CN107988588A - A kind of water-bath dipping method for preparing calcium silicon composite coating - Google Patents

A kind of water-bath dipping method for preparing calcium silicon composite coating Download PDF

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Publication number
CN107988588A
CN107988588A CN201711191046.6A CN201711191046A CN107988588A CN 107988588 A CN107988588 A CN 107988588A CN 201711191046 A CN201711191046 A CN 201711191046A CN 107988588 A CN107988588 A CN 107988588A
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solution
magnesium alloy
water
bath
composite coating
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CN201711191046.6A
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Chinese (zh)
Inventor
蔡舒
江洋洋
李玥
凌瑞
花少帅
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Tianjin University
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Tianjin University
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates

Abstract

The present invention relates to a kind of water-bath dipping method for preparing calcium silicon composite coating, and using the compound of calcium and silicate as raw material, solution is respectively configured, stirs 30min~2h, until all dissolvings；Ca solution will be contained and be added drop-wise to stirring 30min~2h in silicate solutions；Acid solution, which is added dropwise, makes pH maintain 4.5~6, stirs 1~2.5h, obtains calcium silicon solution, wherein Ca2+Concentration be 0.12~0.30mmol/L, SiO3 2‑Concentration be 0.24mmol/L；Magnesium alloy after alkali process is put into calcic silicon solution container, magnesium alloy is totally submerged in solution, moves into and water-bath impregnation is carried out in water-bath；It is cooled to room temperature after reaction with water-bath, takes out container, taken out magnesium alloy, cleaned with detergent, is dried to obtain the magnesium alloy of calcium silicon composite coating cladding.This coating process is simple, economic ring mirror is friendly, and there is larger business promotion to be worth.

Description

A kind of water-bath dipping method for preparing calcium silicon composite coating
Technical field
The invention belongs to technical field of biomedical materials, and in particular to a kind of water-bath dipping for preparing calcium silicon composite coating Method.
Background technology
Magnesium and its alloy become the research hotspot of bone renovating material due to its excellent mechanical property and biological property.Magnesium Density (1.74~2.0g/cm of alloy2) it is close with people's bone density, the elasticity modulus (45GPa) of magnesium alloy far below stainless steel, Cochrome and titanium alloy, can to avoid " stress-shielding effect " and generation；Magnesium is the essential elements in human body, take part in human body Enzymatic reaction in interior up to 300, so beneficial when it is to human body.Secondly, with the extension of time, magnesium can degrade with body fluid Discharge, it is not necessary to which operation is taken out, and it is the pain that patient brings to eliminate second operation.However, the corrosion potentials due to magnesium alloy Relatively low, chemical property is more active, too fast can degrade in vivo, on the one hand bubble hydrogen can be caused to increase, and on the other hand can lead Cause local pH rise causes alkalosis, this greatly limits its clinicing aspect application.And the surface of magnesium alloy is modified quilt It is considered to reduce magnesium alloy degradation rate, delays the effective ways of Corrosion Behaviors of Magnesium Alloys.
One of common inorganic material, calcium silicon compound such as CaSiO are modified as surface3And Ca2SiO4With good life Thing compatibility and bioactivity, be implanted into human body after can be with the growth of inducing peripheral bone tissue, with the firm chemical bond of bon e formation. Quick will extensively waits (106924816 A of patent No. CN) to be prepared for magnesium-base metal ceramics again using plasma discharging technology pressure sintering Condensation material, the composite material have explanation property controllable and can promote the distinguishing feature of skeletonization, can be in sclerous tissues's defect repair Applied in field etc..In addition, calcium silicon compound mostly has preferable chemistry and high-temperature stability, this will delay its Degradation rate in human body fluid, further plays its Long-Term Protection to magnesium alloy.
Calcium silicon composite coating can be prepared in Mg alloy surface using a variety of methods at present, as sol-gal process, chemistry turn Change method, electrophoretic deposition, plasma spraying method etc..Wherein, He Dannong etc. (105327397 A of patent No. CN) is coagulated using colloidal sol Glue method combination high-temperature heat treatment is prepared for mesoporous calcium silicates coating in Mg alloy surface.Composite mesoporous coating improves magnesium alloy Corrosion resisting property and degradation property, the introducing of ethyl cellulose improve the bond strength of coating and matrix.(the CN such as Li Kai 106913905 A) cerium oxide-doped calcium silicates coating is prepared in Mg alloy surface using plasma spraying method.Above-mentioned calcium silicates Coating can improve the corrosion resistance of magnesium alloy, but time-consuming for sol-gal process, and plasma spraying equipment is costly.With above method Compare, water-bath infusion process possesses obvious advantage in all multi-methods, it is with equipment requirement is simple, technique is simple, prepares bar The characteristics of part is easily-controllable, time-consuming short.At present there has been no the report for preparing calcium silicon composite coating on magnesium alloy with water-bath infusion process, therefore The good calcium silicon composite coating of corrosion resistance is prepared in Mg alloy surface using water-bath infusion process herein.
The content of the invention
Existing in the prior art in order to solve the problems, such as, the object of the present invention is to provide a kind of water-bath leaching of calcium silicon composite coating Stain method, technique is simple, and time-consuming short, equipment requirement is low, and significantly improves corrosion resistance of the magnesium alloy in physiological environment.
Technical scheme is as follows：
A kind of method for preparing calcium silicon composite coating, comprises the following steps that：
1) preparation of calcium silicon solution：Using the compound of calcium and silicate as raw material, solution is respectively configured, stirring 30min~ 2h, until all dissolvings；Ca solution will be contained and be added drop-wise to stirring 30min~2h in silicate solutions；Acid solution, which is added dropwise, maintains pH 4.5~6,1~2.5h is stirred, obtains calcium silicon solution, wherein Ca2+Concentration be 0.12~0.30mmol/L, SiO3 2-Concentration be 0.24mmol/L；
2) magnesium alloy after alkali process is put into the container of calcic silicon solution, magnesium alloy is totally submerged in solution, Move into and water-bath impregnation is carried out in water-bath；It is cooled to room temperature after reaction with water-bath, takes out container, and then take out magnesium Alloy, is cleaned with detergent, is dried to obtain the magnesium alloy of calcium silicon composite coating cladding.
The magnesium alloy preferably carries out surface alkali process：Mg alloy surface is polishing to 1500~2000 mesh, Ran Houyi It is secondary to be cleaned by ultrasonic 3~10min, drying in acetone, deionized water, ethanol；Magnesium alloy is immersed in 0.25~1.5mol/L again In 60~90 DEG C of insulations in NaOH solution, then with deionized water rinse, drying.
Described step (2) the water-bath impregnation reacts 1~4h preferably at a temperature of 45 DEG C~60 DEG C.
The compound of the calcium is preferably Ca (NO3)2Or Ca (OH)2。
The compound of the silicon is preferably Na2SiO3Or Na2SiO3·9H2O。
The acid solution is preferably HNO3。
The detergent selects deionized water or ethanol.
In conclusion the core of the present invention is to prepare the solution containing Ca and Si, then by water-bath infusion process in magnesium alloy Matrix surface prepares calcium silicon composite coating.
Compared with prior art, the advantage of the invention is that：
(1) coating prepared by the present invention is mainly by the SiO of well-crystallized2、CaSiO3And Ca2SiO4Crystal forms.
(2) calcium silicon composite coating prepared by the present invention significantly improves corrosion resistance of the magnesium alloy in simulated body fluid.Electrification Learn test and show that its AC impedance is 13K Ω cm2, i.e., obtained composite coating considerably improves the electrochemistry of magnesium alloy Energy；
(3) Preparation equipment of the present invention requires low, and technique is simple, and time-consuming short, economic ring mirror is friendly, and there is larger business to push away Wide value.
(4) reliability of the present invention is high.For the magnesium alloy sample of any shape, size, calcium can be prepared on its surface Silicon composite coating.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the calcium silicon composite coating prepared by the embodiment of the present invention 1.
Fig. 2 is that the calcium silicon composite coating prepared by the embodiment of the present invention 1 coats exchange resistance of the magnesium alloy in simulated body fluid Anti- collection of illustrative plates.
Fig. 3 is that the calcium silicon composite coating prepared by the embodiment of the present invention 1 coats polarization song of the magnesium alloy in simulated body fluid Line chart is composed.
Embodiment
Embodiment 1
The pretreatment of magnesium alloy：AZ31 magnesium alloys are processed into the block of 10mm × 10mm × 2mm, successively with 800#、 1500#、2000#SiC sand paper polishing, be then cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethanol successively. Prepare the NaOH deionized water solutions 100mL of 1.5mol/L.Magnesium alloy after polishing is immersed in NaOH solution in 60 DEG C of guarantors Warm 1h, then by magnesium alloy sample deionized water rinse, drying, the magnesium alloy pre-processed.
The preparation of calcium silicon solution：With Ca (NO3)2And Na2SiO3Solution is respectively configured for raw material, stirs 30min；By Ca (NO3)2Solution instills Na dropwise2SiO3In solution, HNO is added dropwise3PH is maintained 4.5, stir 1h, obtain calcium silicon solution.Wherein Ca(NO3)2Concentration be 0.12mmol/L, PO4 3-Concentration be 0.24mmol/L.
The preparation of calcium silicon composite coating：Magnesium alloy after some alkali process is put into the container of calcic silicon solution, makes magnesium Alloy is totally submerged in solution, is moved in water-bath water-bath 1h at 45 DEG C, is cooled to room with water-bath after reaction Temperature takes out container, then takes out magnesium alloy, is cleaned with deionized water, is dried to obtain the magnesium alloy of composite coating cladding.It is prepared Coating XRD spectrum as shown in Figure 1, synthesis coating be SiO2、CaSiO3And Ca2SiO4Composite coating.The exchange resistance of coating Resist as shown in Fig. 2, the AC impedance of shown composite coating cladding magnesium alloy is 13K Ω cm2.The polarization curve of coating such as Fig. 3 Shown, the corrosion electric current density for obtaining composite coating is 2 μ A/cm2。
Embodiment 2
The pretreatment of magnesium alloy：AZ31 magnesium alloys are processed into the block of 10mm × 10mm × 2mm, successively with 800#、 1500#、2000#SiC sand paper polishing, be then cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethanol successively. Prepare the NaOH deionized water solutions 100mL of 1mol/L.Magnesium alloy after polishing is immersed in NaOH solution in 70 DEG C of insulations 1h, then by magnesium alloy sample deionized water rinse, drying, the magnesium alloy pre-processed.
The preparation of calcium silicon solution：With Ca (NO3)2And Na2SiO3Solution is respectively configured for raw material, stirs 1h；By Ca (NO3)2 Solution instills Na dropwise2SiO3In solution, HNO is added dropwise3PH is maintained 5, stir 1.5h, obtain calcium silicon solution.Wherein Ca (NO3)2Concentration be 0.18mmol/L, PO4 3-Concentration be 0.24mmol/L.
The preparation of composite coating：Magnesium alloy after alkali process is put into the container of calcic silicon solution, makes magnesium alloy complete It is immersed in solution, moves in water-bath water-bath 2h at 50 DEG C, being cooled to room temperature taking-up with water-bath after reaction holds Device, then takes out magnesium alloy, is cleaned with deionized water, is dried to obtain the magnesium alloy of composite coating cladding.Composite coating coats magnesium The AC impedance of alloy is 12K Ω cm2。
Embodiment 3
The pretreatment of magnesium alloy：AZ31 magnesium alloys are processed into the block of 10mm × 10mm × 2mm, successively with 800#、 1500#、2000#SiC sand paper polishing, be then cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethanol successively. Prepare the NaOH deionized water solutions 100mL of 0.5mol/L.Magnesium alloy after polishing is immersed in NaOH solution in 80 DEG C of guarantors Warm 1h, then by magnesium alloy sample deionized water rinse, drying, the magnesium alloy pre-processed.
The preparation of calcium silicon solution：With Ca (NO3)2And Na2SiO3Solution is respectively configured for raw material, stirs 1.5h；By Ca (NO3)2Solution instills Na dropwise2SiO3In solution, HNO is added dropwise3PH is maintained 5.5, stir 2h, obtain calcium silicon solution.Wherein Ca(NO3)2Concentration be 0.24mmol/L, PO4 3-Concentration be 0.24mmol/L.
The preparation of composite coating：Magnesium alloy after some alkali process is put into the container of calcic silicon solution, makes magnesium alloy It is totally submerged in solution, moves in water-bath water-bath 3h at 55 DEG C, be cooled to room temperature take with water-bath after reaction Go out container, then take out magnesium alloy, cleaned with deionized water, be dried to obtain the magnesium alloy of composite coating cladding.The composite coating The AC impedance for coating magnesium alloy is 9K Ω cm2
Embodiment 4
The pretreatment of magnesium alloy：AZ31 magnesium alloys are processed into the block of 10mm × 10mm × 2mm, successively with 800#、 1500#、2000#SiC sand paper polishing, be then cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethanol successively. Prepare the NaOH deionized water solutions 100mL of 0.25mol/L.Magnesium alloy after polishing is immersed in NaOH solution in 90 DEG C of guarantors Warm 1h, then by magnesium alloy sample deionized water rinse, drying, the magnesium alloy pre-processed.
The preparation of calcium silicon solution：With Ca (NO3)2And Na2SiO3Solution is respectively configured for raw material, stirs 2h；By Ca (NO3)2 Solution instills Na dropwise2SiO3In solution, HNO is added dropwise3PH is maintained 6, stir 2.5h, obtain calcium silicon solution.Wherein Ca (NO3)2Concentration be 0.36mmol/L, PO4 3-Concentration be 0.24mmol/L.
The preparation of composite coating：Magnesium alloy after alkali process is put into the container of calcic silicon solution, makes magnesium alloy complete It is immersed in solution, moves in water-bath water-bath 1h at 60 DEG C, being cooled to room temperature taking-up with water-bath after reaction holds Device, then takes out magnesium alloy, is cleaned with deionized water, is dried to obtain the magnesium alloy of composite coating cladding.The composite coating coats The AC impedance of magnesium alloy is 11K Ω cm2。

Claims (7)

  1. A kind of 1. water-bath dipping method for preparing calcium silicon composite coating；Its characterization step is as follows：
    1) preparation of calcium silicon solution：Using the compound of calcium and silicate as raw material, solution is respectively configured, stirs 30min~2h, directly To whole dissolvings；Ca solution will be contained and be added drop-wise to stirring 30min~2h in silicate solutions；Be added dropwise acid solution make pH maintain 4.5~ 6,1~2.5h is stirred, obtains the solution of calcium silicon system, wherein Ca2+Concentration be 0.12~0.30mmol/L, SiO3 2-Concentration For 0.24mmol/L；
    2) magnesium alloy after some alkali process is put into the container of calcic silicon solution, magnesium alloy is totally submerged in solution, Move into and water-bath impregnation is carried out in water-bath；It is cooled to room temperature after reaction with water-bath, takes out container, and then take out magnesium Alloy, is cleaned with detergent, is dried to obtain the magnesium alloy of calcium silicon composite coating cladding.
  2. 2. the method as described in claim 1, it is characterized in that the magnesium alloy method of the alkali process：Mg alloy surface is polishing to 1500~2000 mesh, are then cleaned by ultrasonic 3~10min, drying in acetone, deionized water, ethanol successively；Magnesium alloy is soaked again Bubble, in 60~90 DEG C of insulations, then with deionized water rinse, is dried in 0.25~1.5mol/LNaOH solution.
  3. 3. the method as described in claim 1, it is characterized in that the step 2) water-bath is at a temperature of 45 DEG C~60 DEG C, instead Answer 1~4h.
  4. 4. the method as described in claim 1, it is characterized in that the compound of the calcium is Ca (NO3)2Or Ca (OH)2。
  5. 5. the method as described in claim 1, it is characterized in that the silicate is Na2SiO3Or Na2SiO3·9H2O。
  6. 6. the method as described in claim 1, it is characterized in that the acid solution is HNO3。
  7. 7. the method as described in claim 1, it is characterized in that the detergent selects deionized water or ethanol.
CN201711191046.6A 2017-11-24 2017-11-24 A kind of water-bath dipping method for preparing calcium silicon composite coating Pending CN107988588A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285425A (en) * 2012-03-01 2013-09-11 中国科学院上海硅酸盐研究所 Bio-coating with good anti-degradation property and antibacterial property, and preparation method thereof
CN103446626A (en) * 2013-09-13 2013-12-18 天津大学 Medical degradable bioglass/phytic acid composite coating on surface of magnesium alloy and preparation method thereof
CN104099654A (en) * 2014-07-24 2014-10-15 西安交通大学 Preparation method for porous calcium silicate bioactive coating
CN104404480A (en) * 2014-11-19 2015-03-11 无锡光旭新材料科技有限公司 Method for preparing hydroxyapatite and bone collagen composite coating on surface of magnesium alloy
CN105327397A (en) * 2015-11-17 2016-02-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for degradable implant material of mesoporous calcium silicate coating on surface of medical magnesium alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285425A (en) * 2012-03-01 2013-09-11 中国科学院上海硅酸盐研究所 Bio-coating with good anti-degradation property and antibacterial property, and preparation method thereof
CN103446626A (en) * 2013-09-13 2013-12-18 天津大学 Medical degradable bioglass/phytic acid composite coating on surface of magnesium alloy and preparation method thereof
CN104099654A (en) * 2014-07-24 2014-10-15 西安交通大学 Preparation method for porous calcium silicate bioactive coating
CN104404480A (en) * 2014-11-19 2015-03-11 无锡光旭新材料科技有限公司 Method for preparing hydroxyapatite and bone collagen composite coating on surface of magnesium alloy
CN105327397A (en) * 2015-11-17 2016-02-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for degradable implant material of mesoporous calcium silicate coating on surface of medical magnesium alloy

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