CN106191835A - Preparation method of novel magnesium alloy hydroxyapatite composite membrane - Google Patents
Preparation method of novel magnesium alloy hydroxyapatite composite membrane Download PDFInfo
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- CN106191835A CN106191835A CN201610629388.0A CN201610629388A CN106191835A CN 106191835 A CN106191835 A CN 106191835A CN 201610629388 A CN201610629388 A CN 201610629388A CN 106191835 A CN106191835 A CN 106191835A
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- Prior art keywords
- magnesium alloy
- hydroxyapatite
- whisker
- zno
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Links
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 75
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 75
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 32
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims description 30
- 229960004494 calcium gluconate Drugs 0.000 claims description 30
- 239000004227 calcium gluconate Substances 0.000 claims description 30
- 235000013927 calcium gluconate Nutrition 0.000 claims description 30
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 30
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 20
- 229960002401 calcium lactate Drugs 0.000 claims description 20
- 239000001527 calcium lactate Substances 0.000 claims description 20
- 235000011086 calcium lactate Nutrition 0.000 claims description 20
- 239000002659 electrodeposit Substances 0.000 claims description 13
- 239000008187 granular material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 10
- NSIFOGPAKNSGNW-UHFFFAOYSA-M dodecyl(triphenyl)phosphonium bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCC)C1=CC=CC=C1 NSIFOGPAKNSGNW-UHFFFAOYSA-M 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- HPAVSHLOCSRBQS-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 Chemical compound CCCCCCCCCCCCCCCCCCCl(C)(C)CC1=CC=CC=C1 HPAVSHLOCSRBQS-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 150000002500 ions Chemical group 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 6
- 241000607142 Salmonella Species 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- -1 octadecyldimethyl benzyl Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 241000219095 Vitis Species 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 230000002147 killing effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 2
- 206010007134 Candida infections Diseases 0.000 description 2
- 235000009392 Vitis Nutrition 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- NEEHYRZPVYRGPP-IYEMJOQQSA-L calcium gluconate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEEHYRZPVYRGPP-IYEMJOQQSA-L 0.000 description 2
- 201000003984 candidiasis Diseases 0.000 description 2
- 125000005626 carbonium group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229940032912 zephiran Drugs 0.000 description 1
Classifications
-
- 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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention relates to a preparation method of a novel magnesium alloy hydroxyapatite composite film, which comprises the steps of preparing four-needle ZnOWModifying the surface of the whisker to make the surface of the whisker carry a positive ion group; preparing porous hydroxyapatite layer on the surface of magnesium alloy, and using the four-needle ZnO with positive ion group on the surfaceWAdding electrodeposition liquid into the crystal whisker to carry out composite electrodeposition on the hydroxyapatite layer with the porous structure on the surface of the magnesium alloy by the composite electrodeposition liquid, and leading the four-needle ZnO to be prepared by the preparation method of the inventionWThe whiskers are dispersed in the hydroxyapatite layer to form a hydroxyapatite reinforcing phase, so that the strength and toughness of the hydroxyapatite layer are effectively improved, and the prepared magnesium alloy hydroxyapatite/four-needle ZnOWThe whisker composite membrane has excellent antibacterial property, corrosion resistance and biocompatibility.
Description
Technical field
The present invention relates to medical magnesium alloy surface process field, particularly a kind of novel magnesium alloy hydroxyapatite composite membrane
Preparation method.
Background technology
Magnesium alloy has low-density, high specific strength, and its elastic modelling quantity and yield strength are close with skeleton, is preferable human body
Skeleton implants medical material.But the corrosion resistance that magnesium alloy is under physiological environment is poor, and degradation speed is too fast, becomes skeleton
Implant a difficult problem for medical material application.Hydroxyapatite (Ca5(PO4)3(OH)) there is preferable corrosion resisting property, have excellent life
The thing compatibility, thus prepare hydroxyapatite layer at Mg alloy surface and be conducive to suppression magnesium alloy degraded in physiological environment,
It is also beneficial to improve the biocompatibility of implant.But the intensity of hydroxyapatite is low, poor toughness limits it human bearing
With the application of motion part skeleton, additionally, the excellent biological activity of hydroxyapatite also can cause pathogenic bacteria to be sticked and flourish.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides the system of a kind of novel magnesium alloy hydroxyapatite composite membrane
Preparation Method, this preparation method includes four pin ZnOWWhisker surface moditied processing and magnesium alloy hydroxyapatite/tetra-pin ZnOWWhisker
The preparation of composite membrane.By the present invention, magnesium alloy composite film prepared by method is described, due to its four pin ZnOWWhisker Dispersed precipitate in
Hydroxyapatite layer, is effectively increased hydroxyapatite layer intensity and toughness；Additionally, due to four pin ZnOWWhisker is to yellow Fructus Vitis viniferae
The pathogenic bacterias such as coccus, escherichia coli and Salmonella have a stronger killing action, thus magnesium alloy hydroxyapatite/tetra-pin ZnOWBrilliant
Must have excellent antibacterial, anti-corrosion and biocompatibility by composite membrane.
The technical solution adopted for the present invention to solve the technical problems is: a kind of novel magnesium alloy hydroxyapatite composite membrane
Preparation method, comprise the steps of:
Step [1] four pin ZnOWThe surface moditied processing of whisker；
The preparation of step [2] magnesium alloy loose structure hydroxyapatite layer；
Four pin ZnO of step [3] modified processWThe composite electrodeposition of whisker.
Preferably, described step [1] specifically includes and operates as follows:
A1. the preparation of decorating liquid: be analytically pure dodecyl triphenyl phosphonium bromide, octadecyldimethyl benzyl by concentration
Ammonium chloride and DTAB add in deionized water, form decorating liquid；
A2. four pin ZnOWThe surface of whisker is modified: by 5-20g tetra-pin ZnOWWhisker adds in the described decorating liquid of 1L, in room
0.5-1 hour is disperseed so that four pin ZnO with ultrasound wave under temperatureWWhisker is fully dispersed, then stands 0.5-2 hour, prepares surface
Four pin ZnO of cation base group modificationWWhisker.
Preferably, described in step a1, in decorating liquid, dodecyl triphenyl phosphonium bromide concentration is 0.5-4mmol/L, 18
Zephiran concentration is 1.5-9mmol/L, and DTAB concentration is 4-15mmol/L.
Preferably, described step [2] specifically includes and operates as follows:
B1. the preparation of magnesium alloy phosphorus calcium basic unit: by concentration be analytically pure calcium lactate, calcium gluconate, calcium nitrate and
The phosphoric acid of 60% adds formation treatment fluid in deionized water；Magnesium alloy immersion, to 60-80 DEG C, is carried out 2-5 and divides by heat treated liquid
The chemical conversion treatment of clock, carries out sufficient mechanical agitation in conversion processing process, it is thus achieved that magnesium alloy phosphorus calcium basic unit；
B2. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic
Solvent so that it is percentage by weight is 20%-35%, at room temperature disperses 10-30 minute to form stable hydroxyl phosphorus with ultrasound wave
Lime stone micron particle acetone dispersion.Add the phosphoric acid of calcium lactate, calcium gluconate and 60% in deionized water, form phosphorus
Calcium solution；After the 100-300mL phosphorus calcium solution of preparation and 1L hydroxyapatite micrometre granule acetone dispersion are sufficiently mixed
As electrodeposit liquid, surface obtaining the magnesium alloy of phosphorus calcium basic unit as negative electrode, platinum is anode, and electrodeposition temperature is 60-80 DEG C,
Electro-deposition 10-40 minute under conditions of constant voltage value is 5-20V, thus obtain loose structure hydroxy-apatite at Mg alloy surface
Rock layers.
Preferably, the concentration of the phosphoric acid of calcium lactate, calcium gluconate, calcium nitrate and 60% in treatment fluid described in step b1
It is respectively 85-230g/L, 170-310g/L, 10-45g/L and 240-430mL/L；Lactic acid in phosphorus calcium solution described in step b2
The concentration of calcium, calcium gluconate and 60% phosphoric acid is respectively 25-140g/L, 40-110g/L and 30-70mL/L.
Preferably, described step [3] specifically includes and operates as follows:
C1. four pin ZnOWThe preparation of whisker composite electrodeposition liquid: be analytically pure calcium gluconate, hydroxide by concentration
The four pin ZnO that calcium, 60% phosphoric acid and surface modification processWWhisker adds formation electrodeposit liquid in deionized water；
C2. four pin ZnOWThe composite electrodeposition step of whisker: grown loose structure hydroxyapatite layer with surface
Magnesium alloy is negative electrode, and platinum is anode；It is 380-710mA/cm at current density range2Under conditions of carry out constant current electro-deposition,
Electro-deposition 30-60 minute at 60-80 DEG C, thus define hydroxyapatite/tetra-pin ZnO at Mg alloy surfaceWWhisker is combined
Film.
Preferably, calcium gluconate, calcium hydroxide, the phosphoric acid of 60% and repair through surface in electrodeposit liquid described in step c1
The four pin ZnO that decorations processWThe concentration of whisker is respectively 10-30g/L, 5-20g/L, 10-45mL/L and 160-310g/L.
The positive effect of the present invention: magnesium alloy Antibacterial hydroxyapatite/tetra-pin prepared according to the methods of the invention
ZnOWWhisker composite membrane, has on the one hand given full play to four pin ZnOWWhisker is to Staphylococcus aureus, escherichia coli and Salmonella etc.
Pathogenic bacteria has the feature of stronger killing action, on the other hand also uses four pin ZnOWThe characteristic of whisker superhigh intensity so that four pins
ZnOWWhisker is as strengthening phase Dispersed precipitate in hydroxyapatite layer.
Due to four pin ZnO after modified treatmentWWhisker surface is with carbonium group, four pin ZnOWIt is subject between whisker
Strong electrostatic repulsion, four pin ZnO in electrodeposit liquidWWhisker dispersibility is preferable, in strong the bearing in apatite layer micropore district
Under electric field action, enhance four pin ZnOWThe different in nature electrostatic attraction effect of whisker, so that four pin ZnOWWhisker Dispersed precipitate in
Hydroxyapatite layer, and form the enhancing phase of hydroxyapatite, it is effectively increased hydroxyapatite layer intensity and toughness.This
Outward, due to four pin ZnOWWhisker has stronger killing action to pathogenic bacterias such as Staphylococcus aureus, escherichia coli and Salmonellas, and
Four pin ZnOWWhisker surface is obviously enhanced function with carbonium group to its bactericidal action, thus the magnesium alloy hydroxyl of preparation
Base apatite/tetra-pin ZnOWWhisker composite membrane has excellent antibacterial, anti-corrosion and biocompatibility.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of composite membrane of the present invention；
Fig. 2 is the structural representation of composite membrane of the present invention；
Fig. 3 is the bacteriostatic experiment result of the embodiment of the present invention 1, embodiment 2 and comparative example；
Fig. 4 be the embodiment of the present invention 1, embodiment 2 and comparative example the corrosion potential of 5%NaCl solution, corrosion current and
The experimental result of wear test wear extent.
Detailed description of the invention
Below in conjunction with the accompanying drawings to a preferred embodiment of the present invention will be described in detail.
Seeing figures.1.and.2, the preferred embodiment of the present invention provides a kind of novel magnesium alloy hydroxyapatite composite membrane
Preparation method, follows these steps to order and carries out:
1. the preparation of decorating liquid: be analytically pure dodecyl triphenyl phosphonium bromide, octadecyldimethyl benzyl by concentration
Ammonium chloride and DTAB add in deionized water, and forming dodecyl triphenyl phosphonium bromide concentration is
0.5mmol/L-4mmol/L, stearyl dimethyl benzyl ammonium chloride concentration are 1.5mmol/L-9mmol/L and decyl trimethyl
Ammonium bromide concentration is the decorating liquid of 4mmol/L-15mmol/L.
2. four pin ZnOWThe surface of whisker is modified: by 5-20g tetra-pin ZnOWWhisker adds in the above-mentioned decorating liquid of 1L, in room temperature
Under disperse 0.5-1 hour so that four pin ZnO with ultrasound waveWWhisker is fully dispersed, then stands 0.5-2 hour, and prepared surface is just
The four pin ZnO that ionic group is modifiedWWhisker.
3. the preparation of magnesium alloy phosphorus calcium basic unit: be analytically pure calcium lactate, calcium gluconate, calcium nitrate and 60% by concentration
Phosphoric acid add and deionized water is formed the phosphoric acid concentration of calcium lactate, calcium gluconate, calcium nitrate and 60% be respectively 85g/L-
The treatment fluid of 230g/L, 170g/L-310g/L, 10g/L-45g/L and 240mL/L-430mL/L.Heat treated liquid is to 60-80
DEG C, magnesium alloy is immersed the chemical conversion treatment carried out in treatment fluid 2-5 minute, conversion processing process carries out sufficient machinery
Stirring, it is thus achieved that magnesium alloy phosphorus calcium basic unit.
4. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic molten
Agent so that it is percentage by weight is 20%-35%, at room temperature disperses 10-30 minute to form stable hydroxy-apatite with ultrasound wave
Stone micron particle acetone dispersion.Add the phosphoric acid of calcium lactate, calcium gluconate and 60% in deionized water, form lactic acid
The phosphoric acid concentration of calcium, calcium gluconate and 60% is respectively 25g/L-140g/L, 40g/L-110g/L and 30mL/L-70mL/L
Phosphorus calcium solution.By the most mixed with 1L hydroxyapatite micrometre granule acetone dispersion for the 100mL-300mL phosphorus calcium solution of preparation
Cooperation for electrodeposit liquid, obtains the magnesium alloy of phosphorus calcium basic unit as negative electrode using surface, and platinum is anode, and electrodeposition temperature is 60-80
DEG C, with constant voltage value 5-20V electro-deposition 10-40 minute, thus obtain loose structure hydroxyapatite layer at Mg alloy surface.
5. four pin ZnOWThe preparation of whisker composite electrodeposition liquid: by concentration be analytically pure calcium gluconate, calcium hydroxide,
The four pin ZnO that 60% phosphoric acid and surface modification processWWhisker adds in deionized water, formed calcium gluconate, calcium hydroxide,
The four pin ZnO that the phosphoric acid of 60% and surface modification processWWhisker concentration be respectively 10g/L-30g/L, 5g/L-20g/L,
The electrodeposit liquid of 10mL/L-45mL/L and 160g/L-310g/L.
6. four pin ZnOWThe composite electrodeposition step of whisker: grown the magnesium of loose structure hydroxyapatite layer with surface
Alloy is negative electrode, and platinum is anode；It is 380mA/cm at current density range2-710mA/cm2Under conditions of carry out constant current electricity sink
Long-pending, electro-deposition 30-60 minute at 60-80 DEG C, thus define hydroxyapatite/tetra-pin ZnO at Mg alloy surfaceWWhisker is multiple
Close film.
Concrete comparative example and embodiment be given below:
Comparative example:
Comparative example of the present invention provides the preparation method of a kind of magnesium alloy hydroxyapatite layer, and its preparation process is:
1. the preparation of magnesium alloy phosphorus calcium basic unit: be analytically pure calcium lactate, calcium gluconate, calcium nitrate and 60% by concentration
Phosphoric acid add deionized water is formed the phosphoric acid concentration of calcium lactate, calcium gluconate, calcium nitrate and 60% be respectively 110g/L,
The treatment fluid of 220g/L, 40g/L and 330mL/L.Magnesium alloy, to 75 DEG C, is immersed the change carried out 5 minutes by heat treated liquid
Learning conversion processing, conversion processing process carries out sufficient mechanical agitation, it is thus achieved that magnesium alloy phosphorus calcium basic unit.
2. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic molten
Agent so that it is the percentage ratio of weight is 45%, at room temperature disperses 30 minutes to form stable hydroxyapatite micrometre with ultrasound wave
Granule acetone dispersion.Using surface obtain phosphorus calcium basic unit magnesium alloy as negative electrode, platinum is anode, and electrodeposition temperature is 70
DEG C, with constant voltage value 20V electro-deposition 50 minutes, thus obtain hydroxyapatite layer at Mg alloy surface.
Embodiment 1:
1. the preparation of decorating liquid: be analytically pure dodecyl triphenyl phosphonium bromide, octadecyldimethyl benzyl by concentration
Ammonium chloride and DTAB add in deionized water, and forming dodecyl triphenyl phosphonium bromide concentration is
0.6mmol/L, stearyl dimethyl benzyl ammonium chloride concentration are 2mmol/L and DTAB concentration is 5mmol/
The decorating liquid of L.
2. four pin ZnOWThe surface of whisker is modified: by 7g tetra-pin ZnOWWhisker adds in 1L decorating liquid, at room temperature with ultrasonic
Wavelength-division dissipates 0.5 hour so that four pin ZnOWWhisker is fully dispersed, then stands 1 hour, prepares surface cation base group modification
Four pin ZnOWWhisker.
3. the preparation of magnesium alloy phosphorus calcium basic unit: be analytically pure calcium lactate, calcium gluconate, calcium nitrate and 60% by concentration
Phosphoric acid add deionized water is formed the phosphoric acid concentration of calcium lactate, calcium gluconate, calcium nitrate and 60% be respectively 90g/L,
The treatment fluid of 200g/L, 30g/L and 260mL/L.Magnesium alloy, to 70 DEG C, is immersed treatment fluid and carries out 3 minutes by heat treated liquid
Chemical conversion treatment, conversion processing process carries out sufficient mechanical agitation, it is thus achieved that magnesium alloy phosphorus calcium basic unit.
4. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic molten
Agent so that it is percentage by weight is 30%, at room temperature disperses 20 minutes to form stable hydroxyapatite micrometre with ultrasound wave
Grain acetone dispersion.Add the phosphoric acid of calcium lactate, calcium gluconate and 60% in deionized water, form calcium lactate, Fructus Vitis viniferae
Calciofon and 60% phosphoric acid concentration be respectively the phosphorus calcium solution of 40g/L, 60g/L and 50mL/L.By molten for the 160mL phosphorus calcium of preparation
Liquid and 1L hydroxyapatite micrometre granule acetone dispersion are sufficiently mixed as electrodeposit liquid, obtain phosphorus calcium basic unit with surface
Magnesium alloy is as negative electrode, and platinum is anode, is 70 DEG C at electrodeposition temperature, carries out electro-deposition 30 minutes with constant voltage value 10V, thus
Loose structure hydroxyapatite layer is obtained at Mg alloy surface.
5. four pin ZnOWThe preparation of whisker composite electrodeposition liquid: by concentration be analytically pure calcium gluconate, calcium hydroxide,
The four pin ZnO that 60% phosphoric acid and surface modification processWWhisker add deionized water is formed calcium gluconate, calcium hydroxide,
The four pin ZnO that the phosphoric acid of 60% and surface modification processWWhisker concentration is respectively 10g/L, 6g/L, 15mL/L and 190g/L
Electrodeposit liquid.
6. four pin ZnOWThe composite electrodeposition step of whisker: grown the magnesium of loose structure hydroxyapatite layer with surface
Alloy is negative electrode, and platinum is anode；It is 450mA/cm in electric current density2Under conditions of carry out constant current electro-deposition, at 70 DEG C electricity
Deposit 30 minutes, thus define hydroxyapatite/tetra-pin ZnO at Mg alloy surfaceWWhisker composite membrane.
Embodiment 2:
1. the preparation of decorating liquid: be analytically pure dodecyl triphenyl phosphonium bromide, octadecyldimethyl benzyl by concentration
Ammonium chloride and DTAB add in deionized water, and forming dodecyl triphenyl phosphonium bromide concentration is
1.5mmol/L, stearyl dimethyl benzyl ammonium chloride concentration are 2.5mmol/L and DTAB concentration is
The decorating liquid of 8mmol/L.
2. four pin ZnOWThe surface of whisker is modified: by 10g tetra-pin ZnOWWhisker adds in the decorating liquid that 1L is above-mentioned, in room temperature
Under with ultrasound wave disperse 1 hour so that four pin ZnOW whiskers are fully dispersed, then stand 1.5 hours, prepare surface radical cation
The four pin ZnOW whiskers that group modifies.
3. the preparation of magnesium alloy phosphorus calcium basic unit: be analytically pure calcium lactate, calcium gluconate, calcium nitrate and 60% by concentration
Phosphoric acid add deionized water is formed the phosphoric acid concentration of calcium lactate, calcium gluconate, calcium nitrate and 60% be respectively 95g/L,
The treatment fluid of 180g/L, 15g/L and 250mL/L.Magnesium alloy, to 80 DEG C, is immersed and carries out in treatment fluid 4 minutes by heat treated liquid
Chemical conversion treatment, conversion processing process carries out sufficient mechanical agitation, it is thus achieved that magnesium alloy phosphorus calcium basic unit.
4. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic molten
Agent so that it is the percentage ratio of weight is 25%, at room temperature disperses 15 minutes to form stable hydroxyapatite micrometre with ultrasound wave
Granule acetone dispersion.Add the phosphoric acid of calcium lactate, calcium gluconate and 60% in deionized water, form calcium lactate, Portugal
Grape Calciofon and 60% phosphoric acid concentration be respectively the phosphorus calcium solution of 80g/L, 50g/L and 40mL/L.200mL phosphorus calcium by preparation
Solution and 1L hydroxyapatite micrometre granule acetone dispersion are sufficiently mixed as electrodeposit liquid, obtain phosphorus calcium basic unit with surface
Magnesium alloy as negative electrode, platinum is anode, is 80 DEG C at electrodeposition temperature, carries out electro-deposition 35 minutes under constant voltage value 5V,
Thus obtain loose structure hydroxyapatite layer at Mg alloy surface.
5. four pin ZnOWThe preparation of whisker composite electrodeposition liquid: by concentration be analytically pure calcium gluconate, calcium hydroxide,
The four pin ZnO that 60% phosphoric acid and surface modification processWWhisker add deionized water is formed calcium gluconate, calcium hydroxide,
The four pin ZnO that the phosphoric acid of 60% and surface modification processWWhisker concentration is respectively 15g/L, 10g/L, 10mL/L and 170g/L
Electrodeposit liquid.
6. four pin ZnOWThe composite electrodeposition step of whisker: grown the magnesium of loose structure hydroxyapatite layer with surface
Alloy is negative electrode, and platinum is anode；It is 400mA/cm in electric current density2Under conditions of carry out constant current electro-deposition, at 80 DEG C electricity
Deposit 40 minutes, thus define hydroxyapatite/tetra-pin ZnO at Mg alloy surfaceWWhisker composite membrane.
Preparation is all 10 containing staphylococcus aureus, escherichia coli, Salmonella and candidiasis number3/ ml's is molten
Liquid, measures comparative example, embodiment 1 and embodiment 2 respectively to staphylococcus aureus, escherichia coli, Salmonella and false silk ferment
The bacteriostasis rate of female bacterium.Measurement result is as it is shown on figure 3, test result indicate that, embodiment 1 and embodiment 2 are to Staphylococcus aureus
Bacterium, escherichia coli, Salmonella and candidiasis sterilizing rate reach more than 98%, and comparative example does not possess bactericidal action.Survey
Amount comparative example, embodiment 1 and the dynamic potential polarization curve in the NaCl solution of 5% of embodiment 2；Obtain according to polarization curve
Comparative example, embodiment 1 and embodiment 2 at the corrosion potential in 5%NaCl solution and corrosion current as shown in Figure 4, result table
Bright, the corrosion resisting property of comparative example, embodiment 1 and embodiment 2 is suitable.Additionally, by comparative example, embodiment 1 and embodiment 2 in abrasion
Carrying out the wear test that load is 0.5kg in experimental machine, rotating speed is 200 revs/min, and wearing-in period is 40 minutes.Comparative example, reality
Executing the wear results of example 1 and embodiment 2 as shown in Figure 4, test result indicate that, embodiment 1 and embodiment 2 are at above-mentioned wear test
Wear extent only have the 5% of comparative example, the magnesium alloy hydroxyapatite/tetra-pin ZnO prepared according to the present inventionWWhisker composite membrane has
There is excellent antibacterial, anti-corrosion and biocompatibility.
Above-described only the preferred embodiments of the present invention, the explanation of it should be understood that above example is simply used
In helping to understand method and the core concept thereof of the present invention, the protection domain being not intended to limit the present invention, all the present invention's
Any amendment of being made within thought and principle, equivalent etc., should be included within the scope of the present invention.
Claims (7)
1. the preparation method of a novel magnesium alloy hydroxyapatite composite membrane, it is characterised in that comprise the steps of:
Step [1] four pin ZnOWThe surface moditied processing of whisker；
The preparation of step [2] magnesium alloy loose structure hydroxyapatite layer；
Four pin ZnO of step [3] modified processWThe composite electrodeposition of whisker.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 1, it is characterised in that:
Described step [1] specifically includes and operates as follows:
A1. the preparation of decorating liquid: be analytically pure dodecyl triphenyl phosphonium bromide, octadecyl dimethyl benzyl chlorine by concentration
Change ammonium and DTAB adds in deionized water, form decorating liquid；
A2. four pin ZnOWThe surface of whisker is modified: by 5-20g tetra-pin ZnOWWhisker adds in the described decorating liquid of 1L, at room temperature
0.5-1 hour is disperseed so that four pin ZnO with ultrasound waveWWhisker is fully dispersed, then stand 0.5-2 hour, prepared surface just from
Four pin ZnO of sub-base group modificationWWhisker.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 2, it is characterised in that:
Described in step a1, in decorating liquid, dodecyl triphenyl phosphonium bromide concentration is 0.5-4mmol/L, octadecyl dimethyl benzyl
Ammonium chloride concentration is 1.5-9mmol/L, and DTAB concentration is 4-15mmol/L.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 1, it is characterised in that:
Described step [2] specifically includes and operates as follows:
B1. the preparation of magnesium alloy phosphorus calcium basic unit: be analytically pure calcium lactate, calcium gluconate, calcium nitrate and 60% by concentration
Phosphoric acid adds formation treatment fluid in deionized water；Magnesium alloy, to 60-80 DEG C, is immersed the change carried out 2-5 minute by heat treated liquid
Learn conversion processing, conversion processing process carries out sufficient mechanical agitation, it is thus achieved that magnesium alloy phosphorus calcium basic unit；
B2. the preparation of magnesium alloy loose structure hydroxyapatite layer: hydroxyapatite micrometre granule is added acetone organic solvent,
Making its percentage by weight is 20%-35%, at room temperature disperses to form stable hydroxyapatite 10-30 minute with ultrasound wave micro-
Rice grain acetone dispersion；Add the phosphoric acid of calcium lactate, calcium gluconate and 60% in deionized water, form phosphorus calcium molten
Liquid；The 100-300mL phosphorus calcium solution of preparation and 1L hydroxyapatite micrometre granule acetone dispersion are sufficiently mixed rear as
Electrodeposit liquid, obtains the magnesium alloy of phosphorus calcium basic unit as negative electrode using surface, and platinum is anode, and electrodeposition temperature is 60-80 DEG C, in perseverance
Magnitude of voltage is electro-deposition 10-40 minute under conditions of 5-20V, thus obtains loose structure hydroxyapatite at Mg alloy surface
Layer.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 4, it is characterised in that:
Described in step b1, in treatment fluid, the concentration of the phosphoric acid of calcium lactate, calcium gluconate, calcium nitrate and 60% is respectively 85-230g/
L, 170-310g/L, 10-45g/L and 240-430mL/L；Calcium lactate in phosphorus calcium solution described in step b2, calcium gluconate and
The concentration of 60% phosphoric acid is respectively 25-140g/L, 40-110g/L and 30-70mL/L.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 1, it is characterised in that:
Described step [3] specifically includes and operates as follows:
C1. four pin ZnOWThe preparation of whisker composite electrodeposition liquid: by concentration be analytically pure calcium gluconate, calcium hydroxide, 60%
The four pin ZnO that phosphoric acid and surface modification processWWhisker adds formation electrodeposit liquid in deionized water；
C2. four pin ZnOWThe composite electrodeposition step of whisker: grown the magnesium alloy of loose structure hydroxyapatite layer with surface
For negative electrode, platinum is anode；It is 380-710mA/cm at current density range2Under conditions of carry out constant current electro-deposition, at 60-80
Electro-deposition 30-60 minute at DEG C, thus define hydroxyapatite/tetra-pin ZnO at Mg alloy surfaceWWhisker composite membrane.
The preparation method of a kind of novel magnesium alloy hydroxyapatite composite membrane the most according to claim 6, it is characterised in that:
Four pins that described in step c1, in electrodeposit liquid, calcium gluconate, calcium hydroxide, the phosphoric acid of 60% and surface modification process
ZnOWThe concentration of whisker is respectively 10-30g/L, 5-20g/L, 10-45mL/L and 160-310g/L.
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