CN103979945A - Preparation method of bioactive wollastonite ceramic - Google Patents
Preparation method of bioactive wollastonite ceramic Download PDFInfo
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- CN103979945A CN103979945A CN201410239786.2A CN201410239786A CN103979945A CN 103979945 A CN103979945 A CN 103979945A CN 201410239786 A CN201410239786 A CN 201410239786A CN 103979945 A CN103979945 A CN 103979945A
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- wollastonite
- water
- ceramics
- tetraethoxy
- calcium nitrate
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Links
- 229910052882 wollastonite Inorganic materials 0.000 title claims abstract description 149
- 239000010456 wollastonite Substances 0.000 title claims abstract description 149
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000000975 bioactive effect Effects 0.000 title abstract description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 11
- 239000002019 doping agent Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 28
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 28
- 230000006641 stabilisation Effects 0.000 claims description 26
- 238000011105 stabilization Methods 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000012047 saturated solution Substances 0.000 claims description 22
- 238000012216 screening Methods 0.000 claims description 22
- 239000011787 zinc oxide Substances 0.000 claims description 18
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 15
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 15
- 229940001516 sodium nitrate Drugs 0.000 claims description 14
- 235000010344 sodium nitrate Nutrition 0.000 claims description 14
- 239000004317 sodium nitrate Substances 0.000 claims description 14
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 14
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 12
- 229960001296 zinc oxide Drugs 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000012620 biological material Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 27
- 239000011575 calcium Substances 0.000 description 26
- 235000019738 Limestone Nutrition 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 22
- 239000010703 silicon Substances 0.000 description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 description 20
- 238000005469 granulation Methods 0.000 description 20
- 230000003179 granulation Effects 0.000 description 20
- 238000009413 insulation Methods 0.000 description 20
- 239000006028 limestone Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- 238000000465 moulding Methods 0.000 description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 description 20
- 239000012890 simulated body fluid Substances 0.000 description 19
- 239000000395 magnesium oxide Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 230000004071 biological effect Effects 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 238000012876 topography Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000003980 solgel method Methods 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910004762 CaSiO Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000002241 glass-ceramic Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
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- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 206010061363 Skeletal injury Diseases 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
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- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of bioactive wollastonite ceramic. The preparation method comprises the following steps: pre-hydrolyzing tetraethoxysilane in de-ionized water under a catalytic action of a proper amount of a nitric acid solution for 20-60min, adding calcium nitrate and a dopant and stirring for 0.5-2 hours, completely dissolving to obtain clear sol, placing and drying to obtain dried gel, stabilizing the dried gel at 550-750 DEG C for 1-3 hours, and finally sintering at 800-1100 DEG C for 0.5-3 hours to obtain the wollastonite ceramic. A linear expansion coefficient of the bioactive wollastonite ceramic disclosed by the invention meets a requirement of a titanium alloy coating material on linear expansion coefficient, and elasticity modulus is consistent with that of cancellous bone and compact bone of human body. The wollastonite ceramic can serve as a bone filling, repairing or replacing material. The linear expansion coefficient of the doped wollastonite ceramic meets the requirement of the titanium alloy surface coating on linear expansion coefficient, and the wollastonite ceramic can be used as a coating material as well. Wollastonites in which different oxides are added have significant differences in bioactivity and degrading performance; therefore, proper biomaterials can be selected depending on demands.
Description
Technical field
The preparation method who the present invention relates to a kind of biological active tabular spar ceramics, belongs to technical field of biomedical materials.
Background technology
Biomaterial is the material with specific function that a class can be replaced human lesion organ, repair and regenerate.Along with the development of the causes such as present industry, traffic, physical culture, bone very easily sustains damage in various mishaies as the main load bearing component of human body.In addition the osseous lesion causing due to disease reasons such as congenital or acquired deformity, infection and tumor resections, is also very common in clinical.According to statistics, sclerous tissues of China wound number of hospitalized annual growth reaches 7.2%, is in the 2nd of number of hospitalized, and wherein joint prosthesis valve replacement annual growth is up to 30%, a large amount of bone reparations of bone injury needs of patients and the bone substitution material that newly increase every year.
Along with the development of biomedical and Materials science, the research of synthetic equivalent material is subject to extensive concern, has become an emphasis in current medical research.At present existing multiple planting body material has obtained application clinically.Hydroxyapatite (HA) has good biocompatibility and biological activity because of it, is extensively present in the bone and Ya Deng sclerous tissues of animal, becomes current clinical application planting body material the most widely.Early 1970s, professor L.L.Hench of Univ Florida USA has invented Na
2o-CaO-SiO
2-P
2o
5system biological glass (
).A-W (Apatite-Wollastonite) glass-ceramic of the people such as T.Kokubo invention afterwards, A-W (Apatite-Wollastonite) glass-ceramic is the known best biological active ceramic material of mechanical property at present.Wherein wollastonite (CaSiO
3) as one of two kinds of crystallite phases in A-W glass-ceramic, not only the mechanical property of A-W glass-ceramic is had to significant contribution, also there is high biological activity simultaneously.Kokubo further studies confirm that, CaO-SiO in simulated body fluid
2base glass surface can form bone like apatite layer, and CaO-P
2o
5base glass surface does not have osteoid apatite to form.This shows, CaO and SiO
2composition be bioactivity glass in vivo with the major cause of ostosis chemical bonding.
The preparation method of wollastonite is more, and the experimental technique of preparing at present wollastonite mainly contains scorification, sintering process, the precipitator method and sol-gel method.Sol-gel method is generally to make presoma (as tetraethoxy, triethyl phosphate, Butyl Phthalate etc.) with metal and semi-metal salt to issue unboiled water solution and polycondensation in the effect of water, mutual solvent and catalyzer, forms SiO
2three-dimensional net structure.In colloidal sol forming process, if introduce other components, can be embedded in three-dimensional net structure.Compared with scorification, sol-gel method has that chemical uniformity is high and temperature of reaction is low, particle size is controlled with shape, masking and coating preparation be all for convenience of, the more equal first-class feature that distributes mutually.The method is compared with other preparation methods, and firing temperature is well below the temperature of fusion of glass, thereby can save energy, and the reduction of glass melting temperature simultaneously can also improve the biological activity of glass.In addition, in biological active materials prepared by sol-gel method, contain a large amount of remaining OH-family, and OH-family can with living organism in protein form peptide bond with low energy approach, thereby realize faster bone bonding.On the other hand, material prepared by sol-gel method has higher specific surface area and porosity, and reaction is carried out in solution, and goods can keep the homogeneity on molecular level or atomic level, and material composition meets initial formula and stoichiometric ratio completely; Can expand compositing range, prepare the material that traditional method can not be prepared, greatly expand the compositing range of biological active materials.Therefore, sol-gel method has broad application prospects preparing in biological active materials.
The research of domestic scholars concentrates in the preparation of block materials, and these biological activity blocks mainly directly apply to reparation or the replacement of sclerous tissues.And the thermal expansivity of wollastonite and pure titanium and alloy thereof approach, Young's modulus and natural bone approach, and except being used as hard tissue repair or replacement material, are also suitable as titanium alloy surface active coating material.But mainly concentrate on it is characterized and bioactive research for the research of wollastonite at present, and for the compound of doping different sorts, different content to wollastonite weave construction, mechanical property, the research of the impact of biological activity and degradation property is less, is difficult to prepare according to actual needs the biomaterial with suitable performance.
Summary of the invention
The object of the invention is for Bioactive Ceramic Coating on Titanium Alloy biology and mechanical property requirements, a kind of method that adopts sol-gel method to prepare biological active tabular spar ceramics is provided, by add the sodium oxide of different content in wollastonite, magnesium oxide, zinc oxide or zirconium white regulate its weave construction, mechanical property, biological activity and degradation property, prepare the biomaterial of suitable performance according to the actual requirements.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for biological active tabular spar ceramics, comprises the following steps:
(1) by tetraethoxy under the katalysis of salpeter solution in deionized water prehydrolysis 20-60min, then add the saturated solution of four water-calcium nitrate and dopant, stir 0.5-2h, fully dissolve and form limpid colloidal sol;
(2) colloidal sol step (1) being made is at room temperature positioned in encloses container, after it forms gel, put into 50-70 DEG C of constant water bath box burin-in process 2-4 days, obtain half dry state gel, be placed in loft drier 110-130 DEG C of dry 18-30h, obtain xerogel;
(3) xerogel step (2) being made is placed in ball mill ball milling, and carries out 200 object screenings, obtains the precursor powder of wollastonite, and precursor powder is put into heat treatment furnace, and 550-750 DEG C of stabilization treatment 1-3h, obtains basic powder;
(4) after the wollastonite briquetting of being prepared by step (3) in High Temperature Furnaces Heating Apparatus sintering processes, sintering temperature is 800-1100 DEG C, sintering time is 0.5-3h, obtains wollastonite ceramics after furnace cooling;
In step (1), the mol ratio of tetraethoxy, nitric acid, deionized water, four water-calcium nitrate is 1:(0.02-0.04): (3-5): (0.6-1);
Dopant is SODIUMNITRATE NaNO
3, account for the 10%-50% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate Mg (NO
3)
26H
2o, accounts for the 5%-25% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate Zn (NO
3)
26H
2o, accounts for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride ZrOCl
28H
2o, accounts for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity.
In step (1), the concentration of salpeter solution is 1-3mol/L, is preferably 2mol/L;
Preferably, in step (1), dopant is SODIUMNITRATE, accounts for the 10%-23% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate, account for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate, account for the 5%-12% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride, account for the 5%-12% of tetraethoxy and four water-calcium nitrate integral molar quantity;
Preferably, in step (1), the time of prehydrolysis is 0.5h, and churning time is 1h;
Preferably, in step (2), gel burin-in process 3 days in 60 DEG C of constant water bath box, obtains half dry state gel, is placed in 120 DEG C of dry 24h of loft drier, obtains xerogel;
Preferably, in step (3), for wollastonite and doping sodium oxide, magnesian wollastonite stabilization treatment temperature is 700 DEG C, and the treatment time is 1h; For doping zinc-oxide, zirconic wollastonite stabilization treatment temperature is 600 DEG C, and the treatment time is 1h;
Preferably, in step (4), doping sodium oxide or magnesian wollastonite sintering temperature are 950 DEG C, and sintering time is 1h, and temperature rise rate is 5 DEG C/min.Doping zinc-oxide or zirconic wollastonite sintering temperature are 850 DEG C, and sintering time is 1h, and temperature rise rate is 5 DEG C/min.
The principal crystalline phase of biological active tabular spar ceramics prepared by the present invention is β-CaSiO
3.Add after sodium oxide, in wollastonite ceramics sample, occurred faint Na
2ca
2si
3o
9diffraction peak, along with increasing of sodium oxide content, Na
4ca
4(Si
6o
18) diffraction peak appearance enhancing gradually, β-CaSiO
3diffraction peak intensity dies down.There is β-CaSiO containing in magnesian wollastonite ceramics
3, Ca
3mg (SiO
4)
2and CaMgSi
2o
6diffraction peak.Along with the increase Ca of content of magnesia
3mg (SiO
4)
2and CaMgSi
2o
6it is large that diffraction peak intensity becomes.After interpolation zinc oxide, in sample, there is Zn
2siO
4diffraction peak, along with increasing of zinc oxide content, has Ca
2znSi
2o
7occur, and β-CaSiO
3diffraction peak intensity dies down.After adding zirconium white in sample, there is t-ZrO
2diffraction peak, along with the increase of zirconia content, has Ca
3si
3o
9and CaZrSi
2o
7occur.Wollastonite ceramics surface irregularity, have a small amount of hole and a large amount of irregular particle particle dense distribution at ceramic surface, the interpolation of doping oxide has improved the weave construction of wollastonite coating, adds sodium oxide rear surface to become loose, containing magnesian specimen surface densification, there is a small amount of hole.Loose coarse surface and surperficial hole, be conducive to the circulation of tissue juice, can accelerate the reconstruction of tissue.
The present invention has following beneficial effect:
The linear expansivity of biological active tabular spar ceramics of the present invention, meets the requirement of titanium alloy coated material linear expansivity; The Young's modulus of Young's modulus composite human body spongy bone (3.2-7.8GPa) and dense bone (3.9-11.7GPa).After wollastonite soaks in simulated body fluid, surface has phosphatic rock to generate, and illustrates that the wollastonite ceramics of preparation has good biological activity.Sodium oxide, magnesium oxide, zinc oxide or zirconic interpolation weave construction and the performance on wollastonite has significant impact, not only improve the bending strength of wollastonite, and wollastonite Young's modulus after doping meets the Young's modulus of human body spongy bone and dense bone, can fill as bone, repair or equivalent material.Wollastonite thermal expansivity after doping all meets the requirement as the linear expansivity of titanium alloy surface coating, also can be used as coated material.Biological activity and the degradation property of the interpolation of different oxide compounds to wollastonite has obvious difference, by the kind and the addition that regulate oxide compound to add, can change the character of wollastonite ceramics, thereby select and prepare the biomaterial of suitable performance according to actual demand.
Brief description of the drawings
Fig. 1 is the spectrum of the XRD figure before and after wollastonite sintering in embodiment 1;
Fig. 2 is embodiment 1, the XRD figure spectrum of 7-9 wollastonite, wherein: CS embodiment 1; CS-Na5 embodiment 7; CS-Na10 embodiment 8; CS-Na15 embodiment 9;
Fig. 3 is embodiment 1, the XRD figure of wollastonite spectrum in 11-13, wherein: CS embodiment 1; CS-Mg5 embodiment 11; CS-Mg10 embodiment 12; CS-Mg15 embodiment 13;
Fig. 4 is embodiment 1,15, the XRD figure spectrum of 17 wollastonites, wherein: CS embodiment 1; CS-Zn5 embodiment 15; CS-Zn15 embodiment 17;
Fig. 5 is embodiment 1,18, the XRD figure spectrum of 19 wollastonites, wherein: CS embodiment 1; CS-Zr5 embodiment 18; CS-Zr10 embodiment 19;
Fig. 6 is embodiment 1,8, and 12,16,19 wollastonites soak the XRD figure spectrum after 7d in simulated body fluid, wherein: CS embodiment 1; CS-Na10 embodiment 8; CS-Mg10 embodiment 12; CS-Zn10 embodiment 16; CS-Zr10 embodiment 19;
Fig. 7 a is the XRD figure spectrum comparison diagram that embodiment 8 bulk silicon lime stones soak different time in simulated body fluid;
Fig. 7 b is the XRD figure spectrum comparison diagram that embodiment 12 bulk silicon lime stones soak different time in simulated body fluid;
Fig. 8 a is the surface topography map before the wollastonite of embodiment 1 soaks in simulated body fluid;
Fig. 8 b is that the wollastonite of embodiment 1 soaks the surface topography map after 7 days in simulated body fluid;
Fig. 8 c is the surface topography map before the wollastonite of embodiment 8 soaks in simulated body fluid;
Fig. 8 d is that the wollastonite of embodiment 8 soaks the surface topography map after 7 days in simulated body fluid;
Fig. 8 e is that the wollastonite of embodiment 12 soaks the surface topography map after 7 days in simulated body fluid;
Fig. 8 f is that the wollastonite of embodiment 12 soaks the surface topography map after 7 days in simulated body fluid;
Fig. 9 is embodiment 1,8, and 12 wollastonite soaks not the weightless figure of rear sample on the same day in Tris-Hcl solution.
Embodiment
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only in order to explain the present invention,
Its content is not limited.
Embodiment 1
The preparation of wollastonite ceramics (CS):
Take tetraethoxy Si (OC according to table 1 raw material usage ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate, and stir 1h fully dissolve form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 1 is produced the raw material consumption of 0.5mol base silicon lime stone powder
Embodiment 2
The preparation of wollastonite ceramics (CS):
Take tetraethoxy Si (OC according to table 2 raw material usage ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate, and stir 2h fully dissolve form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 2h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 1100 DEG C insulation 2h obtain wollastonite, heating rate is 5 DEG C/min.
Table 2 is produced the raw material consumption of 0.5mol base silicon lime stone powder
Embodiment 3
Add Na
2the preparation of the wollastonite ceramics (CS-Na10) of O:
Take tetraethoxy Si (OC according to table 3 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, SODIUMNITRATE NaNO
3; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and SODIUMNITRATE and stir 1.0h fully dissolve form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 110 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 1000 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 3 is produced 0.5mol containing Na
2the raw material consumption of the base silicon lime stone powder of O
Embodiment 4
Add the preparation of the wollastonite ceramics (CS-Mg10) of MgO:
Take tetraethoxy Si (OC according to table 4 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, magnesium nitrate hexahydrate Mg (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and magnesium nitrate hexahydrate and stir fully to dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 2h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 1000 DEG C insulation 2h obtain wollastonite, heating rate is 5 DEG C/min.
Table 4 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of MgO
Embodiment 5
Add the preparation of the wollastonite ceramics (CS-Zn10) of ZnO:
Take tetraethoxy Si (OC according to table 5 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zinc nitrate hexahydrate Zn (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zinc nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 2h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 900 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 5 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of ZnO
Embodiment 6
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr10):
Take tetraethoxy Si (OC according to table 6 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zirconium oxychloride, and stir abundant 1h and dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 6 is produced 0.5mol containing ZrO
2the raw material consumption of base silicon lime stone powder
Embodiment 7
Add Na
2the preparation of the wollastonite ceramics (CS-Na5) of O:
Take tetraethoxy Si (OC according to table 7 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, SODIUMNITRATE NaNO
3; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and SODIUMNITRATE, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 7 is produced 0.5mol containing Na
2the raw material consumption of the base silicon lime stone powder of O
Embodiment 8
Add Na
2the preparation of the wollastonite ceramics (CS-Na10) of O:
Take tetraethoxy Si (OC according to table 8 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, SODIUMNITRATE NaNO
3; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and SODIUMNITRATE and stir 1.0h fully dissolve form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 8 is produced 0.5mol containing Na
2the raw material consumption of the base silicon lime stone powder of O
Embodiment 9
Add Na
2the preparation of the wollastonite ceramics (CS-Na15) of O:
Take tetraethoxy Si (OC according to table 9 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, SODIUMNITRATE NaNO
3; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and SODIUMNITRATE, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 9 is produced 0.5mol containing Na
2the raw material consumption of the base silicon lime stone powder of O
Embodiment 10
Add Na
2the preparation of the wollastonite ceramics (CS-Na20) of O:
Take tetraethoxy Si (OC according to table 10 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, SODIUMNITRATE NaNO
3; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and SODIUMNITRATE, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 10 is produced 0.5mol containing Na
2the raw material consumption of the base silicon lime stone powder of O
Embodiment 11
Add the preparation of the wollastonite ceramics (CS-Mg5) of MgO:
Take tetraethoxy Si (OC according to table 11 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, magnesium nitrate hexahydrate Mg (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and magnesium nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 11 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of MgO
Embodiment 12
Add the preparation of the wollastonite ceramics (CS-Mg10) of MgO:
Take tetraethoxy Si (OC according to table 12 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, magnesium nitrate hexahydrate Mg (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and magnesium nitrate hexahydrate and stir fully to dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 12 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of MgO
Embodiment 13
Add the preparation of the wollastonite ceramics (CS-Mg15) of MgO:
Take tetraethoxy Si (OC according to table 13 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, magnesium nitrate hexahydrate Mg (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and magnesium nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 13 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of MgO
Embodiment 14
Add the preparation of the wollastonite ceramics (CS-Mg20) of MgO:
Take tetraethoxy Si (OC according to table 14 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, magnesium nitrate hexahydrate Mg (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and magnesium nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 14 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of MgO
Embodiment 15
Add the preparation of the wollastonite ceramics (CS-Zn5) of ZnO:
Take tetraethoxy Si (OC according to table 15 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zinc nitrate hexahydrate Zn (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zinc nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 15 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of ZnO
Embodiment 16
Add the preparation of the wollastonite ceramics (CS-Zn10) of ZnO:
Take tetraethoxy Si (OC according to table 16 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zinc nitrate hexahydrate Zn (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zinc nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 16 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of ZnO
Embodiment 17
Add the preparation of the wollastonite ceramics (CS-Zn15) of ZnO:
Take tetraethoxy Si (OC according to table 17 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zinc nitrate hexahydrate Zn (NO
3)
26H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zinc nitrate hexahydrate, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 17 is produced the raw material consumption of 0.5mol containing the base silicon lime stone powder of ZnO
Embodiment 18
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr5):
Take tetraethoxy Si (OC according to table 18 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zirconium oxychloride, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 18 is produced 0.5mol containing ZrO
2the raw material consumption of base silicon lime stone powder
Embodiment 19
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr10):
Take tetraethoxy Si (OC according to table 19 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zirconium oxychloride, and stir abundant 1h and dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 19 is produced 0.5mol containing ZrO
2the raw material consumption of base silicon lime stone powder
Embodiment 20
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr15):
Take tetraethoxy Si (OC according to table 20 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By tetraethoxy under the katalysis of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add the saturated solution of four water-calcium nitrate and zirconium oxychloride, and stir 1h and fully dissolve and form limpid colloidal sol; Limpid colloidal sol is at room temperature placed 3 days in encloses container, after it forms gel, put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in to loft drier dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in to ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilization treatment 1h with the moulding of polyvinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, heating rate is 5 DEG C/min.
Table 20 is produced 0.5mol containing ZrO
2the raw material consumption of base silicon lime stone powder
Performance test experiment
Performance test experiment 1: wollastonite ceramics thermal expansivity research
Utilize the thermal expansivity of the wollastonite ceramics of preparation in the thermal expansivity tester test embodiment of the present invention 1,8,12,16,19.
The linear expansivity of bioactive ceramic layer should be close with the linear expansivity of Ti6A14V as far as possible, and linear expansivity between the two is poor should be controlled at 1.7 × 10
-6/ DEG C be advisable.Therefore, the bioactive ceramics linear expansivity taking Ti6Al4V as matrix should be (9.1～12.5) × 10
-6/ DEG C.Add the wollastonite of heterogeneity after Overheating Treatment, its 20～500 DEG C of linear expansivitys are shown in table 21 after tested.The size of thermal expansivity and the chemical constitution of material, crystal content and kind are relevant.The linear expansivity that 5 kinds of samples are 20～500 DEG C is all in (9.28～11.97) × 10
-6/ DEG C between, therefore meet as the close requirement of titanium or titanium alloy coated material linear expansivity.
Table 21 embodiment 1,8,12,16,19 wollastonite ceramicss are at the linear expansivity of 20～500 DEG C
Performance test experiment 2: the mechanical property research of wollastonite ceramics
Adopt RGD-5 type electronic tensile machine to test the embodiment of the present invention 1,8 by three-point bending method, the bending strength of 12,16,19 wollastonite ceramics and Young's modulus.
Embodiment 1,8,12,16, elastic mould value and the bending strength of 19 wollastonite ceramics are shown in table 22.Add after dopant, the elastic mould value of wollastonite is all improved.Young's modulus is at 5.75-6.57GPa, and the Young's modulus of composite human body spongy bone (3.2-7.8GPa) and dense bone (3.9-11.7GPa), makes it can be used as bone and fill or equivalent material.The adjusting of component makes the bending strength of the wollastonite ceramics in the present invention have very large variation, be that sodium oxide, magnesium oxide, zinc oxide and zirconic interpolation all make the bending strength of wollastonite improve, especially zirconic interpolation obviously increases wollastonite bending strength.Ceramic composition, crystallization phases granular size, shape, phase composite, content, pore distribution and unrelieved stress etc. all has impact to the mechanical property of wollastonite ceramics, and in addition, in pottery, separating out of multiple crystal orientation also can produce complicated impact to mechanical property.
Table 22 embodiment 1,8,12,16, the mechanical property of 19 wollastonite ceramicss
Performance test experiment 3: the Bioactivity research of wollastonite ceramics
Wollastonite ceramics sample is soaked respectively in simulated body fluid to 1 day, 3 days, 7 days to determine its biological activity.
(1) after immersion, the phase structure of wollastonite ceramics changes
Fig. 6 is embodiment 1,8, and 12,16,19 wollastonite ceramicss soak the XRD diffracting spectrum after 7 days in simulated body fluid.As can be seen from the figure, after immersion 7d, in sample XRD, there is hydroxyapatite diffraction peak.All there is obvious amorphous bag in diffracting spectrum, illustrates that the settling degree of crystallinity generating is not high.There is the diffraction peak in matrix in sample, this may be that X ray penetrates settling and is irradiated on matrix because soaking wollastonite surface deposition after 7d compares thinly.
Fig. 7 a and Fig. 7 b are that embodiment 8,12 wollastonite ceramicss soak respectively 1d, the XRD diffracting spectrum after 3d and 7d.XRD diffracting spectrum soak not on the same day simulated body fluid from wollastonite after can find out, along with the prolongation of soak time, in each embodiment, matrix peak weakens gradually, and phosphatic rock peak strengthens gradually, and the prolongation along with soak time is described, the degree of crystallinity of phosphatic rock increases.
(2) surface topography and the composition analysis of wollastonite ceramics after immersion
Fig. 8 a to Fig. 8 f is embodiment 1,8, and 12 wollastonite ceramicss soak the front and surface topography of immersion after 7 days in simulated body fluid.Wollastonite ceramics surface irregularity before soaking, has a large amount of particle dense distribution on surface, has also occurred a small amount of hole.Add sodium oxide rear surface and become loose a little.Add magnesian sample and become smooth densification, have a small amount of hole to occur.Coarse loose surface and hole are conducive to the circulation of tissue juice.Sample is after simulated body fluid soaks, and the sediment-filled phase of its Surface Creation is more obvious, and specimen surface is covered by spherical particle substantially, and part settling is reunited to together, forms larger-size coacervate.Soak rear surface and occurred that crackle may be because sample is in drying process, surface tension is large has produced be full of cracks.
(3) soak rear grown layer Surface energy spectrum analysis
Table 23 is embodiment 1,8, and 12 wollastonite ceramicss soak grown layer Surface energy spectrum analysis result after 7 days in simulated body fluid.Can find from power spectrum results of elemental analyses, soak in the grown layer after 7d and all contain O, P, Ca element, and be mainly this several elements, in conjunction with XRD interpretation of result, can judge that surface deposits is phosphatic rock.
Table 23 embodiment 1,8,12 wollastonite ceramicss soak grown layer Surface energy spectrum analysis result after 7 days in simulated body fluid
Performance test experiment 4: the research of wollastonite degradation property
Fig. 9 is embodiment 1,8, and 12 wollastonite ceramicss soak the weightless column diagram after different time in Tris-HCl buffered soln.As can be seen from the figure,, along with the prolongation of soak time, the weightlessness of all ceramic samples all constantly increases.Early stage degradation rate is than very fast.Sample containing sodium oxide is more a lot of soon than wollastonite sample degradation, the slowest containing magnesian sample degradation.
The result of performance test experiment shows:
(1) the wollastonite ceramics surface irregularity that prepared by the present invention, has a small amount of micropore and a large amount of spheroidal particle dense distribution on surface.Add after sodium oxide, it is loose that surface becomes.After adding magnesium oxide, sample becomes more smooth densification, has a small amount of hole to occur.XRD result shows that the settling that soaks rear wollastonite ceramics Surface Creation is mainly hydroxyapatite.Along with the prolongation of soak time, the intensity of phosphatic rock diffraction peak increases, and sample soaks on the diffracting spectrum after 7d and has amorphous bag, illustrates that the degree of crystallinity of phosphatic rock is not high.After wollastonite ceramics soaks in simulated body fluid, sample surfaces has spherical particle to occur, settling is reunited and is covered in wollastonite ceramics surface together.EDS result shows that settling is mainly made up of O, P, Ca element.
(2) the biological active tabular spar ceramics linear expansivity that prepared by the present invention meets the requirement of titanium alloy coated material linear expansivity; The Young's modulus of Young's modulus composite human body spongy bone (3.2-7.8GPa) and dense bone (3.9-11.7GPa).Sodium oxide, magnesium oxide, zinc oxide and zirconic interpolation have improved the intensity of wollastonite and have adjusted its linear expansivity and Young's modulus, make it not only can be used as that bone is filled or equivalent material but also meet the requirement as titanium alloy surface coated component.
(3) each component pottery biodegradability and biological activity show greatly difference, can select according to demand the bioceramic material of different performance.
Claims (10)
1. a preparation method for biological active tabular spar ceramics, is characterized in that, comprises the following steps:
(1) by tetraethoxy under the katalysis of salpeter solution in deionized water prehydrolysis 20-60min, then add the saturated solution of four water-calcium nitrate and dopant, stir 0.5-2h, fully dissolve and form limpid colloidal sol;
(2) colloidal sol step (1) being made is at room temperature positioned in encloses container, after it forms gel, put into 50-70 DEG C of constant water bath box burin-in process 2-4 days, obtain half dry state gel, be placed in loft drier 110-130 DEG C of dry 18-30h, obtain xerogel;
(3) xerogel step (2) being made is placed in ball mill ball milling, and carries out 200 object screenings, obtains the precursor powder of wollastonite, and precursor powder is put into heat treatment furnace, and 550-750 DEG C of stabilization treatment 1-3h, obtains basic powder;
(4) after the wollastonite briquetting of being prepared by step (3) in High Temperature Furnaces Heating Apparatus sintering processes, sintering temperature is 800-1100 DEG C, sintering time is 0.5-3h, obtains wollastonite ceramics after furnace cooling;
In step (1), the mol ratio of tetraethoxy, nitric acid, deionized water, four water-calcium nitrate is 1:(0.02-0.04): (3-5): (0.6-1);
Dopant is SODIUMNITRATE, accounts for the 10%-50% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate, account for the 5%-25% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate, account for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride ZrOCl
28H
2o, accounts for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity.
2. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (1), dopant is SODIUMNITRATE, accounts for the 10%-23% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate, account for the 5%-18% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate, account for the 5%-12% of tetraethoxy and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride, account for the 5%-12% of tetraethoxy and four water-calcium nitrate integral molar quantity;
3. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 2, is characterized in that, in step (1), the concentration of salpeter solution is 2mol/L.
4. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (1), the time of prehydrolysis is 0.5h, and churning time is 1h.
5. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (2), gel burin-in process 3 days in 60 DEG C of constant water bath box, obtain half dry state gel, be placed in 120 DEG C of dry 24h of loft drier, obtain xerogel.
6. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (3), for wollastonite and doping sodium oxide, magnesian wollastonite stabilization treatment temperature is 700 DEG C, and the treatment time is 1h; For doping zinc-oxide, zirconic wollastonite stabilization treatment temperature is 600 DEG C, and the treatment time is 1h.
7. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (4), doping sodium oxide or magnesian wollastonite sintering temperature are 950 DEG C, and sintering time is 1h, and temperature rise rate is 5 DEG C/min; Doping zinc-oxide or zirconic wollastonite sintering temperature are 850 DEG C, and sintering time is 1h, and temperature rise rate is 5 DEG C/min.
8. the wollastonite ceramics that prepared by the preparation method of the biological active tabular spar ceramics described in claim 1 to 7 any one.
9. wollastonite ceramics claimed in claim 8 is in the application as in titanium alloy surface coated material.
10. application as claimed in claim 9, is characterized in that, described titanium alloy is Ti6A14V.
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| CN111544318A (en) * | 2020-04-30 | 2020-08-18 | 四川三泰医药科技有限公司 | Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof |
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| CN105194726A (en) * | 2015-09-15 | 2015-12-30 | 金陵科技学院 | Calcium silicate hydrate gel composite titanium alloy material and preparation method and application thereof |
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| CN108395237A (en) * | 2018-03-02 | 2018-08-14 | 中国科学院上海硅酸盐研究所 | A kind of high intensity silicon calcium phosphate biological ceramic material and preparation method thereof |
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| CN108569896A (en) * | 2018-03-21 | 2018-09-25 | 山东大学 | A kind of calcium polyphosphate/wollastonite composite biological ceramic material and preparation method thereof |
| CN108569896B (en) * | 2018-03-21 | 2021-04-06 | 山东大学 | Calcium polyphosphate/wollastonite biological composite ceramic material and preparation method thereof |
| CN111544318A (en) * | 2020-04-30 | 2020-08-18 | 四川三泰医药科技有限公司 | Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof |
| CN111544318B (en) * | 2020-04-30 | 2021-09-21 | 四川三泰医药科技有限公司 | Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof |
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