CN114129455B - Glass ion water portal powder and preparation method and application thereof - Google Patents
Glass ion water portal powder and preparation method and application thereof Download PDFInfo
- Publication number
- CN114129455B CN114129455B CN202111257601.7A CN202111257601A CN114129455B CN 114129455 B CN114129455 B CN 114129455B CN 202111257601 A CN202111257601 A CN 202111257601A CN 114129455 B CN114129455 B CN 114129455B
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- China
- Prior art keywords
- powder
- acid
- water
- glass
- ion water
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000011521 glass Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004568 cement Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 102
- 239000002002 slurry Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 11
- 239000004575 stone Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001363 water suppression through gradient tailored excitation Methods 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003178 glass ionomer cement Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 150000005691 triesters Chemical class 0.000 claims description 3
- 229910052725 zinc Chemical class 0.000 claims description 3
- 239000011701 zinc Chemical class 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- -1 phosphate ester Chemical class 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000011737 fluorine Substances 0.000 abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 27
- 239000000523 sample Substances 0.000 description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000002609 medium Substances 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000007373 indentation Methods 0.000 description 5
- 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 description 4
- 235000014469 Bacillus subtilis Nutrition 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 244000199866 Lactobacillus casei Species 0.000 description 4
- 241000605862 Porphyromonas gingivalis Species 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 239000013039 cover film Substances 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 241000186044 Actinomyces viscosus Species 0.000 description 3
- 241000194019 Streptococcus mutans Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- 240000008575 Ammannia baccifera Species 0.000 description 2
- 235000001248 Dentaria laciniata Nutrition 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007621 bhi medium Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000013958 Lactobacillus casei Nutrition 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 230000000675 anti-caries Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229940017800 lactobacillus casei Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000011123 type I (borosilicate glass) Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/17—Particle size
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
Abstract
The invention discloses glass ion water portal powder and a preparation method and application thereof. The glass ion water portal powder is prepared by adopting a sol-gel process, and the specific surface area of the material is more than 20m 2 And/g, has high reactivity and short net curing time. The glass ion water portal powder material contains micro-nano mesopores, and forms a mosaic structure after reacting with a liquid agent, the system has higher mechanical property, and the material contains antibacterial components and has antibacterial function. The sol-gel method can be adopted to uniformly mix raw materials at a molecular level, and calcination is carried out at a lower temperature (400-850 ℃) so as to prevent fluorine loss and prepare glass powder with better purity and uniformity. The glass particle cement glass powder prepared by the method has good component uniformity, is matched with a commercially available liquid, has excellent comprehensive performance, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of medical materials, in particular to glass ion water portal powder and a preparation method and application thereof.
Background
Glass ion water gate (glass ion for short, GIC) is a new type of dental water gate, has the characteristics of high strength, translucency and fluorine release, can prevent secondary caries, can form chemical bonding with tooth tissue, has excellent comprehensive performance, and has been developed very rapidly; it is one of the most important repairing materials in the clinic of the present oral cavity, widely applied to the bonding of various repairing bodies, the filling repairing of decayed teeth, lining and the like, and is also the most ideal repairing material for the non-invasive filling repairing treatment of decayed teeth at present.
The glass ion consists of powder and liquid, wherein the powder is fluorine-containing aluminosilicate glass powder, and the liquid is aqueous solution of polyolefin acid (such as polyacrylic acid, polyacrylic acid and itaconic acid or maleic acid copolymer). When the powder and the liquid are mixed, the glass powder is decomposed under the action of acid to release Ca 2+ 、Al 3+ The polymer and the polycarboxylic acid hydrogel are entangled with each other to form a network of interpenetrating polymer and then cured under the action of a chemical initiator.
GlassThe curing reaction of ions is complex, and the mechanism of the reaction is not completely known at present, and the substance is an acid-base reaction between polybasic acid and glass powder. When the powder is mixed, the surface layer of the glass powder is eroded by acid to release divalent metal ions such as Ca 2+ And small amounts of monovalent metal ions, e.g. Na + Subsequently Al is present in the form of a ligand (AlF 2+ ) Moving to liquid phase to completely lose metal ions on surface layer, forming silica gel layer surrounding unreacted glass core. As the pH rises, these cationic and polyanionic chains crosslink, forming calcium and aluminum polycarboxylates, which hydrate to form a gel matrix. Subsequently, hardening due to the formation of a large amount of aluminum polyacrylate (calcium salt only participates in coagulation, cannot cause hardening), sodium ions only form viscous sodium polyacrylate, and do not participate in gelation. Finally, the cured ionomer is composed of a network of polyacid matrix formed by the hydrolysis of calcium (aluminum) polycarboxylate salts, which holds together unreacted glass particles covered by a layer of silica gel. With the deposition of aluminum polyacrylate, the hardening lasts more than 24 hours, and the deposition reaction of the acrylate can last for one year. This reaction results in good retention without sacrificing retention or affecting fluoride release anticaries performance to reduce micro-dissolution. Because the glass powder is selected, the tooth-like dental implant has translucency after solidification, has similar color and luster as teeth, good biocompatibility, stable physical and chemical properties and the like.
Glass ions in the 70 th century appear in the European market for the first time as commodities, and after entering the 21 st century, with the increasing importance of people in oral health, glass ions are widely applied in China, research on glass ions in China also starts to be vigorously developed, and a glass ion water portal material with excellent performance is an indispensable product for repairing tooth defects.
As an oral restoration material, the glass ion water-gate must have high strength to meet the requirement of restoration of the chewing function, and as a water-sensitive material, it must be cured immediately and withstand erosion of oral saliva after curing to ensure that the performance does not deteriorate over time when applied in the oral environment. However, the existing domestic products have large gaps in these aspects, the compressive strength and hardness are insufficient, particularly the wear resistance is poor, and in clinical application, the surface contacted with the oral cavity environment becomes rough in a short time, so that food scraps are easily accumulated and bacteria are easily bred, and finally the clinical repair treatment fails; clinical investigation shows that the success rate of the repair treatment of the domestic product is obviously smaller than that of the imported product; therefore, the glass ion water portal products clinically applied in China at present are mainly imported products (such as companies of GC Fuji, 3M, kerr and the like). In addition, glass powder of commercial glass ion water heater products is mostly prepared by a melting method, and the melting temperature is high (1300-1600 ℃), so that fluorine loss is easy to cause, and the composition and product quality controllability of the glass ion water heater powder are poor.
Disclosure of Invention
The invention aims to provide novel glass ion water portal powder and a preparation method and application thereof.
In order to achieve the object of the invention, the invention provides a composition, which comprises the following components in parts by weight: al (Al) 2 O 3 15-40，SiO 2 20-60，MO 10-40，ZnO 1-10，P 2 O 5 0-10，F 1-20。
Wherein MO is SrO and/or CaO;
SiO 2 with Al 2 O 3 The molar ratio of (2) is (0.5-3): 1.
In a second aspect, the invention provides a preparation method of glass ion water portal powder, which comprises the following raw materials in parts by mass through a sol-gel method: 80-180 parts of silicate substances and/or silica sol, 0-20 parts of phosphate substances, 100-200 parts of water, 120-200 parts of soluble metal salt, 10-100 parts of alcohol solvent, 1-30 parts of fluoride and 0.01-10 parts of pH regulator.
Wherein the silicate substance is at least one selected from methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, etc.
The silica sol may be a neutral silica sol or an acidic silica sol. Preferably, the neutral silica sol has a pH of 7.0 to 8.5 and the acidic silica sol has a pH of 2.0 to 4.0.
The phosphate ester substance can be at least one selected from phosphoric monoester, phosphoric diester, phosphoric triester, phosphoric triethyl ester, phosphoric tributyl ester, etc.
The soluble metal salt may be at least one selected from inorganic salts of calcium, strontium, aluminum, zinc, alkoxides, and the like.
The water may be deionized water.
The alcohol solvent may be at least one selected from methanol, ethanol, ethylene glycol, diethylene glycol, glycerol, etc.
The fluoride may be sodium fluoride and/or fluosilicic acid.
The pH regulator is acid or alkali.
Further, the acid is an inorganic acid or an organic acid. Preferably, the inorganic acid may be selected from at least one of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, and the like. Preferably, the organic acid may be at least one selected from acetic acid, oxalic acid, maleic acid, citric acid, and the like.
The base may be an inorganic base or an organic amine. Preferably, the inorganic base may be selected from at least one of sodium hydroxide, ammonia water, sodium bicarbonate, and the like. Preferably, the organic amine may be ethylenediamine and/or n-propylamine.
Specifically, the method for preparing the glass ion water portal powder comprises the following steps:
1) Preparation of sol: mixing silicate substances and/or silica sol, phosphate substances, fluoride, water and an alcohol solvent, performing room-temperature hydrolysis reaction, adding soluble metal salt after the mixed solution becomes transparent, and stirring until the soluble metal salt is completely dissolved to obtain sol;
2) Preparation of the gel: adjusting the pH value of the sol to 4-6 or 8-10 by using a pH regulator, and then aging for 6-12 hours at 30-100 ℃ (preferably 30-80 ℃) to obtain gel;
3) And (3) heat treatment: baking the gel at 90-150deg.C (preferably 100-120deg.C) for 10-50 hr until the water content is not more than 5% of the gel mass; calcining at 400-800 deg.c (preferably 500-700 deg.c) for 40-120min to obtain glass ion water portal powder precursor;
4) Crushing: carrying out wet ball milling on the glass ion water valve precursor to obtain raw slurry;
specifically, mixing glass ion water gate precursor, ball milling medium and liquid medium in a mass ratio of 1 (1-3) (1-2) in a grinder, and grinding for 0.5-3h at a rotating speed of 300-600 r/min; the ball milling medium is zirconia ball stone and/or alumina ball stone; the liquid medium is preferably water;
5) Surface treatment: diluting the original slurry with water, wherein the volume ratio of the original slurry to the water is 5-10:1, adding an acid solution into the diluted original slurry, wherein the volume of the acid solution accounts for 1-20% of the volume of the diluted original slurry, stirring for 1-2h at room temperature, sieving by a wet method, precipitating and filtering to remove suspension liquid, and obtaining wet powder; the acid solution is acetic acid, oxalic acid, hydrochloric acid, phosphoric acid or nitric acid solution, and the concentration of the acid solution is 0.5-3%.
6) And (3) drying: vacuum drying the wet powder material at 70-120 deg.c (preferably 80-120 deg.c, vacuum degree lower than-0.8 Bar and drying time of 12-24 hr;
7) Grinding: placing the dried powder into a grinder, and grinding for 5-30min at a rotating speed of 300-600 r/min;
8) And (3) screening: and screening the ground powder by adopting a 300-500 mesh screen to obtain the glass ion cement powder.
In a third aspect, the present invention provides a glass ionomer cement powder prepared according to the above method.
The granularity of the glass ion water portal powder is smaller than 40 mu m, the granularity of the powder is uniformly distributed, the d50 is 1-8 mu m, and the d90 is 10-30 mu m. The specific surface area (BET) of the powder is more than 20m 2 And/g, has high reactivity and short net curing time, and effectively shortens the waiting time of patients.
The net curing time of the glass ion water portal powder and the liquid agent after mixing and curing is about 2-5 min.
The glass ion water portal powder material of the invention contains micro-nano mesopores, forms an embedded structure after reacting with liquid, has higher mechanical property (wherein, the compressive strength of the cement type cement is 100-150 MPa, the compressive strength of the restoration type cement is 240-300 MPa), and the bonding strength with teeth reaches more than 5 MPa.
ZnO is added into the glass ion water portal powder, so that the cured glass ion water portal has antibacterial property.
SrO and fluoride are added into the glass ion water portal powder, so that the cured glass ion water portal has the characteristics of X-ray obstruction and continuous fluoride ion release.
In a fourth aspect, the present invention provides the use of said composition or said glass ionomer cement powder for the preparation of dental restorative material.
The glass powder of the invention can be used for glass ion water portal in any dosage form, for example, can be used for tempering water-based glass ion water portal, and can also be mixed with any glass ion water portal liquor, such as commercially available Japanese Fuji GC glass ion water portal liquor, liquor disclosed in CN102174141B, liquor disclosed in CN1187032C and the like, wherein the weight ratio of the glass powder to the liquor is (1.5-4): 1, and the tempering method is carried out according to a conventional method in the field.
By means of the technical scheme, the invention has at least the following advantages and beneficial effects:
aiming at the problems of low mechanical property and poor component controllability of domestic glass ion water portal products, the invention adopts a sol-gel process to provide novel glass ion water portal powder with high reactivity; the Sol-gel method (Sol-gel) can uniformly mix raw materials at a molecular level, and calcine the raw materials at a lower temperature (400-850 ℃) to prevent fluorine loss, so that glass powder with better purity and uniformity can be prepared. The glass ion cement glass powder prepared by the method has good component uniformity, is matched with the liquid agent sold in the market for use, has excellent comprehensive performance, and is suitable for industrial production.
Detailed Description
The invention provides novel glass ion water portal powder.
The glass ion water portal powder material is prepared from Al 2 O 3 、SiO 2 、MO、F、ZnO、P 2 O 5 Composition, in mass percent, of Al 2 O 3 ：15-40％，SiO 2 ：20-60％，MO：10-40％，ZnO：1-10％，P 2 O 5 :0-10%, F:1-20%; the MO is one or a mixture of two of SrO and CaO; siO (SiO) 2 With Al 2 O 3 The molar ratio of (2) is (0.5-3): 1.
The glass ion water portal powder is prepared by adopting a sol-gel method, and the raw materials are as follows in parts by weight:
wherein the silicate/silica sol substance is at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; the silica sol is a neutral silica sol, preferably the neutral silica sol has a pH of 7.0 to 8.5; alternatively, the acidic silica sol, preferably the acidic silica sol has a pH of 2.0 to 4.0.
The phosphate is at least one of phosphoric monoester, phosphoric diester, phosphoric triester, triethyl phosphate and tributyl phosphate.
The soluble metal salt is at least one of inorganic salts of calcium, strontium, aluminum and zinc and alkoxide.
The water is deionized water.
The alcohol solvent is at least one of methanol, ethanol, glycol, diglycol and glycerol.
The fluoride is fluosilicic acid.
The pH regulator is acid or alkali; wherein the acid is an inorganic acid or an organic acid, the inorganic acid is preferably nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, and the organic acid is preferably at least one of acetic acid, oxalic acid, maleic acid and citric acid; the alkali is inorganic alkali or organic amine, wherein the inorganic alkali is preferably at least one of sodium hydroxide, ammonia water and sodium bicarbonate, and the organic amine is preferably at least one of ethylenediamine and n-propylamine.
The granularity of the glass ion water portal powder is smaller than 30 mu m, the granularity distribution of the powder is uniform, d50 is 1-8 mu m, and d90 is 10-20 mu m.
The clean curing time of the glass ion water portal powder and the liquid agent after mixing and curing is about 3 to 6 minutes, the compressive strength of the cement type cement is 100-150 MPa, and the compressive strength of the restoration type cement is 240-300 MPa.
ZnO is added into the glass ion water portal powder, so that the cured glass ion water portal has antibacterial property; srO and fluoride are added, so that the cured glass ion water heater has the characteristics of X-ray obstruction and sustained fluoride ion release.
The preparation method of the glass ion water portal powder sequentially comprises the following steps: preparing sol, preparing gel, heat treating, crushing, surface treating, stoving, grinding and sieving; the method comprises the following steps:
1. preparation of sol: adding silicate substances/silica sol, phosphate, fluoride, water and alcohol solvent into a reactor, performing pre-hydrolysis reaction, adding soluble metal salt after the mixture becomes transparent, and stirring until the mixture is completely dissolved to obtain sol.
2. Preparation of the gel: the pH value of the sol is adjusted to 4-6 or 8-10 by a pH regulator, and then the sol is aged for 6-12 hours at 30-80 ℃ to obtain gel.
3. And (3) heat treatment: after breaking the gel, baking at 90-150 ℃ for 10-50 hours until the water content is not more than 5% of the mass of the gel; and then calcining at 400-800 ℃ for 40-120min to obtain the glass ion water portal powder precursor.
4. Crushing: wet ball milling of the glass ion water gate precursor obtained by the heat treatment to obtain a raw slurry, preferably, wet ball milling means adding the precursor to a rapid grinding mill with a ball milling medium, and adding a liquid medium to the rapid grinding mill, wherein the precursor: ball milling medium: liquid medium=1:1-3:1-2 (mass ratio), then grinding for 0.5-3h at a rotational speed of 300-600 r/min; the ball milling medium may be any of zirconia ball stone or alumina ball stone. The liquid medium is preferably water.
5. Surface treatment: diluting the raw slurry by adding water, wherein the volume ratio of the raw slurry to the water is (5-10): 1, adding acid into diluted raw slurry, wherein the volume of the acid accounts for 1-20% of the volume of the diluted raw slurry, stirring for 1-2h at room temperature, sieving by a wet method, precipitating, filtering and removing suspension liquid to obtain wet powder; the acid can be any one of acetic acid, oxalic acid, hydrochloric acid, phosphoric acid or nitric acid, and the concentration of the acid solution is 0.5-3%.
6. And (3) drying: vacuum drying the wet powder at 70-120deg.C for 12-24 hr.
7. Grinding: and (3) putting the powder obtained through the drying process into a quick grinder, and grinding for 5-30min at a rotating speed of 300-600r/min to obtain the powder.
8. And (3) screening: screening the powder obtained in the grinding process by adopting a 300-500 mesh screen to obtain glass ion cement powder, wherein the granularity of the powder is less than 40 mu m, and d50:1-8 μm, d90:10-30 μm, the specific surface area (BET) of the powder is more than 20m 2 /g。
The glass ion water portal powder material of the invention, (1) is prepared by sol-gel technology; (2) The specific surface area (BET) of the glass ion water portal powder material is more than 20m 2 And/g, the composition has high reactivity, short net curing time and shortened waiting time of patients; (3) The glass ion water valve powder material contains micro-nano mesopores, and forms an embedded structure after reacting with a liquid agent, and the system has higher mechanical property (the compression strength of the filling type water valve reaches more than 240MPa, and the bonding strength of the bonding type water valve and teeth reaches more than 5 MPa); (4) The glass ion water portal powder material contains antibacterial components and has antibacterial function.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art, and all raw materials used are commercially available. Example 1 preparation of glass Ionic Water Portin powder
The glass ion water portal powder formulation in the embodiment is prepared from the following raw materials in parts by mass through a sol-gel method:
the glass ion water portal powder of the embodiment is prepared by the following method:
firstly, preparing sol: 150 parts of water, 120 parts of ethyl orthosilicate, 50 parts of ethanol and 15 parts of triethyl phosphate are added into a reactor for room-temperature pre-hydrolysis reaction, 25 parts of strontium nitrate, 60 parts of calcium nitrate, 55 parts of aluminum nitrate, 5 parts of zinc nitrate and 12 parts of fluosilicic acid are added after the mixed solution becomes transparent and clear, and the mixed solution is stirred until the mixed solution is completely dissolved, so that sol is obtained.
The pH of the sol was adjusted to 5 with concentrated nitric acid, and the gel was aged at 40℃for 10 hours, the solution becoming a homogeneous gel state completely.
Then, after gel breaking, transferring the gel into a baking oven at 120 ℃ for continuous drying until the water content of the system volatilizes to be not more than 5%; and (3) placing the xerogel block in a muffle furnace, and calcining at 500 ℃ for 60min until the organic matters are completely removed, thus obtaining the glass ion water portal powder precursor.
Performing wet ball milling on the glass ion water portal precursor obtained by heat treatment to obtain raw slurry, wherein the precursor is: zirconia ball stone: water=1:1:1 (mass ratio), followed by grinding for 1h at a rotational speed of 400 r/min.
And (3) diluting the slurry by adding water, wherein the volume ratio of the raw slurry to the water is 6:1, adding acetic acid into the diluted raw slurry, wherein the concentration of an acetic acid solution is 2%, the volume of the acetic acid accounts for 5% of the volume of the diluted raw slurry, stirring for 1h at room temperature, sieving by a wet method, and filtering to remove suspension liquid to obtain wet powder.
Vacuum drying the wet powder at 100deg.C for 24 hr. And (3) putting the obtained powder after the drying procedure into a quick grinder, and grinding for 10min at a rotating speed of 500 r/min.
And screening the powder obtained in the grinding process by adopting a 400-mesh screen to obtain the glass ion cement powder.
The glass powder materials synthesized in the embodiment respectively comprise the following components in percentage by mass:
Al 2 O 3 ：18％，SiO 2 ：36％，SrO：10％，CaO：20％，ZnO：2％，P 2 O 5 :5%, F:9% the particle size distribution of the material is uniform, d10 is 1.273 μm, d50 is 5.008 μm, d90 is 19.916 μm, and the specific surface area (BET) of the powder is 85m 2 /g。
Example 2 preparation of glass Ionic Water Portin powder
The glass ion water portal powder formulation in the embodiment is prepared from the following raw materials in parts by mass through a sol-gel method:
the glass ion water portal powder of the embodiment is prepared by the following method:
firstly, preparing sol: 120 parts of water, 100 parts of methyl orthosilicate, 20 parts of ethanol and 10 parts of phosphoric monoester are added into a reactor for room-temperature pre-hydrolysis reaction, 35 parts of strontium acetate, 100 parts of aluminum nitrate, 135 parts of zinc acetate and 15 parts of fluosilicic acid are added after the mixed solution becomes transparent and clear after hydrolysis, and the solution is stirred until the solution is completely dissolved, so that sol is obtained.
The pH of the sol was adjusted to 6 with concentrated hydrochloric acid, and then the gel was aged at 70℃for 12 hours, the solution completely becoming a homogeneous gel state.
Then, after gel breaking, transferring the gel into a baking oven at 120 ℃ for continuous drying until the water content of the system volatilizes to be not more than 5%; and (3) placing the xerogel block in a muffle furnace, and calcining at 700 ℃ for 50min until the organic matters are completely removed, thus obtaining the glass ion water portal powder precursor.
Performing wet ball milling on the glass ion water portal precursor obtained by heat treatment to obtain raw slurry, wherein the precursor is: zirconia ball stone: water=1:2:1 (mass ratio), followed by grinding at 400r/min for 60min.
Adding water into the slurry for dilution, wherein the volume ratio of the raw slurry to the water is 6:1, adding oxalic acid into the diluted raw slurry, wherein the concentration of oxalic acid solution is 2%, the volume of oxalic acid accounts for 15% of the volume of the diluted raw slurry, stirring for 1h at room temperature, sieving by a wet method, and filtering to remove suspension liquid to obtain wet powder.
Vacuum drying the wet powder material at 120 deg.c for 15 hr. And (3) putting the obtained powder after the drying procedure into a quick grinder, and grinding for 20min at a rotating speed of 400 r/min.
And screening the powder obtained in the grinding process by adopting a 500-mesh screen to obtain the glass ion cement powder.
The glass powder materials synthesized in the embodiment respectively comprise the following components in percentage by mass:
Al 2 O 3 ：33％，SiO 2 ：34％，SrO：15％，CaO：0％，ZnO：4％，P 2 O 5 :3%, F:11%, the particle size distribution of the material was uniform, d10 was 1.148 μm, d50 was 3.139 μm, d90 was 15.413 μm, and the specific surface area (BET) of the powder was 123m 2 /g。
Example 3 preparation of glass Ionic Water-portal powder
The glass ion water portal powder formulation in the embodiment is prepared from the following raw materials in parts by mass through a sol-gel method:
the glass ion water portal powder of the embodiment is prepared by the following method:
firstly, preparing sol: 150 parts of water, 140 parts of propyl orthosilicate, 50 parts of ethanol and 10 parts of phosphoric diester are added into a reactor for room-temperature pre-hydrolysis reaction, 25 parts of strontium nitrate, 35 parts of calcium nitrate, 100 parts of aluminum acetate, 20 parts of zinc acetate and 10 parts of fluosilicic acid are added after the mixed solution becomes transparent and clear after hydrolysis, and the mixed solution is stirred until the mixed solution is completely dissolved, so that sol is obtained.
The pH of the sol was adjusted to 4 with concentrated hydrochloric acid, and then the gel was aged at 70℃for 12 hours, the solution completely becoming a homogeneous gel state.
Then, after gel breaking, transferring the gel into a baking oven at 150 ℃ to continue drying until the water content of the system volatilizes to be not more than 5%; and (3) placing the xerogel block in a muffle furnace, and calcining at 500 ℃ for 120min until the organic matters are completely removed, thus obtaining the glass ion water portal powder precursor.
Performing wet ball milling on the glass ion water portal precursor obtained by heat treatment to obtain raw slurry, wherein the precursor is: zirconia ball stone: water=1:2:1 (mass ratio), followed by grinding at 600r/min for 120min.
And (3) diluting the slurry by adding water, wherein the volume ratio of the raw slurry to the water is 8:1, adding phosphoric acid into the diluted raw slurry, wherein the concentration of a phosphoric acid solution is 2%, the volume of the phosphoric acid is 10% of the volume of the diluted raw slurry, stirring for 2 hours at room temperature, sieving by a wet method, and filtering to remove suspension liquid to obtain wet powder.
And drying the wet powder material in vacuum at 80 ℃ for 16 hours. And (3) putting the obtained powder after the drying procedure into a quick grinder, and grinding for 30min at a rotating speed of 400 r/min.
And screening the powder obtained in the grinding process by adopting a 500-mesh screen to obtain the glass ion cement powder.
The glass powder materials synthesized in the embodiment respectively comprise the following components in percentage by mass:
Al 2 O 3 ：30％，SiO 2 ：38％，SrO：10％，CaO：10％，ZnO：8％，P 2 O 5 :2%, F:2% the particle size distribution of the material is uniform, d10 is 0.759 μm, d50 is 2.641 μm, d90 is 12.823 μm, and the specific surface area (BET) of the powder is 177m 2 /g。
Example 4 preparation of glass Ionic Water-portal powder
The glass ion water portal powder formulation in the embodiment is prepared from the following raw materials in parts by mass through a sol-gel method:
the glass ion water portal powder of the embodiment is prepared by the following method:
firstly, preparing sol: 100 parts of water is added into a reactor, then 110 parts of neutral silica sol (solid content is about 50 wt.%), 50 parts of ethanol and 5 parts of phosphotriester are added for prehydrolysis reaction, 40 parts of strontium nitrate, 18 parts of calcium nitrate, 110 parts of aluminum nitrate, 18 parts of zinc acetate and 20 parts of fluosilicic acid are added after the mixed solution becomes transparent and clear after hydrolysis, and the sol is obtained after stirring until complete dissolution.
The pH of the sol was adjusted to 4 with concentrated nitric acid, and the gel was aged at 70℃for 10 hours, the solution becoming a homogeneous gel state completely.
Then, after gel breaking, transferring to a baking oven at 90 ℃ for continuous drying until the water content of the system volatilizes to be not more than 5%; and (3) placing the xerogel block in a muffle furnace, and calcining at 700 ℃ for 40min until the organic matters are completely removed, thus obtaining the glass ion water portal powder precursor.
Performing wet ball milling on the glass ion water portal precursor obtained by heat treatment to obtain raw slurry, wherein the precursor is: zirconia ball stone: water=1:3:2 (mass ratio), followed by grinding at 550r/min for 40min.
Adding water into the slurry for dilution, wherein the volume ratio of the raw slurry to the water is 10:1, adding nitric acid into the diluted raw slurry, wherein the concentration of nitric acid solution is 3%, the volume of nitric acid accounts for 15% of the volume of the diluted raw slurry, stirring for 1.5h at room temperature, sieving by a wet method, and filtering to remove suspension liquid to obtain wet powder.
Vacuum drying the wet powder for 20h at 110 ℃. And (3) putting the obtained powder after the drying procedure into a quick grinder, and grinding for 20min at a rotating speed of 400 r/min.
And screening the powder obtained in the grinding process by adopting a 400-mesh screen to obtain the glass ion cement powder.
The glass powder materials synthesized in the embodiment respectively comprise the following components in percentage by mass:
Al 2 O 3 ：35％，SiO 2 ：23％，SrO：18％，CaO：5％，ZnO：6％，P 2 O 5 :1%, F:12%, the particle size distribution of the material was uniform, D10 was 1.573. Mu.m, D50 was 4.312. Mu.m, D90 was 18.148. Mu.m, and the specific surface area (BET) of the powder was 146m 2 /g。
Example 5 preparation of glass Ionic Water-portal powder
The glass ion water portal powder formulation in the embodiment is prepared from the following raw materials in parts by mass through a sol-gel method:
the glass ion water portal powder of the embodiment is prepared by the following method:
firstly, preparing sol: 100 parts of water is added into a reactor, then 120 parts of neutral silica sol (solid content is about 50 wt.%), 50 parts of ethanol and 5 parts of phosphotriester are added for prehydrolysis reaction, 40 parts of strontium nitrate, 18 parts of calcium nitrate, 110 parts of aluminum nitrate, 18 parts of zinc acetate and 20 parts of fluosilicic acid are added after the mixed solution becomes transparent and clear after hydrolysis, and the sol is obtained after stirring until complete dissolution.
The pH of the sol was adjusted to 4 with nitric acid, and then the gel was aged at 70℃for 10 hours, the solution completely becoming a homogeneous gel state.
Then, after gel breaking, transferring to a baking oven at 90 ℃ for continuous drying until the water content of the system volatilizes to be not more than 5%; and (3) placing the xerogel block in a muffle furnace, and calcining at 700 ℃ for 40min until the organic matters are completely removed, thus obtaining the glass ion water portal powder precursor.
Performing wet ball milling on the glass ion water portal precursor obtained by heat treatment to obtain raw slurry, wherein the precursor is: zirconia ball stone: water=1:3:2 (mass ratio), followed by grinding at 550r/min for 40min.
Adding water into the slurry for dilution, wherein the volume ratio of the raw slurry to the water is 10:1, adding nitric acid into the diluted raw slurry, wherein the concentration of nitric acid solution is 3%, the volume of nitric acid accounts for 15% of the volume of the diluted raw slurry, stirring for 1.5h at room temperature, sieving by a wet method, and filtering to remove suspension liquid to obtain wet powder.
Vacuum drying the wet powder for 20h at 110 ℃. And (3) putting the obtained powder after the drying procedure into a quick grinder, and grinding for 20min at a rotating speed of 400 r/min.
And screening the powder obtained in the grinding process by adopting a 400-mesh screen to obtain the glass ion cement powder.
The glass powder materials synthesized in the embodiment respectively comprise the following components in percentage by mass:
Al 2 O 3 ：34％，SiO 2 :25%, srO:17%, caO:6%, znO:6%, F:12%, the particle size distribution of the material was uniform, D10 was 1.484. Mu.m, D50 was 4.694. Mu.m, D90 was 17.917. Mu.m, and the specific surface area (BET) of the powder was 137m 2 /g。
Example 6 Performance test of glass ionized water portal powder
The glass powders prepared in examples 1 to 5 were subjected to performance test. Wherein the net cure time is determined as per YY 0271.1-2016 dental water-based cement part 1: the method is implemented by powder/liquid acid-base water portal, and comprises the following specific steps:
first, a metal mold heated to 23±2 ℃ was placed on an aluminum foil, and then the metal mold was filled with the water gate paste to be tested, and the surface thereof was scraped.
After 60s after the end of tempering, the assembly consisting of the metal mold, aluminum foil and water gate test pieces was placed on a metal retention block and placed together in a storage box. In addition, a sufficient fit between the metal mold, the aluminum foil sheet and the metal retention block should be ensured.
At 90s end of reconciliation, the durometer was carefully moved vertically down to the surface of the water gate and left for 5s. Subsequently, a test was performed to determine the approximate cure time of the subject water heater and the indentation test was repeated within 30 seconds until no complete indentation ring was made on the water heater surface by the indenter needle using a 2 x magnification magnifying glass. The indenter may be cleaned during the indentation test, if necessary. But the indentation test must be repeated within a time frame of 10s and starting 30s before the approximate cure time.
Finally, the time required from the end of self-tuning to the time when the indenter does not delineate a complete indentation ring on the surface of the water heater is recorded as the cure time of the test specimen.
Determination of compressive Strength according to YY 0271.1-2016 dental Water-based Water-cement part 1: the method is implemented by powder/liquid acid-base water portal, and comprises the following specific steps:
firstly, weighing powder and liquid of the water portal in proportion at the room temperature of 23+/-2 ℃; during blending, the weighed powder is divided into a large pile and a small pile, the small pile of powder is blended into the liquid, and then the rest powder is gradually added for uniform blending, so that the blending time is about 30 seconds. The blended test cement paste was filled into split molds having a height of 6.0 mm.+ -. 0.1mm and an inner diameter of 4.0 mm.+ -. 0.1mm within 60 seconds.
In order to make the water gate mixture in the split mold tightly void-free and avoid the adverse effect of air bubbles, the most applicable part of the mixture should be injected into the split mold. At the same time, the mold is forced aside using a suitable tool until the split mold is filled with excess mix. Then, the split mold with the material is placed on a metal bottom plate and the pressurization is continued.
Then, the mixture at the edge of the split mold is scraped off, the metal plate is covered and pressed, and the split mold and the metal plate are clamped together by a clamp. And (5) when 120 seconds after the water valve mixture is prepared, putting the whole assembly into a storage box.
And (3) when 60 seconds after the blending of the water gate material mixture is finished, removing the metal plate from the split die, and then grinding the end face of the tested sample to be flat, so that the end face plane of the end face is perpendicular to the long axis of the end face. In polishing, 400# wet silicon carbide abrasive paper is generally selected to be suitable, but the end plane of the test sample should not be polished too roughly in any way.
When no air bubbles or flash increase was found by visual inspection, the split mold was immediately opened, the test specimen was removed, and any defective test specimen was removed.
The sample thus prepared should be immediately immersed in deionized or distilled water at 37.+ -. 1 ℃ for 23 h.+ -. 0.5h.
And (3) clamping each test sample with smooth end surfaces between pressing plates of the mechanical property tester 24 hours after the water valve mixture is prepared, and applying pressure along the long axis of the test sample. And then, recording the reading of the mechanical property tester when the tested sample breaks, namely the compressive strength of the sample.
The adhesive strength test was performed according to YY 0518-2009 polymer-based adhesive for dental restorations, the specific method being as follows:
the dental cup samples were prepared according to the requirements of YY 0518-2009 polymer-based adhesive for dental restorations.
The tooth surfaces in the cup were rinsed under running water for 10s and lightly blown with oil-free gas until the surface visible water was removed and the tooth surfaces were dried. A single-sided tape with a circular hole with the diameter of 3mm is attached to the surface of the treated teeth, and glass ion water heater is sequentially coated in the hole and cured. The tooth cup is placed in an adhesive sample preparation device, the screw rod is screwed upwards, the round hole of the single-sided adhesive tape is aligned with the center hole of the split die, and after the tooth plane is tightly contacted with the split die, the screw rod fixing screw is screwed. And then bonding the glass ion water valve in the central hole of the split die with the tooth surface. After the glass ion water valve is used, the screw is loosened, and the tooth cup and the split die are ejected upwards through the rotary screw rod. The split mold was opened and the test piece was placed. The diameter of the glass ion water portal column was measured with a caliper and then the sample was stored (24.+ -. 1) h in water at (37.+ -. 2). Degree.C. The test piece should be tested immediately after being taken out of the water.
The shear strength test is carried out on a universal mechanical testing machine, a shear testing device is placed between two parallel table tops of the testing machine, and the upper table top enables a shear knife to move downwards to apply a shearing action to a sample. When the upper table surface is contacted with the shearing knife, the impact on the sample element is ensured. The shear rate was (0.75.+ -. 0.30) mm/min. And then, recording the reading of the universal mechanical testing machine when the tested sample breaks, namely the shear bonding strength of the sample.
3.2g of the glass powder prepared in the examples 1-5 is taken, 1.0g of the liquid agent of GC II type glass ion water portal of Fuji company is taken, the glass powder is respectively placed on mixing paper for standby, the weighed powder is divided into a large pile and a small pile, the small pile of powder is firstly mixed into the liquid, then the rest powder is gradually added and uniformly mixed for use, the mixing time is about 30s, the net curing time and the compressive strength after the glass powder and the liquid agent are matched and cured are measured according to the method, and the result is shown in the table 1.
1.8g of the glass powder prepared in examples 1-5 is taken, 1.0g of the liquid agent of GC I type glass ion water portal of Fuji company is taken, the glass powder and the liquid agent are respectively placed on mixing paper for standby, the weighed powder is divided into a large pile and a small pile, the small pile of powder is firstly mixed into the liquid, then the rest powder is gradually added and uniformly mixed for use, the mixing time is about 30s, and the shearing bonding strength of the glass powder and the liquid agent after being matched and solidified is measured according to the method, and the result is shown in Table 1.
Comparative examples were set at the same time: the blending method of powder and liquid is carried out according to the specification by adopting GC II glass ion water portal of Fuji company, and the net curing time and the compression strength test result are shown in table 1; the blending method of powder and liquid is carried out according to the specification by adopting GC I type glass ion water portal of Fuji company, and the test result of shear bonding strength is shown in table 1.
TABLE 1 Performance of the glass ionomer cement powder of the invention after being cured in combination with GC liquid
As can be seen from Table 1, the glass powder of the present invention was excellent in performance after curing in combination with a liquid agent, exceeding the level of GC glass ion water portal of Fuji corporation.
The method for evaluating the antibacterial property of the glass ion water valve material comprises the following steps:
(1) Strain activation
Common oral bacteria are adopted: staphylococcus aureus (s.aureus), escherichia coli (e.coli), bacillus subtilis (b.subtilis), candida albicans (c.albicans), streptococcus mutans (s.mutans), lactobacillus casei (l.casei), actinomyces viscosus (a.viscosus), porphyromonas gingivalis (p.gingivalis).
Transferring strains to a plate culture medium for culture respectively: using NA culture medium for aureus, E.coli, B.subtilis and C.albicans, culturing at 37+ -1deg.C under aerobic condition for 24 hr, and transferring 1 time per day; mutans, L.casei, A.viscosus are cultured in BHI medium at 37+ -1deg.C under facultative anaerobic condition for 72 hr, and transferred 1 time per day; the P.gingivalis was cultured in BHI medium at 37.+ -. 1 ℃ for 72 hours with 1 transfer every 3 days. Fresh bacterial cultures after 2 successive transfers of each strain were taken for the experiment.
(2) Preparation of bacterial suspension
Scraping a small amount of fresh bacteria from a plate culture medium by an inoculating loop, putting into a culture solution, blowing uniformly by a sample adding gun, measuring the concentration of bacterial suspension by a laser turbidimetric colorimeter, and diluting the bacterial suspension with known concentration to 7.0X10 5 cfu/mL was used as an experimental bacterial liquid.
(3) Sample testing
The blank sample and the test material sample were placed in a sterilized petri dish. Mu.l of each of the test bacterial liquids was added dropwise to the negative control sample A, the blank sample B and the example sample C. The cover film is clamped by a sterilizing flat forceps and covered on bacterial liquid on the surface of the sample, and each sample is parallel to 5 samples. Spreading the cover film by using flat forceps and sterile cotton swabs to ensure that bacterial liquid is uniformly distributed between the sample and the cover film. The dishes were covered. Culturing at 37+ -1deg.C with relative humidity greater than 90% under proper oxygen tension (aerobic, facultative anaerobic or anaerobic) for 24 hr.
Taking out the sample cultured for 24 hours, adding 2ml of eluent, repeatedly washing the sample and the cover film, and shaking thoroughly. The eluate was serially diluted 10-fold (10 μl of eluate was taken for the first dilution): s.aureus, E.coli, B.subtilis, S.mutans, L.casei eluate diluted to 10 -5 Dilution of the viscosus eluate to 10 -3 Diluting the C.albicans, P.gingivalis eluate to 10 -1 . Respectively taking 20 mu l of the eluent diluent, inoculating the eluent diluent on a proper plate culture medium, and culturing for 24-72 hours under the condition of phase-contrast culture according to different strains until bacterial colonies are clearly distinguished. Colony counts were performed as described in GB/T4789.2 food safety national Standard food microbiology test colony count assay.
(4) Calculation of test results
And multiplying the result of colony counting by the dilution multiple of the eluent and multiplying by 100 to obtain the actual recovered viable bacteria value in each sample eluent, wherein the average value of 5 parallel samples in each experimental group is respectively recorded as A, B, C. The antibacterial rate is calculated according to the formula: rn= (B-C)/Bx 100%.
The antibacterial performance test results of the glass ion water portal material (example 3) and the Fuji GC type I glass ion water portal are shown in table 2:
TABLE 2 antibacterial Property test results
Compared with the glass ion water portal material (example 3), the GC I type glass ion water portal material provided by the invention has no ZnO added, has the antibacterial rate of less than 10% on common colonies in oral cavity, and has no antibacterial capability; the glass ion water portal material is added with 8 percent of zinc oxide, has the antibacterial rate of more than 90 percent on common oral colonies, and has remarkable antibacterial effect.
The novel glass ion water portal powder material and the preparation method thereof provided by the invention have the following beneficial effects:
(1) The glass ion water portal powder material is prepared by adopting a sol-gel process, raw materials are uniformly mixed at a molecular level, and the raw materials are calcined at a lower temperature (400-850 ℃) to prevent fluorine loss, so that the glass powder with better purity and uniformity is prepared.
(2) The specific surface area (BET) of the glass ion water portal powder material is more than 20m 2 And/g, has high reactivity, short net curing time and shortened waiting time of patients.
(3) The glass ion water portal powder material contains micro-nano mesopores, and forms an embedded structure after reacting with a liquid agent, and the system has higher mechanical property (the compressive strength reaches more than 240MPa, and the bonding strength with teeth reaches more than 5 MPa).
(4) The glass ion water portal powder material contains antibacterial components and has antibacterial function.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (6)
1. The preparation method of the glass ion water portal powder is characterized by comprising the following raw materials in parts by mass through a sol-gel method: 80-180 parts of silicate substances and/or silica sol, 0-20 parts of phosphate substances, 100-200 parts of water, 120-200 parts of soluble metal salt, 10-100 parts of alcohol solvent, 1-30 parts of fluoride and 0.01-10 parts of pH regulator;
wherein the silicate substance is at least one selected from methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate;
the silica sol is neutral silica sol or acidic silica sol;
the phosphate ester substance is at least one selected from phosphoric monoester, phosphoric diester, phosphoric triester, phosphoric triethyl and phosphoric tributyl;
the soluble metal salt is selected from at least one of inorganic salts of calcium, strontium, aluminum and zinc and alkoxide;
the water is deionized water;
the alcohol solvent is at least one selected from methanol, ethanol, ethylene glycol, diethylene glycol and glycerol;
the fluoride is sodium fluoride and/or fluosilicic acid;
the pH regulator is acid or alkali;
the method comprises the following steps:
1) Preparation of sol: mixing silicate substances and/or silica sol, phosphate substances, fluoride, water and an alcohol solvent, performing room-temperature hydrolysis reaction, adding soluble metal salt after the mixed solution becomes transparent, and stirring until the soluble metal salt is completely dissolved to obtain sol;
2) Preparation of the gel: adjusting the pH value of the sol to 4-6 or 8-10 by using a pH regulator, and then aging for 6-12 hours at 30-100 ℃ to obtain gel;
3) And (3) heat treatment: after breaking the gel, baking at 90-150 ℃ for 10-50 hours until the water content is not more than 5% of the gel mass; calcining at 400-800 ℃ for 40-120min to obtain glass ion water portal powder precursor;
4) Crushing: carrying out wet ball milling on the glass ion water valve precursor to obtain raw slurry;
specifically, mixing glass ion water gate precursor, ball milling medium and liquid medium in a mass ratio of 1 (1-3) (1-2) in a grinder, and grinding at a rotating speed of 300-600r/min for 0.5-3h; the ball milling medium is zirconia ball stone and/or alumina ball stone; the liquid medium is water;
5) Surface treatment: diluting the original slurry with water, wherein the volume ratio of the original slurry to the water is (5-10): 1, adding an acid solution into the diluted original slurry, wherein the volume of the acid solution accounts for 1-20% of the volume of the diluted original slurry, stirring for 1-2h at room temperature, sieving by a wet method, precipitating and filtering to remove suspension liquid, and obtaining wet powder; the acid solution is acetic acid, oxalic acid, hydrochloric acid, phosphoric acid or nitric acid solution, and the concentration of the acid solution is 0.5-3%;
6) And (3) drying: vacuum drying the wet powder at 70-120 ℃;
7) Grinding: placing the dried powder into a grinder, and grinding for 5-30min at a rotating speed of 300-600 r/min;
8) And (3) screening: and screening the ground powder by adopting a 300-500 mesh screen to obtain the glass ion cement powder.
2. The method according to claim 1, wherein the neutral silica sol has a pH of 7.0-8.5 and the acidic silica sol has a pH of 2.0-4.0;
the acid is an inorganic acid or an organic acid;
wherein the inorganic acid is at least one selected from nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid;
the organic acid is at least one of acetic acid, oxalic acid, maleic acid and citric acid;
the alkali is inorganic alkali or organic amine; wherein the inorganic base is at least one selected from sodium hydroxide, ammonia water and sodium bicarbonate;
the organic amine is ethylenediamine and/or n-propylamine.
3. The method according to claim 1, wherein the vacuum drying temperature in step 6) is 80-120 ℃, the vacuum degree is less than-0.8 Bar, and the drying time is 12-24h.
4. A glass ionomer cement powder prepared according to the method of any one of claims 1 to 3.
5. The glass ionomer cement powder according to claim 4, wherein the particle size of the powder is less than 40 μm, d50:1-8 μm, d90:10-30 μm, the specific surface area of the powder is more than 20m 2 /g。
6. Use of the glass ion water portal powder of claim 4 or 5 for preparing dental restoration material.
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| US3012973A (en) * | 1959-03-18 | 1961-12-12 | Du Pont | Concentrated silica aquasols of low viscosity and their preparation |
| CN1130055A (en) * | 1995-12-29 | 1996-09-04 | 云南省牙科器材厂 | Glass-polyolefine chain cement dental material and its preparing method |
| CN102976618A (en) * | 2012-12-11 | 2013-03-20 | 安泰科技股份有限公司 | Glass powder of water-based glass ionomer cement and preparation method thereof |
| CN110314099A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院化学研究所 | A kind of bioactivity powder, preparation method and the usage |
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