CN108772559A - A kind of bioceramic Base Metal composite material and preparation method and purposes - Google Patents
A kind of bioceramic Base Metal composite material and preparation method and purposes Download PDFInfo
- Publication number
- CN108772559A CN108772559A CN201810620617.1A CN201810620617A CN108772559A CN 108772559 A CN108772559 A CN 108772559A CN 201810620617 A CN201810620617 A CN 201810620617A CN 108772559 A CN108772559 A CN 108772559A
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- China
- Prior art keywords
- powder
- bioceramic
- composite material
- base metal
- ball
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- Granted
Links
- 239000003462 bioceramic Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 239000010953 base metal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000002184 metal Substances 0.000 claims abstract description 84
- 239000011575 calcium Substances 0.000 claims abstract description 73
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 72
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000000919 ceramic Substances 0.000 claims abstract description 52
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010955 niobium Substances 0.000 claims abstract description 25
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000007943 implant Substances 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000004615 ingredient Substances 0.000 claims abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 230000008439 repair process Effects 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000713 high-energy ball milling Methods 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 13
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 13
- 238000003701 mechanical milling Methods 0.000 claims description 12
- 229910052712 strontium Inorganic materials 0.000 claims description 11
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000013590 bulk material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 3
- 239000002905 metal composite material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- 210000000988 bone and bone Anatomy 0.000 description 11
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- 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 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 6
- 210000000963 osteoblast Anatomy 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 5
- 235000019838 diammonium phosphate Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
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- 238000003823 mortar mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 241000699670 Mus sp. Species 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000000975 bioactive effect Effects 0.000 description 3
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000017423 tissue regeneration Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002159 nanocrystal 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
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- UWSONZCNXUSTKW-UHFFFAOYSA-N 4,5-Dimethylthiazole Chemical class CC=1N=CSC=1C UWSONZCNXUSTKW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BKPKZAGCDUUIPH-UHFFFAOYSA-N C(O)(O)=O.[P] Chemical compound C(O)(O)=O.[P] BKPKZAGCDUUIPH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 239000011247 coating layer Substances 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000006028 limestone Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- GFUGMBIZUXZOAF-UHFFFAOYSA-N niobium zirconium Chemical compound [Zr].[Nb] GFUGMBIZUXZOAF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical compound [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
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- 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
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The present invention relates to a kind of bioceramic Base Metal composite material and preparation method and purposes.The bioceramic Base Metal composite material is sintered by the raw material of following mass fraction：60-98 parts of calcium microcosmic salt biological ceramic powder, the first 1-39 parts of metal powder, the second 1-15 parts of metal powder；The ingredient of first metal powder includes niobium and/or tantalum；The ingredient of second metal powder includes silver and/or copper.This composite material plays the synergistic effect of three heavy constituents, and compressive strength is up to 250-340MPa, and fracture toughness is up to 3-4.15MPam1/2, Vickers hardness overcomes the problem of calcium microcosmic salt bioceramic mechanical strength deficiency up to 400-460HV, is a kind of bioceramic base nano metal composite material of high tenacity, is mainly used in human body hard tissue and repairs in implant, has good potential applicability in clinical practice.
Description
Technical field
Enter bone alternate material technical field the present invention relates to biological plants more particularly to one kind having both osteoinductive and antibiotic property
Bioceramic Base Metal composite material and preparation method and purposes.
Background technology
The bone and joint of health are to maintain organization of human body stability and the primary condition of free movement.However, when due to
When the reasons such as accident, disease cause bony segment and joint to lose normal function, need with androgynous or allograph bone, Joint Transplantation come
The tissue that substitution and reparation are damaged.
There is good bioactivity, corrosion resistant with calcium phosphorus (Ca-P) bioceramic similar in natural bone mineralogical composition and structure
Corrosion and self-bone grafting ability, but in it the big (K of brittlenessIC≈1MPa·m1/2) defect limit it and can be only applied to not
The case where bearing load or being subjected only to pressure loading.On the other hand, not the bone implant material of antibiotic property after implant surgery
It is easy due to infection so that implant loosens failure.In fact, homogenous material is not well positioned to meet internal complex load environment
Application, and it is this to strengthen brittle ceramic calcium microcosmic salt bioceramic using bioactive metals such as the niobiums of high tenacity, high intensity
Metal and the respective advantage of ceramics is exactly utilized in method, develops new bio ceramic base-metallic composite, existing bone lures
The property led, antibiotic property, and have enough mechanical strengths, it has broad application prospects in medical fields such as hard tissue repairs.
Although research in recent years is made that bioceramic (such as ZrO) based composites in the preparation of implant and application
Correlation report, but people's bone key component, possess most good osteoinductive calcium microcosmic salt bioceramic base composite material system
It is standby, also non-someone's research and invention.Therefore, to calcium microcosmic salt bioceramic base bioceramic-metal nano composite antibacterial material
It prepares, machine-shaping and biocompatible mechanism carry out system research and has now for solving defect existing for bioceramic material
Real urgency and long-range scientific meaning.
CN102631704A discloses a kind of titanium aluminium base calcium microcosmic salt bio-ceramic coating and preparation method, and the invention is using heavy
Shallow lake method prepares the mixture of calcium microcosmic salt biological ceramic powder and glycerine, is then brushed in the titanium-aluminium alloy Jing Guo corrosion treatment
Surface forms biological coating by high temperature sintering, and prepared coating layer thickness is 0.1-3.0mm.Bio-ceramic coating enhances
The bioactivity of metal is convenient for induced cell growth.But because ceramic coating it is relatively thin and in transplant because coating with gold
Belong to the difference of matrix properties and be easy to fall off, to affect its application.
CN104841018A discloses a kind of multi-layer biological composite material and preparation method.The Biocomposite material with
Titanium alloy is matrix, and titanium alloy+calcium microcosmic salt bioceramic is middle layer, and calcium microcosmic salt bioceramic is biological ceramic surface；Technique
Steps are as follows：It will be dried after titanium, niobium, zirconium powder mechanical alloying ball milling, obtain matrix mixed-powder；By titanium, niobium, zirconium powder machine
After tool aurification, addition calcium microcosmic salt bioceramic ball milling is dried after mixing powder, obtains middle layer mixed-powder.By matrix mixed-powder,
Middle layer mixed-powder and calcium microcosmic salt biological ceramic powder are respectively charged into lower layer, middle level and the upper layer of graphite jig, then utilize
Plasma discharging stove is sintered, and furnace cooling is up to multi-layer biological composite material.Utilize the multilayer materials prepared by the present invention
Not only there is with the comparable mechanical property of people's bone but also substantially increase the bioactivity of material；Present invention process cleaning, simple, cost
It is cheap, it is easy to accomplish industrialization.But middle layer cannot be used separately as implant, overall mechanical properties are dependent on gold
Belong to, and the Young's modulus of coating and matrix, coefficient of thermal expansion are different, coating portion partial volume is easy to crack.
Therefore, it is necessary to develop a kind of bioceramic Base Metal composite material having both osteoinductive and antibiotic property, in conjunction with gold
Category and the respective advantage of bioactive ceramics one pack system, to promote the further development of medical implant.
Invention content
It is not adapted to body tissue mechanics for conventional medical metal implant material material, do not have degradability or degradation
It is mismatched with regeneration and restoration caused by can not regulating and controlling and causes tissue not in body because part harmful ion is discharged
In the problems such as adaptation and Ca-P based biologic active ceramics material fracture toughness it is low, compressive strength is low, can be only applied to not
The defects of bearing load or being subjected only to pressure loading having both osteoinductive one of the objects of the present invention is to provide one kind and resist
The bioceramic Base Metal composite material of bacterium property, in conjunction with metal and the respective advantage of bioactive ceramics one pack system, it would be desirable to push away
Into the further development of medical implant.
For this purpose, the present invention adopts the following technical scheme that：
In a first aspect, the present invention provides a kind of bioceramic Base Metal composite material, burnt by the raw material of following mass fraction
It ties：
60-98 parts of calcium microcosmic salt biological ceramic powder, for example, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78
Part, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts or 98 parts etc., the first 1-39 parts of metal powder, for example, 1 part, 5 parts,
10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 39 parts etc., the second 1-15 parts of metal powder, such as 1 part, 2 parts, 5 parts, 8 parts,
10 parts, 12 parts or 15 parts etc.；
The calcium microcosmic salt biological ceramic powder includes hydroxyapatite powder, strontium containing hydroxyapatite powder, carbonic acid phosphorus ash
In stone powder or calcium octahate phosphate powder any one or at least two combination；The ingredient of first metal powder includes niobium
And/or tantalum；The ingredient of second metal powder includes silver and/or copper.
" comprising " of the present invention, it is intended that it can also include other components, these other components exceptionally except described group
Assign the composite material containing silicon different characteristics.In addition to this, " comprising " of the present invention may be replaced by closed
" for " or " by ... form ".
Calcium microcosmic salt bioceramic is also the main component of people's bone as the biological implantation material being widely used,
It is used as matrix in this composite material, excellent osteoinductive is provided；The ingredient of first metal powder is biocompatible metal, nontoxic
Property, biocompatibility is strong, is easy to powder metallurgy, the main body as Metal toughened phase；The present invention is used with same raw with titanium, zirconium
Niobium, the tantalum metal of object compatibility, there is no titanium, the defects of zirconium powder, that is, is easy that cold welding occurs with ball mill container wall in ball milling
Effect leads to very low yield, component ratio imbalance and must be added to stabilizer come a series of problems, such as reducing cold-welding effect.
Second metal both plays the role of toughening, also assigns composite material antibacterial ability, to minimize Bone Defect Repari in the process because of bacterium
Infect the implant loosening brought or the problem that falls off.This three component presses the compound rear collaboration mutually of mass fraction of the present invention,
So that composite material has up to 3-4.15MPam1/2Fracture toughness, Vickers hardness is up to 400-460HV, calcium microcosmic salt biology pottery
Porcelain, niobium and antibacterial metal are nanocrystal, and crystallite dimension 10-300nm, ceramics are evenly distributed with metal phase, golden
Symbolic animal of the birth year size is 10-20 μm, and composite material of the present invention is a kind of bioceramic base nano metal composite material of high tenacity, and simultaneous
Have excellent biocompatibility and antibiotic property, is suitable for clinical hard tissue repair.
Preferably, the bioceramic Base Metal composite material is sintered by the raw material of following mass fraction：
70-90 parts of calcium microcosmic salt biological ceramic powder, the first 10-20 parts of metal powder, the second 5-10 parts of metal powder.
Preferably, the mass ratio of the calcium microcosmic salt biological ceramic powder, the first metal powder and the second metal powder is 16:
3:1。
Preferably, the ingredient of first metal powder is niobium.
Preferably, the purity of first metal powder and the second metal powder is 99.99wt% or more, such as
99.992wt%, 99.995wt%, 99.998wt% or 99.999wt% etc..
Preferably, the calcium microcosmic salt biological ceramic powder is strontium containing hydroxyapatite powder and/or podolite powder.
Hydroxyapatite is easy to replace, its further functionalization, enhancing can be made to promote the effect of bone uptake with substitutions such as strontium or carbonates
Fruit.
Preferably, the bioceramic Base Metal composite material is bulk, based on calcium microcosmic salt bioceramic, inside points
It is furnished with the metal phase that size is 1-20 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 μm etc..It is described
The metal phase of size effectively hinders microfissure in the extension of composite inner, to effectively avoid Macroscopic.
Preferably, the crystallite dimension of the bioceramic Base Metal composite material be 10-300nm, such as 10nm, 20nm,
50nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm or 300nm etc., preferably 20nm.
Crystallite dimension is smaller, and the strength of materials is higher, it then follows Hall-Page relationship.
Preferably, the consistency of the bioceramic Base Metal composite material be 90%-99.9%, such as 90%,
90.2%, 90.5%, 90.8%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%,
95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5% or 99.9% etc., preferably
99.9%.
Preferably, the fracture toughness of the bioceramic Base Metal composite material is 3-4.15MPam1/2, such as
3MPa·m1/2、3.2MPa·m1/2、3.5MPa·m1/2、3.8MPa·m1/2、4MPa·m1/2Or 4.15MPam1/2Deng.
Second aspect, the present invention provide a kind of preparation side of bioceramic Base Metal composite material as described in relation to the first aspect
Method includes the following steps：
(1) calcium microcosmic salt biological ceramic powder is prepared；
(2) the first metal powder and the second metal powder are mixed to get mixed-powder, ball milling obtains alloy powder；
(3) alloy powder obtained by calcium microcosmic salt biological ceramic powder obtained by step (1) and step (2) is mixed, obtains raw material
Powder；
(4) step (3) raw material powder is subjected to discharge plasma sintering, the bulk material obtained after cooling is made a living
Object ceramic base metallic composite.
Discharge plasma, which is sintered (SPS) technology, can be fine and close block material by powder compacting in lower temperature
Material.For example, the decomposition temperature of calcium microcosmic salt bioceramic is 1100 DEG C, the fusing point of niobium is 2468 DEG C, and the fusing point of tantalum is 2995 DEG C, zirconium
Fusing point be 1852 DEG C, silver point be 962 DEG C, 1083 DEG C of the fusing point of copper.Wherein the fusion temperature of niobium, tantalum is far above calcium microcosmic salt
The decomposition temperature of bioceramic, therefore conventional metallurgical method cannot melt metal niobium, and calcium before calcium microcosmic salt bioceramic decomposes
Microcosmic salt bioceramic can lose its excellent biocompatibility after decomposing.Therefore, conventional metallurgical method prepares calcium microcosmic salt biology pottery
Porcelain-bioactive metal functional composite material has difficulties.And powder of discharge plasma sintering technology when being utilized energization
The local high current heat release of contact, and allow and close on substance phase counterdiffusion fusion, it is i.e. plastic to reach niobium, the fusing point of tantalum,
Sintering can be completed at 700 DEG C or so.So discharge plasma sintering technology solves the high-melting-point and calcium microcosmic salt biology of niobium
This contradiction of the low decomposition temperature of ceramics, and can be energy saving under low temperature conditions, production security can also be improved.
The present invention prepares bioceramic Base Metal composite material by the technique of ball milling+SPS respectively, and the method operation is feasible
Property it is strong, repeatability is high, easily batch production.
Step (1) method for preparing calcium microcosmic salt biological ceramic powder does not limit, and can be straight from the prior art
The method obtained, such as hydro-thermal method.
Illustratively, when calcium microcosmic salt biological ceramic powder used is di salt powder, step (1) specifically includes：
Use Ca:P molar ratios are 5:3 diammonium hydrogen phosphate solution and calcium nitrate solution mixes dropwise, drop rate 2-10mL/min,
Constant pH is to heat 1-3h in 10-12, is transferred in hydrothermal reaction kettle and continues heating progress hydro-thermal reaction 10-15h, hydro-thermal reaction
Temperature be 100-200 DEG C, products therefrom by centrifugation, washing, it is dry after, obtain di salt powder.
Preferably, step (1) the calcium microcosmic salt biological ceramic powder also passes through ball milling.Effect is further to refine.
Preferably, step (1) described ball milling carries out in protective gas environment.
Preferably, the protective gas includes nitrogen and/or argon gas.
Preferably, the rate of step (1) described ball milling be 1600-1800r/min, such as 1600r/min, 1620r/min,
1650r/min, 1680r/min, 1700r/min, 1750r/min or 1800r/min etc., Ball-milling Time 1-3h, such as 1h,
1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h etc..
When calcium microcosmic salt bioceramic Ball-milling Time is more, calcium microcosmic salt bioceramic can begin to decompose into oxygen in high energy process
The impurity such as apatite, tetracalcium phosphate, type alpha tricalcium phosphate, although these three impurity also have a biocompatibility, poor chemical stability,
It cannot be implanted into environment and be stabilized in vivo.
On the other hand, when calcium microcosmic salt bioceramic Ball-milling Time is less, powder not yet refines, and gap is more between powder, reaches
Less than higher-density.Pass through and adjust Ball-milling Time and rate so that crystal grain refinement to nanocrystalline, by dislocation when stress transported by material
Dynamic to be limited by crystal boundary, material can be more difficult to surrender or be broken, and also just be more difficult to fail in Clinical practice.
Preferably, step (2) described mixing and ball milling carries out in protective gas environment.
Preferably, the protective gas includes nitrogen and/or argon gas.
Preferably, the rate of step (2) described mixing and ball milling is 1600-1800r/min, such as 1600r/min, 1620r/
Min, 1650r/min, 1680r/min, 1700r/min, 1750r/min or 1800r/min etc., Ball-milling Time 1-50h, such as
1h, 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 50h etc., preferably 5-20h.
When Ball-milling Time is less, metal not of the same race is forced to dissolve each other not yet in Process During High Energy Ball Milling, can cause to heat
Different melting points are excessive when molding, the problem of to be difficult to be molded.Moreover, when metal Ball-milling Time is less, powder not yet refines, powder
Gap is more between end, and higher-density is not achieved.Meanwhile metal Ball-milling Time it is less when, crystal grain not yet refines, and nanometer is not achieved
This target of material.When crystal grain refinement to it is nanocrystalline when, material can be limited by dislocation motion when stress by crystal boundary, and material can be more
Hardly possible surrender or fracture, are also just more difficult to fail in Clinical practice.
Preferably, in step (2) described mixing and ball milling, the mass ratio of abrading-ball used and the mixed-powder is 1:(3-
, such as 1 7):3,1:3.5,1:4,1:4.5,1:5,1:5.5,1:6,1:6.5 or 1:7 etc., preferably 1:5.
The mass ratio of abrading-ball and mixed-powder suitable for when, can not only improve energy utilization efficiency, it is miscellaneous to reduce abrasive body ingredient
Matter concentration can also promote to obtain Ultra-fine Grained powder.
Preferably, the mode of step (3) described mixing is：By calcium microcosmic salt biological ceramic powder and step obtained by step (1)
(2) gained alloy powder is placed in ball milling of the progress without abrading-ball in high-energy ball milling tank；
Preferably, in the mechanical milling process of the no abrading-ball, the rotational frequency of fixture is 15- in the high-energy ball milling tank
20Hz, such as 15Hz, 16Hz, 17Hz, 18Hz, 19Hz or 20Hz etc., rotating speed 1600-1800r/min, such as 1600r/min,
1650r/min, 1700r/min, 1750r/min or 1800r/min etc..
Preferably, step (4) the discharge plasma sintering carries out in the environment of vacuum.Otherwise in the ring for having oxygen
In border, metal and calcium microcosmic salt bioceramic are easy to generate the impurity such as oxide, to reduce the biocompatibility of material.
Preferably, the vacuum degree of the vacuum environment be 0.001-1Pa, such as 0.001Pa, 0.005Pa, 0.01Pa,
0.05Pa, 0.1Pa, 0.2Pa, 0.5Pa, 0.8Pa or 1Pa etc..
Preferably, apply constant pressure during step (4) the discharge plasma sintering.
Preferably, the constant pressure be 30-60MPa, such as 30MPa, 32MPa, 35MPa, 38MPa, 40MPa,
42MPa, 45MPa, 48MPa, 50MPa, 52MPa, 55MPa, 58MPa or 60MPa etc..
Preferably, the process of step (4) the discharge plasma sintering specifically includes：It is warming up to 700-1100 DEG C of progress
Isothermal sinter, such as 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C or 1100 DEG C etc..
Preferably, the rate of the heating be 50-200 DEG C/min, such as 50 DEG C/min, 80 DEG C/min, 100 DEG C/min,
120 DEG C/min, 150 DEG C/min, 180 DEG C/min or 200 DEG C/min etc..
Preferably, the temperature of the Isothermal sinter is 900 DEG C.
Preferably, the time of step (4) described Isothermal sinter be 5-20min, such as 5min, 8min, 10min, 12min,
15min, 18min or 20min etc..
Preferably, when step (4) is described cooling, vacuum or protective gas environment are kept.
As currently preferred technical solution, the preparation method of the bioceramic Base Metal composite material includes such as
Lower step：
(1) calcium microcosmic salt bioceramic raw material is passed through to ball milling in protective gas environment, the rate of ball milling is 1600-
1800r/min, Ball-milling Time 1-3h obtain calcium microcosmic salt biological ceramic powder；
(2) the first metal powder and the second metal powder are mixed to get mixed-powder, with speed in protective gas environment
Rate is 1600-1800r/min ball millings 5-20h, and the mass ratio of abrading-ball used and the mixed-powder is 1:(3-7) obtains alloy
Powder；
(3) alloy powder obtained by calcium microcosmic salt biological ceramic powder obtained by step (1) and step (2) is placed in high-energy ball milling tank
Middle ball milling of the progress without abrading-ball, the rotational frequency of fixture is 15-20Hz, rotating speed 1600-1800r/ in the high-energy ball milling tank
Min obtains raw material powder；
(4) step (3) raw material powder is applied into constant pressure 30- in the environment of vacuum degree is 0.001-1Pa
60MPa is warming up to 700-1100 DEG C with 50-200 DEG C/min and carries out discharge plasma sintering 5-20min, keeps vacuum or guarantor
It is biological ceramic base metallic composite that shield gaseous environment, which carries out the bulk material obtained after cooling,.
The third aspect, the present invention provides the purposes of bioceramic Base Metal composite material as described in relation to the first aspect, described
Bioceramic Base Metal composite material is used as human body hard tissue and repairs implant.
The form of floating coat compared to the prior art, calcium microcosmic salt bioceramic Base Metal composite material of the invention can be straight
Connect and be used as implant, avoid thermal dilation difference, interface cohesion between coating and matrix it is bad caused by a series of problems.
Compared with prior art, the present invention at least has the advantages that：
1. the present invention by by calcium microcosmic salt biological ceramic powder, the first metal powder and the second metal powder according to specific
Ratio compounds, and composite material made of sintering plays the synergistic effect of three heavy constituents, has excellent comprehensive performance, compressive strength
Up to 250-340MPa, fracture toughness is up to 3-4.15MPam1/2, Vickers hardness is up to 400-460HV, calcium microcosmic salt biology pottery
Porcelain, the first metal and the second metallic element are nanocrystal, and crystallite dimension 10-300nm is ceramic equably to divide with metal phase
Cloth, metal phase size are 10-20 μm, overcome the problem of calcium microcosmic salt bioceramic mechanical strength deficiency, are a kind of high tenacity
And osteoinductive and the bioceramic Base Metal composite material of antibiotic property are had both, it mainly can be applicable to human body hard tissue reparation implantation
In body, there is good potential applicability in clinical practice；
2. the present invention prepares bioceramic Base Metal composite material by the technique of ball milling+SPS respectively, the method operation can
Row is strong, repeatability is high, easily batch production.
Description of the drawings
Fig. 1 is the surface scan electron microscope of bioceramic Base Metal composite material in the embodiment of the present invention 1；
Fig. 2 is the profile scanning electron microscope of bioceramic Base Metal composite material in the embodiment of the present invention 1；
Fig. 3 is bioceramic Base Metal composite material surface culture mice embryonic osteoblast 4 days in the embodiment of the present invention 1
Laser confocal microscope figure afterwards；
Fig. 4 is the bacterium colony of bioceramic Base Metal composite material surface culture Escherichia coli prepared by the embodiment of the present invention 1
Figure；
Fig. 5 is the bacterium colony figure of the orifice surface culture Escherichia coli of inanimate object ceramic base metallic composite.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.But following reality
The simple example that example is only the present invention is applied, the scope of the present invention, protection model of the invention are not represented or limit
It encloses and is subject to claims.
Embodiment 1-5 provides a kind of bioceramic Base Metal composite material respectively, and the raw material of mass fraction is burnt as shown in Table 1
It ties；Bioceramic Base Metal composite material is bulk, and based on calcium microcosmic salt bioceramic, metal is distributed in inner homogeneous
Phase.
Embodiment 1 additionally provides the preparation method of bioceramic Base Metal composite material, and steps are as follows：
(1) hydro-thermal method prepares hydroxyapatite powder
The diammonium hydrogen phosphate solution and a concentration of 500mM calcium nitrate solutions of 50mL for configuring a concentration of 300mM of 50mL, by phosphoric acid
Diammonium hydrogen solution is added dropwise calcium nitrate solution, drop rate 2mL/min, and solution keeps magneton stirring in the process, and
It is 12 that sodium hydroxide solution by the way that a concentration of 1M is added dropwise, which keeps pH,.At 60 DEG C heat 2h after, transfer solution to seal not
It becomes rusty in steel water heating kettle, 12h is heated at 200 DEG C.It then takes out and is centrifuged 20 minutes with the speed of 8000 rev/min, used respectively
Ethyl alcohol and deionization are washed twice, finally the dry 10h in 100 DEG C of baking oven；
(2) ball milling niobium, silver, hydroxyapatite powder
It is the niobium powder of 99.99wt% or more, silver powder according to 3 by purity:1 weight ratio mixing is put into ball grinder
Hydroxyapatite powder obtained is put into high-energy ball milling 3h in ball grinder by middle high-energy ball milling 10h.In the above mechanical milling process,
The weight ratio of ball-tank is 5:1, powder whole process is all in the protective gas environment of glove box；For avoid hydroxyapatite with
It is chemically reacted in metal mixed mechanical milling process, when mixing hydroxyapatite with metal powder, powder is pressed 4:1 weight
Ratio (hydroxyapatite:Niobium:Mass ratio=16 of silver:3:1) with being put into mixing 1h in the ball grinder without ball after mortar mixing；
(3) discharge plasma sintering
Gained powder is transferred to sintering in discharge plasma sintering stove (SPS), obtains block materials.When sintering, heating
Rate is 50 DEG C/min, and maximum temperature reaches 900 DEG C, keeps the temperature 5min, avoids oxygen using 0.001Pa vacuum environments when sintering
Change；To obtain compact block material, in entire sintering process, the constant pressure of 30MPa is provided with built-in pressure device；After taking-up
It is polished with sand paper, polishing fluid polishing obtains bright and clean surface.
As shown in Figure 1, in the bioceramic Base Metal composite material of embodiment 1, size is that 10 μm -20 μm of metal phase is in
Discrete distribution, calcium microcosmic salt bioceramic are filled with the gap between metal phase.
As shown in Fig. 2, to the cross-section of bioceramic Base Metal composite material in embodiment 1, it can be found that metal phase
It is combined closely with calcium microcosmic salt bioceramic, gap is barely perceivable between two-phase.In metal phase, it is observed that grain size is
Tens nanometers of white particle, since the atomic number of silver is larger, atomic number contrast is big, can speculate that white particle is silver
Grain.
Take 48 orifice plates that mice embryonic osteoblast MC3T3-E1 is added, per 20,000, hole.It is yellowish green with 4mM calcium after culture 4 days
Element-AM and 2mM propidium iodide stains 10 minutes, are cleaned twice with phosphate buffer solution, then solid with glutaraldehyde or paraformaldehyde
It is 10 minutes fixed, then cleaned 2 times with phosphate buffer solution, sample is taken out from 48 orifice plates with tweezers, is protected from light natural wind in air
It is dry, it places into laser scanning co-focusing microscope and observes cell Proliferation and sprawl form, as shown in figure 3, giving birth in embodiment 1
In the laser confocal microscope visual field of object ceramic base metallic composite superficial cell, observe that a large amount of forms are good thin
Born of the same parents.Osteoblast is colonized, and starts to occur regularly arranged.
Material is put into 48 orifice plates, in orifice plate bioceramic Base Metal composite material and blank control group add respectively
Enter the Escherichia coli of 1mL 107CFU/mL, bacterial concentration is diluted after the OD values of 600nm calculate with nutrient broth with microplate reader
To 107CFU/mL.After being cultivated 24 hours in 37 DEG C of incubator, the 100 μ L of bacterium solution in orifice plate are taken, then slow with sterile phosphate
Solution dilution is rushed for several times, until dilution becomes 105,106 and 107 times.The dilution for taking 100 μ L respectively, is coated on spreader
Tablet countable in extension rate is chosen in sterile vegetative agar plate, after being cultivated 24 hours in 37 DEG C of incubator to count
Calculate the quantity of bacterium colony.As illustrated in figures 4-5, E. coli clones of bioceramic Base Metal composite material surface in embodiment 1
Reduce 90% compared to negative control group, has embodied the apparent antibiotic property of material.
Embodiment 2 additionally provides the preparation method of bioceramic Base Metal composite material, and steps are as follows：
(1) coprecipitation prepares strontium containing hydroxyapatite biological ceramic powder
Configure the strontium nitrate solution and 25mL of a concentration of 200mM of diammonium hydrogen phosphate solution, 25mL of a concentration of 300mM of 50mL
A concentration of 800mM calcium nitrate solutions, strontium nitrate and calcium nitrate solution are mixed evenly, then dropwise by diammonium hydrogen phosphate solution
It being added in the mixed solution of calcium nitrate and strontium nitrate, drop rate 5mL/min, solution keeps magneton stirring in the process,
Oil bath heating is 12 to 60 DEG C, and by the way that the sodium hydroxide solution of a concentration of 1M is added dropwise to keep pH；Continuation keeps the temperature 1h at 60 DEG C
Afterwards, it is heated to boiling point heat preservation 2h, is kept stirring simultaneously natural cooling；It then takes out and centrifuges 20 points with the speed of 8000 rev/min
Clock uses ethyl alcohol and deionization washing twice respectively, finally the dry 10h in 100 DEG C of baking oven；
(2) ball milling niobium, copper, strontium containing hydroxyapatite biological ceramic powder
Niobium powder, copper powders are proportionally mixed and are put into high-energy ball milling 1h in ball grinder, it will the phosphorus of hydroxyl containing strontium obtained
Lime stone biological ceramic powder is put into high-energy ball milling 3h in ball grinder.In the above mechanical milling process, the weight ratio of ball-tank is 5:1,
Powder whole process is all in the protective gas environment of glove box.To avoid strontium containing hydroxyapatite biological ceramic powder mixed with metal
It closes and is chemically reacted in mechanical milling process, when mixing strontium containing hydroxyapatite biological ceramic powder with metal powder, by powder
By 4:1 weight ratio (strontium containing hydroxyapatite bioceramic:Niobium:Mass ratio=16 of copper:3:1) with being put into after mortar mixing
Mixing 1h in ball grinder without ball；
(3) discharge plasma sintering
Gained powder is transferred to sintering in discharge plasma sintering stove (SPS), obtains block materials, when sintering, heating
Rate is 200 DEG C/min, and maximum temperature reaches 1100 DEG C, keeps the temperature 20min, and when sintering is avoided using 0.001Pa vacuum environments
Oxidation；To obtain fine and close block materials, in entire sintering process, the constant pressure of 60MPa is provided with built-in pressure device；
It is polished with sand paper after taking-up, to obtain bright and clean surface.
Embodiment 3 additionally provides the preparation method of bioceramic Base Metal composite material, and steps are as follows：
(1) hydro-thermal method prepares podolite powder
0.42g sodium bicarbonates are added in the disodium hydrogen phosphate of a concentration of 300mM of 50mL, then with vigorous stirring will
The mixed solution of sodium bicarbonate and disodium hydrogen phosphate is added dropwise in the calcium nitrate solution of a concentration of 500mM of 50mL.It is being added dropwise
In the process, pH is maintained at 12 by the way that 1M sodium hydroxide solutions are added dropwise.After heating 2h at 60 DEG C, mixed solution is transferred to not
It becomes rusty in steel water heating kettle, 12h is heated at 200 DEG C.It then takes out and is centrifuged 20 minutes with the speed of 8000 rev/min, use second respectively
Alcohol and deionization are washed twice, finally the dry 10h in 100 DEG C of baking oven；
(2) ball milling niobium, silver, podolite powder
By niobium powder, silver powder according to 39:1 weight ratio mixing is put into high-energy ball milling 50h in ball grinder, will be obtained
Podolite powder is put into high-energy ball milling 1h in ball grinder；In the above mechanical milling process, the weight ratio of ball-tank is 3:1, powder
Last whole process is all in the protective gas environment of glove box；To avoid podolite powder from being sent out with metal mixed mechanical milling process
Powder is pressed 3 by biochemical reaction in mixed carbonic acid apatite powder and metal powder:2 weight ratio (podolite
Powder:Niobium:Silver-colored mass ratio=60:39:1) with being put into mixing 1h in the ball grinder without ball after mortar mixing；
(3) discharge plasma sintering
Gained powder is transferred to sintering in discharge plasma sintering stove (SPS), obtains block materials；When sintering, heating
Rate is 50 DEG C/min, and maximum temperature reaches 700 DEG C, keeps the temperature 5min, and 0.001Pa vacuum environments are used when sintering；To be caused
Close block materials provide the constant pressure of 30MPa with built-in pressure device in entire sintering process；Sand paper is used after taking-up
Polishing, polishing fluid polishing, obtains bright and clean surface.
Embodiment 4 additionally provides the preparation method of bioceramic Base Metal composite material, and steps are as follows：
(1) hydro-thermal method prepares calcium octahate phosphate powder
The calcium carbonate soln and a concentration of 500mM phosphoric acid solutions of 50mL of a concentration of 700mM of 50mL are configured, it is molten with the nitric acid of 1M
The pH controls of obtained suspension are 4 by liquid, and are heated 6 hours at 60 DEG C；Then take out the speed with 8000 rev/min
Centrifugation 20 minutes uses ethyl alcohol and deionization washing twice respectively, finally the dry 10h in 100 DEG C of baking oven；
(2) ball milling tantalum, copper, calcium octahate phosphate powder
By tantalum powder, copper powders according to 1:1 weight ratio mixing is put into high-energy ball milling 1h in ball grinder, by phosphorus obtained
Sour eight calcium powders are put into high-energy ball milling 1h in ball grinder；In the above mechanical milling process, the weight ratio of ball-tank is 5:1, powder is complete
Journey is all in the protective gas environment of glove box；To avoid calcium octahate phosphate anti-with generation chemistry in metal mixed mechanical milling process
It answers, in eight calcium of mixed phosphate and metal powder, powder is pressed 49:1 weight ratio (calcium octahate phosphate:Tantalum:Copper mass ratio=
98:1:1) with being put into mixing 1h in the ball grinder without ball after mortar mixing；
(3) discharge plasma sintering
Gained powder is transferred to sintering in discharge plasma sintering stove (SPS), obtains block materials；When sintering, heating
Rate is 50 DEG C/min, and maximum temperature reaches 900 DEG C, keeps the temperature 5min, avoids oxygen using 0.001Pa vacuum environments when sintering
Change；Compact block material in order to obtain provides 30MPa constant pressures in entire sintering process with built-in pressure device；After taking-up
It is polished with sand paper, then is polished with polishing fluid, obtain bright and clean surface.
Embodiment 5 additionally provides the preparation method of bioceramic Base Metal composite material, and steps are as follows：
(1) hydro-thermal method prepares hydroxyapatite powder
The diammonium hydrogen phosphate solution and a concentration of 500mM calcium nitrate solutions of 50mL for configuring a concentration of 300mM of 50mL, by phosphoric acid
Diammonium hydrogen solution is added dropwise calcium nitrate solution, drop rate 2mL/min, and solution keeps magneton stirring in the process, and
It is 12 that sodium hydroxide solution by the way that a concentration of 1M is added dropwise, which keeps pH,；At 60 DEG C heat 2h after, transfer solution to seal not
It becomes rusty in steel water heating kettle, 12h is heated at 200 DEG C；It then takes out and is centrifuged 20 minutes with the speed of 8000 rev/min, used respectively
Ethyl alcohol and deionization are washed twice, finally the dry 10h in 100 DEG C of baking oven；
(2) ball milling niobium, silver, hydroxyapatite powder
By niobium powder, silver powder according to 1:1 weight ratio mixing is put into high-energy ball milling 10h in ball grinder, will be obtained
Hydroxyapatite powder is put into high-energy ball milling 3h in ball grinder；In the above mechanical milling process, the weight ratio of ball-tank is 7:1, powder
Last whole process is all in the protective gas environment of glove box；To avoid hydroxyapatite from changing with metal mixed mechanical milling process
Reaction is learned, powder is pressed 9:1 weight ratio (hydroxyapatite:Niobium:Silver-colored mass ratio=18:1:1) with being put into after mortar mixing
Mixing 1h in ball grinder without ball；
(3) discharge plasma sintering
Gained powder is transferred to sintering in discharge plasma sintering stove (SPS), obtains block materials；When sintering, heating
Rate is 200 DEG C/min, and maximum temperature reaches 1100 DEG C, keeps the temperature 5min, and when sintering avoids aoxidizing using 1Pa vacuum environments；
Fine and close block materials provide the constant pressure of 600MPa with built-in pressure device in entire sintering process in order to obtain；
It is polished with sand paper after taking-up, then is polished with polishing fluid, to obtain bright and clean surface.
Comparative example 1
With differing only in for embodiment 1：High-energy ball milling and discharge plasma sintering behaviour are carried out in non-protected atmosphere
Make.
Comparative example 2
With differing only in for embodiment 1：Common mixing mortar grinder is used to substitute mixing after high-energy ball milling in step (2),
Other are same as Example 1.
Comparative example 3
With differing only in for embodiment 1：It is sintered instead of discharge plasma using traditional hot pressed sintering.
Specifically, step (3) is：Powder obtained by step (2) is transferred in hot-pressed sintering furnace and is sintered, block material is obtained
Material when sintering, applies constant pressure 30MPa, and heating rate is 5 DEG C/min, and maximum temperature reaches 1100 DEG C, keeps the temperature 3h, sintering
When avoid aoxidizing using 0.001Pa vacuum environments；It is polished with sand paper after taking-up, polishing fluid polishing obtains bright and clean surface.
Comparative example 4
With differing only in for embodiment 1：The mass fraction of niobium is 20 parts, without containing silver.
Comparative example 5
With differing only in for embodiment 1：The mass fraction of silver is 20 parts, does not contain niobium.
Embodiment 6-10, comparative example 6-10 provide that there is only the bioceramics of three component ratio differences with embodiment 1 respectively
Base Metal composite material, concrete composition are shown in Table 1.
Table 1
" part " indicates that mass fraction, "-" indicate that corresponding constituent content is 0 in table 1.
The performance test results of the bioceramic Base Metal composite material of each embodiment and comparative example are shown in Table 2.Table 2
Corresponding performance indicator can not be investigated since material can not be molded in comparative example 3 in table 2.
Osteoinductive is investigated by osteoblast in the proliferation rate of material surface culture, be embodied as MTT (3- (4,
5- dimethylthiazoles -2) -2,5- diphenyltetrazolium bromide bromides) dyeing after OD value (OD values), OD values are got in this experiment
Greatly, then it is assumed that osteoblast is higher in the proliferation rate of material surface culture, represents bioceramic Base Metal composite material used
Osteoinductive is better.Experimentation is as follows：
Each material is put into 48 orifice plates, mice embryonic osteoblast MC3T3-E1 is added, per 30,000, hole cell, respectively
Three orifice plates are cultivated 7 days in 37 DEG C of insulating boxs, 3 parallel samples of each materials'use carry out the repeatability of inspection data.?
Scheduled time point replaces original culture medium with the MTT solution of 0.5mg/mL, continues in incubator culture 4 hours, then
Replace with the dimethyl sulfoxide (DMSO) of 500 μ L again per hole, shaking table shakes up 30min.Take 100 μ L dimethyl sulfoxide (DMSO)s of above-mentioned every hole in 96 holes
OD value at board test 570nm.
As shown in table 2,60-98 parts of calcium microcosmic salt biological ceramic powder of the present invention, 1-39 parts of the first metal powder, the second metal
In bioceramic Base Metal composite material made of the formula sintering that 1-15 parts of power formulations, three components generate synergistic effect, multiple
Condensation material compressive strength is up to 250-340MPa, and fracture toughness is up to 3-4.15MPam1/2, Vickers hardness is up to 400-
460HV overcomes the problem of calcium microcosmic salt bioceramic mechanical strength deficiency, is a kind of bioceramic base nano metal of high tenacity
Composite material, if it contains only the first metal or contains only the second metal (comparative example 4-5), or formula is not within the scope of the invention
When, the comprehensive performance of the mechanical performance of composite material, osteoinductive and antibiotic property will decline to a great extent, and cannot be used alone as clinical hard
Tissue repair implant.Such as when without containing the second metal (comparative example 4), for material is compared to 1 material of embodiment, biofacies
Capacitive and 1 material proximate of embodiment, but antibiotic property difference is more, and the mistake that loosens or even fall off because of infection is easy after being implanted into human body
Effect, mechanical performance are also declined；When without containing the first metal (comparative example 4), for this material is compared to 1 material of embodiment,
Biocompatibility can not show a candle to 1 material of embodiment, and antibiotic property improves unobvious, and mechanical performance is also declined.
In the scheme advanced optimized, that is, 70-90 parts of calcium microcosmic salt biological ceramic powder, the first metal powder 10-20
Part, the second 5-10 parts of metal powder；The synergistic effect that three components generate is optimal, the mechanical performance of composite material, osteoinductive and
The comprehensive performance of antibiotic property steps a stage again.
If with mixing (comparative example 2) after common mixing mortar grinder replacement high-energy ball milling, powder before being sintered will be caused thick
Rough, obtained composite material microstructure is uneven, thus the problems such as local biologic poor compatibility, part are without antibiotic property.In addition
Consistency is low, results in gained composite material strength, is not suitable in the application of sclerous tissues' implantation.
If discharge plasma sintering technology (comparative example 3) is replaced using traditional Thermocompressed sintering and forming, due to temperature
Far below the fusion temperature of niobium, composite material is difficult to be molded or consistency is very low.If improving sintering temperature again, calcium microcosmic salt biology
Ceramics can be decomposed into plurality of impurities, lose the function of osteoinductive.In addition, the time that conventional thermocompression sintering needs is very long, it is economical
The feature of environmental protection is poor.
When carrying out high-energy ball milling and discharge plasma sintering operation in non-protected atmosphere (comparative example 1), obtain
In composite material, impurity is generated in ceramic phase and metal phase.And calcium microcosmic salt bioceramic is that biocompatibility is good with niobium
Material, generate the original intention that other substances have deviated from selection in non-protected atmosphere, thus cannot reach outstanding osteoinductive this
One target.Meanwhile atmosphere can allow the repeatability of material property not high when not controlling preparation, and it is next excellent to not readily pass through characterization performance
Change parameter, is also not susceptible to large-scale production.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of bioceramic Base Metal composite material, which is characterized in that be sintered by the raw material of following mass fraction：
60-98 parts of calcium microcosmic salt biological ceramic powder, the first 1-39 parts of metal powder, the second 1-15 parts of metal powder；
The calcium microcosmic salt biological ceramic powder includes hydroxyapatite powder, strontium containing hydroxyapatite powder, podolite powder
End or calcium octahate phosphate powder in any one or at least two combination；The ingredient of first metal powder include niobium and/
Or tantalum；The ingredient of second metal powder includes silver and/or copper.
2. bioceramic Base Metal composite material as described in claim 1, which is characterized in that the bioceramic Base Metal is multiple
Condensation material is sintered by the raw material of following mass fraction：
70-90 parts of calcium microcosmic salt biological ceramic powder, the first 10-20 parts of metal powder, the second 5-10 parts of metal powder；
Preferably, the mass ratio of the calcium microcosmic salt biological ceramic powder, the first metal powder and the second metal powder is 16:3:1.
3. bioceramic Base Metal composite material as claimed in claim 1 or 2, which is characterized in that first metal powder
Ingredient be niobium；
Preferably, the purity of first metal powder and the second metal powder is 99.99wt% or more.
4. bioceramic Base Metal composite material as described in any one of claims 1-3, which is characterized in that the calcium microcosmic salt life
Object ceramic powders are strontium containing hydroxyapatite powder and/or podolite powder；
Preferably, the bioceramic Base Metal composite material is bulk, and based on calcium microcosmic salt bioceramic, inside is distributed with
The metal phase that size is 10-20 μm；
Preferably, the crystallite dimension of the bioceramic Base Metal composite material is 10-300nm, preferably 20nm；
Preferably, the consistency of the bioceramic Base Metal composite material be 90%-99.9%, preferably 99.9%；
Preferably, the fracture toughness of the bioceramic Base Metal composite material is 3-4.15MPam1/2。
5. a kind of according to any one of claims 1-4 and bioceramic Base Metal composite material preparation method, feature
It is, includes the following steps：
(1) calcium microcosmic salt biological ceramic powder is prepared；
(2) the first metal powder and the second metal powder are mixed to get mixed-powder, ball milling obtains alloy powder；
(3) alloy powder obtained by calcium microcosmic salt biological ceramic powder obtained by step (1) and step (2) is mixed, obtains raw material powder；
(4) step (3) raw material powder is subjected to discharge plasma sintering, the bulk material obtained after cooling is that biology is made pottery
Porcelain Base Metal composite material.
6. the preparation method of bioceramic Base Metal composite material as claimed in claim 5, which is characterized in that step (1) institute
It states calcium microcosmic salt biological ceramic powder and also passes through ball milling；
Preferably, step (1) described ball milling carries out in protective gas environment；
Preferably, the protective gas includes nitrogen and/or argon gas；
Preferably, the rate of step (1) described ball milling is 1600-1800r/min, Ball-milling Time 1-3h；
Preferably, step (2) described ball milling carries out in protective gas environment；
Preferably, the protective gas includes nitrogen and/or argon gas；
Preferably, the rate of step (2) described mixing and ball milling is 1600-1800r/min, Ball-milling Time 1-50h, preferably 5-
20h；
Preferably, in step (2) described mixing and ball milling, the mass ratio of abrading-ball used and the mixed-powder is 1:(3-7), it is excellent
Select 1:5.
7. such as the preparation method of bioceramic Base Metal composite material described in claim 5 or 6, which is characterized in that step (3)
The mode of the mixing is：Alloy powder obtained by calcium microcosmic salt biological ceramic powder obtained by step (1) and step (2) is placed in high energy
The ball milling without abrading-ball is carried out in ball grinder；
Preferably, in the mechanical milling process of the no abrading-ball, the rotational frequency of fixture is 15-20Hz in the high-energy ball milling tank, is turned
Speed is 1600-1800r/min.
8. such as the preparation method of claim 5-7 any one of them bioceramic Base Metal composite materials, which is characterized in that step
Suddenly (4) described discharge plasma sintering carries out in the environment of vacuum；
Preferably, the vacuum degree of the vacuum environment is 0.001-1Pa；
Preferably, apply constant pressure during step (4) the discharge plasma sintering；
Preferably, the constant pressure is 30-60MPa；
Preferably, the process of step (4) the discharge plasma sintering specifically includes：It is warming up to 700-1100 DEG C of progress constant temperature
Sintering；
Preferably, the rate of the heating is 50-200 DEG C/min；
Preferably, the time of step (4) described Isothermal sinter is 5-20min；
Preferably, when step (4) is described cooling, vacuum or protective gas environment are kept.
9. such as the preparation method of claim 5-8 any one of them bioceramic Base Metal composite materials, which is characterized in that packet
Include following steps：
(1) calcium microcosmic salt bioceramic raw material is passed through to ball milling in protective gas environment, the rate of ball milling is 1600-1800r/
Min, Ball-milling Time 1-3h obtain calcium microcosmic salt biological ceramic powder；
(2) the first metal powder and the second metal powder are mixed to get mixed-powder, are with rate in protective gas environment
The mass ratio of 1600-1800r/min ball millings 5-20h, abrading-ball used and the mixed-powder is 1:(3-7) obtains alloyed powder
End；
(3) by alloy powder obtained by calcium microcosmic salt biological ceramic powder obtained by step (1) and step (2) be placed in high-energy ball milling tank into
Ball milling of the row without abrading-ball, the rotational frequency of fixture is 15-20Hz, rotating speed 1600-1800r/min in the high-energy ball milling tank,
Obtain raw material powder；
(4) step (3) raw material powder is applied into constant pressure 30-60MPa in the environment of vacuum degree is 0.001-1Pa,
It is warming up to 700-1100 DEG C with 50-200 DEG C/min and carries out discharge plasma sintering 5-20min, keeps vacuum or protective gas
It is biological ceramic base metallic composite that environment, which carries out the bulk material obtained after cooling,.
10. the purposes of bioceramic Base Metal composite material as described in right will go any one of 1-4, which is characterized in that the life
Object ceramic base metallic composite is used as human body hard tissue and repairs implant.
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