CN111994914A - Ion co-doped beta-dicalcium silicate powder, preparation method and application - Google Patents
Ion co-doped beta-dicalcium silicate powder, preparation method and application Download PDFInfo
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- CN111994914A CN111994914A CN202010793906.9A CN202010793906A CN111994914A CN 111994914 A CN111994914 A CN 111994914A CN 202010793906 A CN202010793906 A CN 202010793906A CN 111994914 A CN111994914 A CN 111994914A
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- Prior art keywords
- ion
- powder
- salt
- calcium
- beta
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- 239000000843 powder Substances 0.000 title claims abstract description 265
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 147
- 150000002500 ions Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 70
- 230000008439 repair process Effects 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000017423 tissue regeneration Effects 0.000 claims abstract description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229940063013 borate ion Drugs 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 88
- 239000011575 calcium Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 71
- 238000001354 calcination Methods 0.000 claims description 63
- 239000002639 bone cement Substances 0.000 claims description 62
- 239000008367 deionised water Substances 0.000 claims description 61
- 229910021641 deionized water Inorganic materials 0.000 claims description 61
- 210000000988 bone and bone Anatomy 0.000 claims description 60
- -1 iron ion Chemical class 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000002244 precipitate Substances 0.000 claims description 43
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 32
- 239000011812 mixed powder Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 239000004115 Sodium Silicate Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 21
- 239000013067 intermediate product Substances 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910001431 copper ion Inorganic materials 0.000 claims description 16
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000000378 calcium silicate Substances 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910001427 strontium ion Inorganic materials 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 229960003563 calcium carbonate Drugs 0.000 claims description 7
- 235000010216 calcium carbonate Nutrition 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 229960005069 calcium Drugs 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 6
- 235000011092 calcium acetate Nutrition 0.000 claims description 6
- 239000001639 calcium acetate Substances 0.000 claims description 6
- 229960005147 calcium acetate Drugs 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 235000013904 zinc acetate Nutrition 0.000 claims description 6
- 235000010338 boric acid Nutrition 0.000 claims description 5
- 229960002645 boric acid Drugs 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 150000000918 Europium Chemical class 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- 159000000008 strontium salts Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229960003975 potassium Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- 238000013268 sustained release Methods 0.000 claims description 3
- 239000012730 sustained-release form Substances 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 2
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 2
- NCOYDQIWSSMOEW-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;lanthanum(3+) Chemical compound [La+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NCOYDQIWSSMOEW-UHFFFAOYSA-K 0.000 claims description 2
- ZOLZOTLXESSOMN-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+);decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZOLZOTLXESSOMN-UHFFFAOYSA-H 0.000 claims description 2
- OMGKKRHVRFEREE-UHFFFAOYSA-K 2-hydroxypropanoate;lanthanum(3+) Chemical compound [La+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O OMGKKRHVRFEREE-UHFFFAOYSA-K 0.000 claims description 2
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 claims description 2
- NNNRGWOWXNCGCV-UHFFFAOYSA-N 4-(2-bromoethyl)benzonitrile Chemical compound BrCCC1=CC=C(C#N)C=C1 NNNRGWOWXNCGCV-UHFFFAOYSA-N 0.000 claims description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 2
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 claims description 2
- AETFVXHERMOZAM-UHFFFAOYSA-N B(O)(O)O.N.N Chemical compound B(O)(O)O.N.N AETFVXHERMOZAM-UHFFFAOYSA-N 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- DKKCQDROTDCQOR-UHFFFAOYSA-L Ferrous lactate Chemical compound [Fe+2].CC(O)C([O-])=O.CC(O)C([O-])=O DKKCQDROTDCQOR-UHFFFAOYSA-L 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 2
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 2
- 239000001354 calcium citrate Substances 0.000 claims description 2
- 229960004256 calcium citrate Drugs 0.000 claims description 2
- 235000013927 calcium gluconate Nutrition 0.000 claims description 2
- 239000004227 calcium gluconate Substances 0.000 claims description 2
- 229960004494 calcium gluconate Drugs 0.000 claims description 2
- 229940095643 calcium hydroxide Drugs 0.000 claims description 2
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 2
- 235000011086 calcium lactate Nutrition 0.000 claims description 2
- 239000001527 calcium lactate Substances 0.000 claims description 2
- 229960002401 calcium lactate Drugs 0.000 claims description 2
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229940087373 calcium oxide Drugs 0.000 claims description 2
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
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Abstract
The invention discloses ion co-doped beta-dicalcium silicate powder, a preparation method and application thereof, wherein the general formula of the ion co-doped beta-dicalcium silicate powder is Ca2‑xMx(SiO4)1‑y(BO3)yWherein M ion is Ca capable of being replaced2+One or more metal cations of the ionX is more than 0 and less than or equal to 1; borate ion BO3 3‑To partially replace SiO4 4‑The anion of the ion, y is more than or equal to 0 and less than or equal to 0.05. The ion co-doped beta-dicalcium silicate powder provided by the invention can realize various biological functions such as osteocyte induction, vascularization promotion, antibiosis and bacteriostasis and the like, and can meet the clinical application requirements of tooth repair, jaw repair, spine repair, joint repair, other hard tissue repair and the like; the preparation method provided by the invention has the advantages of low synthesis temperature, short synthesis time, no environmental pollution, mass production and the like.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to ion co-doped beta-dicalcium silicate powder, a preparation method and application.
Background
Dicalcium silicate (Ca)2SiO4C2S) is one of the most important components of portland cement clinker, and dicalcium silicate has been widely studied and used in cement and refractory materials. Dicalcium silicate has various crystal forms, wherein metastable beta-dicalcium silicate has hydration activity, i.e. hydraulic property. When the beta-dicalcium silicate powder contacts with water, the surface layer of the particles is dissolved and accompanied with ion migration, silicate hydrate (C-S-H) gel with a nano-pore structure is deposited on the surface of the powder particles, and meanwhile, calcium hydroxide crystal grains nucleate and grow in the capillary hole area of the hydrate gel. As the reaction proceeds, the silicate hydrate gel polymerizes and hardens to form a bulk material having certain porosity and strength. The hydration and solidification properties, together with the excellent biocompatibility and bioactivity of dicalcium silicate and the moderate release and degradation performance of silicon ions, make beta-dicalcium silicate become a bone tissue repair replacement biomaterial with very potential and ideal characteristics of bone tissue engineering materials, which has attracted the extensive attention of worldwide material workers and medical workers.
Clinical applications show that the ideal artificial bone grafting material not only has good biocompatibility, biodegradation, bone conduction and bone induction, but also needs good vascularization capability. The growth of the blood vessel can provide stable internal environment for cells, provide sufficient nutrition for the functional activities of division, proliferation and the like of osteoblasts, promote the growth of the cells and the osteogenic differentiation, and promote the growth and the stability of the blood vessel by the differentiation and the gene expression of the osteoblasts, so that the growth and the repair of the bone are promoted by the cooperation of the two. A large number of researches show that the cobalt element can induce the generation of local anoxic environment in the microenvironment of an organism, so as to promote the generation of an anoxic induction factor (HIF-1 alpha) and promote the generation of local environment neovascularization; the strontium element has good compatibility with osteoblasts, can promote the proliferation of endothelial cells and induce the formation of new vessels, and can solve the problem of vascularization of the bone grafting material.
At present, two main methods for preparing beta-dicalcium silicate are provided, one is a sol-gel method, and the other is a solid-phase synthesis method. The sol-gel method has the advantages of low synthesis temperature, small particle size and good uniformity, but the chemical process is complex, the raw materials are expensive, the used organic solvent has certain toxicity, and the potential safety hazard in the production process is large. In the industrial preparation process, the sol-gel method needs to dry the water in the sol in the working procedure, so that a large amount of energy is consumed, and the cost is high; the traditional solid phase synthesis method has high reaction temperature (generally not lower than 1400 ℃), long synthesis time and needs to add a stabilizer additionally to stabilize beta-dicalcium silicate, the phase purity and hydration activity of the beta-dicalcium silicate obtained by the method are low, the grain size is large (generally 60 micrometers), the energy consumption in the production process is large, and the method is not suitable for industrial production. CN 101445247A discloses a preparation method of microwave-synthesized bioactive beta-dicalcium silicate, which adopts sol-gel spray drying to prepare precursor powder, and then carries out procedures of presintering, microwave low-temperature rapid synthesis and the like, so that the method has the advantages of high raw material cost, various procedures, no ion doping, and incapability of simultaneously obtaining various biological functions of bone induction, vascularization, antibiosis, bacteriostasis and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides the ion co-doped beta-dicalcium silicate powder, the preparation method and the application, which have the advantages of good biological function, low synthesis temperature, short synthesis time, no environmental pollution and batch production.
The technical scheme adopted by the invention is as follows:
on one hand, the invention provides ion co-doped beta-dicalcium silicate powder, and the composition general formula of the ion co-doped beta-dicalcium silicate powder is Ca2-xMx(SiO4)1-y(BO3)yWherein M ion is Ca capable of being replaced2+One or more metal cations of the ions, x is more than 0 and less than or equal to 1; BO3 3-The borate ion is substituted for SiO4 4-The anion of the ion, y is more than or equal to 0 and less than or equal to 0.05.
Further, M is K+、Na+、Mg2+、Al3+、Zn2+、Sr2+Manganese ion, cobalt ion, Ag+Copper ion, iron ion, La3+Cerium ion and europium ion.
Further, the manganese ions include Mn3+And Mn2+(ii) a The cobalt ions comprise Co3+And Co2+(ii) a The copper ions comprise Cu+And Cu2+Said iron ions comprise Fe3+And Fe2+(ii) a The cerium ions include Ce3+And Ce4+Said europium ion comprises Eu2+And Eu3+。
On the other hand, the invention also provides a preparation method of the ion co-doped beta-dicalcium silicate powder, which is a two-step synthesis method and comprises the following steps:
s1, preparing an intermediate product of nano-calcium metasilicate or nano-calcium borosilicate powder, dropwise adding a solution of silicate and/or a compound containing borate ions into a calcium salt solution under the conditions of heating and stirring for reaction to obtain a precipitate, filtering and washing the precipitate, drying and calcining to obtain the intermediate product of nano-calcium metasilicate or nano-calcium borosilicate powder;
s2, preparing ion co-doped beta-dicalcium silicate powder, mixing the intermediate product nano-monocalcium silicate or nano-monocalcium borosilicate powder with the doped metal salt powder, grinding and calcining to obtain the ion co-doped beta-dicalcium silicate powder.
Further, the air conditioner is provided with a fan,
in the S1, the pH value of the calcium salt solution is 7-12; the dripping speed of the solution of the silicate and/or the compound containing borate ions is 25-400mL/h, the precipitation reaction temperature is 20-90 ℃, and the stirring time is 1-10 h; the drying temperature is 50-120 ℃, the calcining temperature is 600-950 ℃, and the calcining time is 0.5-10 h;
in the S2, the calcination temperature is 800-1300 ℃, the calcination time is 10-600min, the calcination temperature rise rate is 1-2000 ℃/min, and the calcination mode is resistance furnace calcination, infrared calcination or microwave calcination.
Further, a spray granulation step is further included between the grinding and calcining steps in S2, and the specific processing steps include: and adding deionized water into the mixed powder to prepare slurry with the solid content of not less than 20 voL%, and then carrying out spray granulation treatment.
Further, the spray granulation conditions are that the feeding speed is 5-50 mL/min, the air inlet temperature during spray granulation is 130-250 ℃, the air outlet temperature is greater than 100 ℃, and the rotating speed of a spray head is 180-300 rpm.
Further, the silicate is one or more of potassium silicate, sodium potassium silicate, anhydrous sodium metasilicate, sodium metasilicate pentahydrate, sodium metasilicate hexahydrate, sodium metasilicate octahydrate and sodium metasilicate nonahydrate; the compound containing borate ions is one or more of orthoboric acid, sodium tetraborate, sodium borohydride, ammonium hydrogen borate and potassium borohydride; the calcium salt is one or more of calcium nitrate, calcium oxalate, calcium acetate, calcium lactate, calcium gluconate, calcium citrate, calcium hydroxide, calcium carbonate, calcium oxide and calcium bicarbonate, and the doped metal salt is one or more of sodium salt, potassium salt, magnesium salt, aluminum salt, zinc salt, strontium salt, manganese salt, cobalt salt, silver salt, copper salt, iron salt, lanthanum salt, cerium salt and europium salt.
Further, the potassium salt is one or more of potassium nitrate, potassium carbonate, potassium bicarbonate, potassium acetate, potassium hydroxide, potassium oxide, potassium lactate, potassium citrate and potassium gluconate; the sodium salt is one or more of sodium nitrate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, sodium oxide, sodium lactate, sodium citrate and sodium gluconate; the magnesium salt is one or more of magnesium nitrate, magnesium acetate, magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium lactate, magnesium chloride, magnesium citrate and magnesium gluconate; the aluminum salt is one or more of aluminum nitrate, aluminum carbonate, aluminum chloride, aluminum lactate and aluminum citrate; the zinc salt is one or more of zinc nitrate, zinc carbonate, zinc chloride, zinc acetate, zinc lactate, zinc citrate and zinc gluconate; the strontium salt is one or more of strontium nitrate, strontium carbonate, strontium chloride, strontium acetate, strontium lactate, strontium citrate and strontium gluconate; the manganese salt is one or more of manganese nitrate, manganese carbonate, manganese chloride, manganese acetate, manganese lactate, manganese citrate and manganese gluconate; the cobalt salt is one or more of cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt acetate and cobalt gluconate; the silver salt is one or more of silver nitrate, silver carbonate, silver chloride, silver acetate, silver lactate and silver citrate; the copper salt is one or more of cupric nitrate, cupric carbonate, cupric chloride, cupric acetate, cuprous acetate, cupric citrate and cupric gluconate; the ferric salt is one or more of ferric nitrate, ferric carbonate, ferric chloride, ferric acetate, ferrous lactate, ferric citrate and ferrous gluconate; the lanthanum salt is one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum acetate, lanthanum citrate and lanthanum lactate; the cerium salt is one or more of cerium nitrate, hydrated cerium carbonate, cerium chloride, cerium acetate and cerium citrate; the europium salt is one or more of europium nitrate, europium carbonate, europium chloride and europium acetate.
On the other hand, the invention also provides the application of the ion co-doped beta-dicalcium silicate powder in filling paste, bone cement, artificial bone and drug sustained-release carriers; application of ion co-doped beta-dicalcium silicate powder in tooth repair, jaw repair, spine repair, joint repair and other hard tissue repair
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
(1) according to the mineral content of human bone tissues, the bionic simulation of the composition of the beta-dicalcium silicate is realized, and meanwhile, through co-doping of various ions, the beta-dicalcium silicate not only can obtain good biocompatibility, bioactivity and high water hardness, but also can realize various biological functions of bone cell induction, vascularization, antibiosis, bacteriostasis and the like;
(2) the preparation method of the ion co-doped beta-dicalcium silicate provided by the invention adopts a two-step calcination method, wherein a nano-monocalcium silicate or boron-doped nano-monocalcium silicate intermediate product is obtained by calcination in the first step, and an ion co-doped beta-dicalcium silicate particle powder or solid or hollow microspheres is obtained by calcination in the second step; the two-step calcination preparation method has the advantages that the prepared ion co-doped beta-dicalcium silicate is high in phase purity, low in synthesis temperature, short in synthesis time, free of environmental pollution, capable of being produced in batches and the like;
(3) the ion co-doped beta-dicalcium silicate microsphere powder provided by the invention also has good slow release capability;
(4) the ion co-doped beta-dicalcium silicate powder prepared by the invention can meet the clinical application requirements of tooth repair, jaw repair, spine repair, joint repair, other hard tissue repair and the like.
Drawings
FIG. 1 is a process flow diagram of ion co-doping beta-dicalcium silicate;
FIG. 2 is an XRD spectrum of the intermediate nano-calcium silicate of example 1;
FIG. 3 shows β -Ca in example 11.7(Sr0.1Mn0.1Zn0.1)SiO4XRD spectrum of the particle powder;
FIG. 4 shows β -Ca in example 71.5(Sr0.3Cu0.2)SiO4SEM photo of solid microsphere powder;
FIG. 5 shows β -Ca in example 71.5(Sr0.3Cu0.2)SiO4Enlarging SEM picture of solid microsphere powder;
FIG. 6 shows β -Ca in example 71.5(Sr0.3Cu0.2)SiO4XRD (X-ray diffraction) spectrums of the solid microsphere powder after mineralization of simulated body fluid for different times;
FIG. 7 shows β -Ca in example 131.7(Eu0.1Sr0.2)SiO4In-situ compounding in bone cementA sustained release curve of the antibacterial drug gentamicin;
FIG. 8 is an XRD spectrum of the ion co-doped beta-dicalcium silicate powder in examples 2, 3, 4 and 5;
FIG. 9 is an XRD spectrum of the ion co-doped beta-dicalcium silicate powder in examples 6, 7, 8, 9 and 10;
fig. 10 is an XRD spectrum of ion-codoped beta-dicalcium silicate powder in examples 11, 12, 13 and 14.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of the present invention and the above-described drawings, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The materials and methods used in the following examples are, unless otherwise specified, conventional in the art.
The simulated body fluid composition used in the following examples was Na+:Na+:142.0mM·L-1、K+:5.0mM·L-1、Mg2+:1.5mM·L-1、Ca2+:2.5mM·L-1、Cl-1:147.8mM·L-1、HCO3-:4.2mM·L-1、HPO4 2-:1.0mM·L-1、SO4 2-:0.5mM·L-1。
Example 1
β-Ca1.7(Sr0.1Mn0.1Zn0.1)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water into the calcium nitrate solution, heating in a water bath at 70 ℃ and stirring for 30min to obtain a calcium nitrate solution with the pH of 9; weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water to obtain a sodium silicate solution, dripping the prepared sodium silicate solution into the calcium nitrate solution at the speed of 100mL/h, and mixing and stirring for 5h to obtain a first mixed solution; carrying out suction filtration on the first mixed solution to obtain a precipitate, washing the precipitate with deionized water, and then placing the precipitate in a vacuum drying oven to be dried for 8 hours at the temperature of 80 ℃ to obtain precursor powder; and placing the precursor powder in a resistance furnace, calcining for 3h at 800 ℃, heating at the speed of 10 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano monocalcium silicate powder, 0.519g of calcium hydroxide powder, 0.179g of manganese nitrate powder, 0.212g of strontium nitrate powder and 0.297g of zinc nitrate nonahydrate powder, adding the powder into an agate mortar, and grinding uniformly to obtain mixed powder; and (3) calcining the mixed powder in a resistance furnace at 1100 ℃ for 7h at the heating rate of 10 ℃/min, and naturally cooling to room temperature to obtain manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder, the result is shown in figure 2, and the result shows that the phase purity of the manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder is 96%;
performing scanning electron microscope analysis on the manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder, wherein the grain size of the manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder is 10-26 mu m;
reacting beta-Ca1.7(Sr0.1Mn0.1Zn0.1)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with liquid/solid ratio of 0.5mL/1g, injecting into stainless steel mold with diameter of 5mm and height of 12mm, curing for 15-25min, and maintaining in constant temperature oven with humidity of 100% RH at 37 deg.C for 24 hrWhen the alloy is taken out, the compressive strength is measured to be 60MPa +/-12 MPa and is more than that of the element-free doped beta-Ca2SiO4Bone cement.
Selecting New Zealand white rabbit, inducing chronic periapical bone defect model by apical operation, and treating with beta-Ca1.7(Sr0.1Mn0.1Zn0.1)SiO4The bone cement fills the bone defect. Histological observation shows that after 12 weeks, with the degradation of the bone cement, obvious new bone tissues and a small amount of microangiogenesis around the bone cement can be found, no inflammation occurs, and the growth of new bone is obviously larger than that of the non-element doped beta-Ca2SiO4Bone cement, Explanation beta-Ca1.7(Sr0.1Mn0.1Zn0.1)SiO4Has good biocompatibility, degradability, osteogenesis performance and vascularization capacity, and can be used in the field of dental restoration.
Example 2
β-Ca1.7(Eu0.1Sr0.2)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 70 ℃, and stirring for 30min to obtain the calcium nitrate solution with the pH value of 7-8. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the rate of 100mL/h, and mixing and stirring for 5h to obtain a first mixed solution; filter-pressing the first mixed solution in a positive pressure filter to obtain a precipitate, washing the precipitate with deionized water, and then placing the precipitate in a normal pressure drying box to dry for 8 hours at the temperature of 80 ℃ to obtain precursor powder; and placing the precursor powder in a microwave oven, calcining for 0.5h at 950 ℃, heating at the speed of 300 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano monocalcium silicate powder, 0.519g of calcium hydroxide powder, 0.669g of europium nitrate hexahydrate and 0.317g of strontium nitrate powder, adding into an agate mortar for grinding, and uniformly grinding to obtain mixed powder; and adding the mixed powder into a microwave oven, calcining for 1h at 1200 ℃, heating at the speed of 300 ℃/min, and naturally cooling to room temperature to obtain europium-strontium ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the europium-strontium ion codoped beta-dicalcium silicate particle powder, and the result is shown in FIG. 8, which shows that the phase purity of the europium-strontium ion codoped beta-dicalcium silicate particle powder is 98%;
analyzing the europium-strontium ion codoped beta-dicalcium silicate particle powder by a scanning electron microscope, wherein the grain size is 0.1-2 mu m;
reacting beta-Ca1.7(Eu0.1Sr0.2)SiO4Mixing the granular powder with deionized water to form bone cement slurry with a liquid/solid ratio of 0.5mL/1g, injecting the bone cement slurry into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 12-20min, placing the bone cement slurry into a constant temperature box with a humidity of 100% RH at 37 ℃ for curing for 24 hours, taking out the bone cement slurry, and measuring the compressive strength of the bone cement slurry to be 55MPa +/-15 MPa, which is about 20% higher than that of the bone cement slurry without element doped beta-Ca 2SiO 4.
Using beta-Ca1.7(Eu0.1Sr0.2)SiO4The bone cement is made into an implant with the diameter of 3mm and the length of 10mm, and the implant is implanted into the femoral defect part by means of a femoral defect model of an adult male New Zealand white rabbit. Histological observation shows that the implant material begins to be partially degraded at 4 weeks, and osteoblasts are attached to the junction of the material and the bone and new bone is formed; the bone formation is active in 12 weeks, new bones become compact, and the network of small vessels grows well, indicating that beta-Ca1.7(Eu0.1Sr0.2)SiO4The bone cement has good biocompatibility, degradability, vascularization capacity and osteogenesis in vivo, and can be used for repairing bone defects.
Example 3
β-Ca1.6(Na0.1Sr0.1Fe0.2)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a solution, dropwise adding 1.5mL of concentrated ammonia water, adjusting the pH value of the calcium nitrate water solution to 8-9, and heating and stirring in a water bath at 70 ℃ for 30 min. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, and dissolving the prepared sodium silicate solutionDropwise adding the calcium nitrate solution into the calcium nitrate solution at the speed of 50mL/h, heating in a water bath at the temperature of 50 ℃, mixing and stirring for 8h to obtain a first mixed solution; centrifuging the first mixed solution to obtain a precipitate, washing the precipitate with deionized water, and drying in a freeze drying box for 12h through the steps of pre-freezing, subliming and desorbing to obtain precursor powder; and placing the precursor powder in an infrared radiation furnace, calcining for 3h at 800 ℃, heating at 2000 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: 1.171g of nano monocalcium silicate powder, 0.519g of calcium hydroxide powder, 0.085g of sodium nitrate powder, 0.148g of strontium carbonate powder and 0.242g of ferric nitrate powder are respectively weighed and added into an agate mortar for grinding, and the mixture is uniformly ground to obtain mixed powder. And (3) calcining the mixed powder in an infrared radiation furnace at 1200 ℃ for 0.5h at the heating speed of 2000 ℃/min, and naturally cooling to room temperature to obtain the sodium-strontium-iron ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the sodium-strontium-iron ion co-doped beta-dicalcium silicate particle powder, and the result is shown in FIG. 8, and the result shows that the phase purity of the manganese-strontium-zinc ion co-doped beta-dicalcium silicate particle powder is 96.5%;
performing scanning electron microscope analysis on the sodium-strontium-iron ion co-doped beta-dicalcium silicate particle powder, wherein the grain size of the sodium-strontium-iron ion co-doped beta-dicalcium silicate particle powder is 0.05-1 mu m;
reacting beta-Ca1.6(Na0.1Sr0.1Fe0.2)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.6mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 25-35min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, and taking out to obtain a compressive strength of 42MPa +/-10 MPa.
beta-Ca is extracted from the bone cavity defect model of canine periapical area caused by surgical operation1.6(Na0.1Sr0.1Fe0.2)SiO4The bone cement fills the bone defect. Histological observation shows that after 8 weeks, with the degradation of the bone cement, obvious new bone tissues and a small amount of microangiogenesis are observed around the bone cement, and the growth of new bones is obviously larger than that of the non-element doped beta-Ca2SiO4Bone cement, Explanation beta-Ca1.6(Na0.1Sr0.1Fe0.2)SiO4Has good biocompatibility, degradability, osteogenesis performance and vascularization capacity, and can be used in the field of dental restoration.
Example 4
β-Ca1.85(Sr0.1Ag0.05)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.4mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 9. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the rate of 300mL/h, and mixing and stirring for 9h to obtain a first mixed solution; carrying out vacuum filtration on the first mixed solution to obtain a precipitate, washing the precipitate with deionized water, and drying in a vacuum drying oven at 120 ℃ for 4h to obtain precursor powder; calcining the precursor powder in an infrared radiation furnace at 700 ℃ for 1h at the heating rate of 650 ℃/min, and naturally cooling to room temperature to obtain an intermediate product, namely nano-calcium silicate powder;
the second step is that: respectively weighing 1.171g of nano-calcium metasilicate powder, 0.519g of calcium hydroxide powder, 0.423g of strontium nitrate powder and 0.170g of silver nitrate powder, adding the powder into an agate mortar for grinding, and uniformly grinding to obtain mixed powder. Calcining the mixed powder in a resistance furnace at 1000 ℃ for 9h at the heating rate of 30 ℃/min, and naturally cooling to room temperature to obtain strontium-silver ion co-doped beta-dicalcium silicate powder;
XRD analysis is carried out on the strontium-silver ion co-doped beta-dicalcium silicate powder, and the result is shown in FIG. 8, which shows that the phase purity of the strontium-silver ion co-doped beta-dicalcium silicate powder is 97%;
carrying out scanning electron microscope analysis on the strontium-silver ion co-doped beta-dicalcium silicate powder, wherein the grain size is 10-25 mu m;
reacting beta-Ca1.85(Sr0.1Ag0.05)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with liquid/solid ratio0.4mL/1g, injecting into a stainless steel mold with diameter of 5mm and height of 12mm, curing for 8-15min, placing into a constant temperature oven with humidity of 100% RH at 37 deg.C for 24 hr, taking out to obtain a product with compressive strength of 75MPa + -15 MPa, and specific element-free doped beta-Ca2SiO4The bone cement is about 63 percent higher.
By means of healthy adult male New Zealand white rabbit skull defect model, beta-Ca is extracted1.85(Sr0.1Ag0.05)SiO4The bone cement is implanted into the skull defect part, and histological observation shows that after 12 months of operation, the bone formation is active, new bones replace about 65 percent of the implantation volume of the bone cement, small blood vessels grow well, and no inflammatory reaction occurs. From this, it is known that beta-Ca1.85(Sr0.1Ag0.05)SiO4The bone cement can be used for repairing bone defects.
Example 5
β-Ca1.5(Sr0.2Co0.1Zn0.2)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.3mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 1h, and adjusting the pH value of the calcium nitrate solution to 11-12. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the rate of 200mL/h, and mixing and stirring for 7h to obtain a first mixed solution; filter-pressing the first mixed solution by a positive pressure filter to obtain a precipitate, washing the precipitate by deionized water, and then placing the precipitate in a vacuum drying oven to dry for 8 hours at 80 ℃ to obtain precursor powder; and placing the precursor powder in a microwave oven to calcine for 1h at the temperature of 600 ℃, heating at the rate of 350 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: 1.171g of nano monocalcium silicate powder, 0.701g of calcium carbonate powder, 0.212g of strontium nitrate powder, 0.297g of cobalt nitrate hexahydrate and 0.136g of zinc chloride powder are respectively weighed and added into an agate mortar for grinding, and the mixture is uniformly ground to obtain mixed powder. And placing the mixed powder in a resistance furnace, calcining for 11h at 900 ℃, heating at the rate of 50 ℃/min, and naturally cooling to room temperature to obtain the strontium-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the strontium-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder, and the result is shown in FIG. 8, which shows that the phase purity of the strontium-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder is 98.5%;
carrying out scanning electron microscope analysis on the strontium-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder, wherein the grain size is 5-15 μm;
reacting beta-Ca1.5(Sr0.2Co0.1Zn0.2)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.45mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 15-25min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, and taking out to obtain a compressive strength of 48MPa +/-12 MPa.
beta-Ca is extracted from the bone cavity defect model of canine periapical area caused by surgical operation1.5(Sr0.2Co0.1Zn0.2)SiO4The bone cement fills the bone defect. Histological observation shows that after 8 weeks, with the degradation of the bone cement, obvious new bone tissues and a small amount of microangiogenesis are observed around the bone cement, no inflammatory reaction is caused, and the new bone formation is superior to the non-element doped beta-Ca2SiO4Bone cement, Explanation beta-Ca1.5(Sr0.2Co0.1Zn0.2)SiO4Has good biocompatibility, degradability, osteogenesis performance and vascularization capacity, and can be used in the field of dental restoration.
Example 6
β-Ca1.4(Sr0.2 Mg0.1Mn0.1Co0.1Zn0.2)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 10-11. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water to obtain siliconSodium silicate solution, namely dripping the prepared sodium silicate solution into calcium nitrate solution at the speed of 400mL/h, and mixing and stirring for 5h to obtain precipitate; carrying out vacuum filtration on the precipitate, washing the precipitate with deionized water, and drying in a vacuum drying oven at 80 ℃ for 8h to obtain precursor powder; and placing the precursor powder in an electric furnace, calcining for 5h at 900 ℃, heating at the rate of 50 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: 1.171g of nano monocalcium silicate powder, 0.500g of calcium carbonate powder, 0.159g of strontium chloride powder, 0.148g of magnesium nitrate powder, 0.179g of manganese nitrate powder, 0.291g of cobalt nitrate hexahydrate and 0.125g of zinc carbonate powder are respectively weighed, added into an agate mortar for grinding, and uniformly ground to obtain mixed powder. And (3) calcining the mixed powder in a resistance furnace at 800 ℃ for 10h at the heating rate of 30 ℃/min, and naturally cooling to room temperature to obtain the strontium-magnesium-manganese-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder.
XRD analysis was performed on the strontium-magnesium-manganese-cobalt-zinc ion co-doped beta-dicalcium silicate particulate powder, and the result is shown in fig. 9, which shows that the phase purity of the strontium-magnesium-manganese-cobalt-zinc ion co-doped beta-dicalcium silicate particulate powder is 95.8%;
carrying out scanning electron microscope analysis on the strontium-magnesium-manganese-cobalt-zinc ion co-doped beta-dicalcium silicate particle powder, wherein the grain size is 3-12 mu m;
reacting beta-Ca1.4(Sr0.2Mg0.1Mn0.1Co0.1Zn0.2)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.40mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 10-15min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, and taking out to obtain a compressive strength of 55MPa +/-15 MPa.
Reacting beta-Ca1.4(Sr0.2Mg0.1Mn0.1Co0.1Zn0.2)SiO4The bone cement is implanted into the femoral bone defect of the goat and is subjected to X-ray and histomorpholo detection at 4 weeks and 12 weeks after operation respectively, so that the bone cement begins to be partially degraded and new bones and a small amount of capillaries are formed at 4 weeks without inflammatory reaction(ii) a The implant was substantially degraded and replaced by new bone in large amounts for 12 weeks, forming an osseous connection, demonstrating β -Ca1.4(Sr0.2Mg0.1Mn0.1Co0.1Zn0.2)SiO4Has good biocompatibility, degradability, osteogenic performance and vascularization capacity, and can be used in the field of bone repair.
Example 7
β-Ca1.5(Sr0.3 Cu0.2)SiO4Solid microsphere powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 8. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water to obtain a sodium silicate solution, dripping the prepared sodium silicate solution into the calcium nitrate solution at the speed of 100mL/h, and mixing and stirring for 5h to obtain a precipitate; carrying out vacuum filtration, washing the precipitate with deionized water, and drying in a vacuum drying oven at 80 ℃ for 8h to obtain precursor powder; and calcining the precursor powder in an electric furnace at 800 ℃ for 3h at the heating rate of 20 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: 1.171g of nano-monocalcium silicate powder, 0.519g of calcium hydroxide powder, 0.281g of copper nitrate powder and 0.221g of strontium carbonate powder are respectively weighed and added into an agate mortar for grinding, and the mixture is uniformly ground to obtain mixed powder. Adding the uniformly ground mixed powder into deionized water to prepare suspension slurry with the solid content of 35 vol%, performing spray granulation (the feeding speed is 15mL/min, the air inlet temperature during spray granulation is 200 ℃, the air outlet temperature is 120 ℃, and the rotating speed of a sprayer is 200rpm) to obtain a copper-strontium ion co-doped beta-dicalcium silicate solid microsphere blank, and performing rapid calcination in a microwave oven at 950 ℃ for 80min (the heating rate is 400 ℃/min) to finally obtain strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder.
XRD analysis is carried out on the strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder, and the result is shown in FIG. 8, which shows that the phase purity of the strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder is 98.6%;
FIG. 4 is a scanning electron micrograph of strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder, which shows that the diameter of the solid microsphere is 10-100 μm; FIG. 5 is a scanning electron micrograph of strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder showing that the grain size is about 0.2-1 μm.
FIG. 6 shows the results of bioactivity tests of strontium-copper ion co-doped beta-dicalcium silicate solid microsphere powder. From XRD analysis of strontium and copper ion co-doped beta-dicalcium silicate solid microsphere powder soaked in simulated body fluid for different times, the final reactant is hydroxyapatite, so that the strontium and copper ion co-doped beta-dicalcium silicate solid microsphere powder has good biological activity.
Reacting beta-Ca1.5(Sr0.3Cu0.2)SiO4Mixing the solid microsphere powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.5mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 12-20min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, and taking out to obtain a compressive strength of 45MPa +/-8 MPa.
Based on the tooth root periapical bone defect model of New Zealand white rabbit, beta-Ca is added1.5(Sr0.3Cu0.2)SiO4The bone cement is injected by a syringe to fill the bone defect. Histological observation shows that after 8 weeks, the bone cement begins to degrade, obvious new bone tissue and microangiogenesis around the bone cement, and the growth of new bone is obviously larger than that of the non-element doped beta-Ca2SiO4Bone cement and no inflammatory reaction, indicating beta-Ca1.5(Sr0.3Cu0.2)SiO4Has excellent biocompatibility, degradability, osteogenesis performance, vascularization capacity and antibacterial and bacteriostatic performance, and can be used in the field of dental restoration.
Example 8
β-Ca1.48(K0.1Sr0.3 Co0.1Fe0.1Ag0.02)SiO4Solid microsphere powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.2mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 8-9. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the speed of 150mL/h, and mixing and stirring for 8h to obtain a precipitate; filter-pressing the precipitate by a positive pressure filter, washing the precipitate by deionized water, and drying the precipitate in a vacuum drying oven at 50 ℃ for 24 hours to obtain precursor powder; and placing the precursor powder in an electric furnace, calcining for 8h at 650 ℃, heating at the rate of 1000 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano monocalcium silicate powder, 0.370g of calcium hydroxide powder, 0.101g of potassium nitrate powder, 0.212g of strontium nitrate powder, 0.291g of cobalt nitrate powder, 0.242g of iron nitrate powder and 0.170g of silver nitrate powder, adding the mixture into an agate mortar, grinding, and uniformly grinding to obtain mixed powder. Adding the uniformly ground mixed powder into deionized water to prepare suspension slurry with the solid content of 50 vol%, performing spray granulation (the feeding speed is 15mL/min, the air inlet temperature during spray granulation is 200 ℃, the air outlet temperature is 120 ℃, and the rotating speed of a spray head is 200rpm) to obtain a solid microsphere blank body codoped with potassium, strontium, cobalt, iron and silver ions, and then rapidly calcining the blank body for 30min (the heating rate is 100 ℃/min) by a microwave oven at 950 ℃ to finally obtain the solid microsphere powder codoped with potassium-strontium-cobalt-iron-silver ions and beta-dicalcium silicate.
XRD analysis is carried out on the potassium-strontium-cobalt-iron-silver ion co-doped beta-dicalcium silicate solid microsphere powder, and the result is shown in figure 8, which shows that the phase purity of the potassium-strontium-cobalt-iron-silver ion co-doped beta-dicalcium silicate solid microsphere powder is 98.6%;
scanning electron microscope analysis is carried out on the potassium-strontium-cobalt-iron-silver ion co-doped beta-dicalcium silicate solid microsphere powder, and the diameter of the solid microsphere is 60-240 mu m; the grain size is 0.5 to 5 μm.
Removing bilateral ovaries of rats by operation to reduce estrogen level, obtaining castration type osteoporosis animal model, and making modelThe rats successfully make the far-end cancellous bone fracture of the right femur and are randomly divided into two groups, and the experimental group adopts beta-Ca1.48(K0.1Sr0.3Co0.1Fe0.1Ag0.02)SiO4Bone cement, control group will not be doped with element beta-Ca2SiO4The bone cement is respectively implanted into the femoral fracture of the rat, and the beta-Ca can be seen in the histomorphometry examination of 8 weeks1.48(K0.1Sr0.3Co0.1Fe0.1Ag0.02)SiO4The bone cement fiber callus and bone-like callus appear more than beta-Ca2SiO4The bone cement is early and more in quantity, the bone healing quality is obviously higher than that of a control group, and no inflammatory reaction exists; demonstration of beta-Ca1.48(K0.1Sr0.3Co0.1Fe0.1Ag0.02)SiO4The solid microsphere powder has good biocompatibility and bone induction capability, and can be used in the field of bone repair.
The antibacterial performance detection shows that (according to the antibacterial performance test method of the SNT 3122-1.48(K0.1Sr0.3Co0.1Fe0.1Ag0.02)SiO4The solid microsphere powder has the antibacterial rates of 95.8 percent, 98.5 percent and 99.5 percent on escherichia coli, staphylococcus aureus and candida albicans respectively, and has broad-spectrum antibacterial performance.
Example 9
β-Ca1.2(Na0.1Co0.1Mn0.1Sr0.3Fe0.1Zn0.1)SiO4Hollow microsphere powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 10. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the speed of 100mL/h, and mixing and stirring for 5h to obtain a precipitate; filtering, washing the precipitate with deionized water, and drying in a forced air drying oven at 100 deg.C for 12 hr to obtain precursor powderA body; and placing the precursor powder in an electric furnace, calcining for 1.5h at 850 ℃, heating at the rate of 650 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano monocalcium silicate powder, 0.400g of calcium carbonate powder, 0.106g of sodium carbonate powder, 0.130g of cobalt chloride powder, 0.115g of manganese carbonate powder, 0.206g of strontium acetate powder, 0.363g of iron nitrate powder and 0.068g of zinc chloride powder, adding the mixture into an agate mortar for grinding, and uniformly grinding to obtain mixed powder. Adding the uniformly ground mixed powder into deionized water to prepare suspension slurry with the solid content of 25 vol%, performing spray granulation (the feeding speed is 25mL/min, the air inlet temperature during spray granulation is 250 ℃, the air outlet temperature is 150 ℃, and the rotating speed of a spray head is 320rpm) to obtain a sodium-cobalt-manganese-strontium-iron-zinc ion co-doped beta-dicalcium silicate microsphere blank, performing microwave rapid calcination at 1000 ℃ for 20min, (the heating rate is 50 ℃/min), and finally obtaining the sodium-cobalt-manganese-strontium-iron-zinc ion co-doped beta-dicalcium silicate hollow microsphere powder.
XRD analysis is carried out on the sodium-cobalt-manganese-strontium-iron-zinc ion co-doped beta-dicalcium silicate hollow microsphere powder, and the result is shown in figure 9, which shows that the phase purity of the sodium-cobalt-manganese-strontium-iron-zinc ion co-doped beta-dicalcium silicate hollow microsphere powder is 96.3%;
scanning electron microscope analysis is carried out on the sodium-cobalt-manganese-strontium-iron-zinc ion co-doped beta-dicalcium silicate hollow microsphere powder, so that the diameter of the solid microsphere is 20-200 mu m, and the grain size is 1-10 mu m.
Reacting beta-Ca1.2(Na0.1Co0.1Mn0.1Sr0.3Fe0.1Zn0.1)SiO4The hollow microsphere powder is used as a rhBMP-2 slow release carrier, is mixed with deionized water and carboxymethyl cellulose and then is implanted into the femoral bone defect of a goat, and X-ray and histomorphometry tests are carried out for 4 weeks and 12 weeks after operation respectively, so that the implant begins to be partially degraded and has new bone formation when 4 weeks later; the implant is basically degraded after 12 weeks, is greatly replaced by new bone, the internal space of the implant is more vascularized, a large amount of new bone tissues like the self trabecular bone grow into the implant and form bone connection, and the evidence of beta-Ca is provided1.2(Na0.1Co0.1Mn0.1Sr0.3Fe0.1Zn0.1)SiO4The hollow microsphere powder has good rhBMP-2 slow release and bone induction capability, and can be used in the field of bone repair.
Example 10
β-Ca1.6(Sr0.3Zn0.1)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 50 ℃ and stirring for 1h, and adjusting the pH value of the calcium nitrate solution to 9-10. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the rate of 30mL/h, and mixing and stirring for 10h to obtain a white precipitate; carrying out vacuum filtration on the white precipitate, washing the precipitate with deionized water, and drying in a vacuum drying oven at 50 ℃ for 24h to obtain precursor powder; and placing the precursor powder in an infrared electric furnace, calcining for 1.5h at 600 ℃, heating at the rate of 1500 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: 1.171g of nano-calcium metasilicate powder, 0.9912g of calcium acetate powder, 0.617g of strontium acetate powder and 0.550g of zinc acetate powder were weighed, mixed, and ground in an agate mortar to be uniform. And placing the mixed powder in an infrared electric furnace, calcining for 0.5h at 1100 ℃, heating up at the speed of 280 ℃/min, and naturally cooling to room temperature to obtain the strontium-zinc ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the strontium-zinc ion co-doped beta-dicalcium silicate particle powder, and the result is shown in FIG. 9, which shows that the phase purity of the strontium-zinc ion co-doped beta-dicalcium silicate solid microsphere powder is 97.8%;
and (3) carrying out scanning electron microscope analysis on the strontium-zinc ion co-doped beta-dicalcium silicate particle powder, wherein the grain size is 0.5-12 mu m.
Reacting beta-Ca1.6(Sr0.3Zn0.1)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry,the liquid/solid ratio is 0.40mL/1g, then the mixture is injected into a stainless steel mould with the diameter of 5mm and the height of 12mm, the curing time is 8-15min, the mixture is placed into a constant temperature box with the humidity of 100% RH for curing for 24 hours at 37 ℃, and the mixture is taken out to obtain the compressive strength of 55MPa +/-12 MPa.
beta-Ca was administered via femoral defect model in healthy adult male beagle dogs1.6(Sr0.3Zn0.1)SiO4The histological observation shows that 12 months after the operation, the bone cement has obvious degradation, active bone formation, a large amount of new bones, good growth of small blood vessels and no inflammatory reaction. From this, it is known that beta-Ca1.6(Sr0.3Zn0.1)SiO4The bone cement can be used for repairing bone defects.
Example 11
β-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.7mL of concentrated ammonia water, heating in a water bath at 80 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 9. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the speed of 400mL/h, and mixing and stirring for 1h to obtain a white precipitate; centrifuging the white precipitate, washing the white precipitate with deionized water, and drying in a freeze drying oven through pre-freezing, sublimating and desorbing to obtain precursor powder; and placing the precursor powder in a microwave electric furnace, calcining for 0.5h at 950 ℃, heating at the speed of 280 ℃/min, and naturally cooling to room temperature to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano-calcium metasilicate powder, 0.316g of calcium acetate powder, 0.3g of calcium carbonate powder, 0.206g of strontium acetate powder, 0.214g of magnesium acetate powder, 0.183g of zinc acetate powder, 0.177g of cobalt acetate powder and 0.2g of copper acetate powder, and grinding the mixed powder in an agate mortar to uniformly grind the mixed powder to obtain the mixed powder. And (3) calcining the mixed powder in a microwave oven at 1000 ℃ for 1h at the heating speed of 380 ℃/min, and naturally cooling to room temperature to obtain the strontium-magnesium-zinc-cobalt-copper ion co-doped beta-dicalcium silicate particle powder.
XRD analysis was performed on the strontium-magnesium-zinc-cobalt-copper ion co-doped beta-dicalcium silicate particulate powder, and the result is shown in fig. 10, which shows that the phase purity of the strontium-magnesium-zinc-cobalt-copper ion co-doped beta-dicalcium silicate particulate powder is 96.7%;
the scanning electron microscope analysis is carried out on the strontium-magnesium-zinc-cobalt-copper ion co-doped beta-dicalcium silicate particle powder, and the grain size is 3-15 mu m.
Reacting beta-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.45mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 12-22min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24h, and taking out to obtain a compressive strength of 45MPa +/-8 MPa.
By means of healthy adult male New Zealand white rabbit skull defect model, beta-Ca is extracted1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)SiO4The bone cement is implanted into the skull defect, and histological observation shows that 12 months after operation, the bone cement is obviously degraded, the bone formation is active, a large amount of new bones are formed, small blood vessels grow well, and no inflammatory reaction exists. From this, it is known that beta-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)SiO4The bone cement can be used for repairing bone defects.
Example 12
β-Ca1.6(Sr0.3Zn0.1)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 50 ℃ and stirring for 1h, and adjusting the pH value of the calcium nitrate solution to 9-10. Weighing 2.842 g of Na2SiO3·9H2O was dissolved in 100mL of deionized water to give a sodium silicate solution. Will be provided withDropwise adding the sodium silicate solution into the calcium nitrate solution at the speed of 30mL/h, and continuously stirring for 10h to obtain a white precipitate; filter-pressing the white precipitate and washing the white precipitate with deionized water for 3 times; adding 200mL of deionized water into the precipitate to prepare suspension slurry with uniform mixing and 25 vol% of solid content, and then passing through a spray dryer (the feeding speed is 25mL/min, the air inlet temperature of the dryer is 200 ℃, the air outlet temperature is 100 ℃, and the rotating speed of a nozzle is 180 rpm) to obtain dried precursor powder; and calcining the precursor powder in an infrared electric furnace at 600 ℃ at the heating rate of 850 ℃/min, and naturally cooling to room temperature after calcining for 1h to obtain the intermediate product nano-calcium silicate powder.
The second step is that: respectively weighing 1.171g of nano-calcium metasilicate powder, 0.9912g of calcium acetate powder, 0.617g of strontium acetate powder and 0.550g of zinc acetate powder, mixing the above powders, and fully grinding for 10h to obtain mixed powder; then placing the mixture in an infrared radiation electric furnace for calcination, wherein the calcination temperature is 1100 ℃, the heating rate is 850 ℃/min, and the calcination time is 0.5 h; and naturally cooling to room temperature to obtain the strontium-zinc ion co-doped beta-dicalcium silicate particle powder.
XRD analysis was performed on the strontium-zinc ion co-doped β -dicalcium silicate particulate powder, and the result is shown in fig. 10, which shows that the phase purity of the strontium-zinc ion co-doped β -dicalcium silicate particulate powder is 96.6%.
And (3) carrying out scanning electron microscope analysis on the strontium-zinc ion co-doped beta-dicalcium silicate particle powder, wherein the grain size is 2-20 microns.
Reacting beta-Ca1.6(Sr0.3Zn0.1)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.4mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 10-15min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, taking out, and measuring the compressive strength to be 70MPa +/-15 MPa.
Selecting New Zealand white rabbit, inducing chronic periapical bone defect model by apical operation, and treating with beta-Ca1.6(Sr0.3Zn0.1)SiO4The bone cement fills the bone defect. Histological observations showed that after 12 weeks, as the bone cement degraded,has obvious new bone tissue and micro-angiogenesis, and the growth of new bone is obviously larger than that of the non-element doped beta-Ca2SiO4Bone cement, no inflammatory reaction, indicating beta-Ca1.6(Sr0.3Zn0.1)SiO4Has excellent biocompatibility, degradability, osteogenesis performance, vascularization capacity and antibacterial and bacteriostatic performance, and can be used in the field of dental restoration.
Example 13
β-Ca1.7(Eu0.1Sr0.2)SiO4Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL of deionized water to prepare a calcium nitrate solution, dropwise adding 1.5mL of concentrated ammonia water, heating in a water bath at 70 ℃, stirring for 30min, and adjusting the pH value of the calcium nitrate solution to 9. Weighing 2.842 g of Na2SiO3·9H2Dissolving O in 100mL of deionized water, dropwise adding the prepared sodium silicate solution into the calcium nitrate solution at the speed of 100mL/h, and continuously stirring for 5h to obtain a white precipitate; then, centrifugally filtering the white precipitate, repeatedly washing the white precipitate for 3 times by using deionized water, and then placing the white precipitate in a microwave drying oven for drying for 4 hours at 120 ℃ to obtain precursor powder; calcining the precursor powder in a microwave electric furnace at 950 ℃ and at a temperature rise rate of 250 ℃/min for 1 h; then naturally cooling to room temperature to obtain the intermediate product nano-calcium metasilicate powder.
The second step is that: respectively weighing 1.171g of nano monocalcium silicate powder, 0.519g of calcium hydroxide powder, 0.669g of europium nitrate hexahydrate powder and 0.317g of strontium nitrate powder, mixing the powders, grinding the powders for 8 hours to obtain mixed powder; placing the mixed powder in an infrared radiation electric furnace for calcining, wherein the calcining temperature is 1000 ℃, the heating rate is 580 ℃/min, and the calcining time is 0.5 h; then naturally cooling to room temperature to obtain europium-strontium ion co-doped beta-dicalcium silicate particle powder.
XRD analysis is carried out on the europium-strontium ion codoped beta-dicalcium silicate particle powder, and the result is shown in figure 10, which shows that the phase purity of the europium-strontium ion codoped beta-dicalcium silicate particle powder is 96.8%;
and analyzing the europium-strontium ion co-doped beta-dicalcium silicate particle powder by a scanning electron microscope, wherein the grain size is 1-10 mu m.
Adding Ca1.7(Eu0.1Sr0.2)SiO4Mixing the granular powder with deionized water to obtain bone cement slurry with a liquid/solid ratio of 0.6mL/1g, injecting into a stainless steel mold with a diameter of 5mm and a height of 12mm, curing for 15-25min, placing into a constant temperature oven with a humidity of 100% RH at 37 ℃ for curing for 24 hours, and taking out to obtain a compressive strength of 45MPa +/-10 MPa.
In beta-Ca1.7(Eu0.1Sr0.2)SiO4After the antibacterial gentamicin is compounded in situ in the bone cement, a slow release experiment is carried out. FIG. 7 shows β -Ca1.7(Eu0.1Sr0.2)SiO4The slow release curve of the in-situ composite antibacterial drug gentamicin in the bone cement shows that the release speed of gentamicin in simulated body fluid is slow along with the increase of time extension line, the gentamicin is quickly released in higher concentration within the first 10 days, and the gentamicin is released at constant speed after the whole process reaches 21 days, so that a good release control function is embodied.
Selecting New Zealand white rabbit, inducing chronic periapical bone defect model by apical operation, and treating with beta-Ca1.7(Eu0.1Sr0.2)SiO4The bone cement is filled with the antibacterial gentamicin in situ.
Histological observation shows that after 8 weeks, with the degradation of bone cement, obvious new bone tissue and micro-angiogenesis exist, which indicates that beta-Ca is generated1.7(Eu0.1Sr0.2)SiO4Has excellent biocompatibility, degradability, osteogenesis performance and vascularization capacity, and can be used in the field of dental restoration.
Example 14
β-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)(SiO4)0.98(BO3)0.02Granular powder
The first step is as follows: 2.362 g Ca (NO) are weighed out3)2·4H2Dissolving O in 100mL deionized water to obtain calcium nitrate solution, adding 1.7mL concentrated ammonia water dropwise, heating in 80 deg.C water bath, stirring for 30minAnd adjusting the pH value of the calcium nitrate solution to 8-9. 2.785 g of Na are weighed out2SiO3·9H2O, 0.012 g H3BO3Respectively dissolving the sodium silicate solution and the boric acid solution in 100mL of deionized water to obtain a sodium silicate solution and a boric acid solution; respectively dripping the prepared sodium silicate solution and boric acid solution into the calcium nitrate solution at the speed of 400mL/h, and continuously stirring for 1h to obtain a white precipitate; then centrifugally filtering the precursor powder, repeatedly washing the precursor powder for 3 times by using deionized water, and then placing the product in a freeze drying box to be dried for 24 hours through the steps of pre-freezing, subliming and desorbing to obtain precursor powder; and placing the precursor powder in a microwave electric furnace for calcining at 950 ℃ and at the heating rate of 280 ℃/min, and naturally cooling to room temperature after calcining for 1h to obtain the intermediate product nano-calcium borosilicate powder.
The second step is that: respectively weighing 1.154g of nano calcium borosilicate powder, 0.316g of calcium acetate powder, 0.3g of calcium carbonate powder, 0.206g of strontium acetate powder, 0.214g of magnesium acetate powder, 0.183g of zinc acetate powder, 0.177g of cobalt acetate powder and 0.2g of copper acetate powder, mixing the powders and grinding for 6 hours to obtain mixed powder; then placing the mixed powder into a microwave oven for calcination, wherein the calcination temperature is 1000 ℃, the heating rate is 380 ℃/min, and the calcination is carried out for 1 h; then naturally cooling to room temperature to obtain strontium-magnesium-zinc-cobalt-copper-boron ion co-doped beta-dicalcium silicate particle powder;
XRD analysis was performed on the strontium-magnesium-zinc-cobalt-copper-boron ion co-doped beta-dicalcium silicate particulate powder, and the result is shown in fig. 10, which shows that the phase purity of the strontium-magnesium-zinc-cobalt-copper-boron ion co-doped beta-dicalcium silicate particulate powder is 96.8%;
carrying out scanning electron microscope analysis on the strontium-magnesium-zinc-cobalt-copper-boron ion co-doped beta-dicalcium silicate particle powder, wherein the grain size is 2-15 mu m;
reacting beta-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)(SiO4)0.98(BO3)0.02Mixing the granular powder with deionized water to obtain bone cement slurry with liquid/solid ratio of 0.5mL/1g, injecting into stainless steel mold with diameter of 5mm and height of 12mm, curing for 10-15min, and placing into constant-humidity RH chamber with humidity of 100%Curing for 24 hours at 37 ℃ in an incubator, and taking out to obtain the compressive strength of 65MPa +/-12 MPa;
selecting New Zealand white rabbit, inducing chronic periapical bone defect model by apical operation, and treating with beta-Ca1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)(SiO4)0.98(BO3)0.02The bone cement fills the bone defect. Histological observation shows that after 12 weeks, a great amount of new bone tissues and microangioses are generated along with the degradation of bone cement, no obvious inflammatory reaction is caused, and the results show that the beta-Ca is1.3(Sr0.3Mg0.1Zn0.1Co0.1Cu0.1)(SiO4)0.98(BO3)0.02Has excellent biocompatibility, degradability, osteogenic property, vascularization capacity and certain antibacterial and bacteriostatic properties, and can be used in the field of dental restoration.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The ion co-doped beta-dicalcium silicate powder is characterized in that the composition general formula of the ion co-doped beta-dicalcium silicate powder is Ca2-xMx(SiO4)1-y(BO3)yWherein M ion is Ca capable of being replaced2+One or more metal cations of the ions, x is more than 0 and less than or equal to 1; BO3 3-The borate ion is substituted for SiO4 4-The anion of the ion, y is more than or equal to 0 and less than or equal to 0.05.
2. The ion-codoped beta-dicalcium silicate powder of claim 1, wherein M is K+、Na+、Mg2+、Al3+、Zn2+、Sr2+Manganese ion, cobalt ion, Ag+Copper ion, iron ion, La3+Cerium ion and europium ion.
3. The ion-codoped beta-dicalcium silicate powder of claim 2, wherein the manganese ions comprise Mn3 +And Mn2+(ii) a The cobalt ions comprise Co3+And Co2+(ii) a The copper ions comprise Cu+And Cu2+Said iron ions comprise Fe3+And Fe2+(ii) a The cerium ions include Ce3+And Ce4+Said europium ion comprises Eu2+And Eu3+。
4. The preparation method of ion co-doped beta-dicalcium silicate powder according to any one of claims 1 to 3, which is a two-step synthesis method and comprises the following steps:
s1, preparing an intermediate product of nano-calcium metasilicate or nano-calcium borosilicate powder, dropwise adding a solution of silicate and/or a compound containing borate ions into a calcium salt solution under the conditions of heating and stirring for reaction to obtain a precipitate, filtering and washing the precipitate, drying and calcining to obtain the intermediate product of nano-calcium metasilicate or nano-calcium borosilicate powder;
s2, preparing ion co-doped beta-dicalcium silicate powder, mixing the intermediate product nano-monocalcium silicate powder or nano-monocalcium borosilicate with the doped metal salt powder, grinding and calcining to obtain the ion co-doped beta-dicalcium silicate powder.
5. The method according to claim 4, wherein the ionic co-doped beta-dicalcium silicate powder is prepared by mixing a calcium silicate,
in the S1, the pH value of the calcium salt solution is 7-12; the dripping speed of the solution of the silicate and/or the compound containing borate ions is 25-400mL/h, the precipitation reaction temperature is 20-90 ℃, and the stirring time is 1-10 h; the drying temperature is 50-120 ℃, the calcining temperature is 600-950 ℃, and the calcining time is 0.5-10 h;
in the S2, the calcination temperature is 800-1300 ℃, the calcination time is 10-600min, the calcination temperature rise rate is 1-2000 ℃/min, and the calcination mode is resistance furnace calcination, infrared calcination or microwave calcination.
6. The method for preparing ion co-doped beta-dicalcium silicate powder according to claim 5, wherein a spray granulation step is further included between the grinding and calcining steps in S2, and the specific treatment steps include: and adding deionized water into the mixed powder to prepare slurry with the solid content of not less than 20 voL%, and then carrying out spray granulation treatment.
7. The preparation method of the ion co-doped beta-dicalcium silicate powder as claimed in claim 6, wherein the spray granulation conditions are that the feeding speed is 5-50 mL/min, the air inlet temperature during spray granulation is 130-250 ℃, the air outlet temperature is greater than 100 ℃, and the rotating speed of a spray head is 180-300 rpm.
8. The method for preparing ion co-doped beta-dicalcium silicate powder according to claim 7, wherein the silicate is one or more of potassium silicate, potassium sodium silicate, anhydrous sodium metasilicate, sodium metasilicate pentahydrate, sodium metasilicate hexahydrate, sodium metasilicate octahydrate and sodium metasilicate nonahydrate; the compound containing borate ions is one or more of orthoboric acid, sodium tetraborate, sodium borohydride, ammonium hydrogen borate and potassium borohydride; the calcium salt is one or more of calcium nitrate, calcium oxalate, calcium acetate, calcium lactate, calcium gluconate, calcium citrate, calcium hydroxide, calcium carbonate, calcium oxide and calcium bicarbonate, and the doped metal salt is one or more of sodium salt, potassium salt, magnesium salt, aluminum salt, zinc salt, strontium salt, manganese salt, cobalt salt, silver salt, copper salt, iron salt, lanthanum salt, cerium salt and europium salt.
9. The method for preparing the ion co-doped beta-dicalcium silicate powder according to claim 8, wherein the potassium salt is one or more of potassium nitrate, potassium carbonate, potassium bicarbonate, potassium acetate, potassium hydroxide, potassium oxide, potassium lactate, potassium citrate and potassium gluconate; the sodium salt is one or more of sodium nitrate, sodium carbonate, sodium bicarbonate, sodium acetate, sodium hydroxide, sodium oxide, sodium lactate, sodium citrate and sodium gluconate; the magnesium salt is one or more of magnesium nitrate, magnesium acetate, magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium lactate, magnesium chloride, magnesium citrate and magnesium gluconate; the aluminum salt is one or more of aluminum nitrate, aluminum carbonate, aluminum chloride, aluminum lactate and aluminum citrate; the zinc salt is one or more of zinc nitrate, zinc carbonate, zinc chloride, zinc acetate, zinc lactate, zinc citrate and zinc gluconate; the strontium salt is one or more of strontium nitrate, strontium carbonate, strontium chloride, strontium acetate, strontium lactate, strontium citrate and strontium gluconate; the manganese salt is one or more of manganese nitrate, manganese carbonate, manganese chloride, manganese acetate, manganese lactate, manganese citrate and manganese gluconate; the cobalt salt is one or more of cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt acetate and cobalt gluconate; the silver salt is one or more of silver nitrate, silver carbonate, silver chloride, silver acetate, silver lactate and silver citrate; the copper salt is one or more of cupric nitrate, cupric carbonate, cupric chloride, cupric acetate, cuprous acetate, cupric citrate and cupric gluconate; the ferric salt is one or more of ferric nitrate, ferric carbonate, ferric chloride, ferric acetate, ferrous lactate, ferric citrate and ferrous gluconate; the lanthanum salt is one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum acetate, lanthanum citrate and lanthanum lactate; the cerium salt is one or more of cerium nitrate, hydrated cerium carbonate, cerium chloride, cerium acetate and cerium citrate; the europium salt is one or more of europium nitrate, europium carbonate, europium chloride and europium acetate.
10. The application of the ion co-doped beta-dicalcium silicate powder as claimed in any one of claims 1 to 3, which is characterized in that the ion co-doped beta-dicalcium silicate powder is applied to filling paste, bone cement, artificial bone and drug sustained release carriers; the ion co-doped beta-dicalcium silicate powder is applied to tooth repair, jaw repair, spine repair, joint repair and other hard tissue repair.
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