates afterwards
Utilizing high pH environment to promote film layer height crystallization during reason, in precursor film, Sn element participates in building layer structure main body,
CO3 2-Entering interlayer balancing charge, film layer tends to fine and close, uniform, Stability Analysis of Structures.Film layer and matrix are chemical bond, adhesion
Good, overcome the Mg (OH) of loose and porous structure in Mg-Sn houghite powder prepared by co-electrodeposition method2It is not used to magnesium and magnesium closes
The problem of gold protection.
2) membranous layer ingredient that the present invention prepares is houghite (Mg6Sn2(OH)16(CO3)2·yH2O, y=1,2,3)
With Mg (OH)2, this inorganic functional material with intercalation configuration, Mg (OH)2Stability Analysis of Structures, dense uniform, Mg-Sn class neatly
Stone interlayer anion has interchangeability, the thin film of available multi-functional supermolecular intercalation structure, and makes film layer have self-healing
Characteristic, it is possible to improve the corrosion resistance of magnesium alloy further.
3) present invention is at magnesium and Mg alloy surface growth in situ Mg (OH)2/ Mg-Sn houghite composite membrane, film layer element
There is biological safety, it is to avoid aluminum ions introducing and Mg (OH) in Mg-Al hydrotalcite film preparation process in original technology2Film
The shortcoming of layer corrosion resistance difference；In original technology, in hydrotalcite film, its layer structure main body is+trivalent ion, uses Sn in the present invention4+
Ion substitution Mg (OH)2In Mg2+Build Mg (OH)2/ Mg-Sn houghite composite membrane, tin ion is the trace unit in human body
Element, tin element in human body in play enhancing development, affect hemoglobin function and promote wound healing effect, for reality
Existing film layer medical functionization provides theoretical direction.
4) abundant raw material source of the present invention, with low cost, preparation process environmental protection, and technique are simple, are suitable for industrialization
Produce.
Accompanying drawing explanation
Fig. 1 is Mg (OH) in the embodiment of the present invention 12The XRD figure spectrum of/Mg-Sn houghite composite membrane.
Fig. 2 is Mg (OH) in the embodiment of the present invention 12The SEM photograph of/Mg-Sn houghite composite membrane.
Fig. 3 is Mg (OH) in the embodiment of the present invention 12The polarization curve of/Mg-Sn houghite composite membrane.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the present invention is clearly and completely retouched
State.Following example are only used for clearly illustrating technical scheme, and can not limit the guarantor of the present invention with this
Protect scope.
A kind of magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2The preparation side of/Mg-Sn houghite composite membrane
Method, comprises the steps:
S1, magnesium and magnesium alloy sample are carried out pretreatment: include polishing, clean.Use 400,800 and 1000 purposes successively
Abrasive paper for metallograph carries out mechanical grinding, then by the magnesium after polishing and magnesium alloy sample in dehydrated alcohol ultrasonic cleaning 5～
10min, then it is placed in ultrasonic cleaning 5～10min in deionized water；It is suitable for using the magnesium of this PROCESS FOR TREATMENT and magnesium alloy to include Mg-
Zn system, Mg-RE system, Mg-Ca system, Mg-Sn system, Mg-Mn system alloy and pure magnesium；
S2, pretreated sample is carried out pre-treatment: preparation 0.01～0.04mol/L tin ion saline solution, wherein, stannum
Ion salt solution is SnCl4Or Sn (SO4)2, and with 0～2mol/L NaOH/KOH and 0.5～1mol/L Na2CO3/NaHCO3/
K2CO3/KHCO3Mixed solution regulation pH to 3.8～5.0, prepare pretreatment solution；Magnesium alloy surface area of sample and treatment fluid
The ratio of volume is 1:20～1:60；Magnesium and magnesium alloy sample are placed in and are continually fed into CO2Pretreatment solution in soak 0.5～
3h, treatment temperature is 20～50 DEG C, grows precursor film at sample surfaces；
S3, the sample after pre-treatment is carried out post processing: preparation 0.5～1mol/L Na2CO3/NaHCO3/K2CO3/KHCO3
Solution or unsaturated carbonate solution, and with 0～2mol/L NaOH/KOH solution regulate pH be 8.5～13, prepare post processing molten
Liquid；Magnesium alloy surface area of sample is 1:20～1:60 with the ratio for the treatment of fluid volume.Sample after pre-treatment is placed in post processing molten
Soaking 12～48h in liquid, treatment temperature is 50～80 DEG C, at sample surfaces growth Mg (OH)2/ Mg-Sn houghite film.
S4, post processing sample is carried out: sample is placed in ultrasonic cleaning 5～10min in deionized water, then by sample
Cold wind dries up or natural air drying.
Use the present invention at magnesium and Mg alloy surface growth in situ Mg (OH)2/ Mg-Sn houghite composite membrane, it converts
Film be mainly composed of Mg6Sn2(OH)16(CO3)2·yH2O (y=1,2,3) and Mg (OH)2, it is possible to magnesium and magnesium alloy are played bright
Aobvious protective action.
Embodiment 1
The present embodiment magnesium and magnesium alloy sample use pure magnesium.
S1, magnesium and magnesium alloy sample are carried out pretreatment: include polishing, clean.Use 400,800 and 1000 purposes successively
Abrasive paper for metallograph carries out mechanical grinding to pure magnesium, then by the pure magnesium sample ultrasonic cleaning 5min in dehydrated alcohol after polishing, then
It is placed in ultrasonic cleaning 5min in ionized water.
S2, pretreated sample is carried out pre-treatment: the SnCl of preparation 0.02mol/L4Solution, and use 1mol/L
NaOH Yu 0.5mol/L Na2CO3Mixed solution regulation pH to 3.8, prepare pretreatment solution.Pure magnesium sample is placed in and persistently leads to
Enter CO2Pretreatment solution in soak 1h, treatment temperature is 25 DEG C, and surface area of sample is 1:40 with the ratio of pretreatment liquid volume,
Precursor film is grown at sample surfaces.
S3, the sample after pre-treatment is carried out post processing: preparation 0.5mol/L Na2CO3Solution, through NaOH regulation pH be
12, prepare post-treatment solution.Sample after pre-treatment is placed in post-treatment solution immersion 24h, and treatment temperature is 60 DEG C, sample
Surface area is 1:40 with the ratio of aftertreatment fluid volume, at sample surfaces growth Mg (OH)2/ Mg-Sn houghite composite membrane.
S4, post processing sample is carried out: sample is placed in ultrasonic cleaning 5min in deionized water, then by sample cold wind
Dry up or natural air drying.
Embodiment 2
With embodiment 1, except that: the present embodiment uses Mg-2Zn magnesium alloy (i.e. the magnesium alloy containing 2wt%Zn)；Step
Rapid S2 prepares 0.01mol/L Sn (SO4)2Solution, and with 1mol/L NaOH and 1mol/L Na2CO3Mixed solution regulation pH
To 5.0, prepare pretreatment solution；Pre-treatment temperature is 40 DEG C, and the time is 2h, and surface area of sample with the ratio of pretreatment liquid volume is
1:30；In step S3, post-treatment solution is the NaHCO of 1mol/L3Solution, regulates pH～13 through NaOH, and post-processing temperature is 70
DEG C, the time is 12h, and surface area of sample is 1:30 with the ratio of aftertreatment fluid volume.
Embodiment 3
With embodiment 1, except that: the present embodiment uses Mg-1Ca magnesium alloy；Step S2 is prepared 0.04mol/L
SnCl4Solution, and with 2mol NaOH and 0.5mol/L Na2CO3Mixed solution regulation pH to 4.0, prepares pretreatment solution, front
Treatment temperature is 50 DEG C, and the time is 0.5h, and surface area of sample is 1:50 with the ratio of pretreatment liquid volume；In step S3, post processing is molten
Liquid be NaOH regulation pH to 13 unsaturated carbonate aqueous solution, post-processing temperature is 60 DEG C, and the time is 24h, surface area of sample with after
The ratio for the treatment of fluid volume is 1:50.
Embodiment 4
With embodiment 1, except that: the Mg-1Zr magnesium alloy that the present embodiment uses；Step S2 is prepared 0.03mol/L
Sn(SO4) solution, and with 1mol/L KOH and 1mol/L KHCO3Mixed solution regulation pH to 4.5, prepares pretreatment solution, front
Treatment temperature is 30 DEG C, and the time is 3h, and surface area of sample is 1:30 with the ratio of pretreatment liquid volume；Post-treatment solution in step S3
KHCO for 0.5mol/L3Solution, through the solution of KOH regulation pH to 10.5, post-processing temperature is 50 DEG C, and the time is 48h, sample
Surface area is 1:50 with the ratio of aftertreatment fluid volume.
Embodiment 5
With embodiment 1, except that: the Mg-1Sn magnesium alloy that the present embodiment uses；Step S2 is prepared 0.02mol/L
Sn(SO4)2Solution, and use 1mol/L K2CO3Mixed solution regulation pH to 4.0, prepares pretreatment solution, and surface area of sample is with front
The ratio for the treatment of fluid volume is 1:30；In step S3, post-treatment solution is the KHCO of 0.7mol/L3Solution, through NaOH regulation pH extremely
12, post-processing temperature is 80 DEG C, and the time is 24h, and surface area of sample is 1:30 with the ratio of aftertreatment fluid volume.
Embodiment 6
With embodiment 1, except that: the Mg-2Mn magnesium alloy that the present embodiment uses；Step S2 is prepared 0.04mol/L
Sn(SO4)2Solution, and with 1mol/L KOH and 1mol/L K2CO3Mixed solution regulation pH to 4.0, prepares pretreatment solution, front
Treatment temperature is 30 DEG C, and the process time is 3h.Surface area of sample is 1:60 with the ratio of pretreatment liquid volume；Post processing in step S3
Solution be pH 8.5 KOH and the mixed solution of unsaturated carbonate aqueous solution, post-processing temperature is 70 DEG C, and the time is 36h, sample
Surface area is 1:60 with the ratio of aftertreatment fluid volume.
Comparative example 1
The present embodiment magnesium and magnesium alloy sample use pure magnesium.
S1, magnesium and magnesium alloy sample are carried out pretreatment: include polishing, clean.Use 400,800 and 1000 purposes successively
Abrasive paper for metallograph carries out mechanical grinding, then by pure magnesium sample ultrasonic cleaning 5～10min in dehydrated alcohol after polishing, then puts
Ultrasonic cleaning 5～10min in ionized water.
S2, pretreated sample is carried out pre-treatment: preparation 0.005mol/L SnCl4Solution, and use 1mol/L
NaOH Yu 0.5mol/L Na2CO3Mixed solution regulation pH to 3.8, prepare pretreatment solution.Magnesium and magnesium alloy sample are soaked
1h, treatment temperature is 25 DEG C, and surface area of sample is 1:40 with the ratio of pretreatment liquid volume, grows precursor film at sample surfaces.
S3, the sample after pre-treatment is carried out post processing: preparation 0.5mol/L Na2CO3Solution, through NaOH regulation pH extremely
12, prepare post-treatment solution.Sample after pre-treatment is placed in post-treatment solution immersion 24h, and treatment temperature is 60 DEG C, sample
Surface area is 1:40 with the ratio of aftertreatment fluid volume, at sample surfaces growing film layer.
S4, post processing sample is carried out: sample is placed in ultrasonic cleaning 5min in deionized water, then by sample cold wind
Dry up or natural air drying.
Comparative example 2
The present embodiment uses Mg-1Zr magnesium alloy.
S1, magnesium and magnesium alloy sample are carried out pretreatment: include polishing, clean.Use 400,800 and 1000 purposes successively
Abrasive paper for metallograph carries out mechanical grinding, then by the magnesium alloy sample ultrasonic cleaning 5min in dehydrated alcohol after polishing, then is placed in
Ultrasonic cleaning 5min in ionized water..
S2, pretreated sample is carried out a step process: preparation 0.02mol/L SnCl4Solution, and use 1mol/L
NaOH Yu 0.5mol/L Na2CO3Mixed solution regulation pH to 12, prepare process solution.Magnesium and magnesium alloy sample are soaked 1h,
Treatment temperature is 25 DEG C, and surface area of sample is 1:40 with the ratio for the treatment of fluid volume, at sample surfaces growing film layer.
S3, post processing sample is carried out: sample is placed in ultrasonic cleaning 5min in deionized water, then by sample cold wind
Dry up or natural air drying.
Characterization result
The thing phase constituent of film layer is determined according to X-ray diffraction, and by electrochemical tests test evaluation film layer sample
Corrosion resistance, characterization result is as shown in table 1.
Table 1 present invention is through the thing phase constituent of above-mentioned preparation technology Mg alloy surface film layer and corrosion resistance
Electro-chemical test etchant solution is simulated body fluid, and its composition is NaCl (8.0g/L), KCl (0.4g/L), MgCl2·
6H2O(0.1g/L)、NaHCO3(0.35g/L)、MgSO4·7H2O(0.06g/L)、CaCl2(0.14g/L)、Na2HPO4·2H2O
(0.06g/L)、KH2PO4(0.06g/L), glucose (1.0g/L).
Fig. 1 is Mg (OH) in embodiment 12The XRD figure spectrum of/Mg-Sn houghite composite membrane, XRD result shows, the master of film
Wanting composition is Mg (OH)2With Layered Double Hydroxide (LDH), Mg peak comes from magnesium matrix.Fig. 2 is in embodiment 1
Mg(OH)2The SEM photograph of/Mg-Sn houghite composite membrane, SEM result shows, film layer has typical hydrotalcite intercalation knot
Structure.Fig. 3 is Mg (OH) in embodiment 12The polarization curve of/Mg-Sn houghite composite membrane, electrochemical tests result table
Bright, Mg (OH)2/ Mg-Sn houghite composite films corrosion electric current density is 9.5 × 10-6A·cm2, the corrosion of the purest magnesium
Electric current density (3.0 × 10-4A·cm2) 3/100.
Comparative example 1 reduces the concentration of tin ion saline solution, the Sn of low concentration4+Cannot complete in stratiform main structure body
Mg2+Replacement, cause LDH composition in film layer to observe；Owing to intercalation configuration is unstable, the Mg of corrosion resistance difference5(CO3)4
(OH)2·4H2O produces, and film layer does not have protective action.Comparative example 2 is added tin ion saline solution the most in acid condition,
But add under high ph conditions and cause Sn4+Change in the solution with SnO4 2-Form exists, it is impossible to formed at Mg alloy surface
The Mg (OH) of intercalation configuration2/ Mg-Sn LDH composite membrane.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and deformation, these improve and deformation
Also should be regarded as protection scope of the present invention.
Claims (7)
1. a magnesium and Mg alloy surface have the Mg (OH) of intercalation configuration2The preparation method of/Mg-Sn houghite composite membrane, its
It is characterised by, comprises the steps:
S1, magnesium and magnesium alloy pretreatment: magnesium and magnesium alloy are successively carried out mechanical grinding, ethanol ultrasonic cleaning, ultrasonic deionization
Water cleans；
S2, magnesium and magnesium alloy sample are carried out pre-treatment: the first tin ion saline solution of preparation 0.01～0.04mol/L, and adjust
Joint pH to 3.8～5.0, prepares pretreatment solution, is placed in and is continually fed into CO by magnesium and the magnesium alloy through pretreatment2Pre-treatment
In solution 0.5～3h, pre-treatment temperature is 20～50 DEG C, it is thus achieved that be covered with magnesium and the magnesium alloy of precursor film；
S3, the magnesium and magnesium alloy being covered with precursor film is carried out post processing: the sample that step S2 prepares is placed in 50～80 DEG C
Containing CO3 2-, pH be 8.5～13 post-treatment solution in soak 12～48h, thus magnesium and Mg alloy surface have intercalation configuration
Mg (OH)2/ Mg-Sn houghite composite membrane；
S4, follow-up cleaning: use the sample that deionized water ultrasonic cleaning step S3 processes, then sample cold wind is dried up or natural wind
Dry.
Magnesium the most according to claim 1 and Mg alloy surface have the Mg (OH) of intercalation configuration2/ Mg-Sn houghite is combined
The preparation method of film, it is characterised in that: in step S1, described magnesium and magnesium alloy are pure magnesium or the magnesium conjunction that bio-medical does not contains Al
Gold, including Mg-Zn system, Mg-RE system, Mg-Ca system, Mg-Sn system, Mg-Mn system alloy and pure magnesium.
Magnesium the most according to claim 1 and Mg alloy surface growth in situ have the Mg (OH) of intercalation configuration2/ Mg-Sn class water
The preparation method of Talcum composite membrane, it is characterised in that: in step S2, described tin ion saline solution is SnCl4Or Sn (SO4)2。
Magnesium the most according to claim 1 and Mg alloy surface growth in situ have the Mg (OH) of intercalation configuration2/ Mg-Sn class water
The preparation method of Talcum composite membrane, it is characterised in that: in step S2, described tin ion saline solution by alkaline solution 0～
The NaOH/KOH and 0.5～the Na of 1mol/L of 2mol/L2CO3/NaHCO3/K2CO3/KHCO3Mixed solution, regulate pre-treatment
The pH value of solution.
Magnesium the most according to claim 1 and Mg alloy surface growth in situ have the Mg (OH) of intercalation configuration2/ Mg-Sn class water
The preparation method of Talcum composite membrane, it is characterised in that: in step S3, described post-treatment solution is 0.5～1mol/L
Na2CO3/NaHCO3/K2CO3/KHCO3Solution or unsaturated carbonate solution, and regulate pH with the NaOH/KOH solution of 0～2mol/L
It is 8.5～13.
Magnesium the most according to claim 1 and Mg alloy surface growth in situ have the Mg (OH) of intercalation configuration2/ Mg-Sn class water
The preparation method of Talcum composite membrane, it is characterised in that: in step S2 and S3, the ratio of the surface area of described sample and treatment fluid volume
All in the range of 1:20～1:60.
7. the brucite composite membrane obtained according to preparation method described in any one of claim 1 to 6, it is characterised in that: institute
The chemical formula stating Mg-Sn houghite is Mg6Sn2(OH)16(CO3)2·yH2O, wherein Sn is+4 valencys, and y is 1,2 or 3.
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