CN101411892A - Method for preparing hydroxylapatite/polylactic acid composite biological coating on surface of magnesium alloy - Google Patents
Method for preparing hydroxylapatite/polylactic acid composite biological coating on surface of magnesium alloy Download PDFInfo
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- CN101411892A CN101411892A CN 200710157568 CN200710157568A CN101411892A CN 101411892 A CN101411892 A CN 101411892A CN 200710157568 CN200710157568 CN 200710157568 CN 200710157568 A CN200710157568 A CN 200710157568A CN 101411892 A CN101411892 A CN 101411892A
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- polylactic acid
- coating
- phosphate
- magnesium alloy
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 85
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 85
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 70
- 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 47
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims description 85
- 238000000576 coating method Methods 0.000 title claims description 85
- 238000000034 method Methods 0.000 title description 17
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 24
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 24
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000010839 body fluid Substances 0.000 claims abstract description 7
- 210000001124 body fluid Anatomy 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 238000004070 electrodeposition Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000011247 coating layer Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 9
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 9
- 238000005554 pickling Methods 0.000 claims description 9
- 239000001488 sodium phosphate Substances 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 9
- 235000011008 sodium phosphates Nutrition 0.000 claims description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 6
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims 1
- 239000012620 biological material Substances 0.000 abstract description 12
- 230000004071 biological effect Effects 0.000 abstract description 5
- 238000001727 in vivo Methods 0.000 abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 239000012890 simulated body fluid Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000004060 metabolic process Effects 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- GHPYJLCQYMAXGG-WCCKRBBISA-N (2R)-2-amino-3-(2-boronoethylsulfanyl)propanoic acid hydrochloride Chemical compound Cl.N[C@@H](CSCCB(O)O)C(O)=O GHPYJLCQYMAXGG-WCCKRBBISA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 230000002980 postoperative effect Effects 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 208000010444 Acidosis Diseases 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010061363 Skeletal injury Diseases 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007950 acidosis Effects 0.000 description 1
- 208000026545 acidosis disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 230000037182 bone density Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000005859 cell recognition Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 210000004351 coronary vessel Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 230000002232 neuromuscular Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to the field of a biomaterial, in particular to a preparation method for hydroxyapatite/polylactic acid composite biological coat on magnesium alloy surface, and solves the problem that an electrolytic deposition hydroxyapatite (HA) coat is not quite compact through sealing treatment of polylactic acid, so that the composite coat can improve corrosion resistance of magnesium alloy in human body fluid remarkably, and biological degradability of the composite coat is used for adjusting service cycle of the magnesium alloy in vivo. The preparation method is as follows: the magnesium alloy is subjected to electrolytic deposition in water solution consisting of calcium salt, dihydrogen phosphate or hydrogen phosphate or other additives, so as to obtain a mixture coat of several calcium phosphates; the mixture coat is treated by alkali metal hydroxide solution and then transformed into an even HA coat; the HA coat is soaked in polylactic acid solution and subjected to the sealing treatment; and finally the HA coat is dried to obtain the hydroxyapatite/polylactic acid composite coat. The preparation method which combines biological activity of the HA and biological degradability of the polylactic acid organically is used for corrosion protection of the magnesium alloy in biotic environment.
Description
Technical field
The present invention relates to the application of magnesium alloy aspect biomaterial, belong to technical field of biological material, specifically the preparation method of Mg alloy surface hydroxylapatite/polylactic acid composite biological active coating.
Background technology
Since the sixties in 20th century, biomaterial has obtained development rapidly as the substitute of repairing bone injury.At present mainly comprise metal material, ceramic material and macromolecular material etc. at the biomaterial of clinical practice.But every kind of material all has its drawback, and, macromolecular material big as the fragility of can the stripping harmful metal ion of metal material, ceramic material be undercapacity then.Comparatively speaking, magnesium and alloy thereof have a lot of potential advantages as biomaterial for medical purpose: (1) magnesium resource is abundant, and is cheap; (2) density of magnesium is 1.74g/cm
3, density minimum in all structural materials is with the Compact bone density (1.75g/cm of people's bone
3) very approaching; (3) magnesium and alloy have high specific strength and specific stiffness, and processing characteristics is good, and the specific strength of pure magnesium is 133GPa/ (g/cm
3), the specific strength of superhigh strength magnesium alloy has reached 480GPa/ (g/cm
3); (4) Young's modulus of elasticity of magnesium and alloy is about 45GPa, and more near the elastic modelling quantity (about 20GPa) of people's bone, the magnesium metal can be avoided stress-shielding effect as implant than other medical metal material; (5) magnesium and alloy have excellent biological compatibility, magnesium is the macroelement that is only second to calcium, sodium and potassium in the human body, everyone the daily requirement amount of being grown up surpasses 350mg, it participates in protein synthesis, can swash in vivo plurality of enzymes, regulates neuromuscular and central nervous system's activity, and magnesium almost participates in all metabolic processes in the human body, not only the growth to medullary cell does not have inhibitory action, does not find the cytolysis phenomenon yet, can also quicken symphysis; (6) magnesium and alloy have biodegradability, the short-term that only needs many medical embedded devices plays medical function (as angiocarpy bracket, nail and blade plate etc.), keep somewhere in vivo if implant is long-term, just have the potential danger of long-term release toxicant, need operation once more to take out.The corrosion resistance of magnesium alloy is poor, can progressively degrade and be absorbed or metabolism by body under the physiological environment in vivo, need not the taking-up of performing the operation once more.
Yet magnesium is the most active structural material, is easy to be corroded, and is especially all the more so in containing the Human Physiology environment of chloride ion.The pH value of human body is about 7.4, may cause secondary acidosis in the human body in postoperative metabolism absorption process, makes intravital pH value be lower than 7.4, more quickens the corrosion of magnesium alloy.For example, adopt magnesium or magnesium alloy to make degradable coronary artery bracket (the silk footpath is at 70-80 μ m, in the quality 300mg), postoperative needs the active time in 180 days-1 year, calculates that thus the corrosion rate of magnesium or magnesium alloy should be controlled in the 0.1mm/.But studies show that the corrosion degradation rate of pure magnesium in simulated body fluid is about 0.2-1mm/, bigger than normal than the corrosion rate of estimation, this will cause the premature failure of biomaterial.Therefore, researcheres improve the biodegradation rate of magnesium alloy in body fluid by the way of using protective coating.These protective finish also need to satisfy the requirement of biomaterial, not only good biocompatibility and degradability will be arranged, and magnesium alloy is had the certain protection effect, can regulate degradation rate and reach instructions for use.Hydroxyapatite (HA) is the more successful biomaterial of clinical practice.It is the main inorganic composition in vertebrates skeleton and the tooth, have excellent biological compatibility and biodegradability, to human body safety, nontoxic, can be spontaneous directly form very strong chemical bond with bone, along with the growth from the body osseous tissue, material is degraded gradually, and final catabolite absorbs by effect dissolving in the body or discharged by metabolic system, and defect is replaced by new life's osseous tissue gradually, thereby reaches the purpose that bone is repaired.But the mechanical property of HA is relatively poor, can not independently use as stressed member.Therefore, prepare the HA coating, can realize the mutual supplement with each other's advantages of metal and HA to a great extent, make material have favorable mechanical performance and biological activity at metal material surface.At present, the method that material surface prepares hydroxyapatite coating layer is a lot, uses wider have plasma spraying method, magnetron sputtering method, electrochemical process, detonation flame spraying method and biomimetic method etc.Wherein electrochemical deposition method can directly prepare the perfect hydroxyapatite coating layer of crystallization from calcium microcosmic salt aqueous solution under temperate condition, and electrochemical deposition method is simple to operate, and controllability is strong, and is with low cost.But at the hydroxyapatite coating layer that the Mg alloy surface electro-deposition obtains is not very fine and close, can't reach requirement of actual application.
Summary of the invention
The object of the invention is to provide a kind of environmental protection, simple Mg alloy surface to prepare the method for hydroxylapatite/polylactic acid composite biological active coating, makes magnesium alloy have good biological activity, and can realize the adjustability of degradation rate.The present invention can solve magnesium alloy and degrade too soon as biomaterial in body fluid, can not satisfy desired useful life's a difficult problem.The mechanical property that has solved simultaneously HA again is relatively poor, can not independently use as stressed member, and the hydroxyapatite coating layer that electro-deposition obtains is not very fine and close, can't reach problems such as application request.
To achieve these goals, technical scheme of the present invention is:
The preparation method of Mg alloy surface hydroxylapatite/polylactic acid composite biological active coating is as follows:
(1) oil removing: remove the greasy dirt of matrix surface with alkaline solution, temperature 60-90 ℃, time 2-20min;
(2) pickling: remove the oxide and the rusty scale of matrix surface, room temperature, time 10-90s with weakly acidic solution;
(3) electro-deposition calcium phosphate coating: in the aqueous solution that contains calcium salt, dihydric phosphate, hydrophosphate and other additive composition, carry out electro-deposition, pH value of solution 4-5, the magnesium alloy sample is as negative electrode, corrosion resistant plate or titanium plate are as anode, deposition voltage 1-8V, time 0.5-4h, room temperature, magnetic agitation; Obtain the mixture coating be made up of multiple calcium phosphate, coating layer thickness is 3-40 μ m.
(4) alkali liquor is handled: the coating after the electro-deposition is immersed in 0.5-4h in the alkali liquor, temperature 50-90 ℃, obtains the HA coating;
(5) configuration polylactic acid solution: polylactic acid is dissolved in the polylactic acid solution of making variable concentrations in the organic solvent;
(6) preparation polylactic acid coating: the magnesium alloy sample of surface coverage hydroxyapatite coating layer is immersed in the polylactic acid solution room temperature, time 5-60s;
(7) oven dry: it is the hydroxyapatite/polylactic acid composite coating of 4-45 μ m that 5-60min acquisition thickness is handled in 50-150 ℃ of oven dry.
Described degreasing fluid is wherein one or more composite aqueous solutions of alkali metal hydroxide 10-70g/l, carbonate 15-50g/l, phosphate 20-70g/l, bicarbonate 10-80g/l.Hydroxide can be sodium hydroxide, potassium hydroxide, and carbonate can be sodium carbonate, potassium carbonate, and phosphate can be sodium phosphate, potassium phosphate, and bicarbonate can be sodium bicarbonate, potassium bicarbonate.
That described acid washing water solution adopts is dihydric phosphate 10-80g/l and corrosion inhibiter 0.1-2g/l.
Calcium salt in the described electro-deposition calcium phosphate aqueous solution is calcium chloride, lime nitrate a kind of or its compound wherein, and its concentration is calcium chloride 0.01-0.3M, lime nitrate 0.01-0.3M; Dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate a kind of or its compound wherein, and its concentration is sodium dihydrogen phosphate 0.005-0.2M, potassium dihydrogen phosphate 0.005-0.2M, Ammonium biphosphate 0.005-0.2M; Hydrophosphate is ammonium hydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate a kind of or its compound wherein, and its concentration is ammonium hydrogen phosphate 0.005-0.2M, potassium hydrogen phosphate 0.005-0.2M, dibastic sodium phosphate 0.005-0.2M; Other additive is hydrogen peroxide, ethanol a kind of or its compound wherein, and its concentration is hydrogen peroxide 5-40ml/l, ethanol 50-400ml/l.
Described corrosion inhibiter is a kind of or its compound in magnesium alloy corrosion inhibiter potassium fluoride commonly used, the sodium fluoride.
The molar concentration ratio of calcium salt and phosphate radical is 1-2 in the described electro-deposition calcium phosphate aqueous solution.
It is sodium hydroxide or potassium hydroxide a kind of or its compound wherein that described alkali liquor is handled employed aqueous solution, and its concentration is sodium hydroxide 0.1-2M, potassium hydroxide 0.1-2M.
Described polylactic acid is white powder body, and molecular weight is 20-80 ten thousand.The organic solvent that is used to prepare polylactic acid solution is acetone, dehydrated alcohol etc.The polylactic acid solution concentration of preparing is 20-300g/l, can be by the concentration of adjusting polylactic acid and the polylactic acid coating that soak time is prepared different-thickness, composition.
The degradation rate of described magnesium alloy in body fluid can be realized the degradation rate controllability by the composition of regulating the hydroxyapatite/polylactic acid composite coating.
Principle of the present invention is as follows:
The present invention carries out the compound biodegradability of magnesium alloy in people's body fluid of improving with polylactic acid and hydroxyapatite.Polylactic acid belongs to macromolecular material, have excellent biocompatibility and biodegradability, the degraded back generates water and carbon dioxide, nontoxic, aspects such as constituent, microstructure, mechanical performance and degradation speed at material can be regulated and control in advance, but its maximum defective is to lack the cell recognition signal.The hydroxyapatite/polylactic acid composite can be realized both mutual supplement with each other's advantages to a great extent, gives material bone conductibility and biodegradability when having good mechanical performance and biocompatibility.Therefore, the present invention adopts the method for electro-deposition at Mg alloy surface deposition one deck hydroxyapatite coating layer, be dipped into then and carry out the sealing of hole processing in the polylactic acid solution, the surface obtains the polylactic acid coating, the biomaterial that obtains thus not only has the metallic character of magnesium alloy excellence, and can regulate degradation rate by the content of hydroxyapatite and polylactic acid in the change composite coating, realize the controllability of degradation rate.
The present invention has following advantage:
1, processing method of the present invention does not contain human body and the deleterious material of environment, belongs to environmental type technology.
2, solution composition of the present invention and operating procedure are simple, are easy to control, process stabilizing.
3, the composite coating prepared of the present invention is even, and is good with basal body binding force, has good biological activity, and can improve the biodegradability of magnesium alloy in body fluid.
4, the present invention can realize the controllability of magnesium alloy degradation rate by the composition of adjusting the hydroxyapatite/polylactic acid composite coating.
5, the present invention makes full use of the biodegradability of biological activity and the polylactic acid of HA, and both are organically combined, and learns from other's strong points to offset one's weaknesses, and will promote the extensive use of magnesium alloy aspect biomaterial.
The specific embodiment
The preparation method of Mg alloy surface hydroxylapatite/polylactic acid composite biological active coating of the present invention, step is as follows:
(1) pre-treatment: pre-treatment comprises oil removing and two steps of pickling, all will wash after each step.
Described degreasing fluid is alkali metal hydroxide 10-70g/l, carbonate 15-50g/l, phosphate 20-70g/l, bicarbonate 10-80g/L, wherein one or more composite aqueous solutions.It is 2-20min in 60-90 ℃ the degreasing fluid that the magnesium alloy sample is immersed in temperature, removes oils and fats and the dirt of Mg alloy surface remnants.
Described hydroxide can be sodium hydroxide, potassium hydroxide, and carbonate can be sodium carbonate, potassium carbonate, and phosphate can be sodium phosphate, potassium phosphate, and bicarbonate can be sodium bicarbonate, potassium bicarbonate.
That described acid washing water solution adopts is dihydric phosphate 10-80g/l and corrosion inhibiter 0.1-2g/l.Magnesium alloy sample after the oil removing is immersed in 10-90s in the pickle, room temperature, the oxide and the rusty scale of removal sample surfaces are beneficial to the adhesion that improves coating and parent metal.
Described dihydric phosphate is a kind of or its compound in potassium dihydrogen phosphate, sodium dihydrogen phosphate, the Ammonium biphosphate; Corrosion inhibiter is a kind of or its compound in magnesium alloy corrosion inhibiter potassium fluoride commonly used, the sodium fluoride.
(2) electro-deposition calcium phosphate coating
At first, preparing the required solution of electro-deposition places stand-by.Its method is to get the calcium salt of metering, dihydric phosphate or hydrophosphate respectively to put into exsiccant beaker, adds an amount of distilled water, is placed in 60~100 ℃ the water-bath it is dissolved fully.The solution that dissolving is good mixes, and stirs with Glass rod it is mixed fully, adds an amount of additive, the pH value that uses a kind of regulator solution in sodium hydroxide, ammonia, nitric acid or the hydrochloric acid as 4-5 after, adding distil water is extremely volume required.
Calcium salt in the described electro-deposition calcium phosphate coating aqueous solution is calcium chloride, lime nitrate a kind of or its compound wherein, and its concentration is calcium chloride 0.01-0.3M, lime nitrate 0.01-0.3M; Dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate a kind of or its compound wherein, and its concentration is sodium dihydrogen phosphate 0.005-0.2M, potassium dihydrogen phosphate 0.005-0.2M, Ammonium biphosphate 0.005-0.2M; Hydrophosphate is ammonium hydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate a kind of or its compound wherein, and its concentration is ammonium hydrogen phosphate 0.005-0.2M, potassium hydrogen phosphate 0.005-0.2M, dibastic sodium phosphate 0.005-0.2M; Other additive is hydrogen peroxide, ethanol a kind of or its compound wherein, and its concentration is hydrogen peroxide 5-40ml/l, ethanol 50-400ml/l.The molar concentration ratio of calcium salt and phosphate radical is 1-2 in the electro-deposition calcium phosphate coating solution.
Secondly, carry out electro-deposition HA coating.Its method is for to be connected the magnesium alloy sample after the pickling with power cathode, corrosion resistant plate or titanium plate are connected with power anode, voltage transfers to 1-8V, room temperature, magnetic agitation is behind the electro-deposition 0.5-4h, take out, oven dry obtains the mixture coating be made up of multiple calcium phosphate, and coating layer thickness is 3-40 μ m.
(3) alkali liquor is handled
It is that calcium phosphate coating with the electro-deposition after drying is immersed in 0.5-4h in the alkali liquor that described alkali liquor is handled, and makes multiple calcium phosphate mixture coating be transformed into uniform HA coating, temperature 50-90 ℃.
It is sodium hydroxide or potassium hydroxide a kind of or its compound wherein that described alkali liquor is handled employed aqueous solution, and its concentration is sodium hydroxide 0.1-2M, potassium hydroxide 0.1-2M.
(4) polylactic acid coating
At first, configure the polylactic acid solution for later use.Take by weighing a certain amount of polylactic acid powder body and put in the appropriate amount of organic, stir, polylactic acid is dissolved fully.
Described polylactic acid is white powder body, and molecular weight is 20-80 ten thousand, and organic solvent is acetone, dehydrated alcohol etc., and the polylactic acid solution concentration of preparing is 20-300g/l.
Secondly, the magnesium alloy sample of surface coverage hydroxyapatite coating layer is immersed in obtains polylactic acid coating, room temperature, time 5-60s in the polylactic acid solution;
Described polylactic acid coating layer thickness and structure can be adjusted by adjusting polylactic acid solution concentration and soak time.
At last, oven dry is handled and is obtained the hydroxyapatite/polylactic acid composite coating, and temperature 50-150 ℃, time 5-60min, obtaining thickness is the hydroxyapatite/polylactic acid composite coating of 4-45 μ m.
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
Sample is a die casting AZ91D magnesium alloy, is of a size of 30mm * 25mm * 5mm, and its concrete operations step is as follows:
1, oil removing: degreasing fluid consists of the aqueous solution of sodium hydroxide 50g/L, sodium phosphate 40g/l, sodium carbonate 30g/l, 70 ℃ of temperature, time 8min, oils and fats and the dirt of removal Mg alloy surface remnants;
2, pickling: that acid washing water solution adopts is Ammonium biphosphate 30g/l and potassium fluoride 0.5g/l.Magnesium alloy sample after the oil removing is immersed in 60s in the pickle of room temperature, removes the oxide and the rusty scale of sample surfaces.
3, electro-deposition calcium phosphate coating: the electro-deposition aqueous solution consists of lime nitrate 0.1M, sodium dihydrogen phosphate 0.06M, hydrogen peroxide 20ml/l.It is 4.3 that sodium hydroxide is regulated pH.Magnesium alloy sample after the pickling is as negative electrode, and corrosion resistant plate is as anode, and supply voltage transfers to 3V, behind the electro-deposition 2h, takes out, and oven dry obtains the mixture coating be made up of multiple calcium phosphate, and coating layer thickness is 15 μ m.
4, alkali liquor is handled: the coating after the electro-deposition is immersed in 2h in the 0.5M sodium hydrate aqueous solution, and 70 ℃ of temperature obtain uniform HA coating, oven dry.
5, polylactic acid solution: the polylactic acid powder body 5g that takes by weighing molecular weight and be 40-50 ten thousand puts into beaker, adds the acetone of 50ml then, stirs, and polylactic acid is dissolved fully.
6, polylactic acid coating: the magnesium alloy sample of surface coverage hydroxyapatite coating layer is dipped in the polylactic acid solution, obtains the polylactic acid coating, room temperature, time 30s;
7, oven dry is handled: 100 ℃ of oven dry 10min obtain the hydroxyapatite/polylactic acid composite coating.
Present embodiment finally obtain thickness be 18 μ m evenly, composite coating that adhesion is good, the magnesium alloy sample that applies this composite coating is immersed in 48h does not see significant change in the rear surface in the simulated body fluid.
Embodiment 2
Sample is of a size of 30mm * 25mm * 2mm for extruding attitude AZ31 D magnesium alloy, and difference from Example 1 is:
1, pickling: that acid washing water solution adopts is sodium dihydrogen phosphate 50g/l and sodium fluoride 1g/l.Magnesium alloy sample after the oil removing is immersed in 30s in the pickle of room temperature, removes the oxide and the rusty scale of sample surfaces.
2, electro-deposition calcium phosphate coating: the electro-deposition aqueous solution consists of calcium chloride 0.05M, ammonium hydrogen phosphate 0.03M, ethanol 200ml/l, and it is 4.1 that hydrochloric acid is regulated pH.The magnesium alloy sample is as negative electrode, and the titanium plate is as anode, and supply voltage transfers to 1.5V, behind the electro-deposition 3h, takes out, and oven dry obtains the mixture coating be made up of multiple calcium phosphate, and coating layer thickness is 20 μ m.
3, polylactic acid solution: the polylactic acid powder body 2.5g that takes by weighing molecular weight and be 30-40 ten thousand puts into beaker, adds the ethanol solution of 50ml then, stirs, and polylactic acid is dissolved fully.
4, polylactic acid coating: the magnesium alloy sample of surface coverage hydroxyapatite coating layer is dipped in the polylactic acid solution, obtains the polylactic acid coating, room temperature, time 60s;
It is that the hydroxyapatite/polylactic acid composite coating of 23 μ m is even, adhesion is good that present embodiment finally obtains thickness, the magnesium alloy sample that applies this composite coating is immersed in 48h does not see significant change in the rear surface in the simulated body fluid.
Embodiment 3
Sample is of a size of 30mm * 25mm * 2mm for extruding attitude AM60 magnesium alloy, and difference from Example 1 is:
1, electro-deposition calcium phosphate coating: the electro-deposition aqueous solution consists of lime nitrate 0.2M, potassium dihydrogen phosphate 0.1M, ethanol 100ml/l, hydrogen peroxide 10ml/l, and it is 4.2 that ammonia is regulated pH.The magnesium alloy sample is as negative electrode, and corrosion resistant plate is as anode, and supply voltage transfers to 5V, behind the electro-deposition 1h, takes out, and oven dry obtains the mixture coating be made up of multiple calcium phosphate, and coating layer thickness is 13 μ m.
2, alkali liquor is handled: the coating after the electro-deposition is immersed in 1h in the 1.5M potassium hydroxide aqueous solution, 80 ℃ of temperature, and the mixture coating of being made up of multiple calcium phosphate is transformed into uniform HA coating, oven dry.
3, polylactic acid coating: the magnesium alloy sample of surface coverage hydroxyapatite coating layer is dipped in the polylactic acid solution, obtains the polylactic acid coating, room temperature, time 20s;
4, oven dry is handled: 80 ℃ of oven dry 30min obtain the hydroxyapatite/polylactic acid composite coating.
Present embodiment finally obtain thickness be 14 μ m evenly, composite coating that adhesion is good, the magnesium alloy sample that applies this composite coating is immersed in 48h does not see significant change in the rear surface in the simulated body fluid.
Comparative Examples 1
Sample is of a size of 30mm * 25mm * 2mm for extruding attitude AZ91 D magnesium alloy, and difference from Example 1 is: the magnesium alloy sample does not apply the polylactic acid coating after obtaining the HA coating through oil removing, pickling, electro-deposition calcium phosphate coating and alkali liquor processing.
What finally obtain is the HA coating of white, and the magnesium alloy sample that covers the HA coating is immersed in 48h in the simulated body fluid, section H A coating shedding.
Comparative Examples 2
Sample is of a size of 30mm * 25mm * 2mm for extruding attitude AZ31D magnesium alloy, and difference from Example 1 is: after the oil removing of magnesium alloy sample process, the pickling processes, do not have electro-deposition HA coating, directly be dipped into and obtain the polylactic acid coating in the polylactic acid solution.
Because it is acid that polylactic acid shows, magnesium alloy is immersed in appearance corrosion in rear surface in the polylactic acid solution, and final resulting polylactic acid coating is a clear films, but coating is inhomogeneous, is easy to peel off from matrix surface.Sample is immersed in just occurred obvious corrosion in the simulated body fluid behind the 24h.
Claims (7)
1. the preparation method of a Mg alloy surface hydroxylapatite/polylactic acid composite biological coating is characterized in that operating as follows:
(1) oil removing: remove the greasy dirt of matrix surface with alkaline solution, temperature 60-90 ℃, time 2-20min;
(2) pickling: remove the oxide and the rusty scale of matrix surface, room temperature, time 10-90s with weakly acidic solution;
(3) electro-deposition calcium phosphate coating: in the aqueous solution that contains calcium salt, dihydric phosphate or hydrophosphate and other additive composition, carry out electro-deposition, pH value of solution 4-5, the magnesium alloy sample is as negative electrode, corrosion resistant plate or titanium plate be as anode, deposition voltage 1-8V, room temperature, magnetic agitation, sedimentation time 0.5-4h obtains the mixture coating be made up of multiple calcium phosphate, and coating layer thickness is 3-40 μ m;
(4) alkali liquor is handled: the coating after the electro-deposition is immersed in 0.5-4h in the alkali liquor, makes multiple calcium phosphate mixture coating be transformed into uniform HA coating, temperature 50-90 ℃;
(5) polylactic acid is dissolved in the polylactic acid solution of making variable concentrations in the organic solvent;
(6) the magnesium alloy sample that will cover hydroxyapatite coating layer is immersed in and carries out sealing of hole in the polylactic acid solution and handle, and the surface obtains the polylactic acid coating, room temperature, time 5-60s;
(7) oven dry processing acquisition thickness is the hydroxyapatite/polylactic acid composite coating of 4-45 μ m, temperature 50-150 ℃, and time 5-60min.
2. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological coating of claim 1, it is characterized in that: that described acid washing water solution adopts is dihydric phosphate 10-80g/l and corrosion inhibiter 0.1-2g/l; Dihydric phosphate is a kind of or its compound in potassium dihydrogen phosphate, sodium dihydrogen phosphate, the Ammonium biphosphate; Corrosion inhibiter is a kind of or its compound in magnesium alloy corrosion inhibiter potassium fluoride commonly used, the sodium fluoride.
3. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological coating of claim 1, it is characterized in that: the calcium salt in the described electro-deposition calcium phosphate coating aqueous solution is calcium chloride, lime nitrate a kind of or its compound wherein, its concentration is calcium chloride 0.01-0.3M, lime nitrate 0.01-0.3M; Dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate a kind of or its compound wherein, and its concentration is sodium dihydrogen phosphate 0.005-0.2M, potassium dihydrogen phosphate 0.005-0.2M, Ammonium biphosphate 0.005-0.2M; Hydrophosphate is ammonium hydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate a kind of or its compound wherein, and its concentration is ammonium hydrogen phosphate 0.005-0.2M, potassium hydrogen phosphate 0.005-0.2M, dibastic sodium phosphate 0.005-0.2M; Other additive is hydrogen peroxide, ethanol a kind of or its compound wherein, and its concentration is hydrogen peroxide 5-40ml/l, ethanol 50-400ml/l.
4. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological of claim 3 active coating, it is characterized in that: the molar concentration ratio of calcium salt and phosphate radical is 1-2 in the described electro-deposition calcium phosphate coating solution.
5. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological coating of claim 1, it is characterized in that: described alkali liquor is handled the aqueous solution that uses and is sodium hydroxide or potassium hydroxide a kind of or its compound wherein, its concentration is sodium hydroxide 0.1-2M, potassium hydroxide 0.1-2M.
6. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological coating of claim 1, it is characterized in that: described polylactic acid is white powder body, and molecular weight is 20-80 ten thousand; The organic solvent that is used to prepare polylactic acid is acetone or dehydrated alcohol, and the polylactic acid solution concentration of preparing is 20-300g/l, by the concentration of adjusting polylactic acid and the polylactic acid coating that soak time is prepared different-thickness, composition.
7. according to the preparation method of the described Mg alloy surface hydroxylapatite/polylactic acid composite biological coating of claim 1, it is characterized in that: the degradation rate of described magnesium alloy in body fluid realized the degradation rate controllability by the composition of regulating the hydroxyapatite/polylactic acid composite coating.
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