CN103979945B - A kind of preparation method of biological active tabular spar ceramics - Google Patents
A kind of preparation method of biological active tabular spar ceramics Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of biological active tabular spar ceramics, by ethyl orthosilicate under the catalytic action of appropriate salpeter solution in deionized water prehydrolysis 20-60min, then lime nitrate and dopant stirring 0.5-2h is added, abundant dissolving forms limpid colloidal sol, placing dry xerogel, then at 550-750 DEG C of stabilizing treatment 1-3h, is finally 800-1100 DEG C in sintering temperature, sintering time is 0.5-3h, obtains wollastonite ceramics through sintering processes.The linear expansion coefficient of biological active tabular spar ceramics of the present invention, meets the requirement of titanium alloy coating material linear expansion coefficient; The elastic modelling quantity of elastic modelling quantity composite human body spongy bone and compact bone.Bone can be used as fill, repair or substitution material.Wollastonite thermal coefficient of expansion after doping all meets the requirement of the linear expansion coefficient as titanium alloy surface coating, also can as coating material.The interpolation of different oxide has obvious difference to the biological activity of wollastonite and degradation property, can select suitable biomaterial according to demand.
Description
Technical field
The present invention relates to a kind of preparation method of biological active tabular spar ceramics, belong to technical field of biomedical materials.
Background technology
Biomaterial is the material with specific function that a class can replace, repair and regenerate human lesion organ.Along with the development of the causes such as industry, traffic, physical culture now, bone very easily sustains damage in various contingency as the main load bearing component of human body.In addition, the osseous lesion caused 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 rate of growth reaches 7.2%, and be in number of hospitalized the 2nd, wherein artificial joint valve replacement annual rate of growth is up to 30%, a large amount of Bone Defect Repari of bone injury needs of patients newly increased every year and bone substitution material.
Along with development that is biomedical and material science, the research of synthetic substitution material is subject to extensive concern, has become an emphasis in current medical research.Existing multiple implantation body material obtains application clinically at present.Hydroxyapatite (HA) has good biocompatibility and biological activity because of it, in the bone being extensively present in animal and Ya Deng sclerous tissues, becomes current clinical practice implantation body's material the most widely.Early 1970s, Univ Florida USA L.L.Hench teaching inventive Na
2o-CaO-SiO
2-P
2o
5system biological glass (
).A-W (Apatite-Wollastonite) glass ceramics of the people such as T.Kokubo invention afterwards, A-W (Apatite-Wollastonite) glass ceramics is the best biological active ceramic material of known at present mechanical property.Wherein wollastonite (CaSiO
3) as one of two kinds of crystallite phases in A-W glass ceramics, not only to the mechanical property of A-W glass ceramics, there is significant contribution, also there is high biological activity simultaneously.The further research of Kokubo confirms, 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 be formed.This shows, CaO and SiO
2composition be bioactivity glass in vivo with the main cause of ostosis chemical bonding.
The preparation method of wollastonite is more, and the experimental technique preparing wollastonite at present mainly contains fusion method, sintering process, the sedimentation method and sol-gal process.Sol-gal process is generally make presoma (as ethyl orthosilicate, triethyl phosphate, Butyl Phthalate etc.) with metal and semimetal salt to issue raw poly-condensation and hydrolysis in the effect of water, mutual solvent and catalyst, 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 fusion method, sol-gal process has that chemical uniformity is high and reaction temperature is low, particle size and the preparation of controlled shape, masking and coating be all comparatively for convenience of, the more equal first-class feature of Entropy density deviation.The method is compared with other preparation methoies, and firing temperature, thus can energy savings well below the fusion temperature of glass, and the reduction of glass melting temperature simultaneously can also improve the biological activity of glass.In addition, containing a large amount of remaining OH-races in bioactive materials prepared by sol-gal process, and OH-race can form peptide bond with the protein in living organism with mental retardation approach, thus realizes bone bonding faster.On the other hand, material prepared by sol-gal process has higher specific surface area and porosity, and reaction is carried out in the solution, and goods can keep the uniformity on molecular level or atomic level, and material composition meets initial formula and stoichiometric proportion completely; Easily extensible compositing range, the material that preparation traditional method can not be prepared, extends the compositing range of bioactive materials greatly.Therefore, sol-gal process has broad application prospects preparing in bioactive 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 coefficient of expansion of wollastonite and pure titanium and titanium alloys close, elastic modelling quantity and natural bone close, except being used as hard tissue repair or alternate material, be also suitable as titanium alloy surface active coating material.But the current research for wollastonite mainly concentrates on and characterizes and bioactive research it, and for doping variety classes, different content compound to wollastonite organizational structure, mechanical property, the research of the impact of biological activity and degradation property is less, is difficult to prepare the biomaterial with suitable performance according to actual needs.
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 adopting sol-gal process to prepare biological active tabular spar ceramics is provided, by adding the sodium oxide of different content in wollastonite, magnesium oxide, zinc oxide or zirconium oxide regulate its organizational structure, 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 ethyl orthosilicate under the catalytic action 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 that step (1) is obtained is at room temperature positioned in hermetic container, formed after gel until it, 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 drying baker 110-130 DEG C of dry 18-30h, obtain xerogel;
(3) xerogel that step (2) is obtained is placed in ball mill ball milling, and carries out 200 object screenings, obtain the precursor powder of wollastonite, precursor powder is put into heat-treatment furnace, 550-750 DEG C of stabilizing treatment 1-3h, obtains basic powder;
(4) after the wollastonite briquetting prepared by step (3) in high temperature furnace sintering processes, sintering temperature is 800-1100 DEG C, and sintering time is 0.5-3h, obtains wollastonite ceramics after furnace cooling;
In step (1), the mol ratio of ethyl orthosilicate, nitric acid, deionized water, four water-calcium nitrate is 1:(0.02-0.04): (3-5): (0.6-1);
Dopant is Chile saltpeter NaNO
3, account for the 10%-50% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate Mg (NO
3)
26H
2o, accounts for the 5%-25% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate Zn (NO
3)
26H
2o, accounts for the 5%-18% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride ZrOCl
28H
2o, accounts for the 5%-18% of ethyl orthosilicate 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 Chile saltpeter, accounts for the 10%-23% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or magnesium nitrate hexahydrate, account for the 5%-18% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or zinc nitrate hexahydrate, account for the 5%-12% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity; Or zirconium oxychloride, account for the 5%-12% of ethyl orthosilicate and four water-calcium nitrate integral molar quantity;
Preferably, in step (1), the time of prehydrolysis is 0.5h, and mixing 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 drying baker 120 DEG C of dry 24h, obtains xerogel;
Preferably, in step (3), for wollastonite and doping sodium oxide, magnesian wollastonite stabilizing treatment temperature is 700 DEG C, and the processing time is 1h; For doping zinc-oxide, zirconic wollastonite stabilizing treatment temperature is 600 DEG C, and the processing 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 heating rate is 5 DEG C/min.Doping zinc-oxide or zirconic wollastonite sintering temperature are 850 DEG C, and sintering time is 1h, and heating 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.After adding sodium oxide, in wollastonite ceramics sample, there is faint Na
2ca
2si
3o
9diffraction maximum, along with increasing of sodium oxide content, Na
4ca
4(Si
6o
18) diffraction maximum occur and strengthen gradually, β-CaSiO
3diffraction peak intensity dies down.β-CaSiO has been there is containing in magnesian wollastonite ceramics
3, Ca
3mg (SiO
4)
2and CaMgSi
2o
6diffraction maximum.Along with the increase Ca of content of magnesia
3mg (SiO
4)
2and CaMgSi
2o
6diffraction peak intensity becomes large.Zn has been there is in sample after adding zinc oxide
2siO
4diffraction maximum, along with increasing of zinc oxide content, has Ca
2znSi
2o
7occur, and β-CaSiO
3diffraction peak intensity dies down.T-ZrO is there is after adding zirconium oxide in sample
2diffraction maximum, along with the increase of zirconia content, has Ca
3si
3o
9and CaZrSi
2o
7occur.Wollastonite ceramics rough surface, have a small amount of hole and a large amount of irregular particle granule dense distribution at ceramic surface, the interpolation of doping oxide improves the organizational structure of wollastonite coating, adds sodium oxide rear surface and becomes loose, fine and close containing magnesian specimen surface, there is a small amount of hole.The hole on loose coarse surface and surface, is conducive to the circulation of tissue fluid, can accelerates the reconstruction of tissue.
The present invention has following beneficial effect:
The linear expansion coefficient of biological active tabular spar ceramics of the present invention, meets the requirement of titanium alloy coating material linear expansion coefficient; The elastic modelling quantity of elastic modelling quantity composite human body spongy bone (3.2-7.8GPa) and compact bone (3.9-11.7GPa).After wollastonite soaks in simulated body fluid, surface has apatite to generate, and illustrates that the wollastonite ceramics of preparation has good biological activity.Sodium oxide, magnesium oxide, zinc oxide or zirconic interpolation have significant impact to the organizational structure of wollastonite and performance, not only improve the bending strength of wollastonite, and the wollastonite elastic modelling quantity after doping meets the elastic modelling quantity of human body spongy bone and compact bone, bone can be used as fill, repair or substitution material.Wollastonite thermal coefficient of expansion after doping all meets the requirement of the linear expansion coefficient as titanium alloy surface coating, also can as coating material.The interpolation of different oxide has obvious difference to the biological activity of wollastonite and degradation property, the kind of adding by regulating oxide and addition, the character of wollastonite ceramics can be changed, thus select according to the demand of reality and prepare the biomaterial of suitable performance.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum in embodiment 1 before and after wollastonite sintering;
Fig. 2 is the XRD figure spectrum of embodiment 1,7-9 wollastonite, wherein: CS embodiment 1; CS-Na5 embodiment 7; CS-Na10 embodiment 8; CS-Na15 embodiment 9;
Fig. 3 is the XRD figure spectrum of wollastonite in embodiment 1,11-13, wherein: CS embodiment 1; CS-Mg5 embodiment 11; CS-Mg10 embodiment 12; CS-Mg15 embodiment 13;
Fig. 4 is embodiment 1, the XRD figure spectrum of 15,17 wollastonites, wherein: CS embodiment 1; CS-Zn5 embodiment 15; CS-Zn15 embodiment 17;
Fig. 5 is embodiment 1, the XRD figure spectrum of 18,19 wollastonites, wherein: CS embodiment 1; CS-Zr5 embodiment 18; CS-Zr10 embodiment 19;
Fig. 6 is embodiment 1, and 8,12,16,19 wollastonites soak the spectrum of the XRD figure 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 stone soaks different time in simulated body fluid;
Fig. 7 b is the XRD figure spectrum comparison diagram that embodiment 12 bulk silicon lime stone soaks 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, and the wollastonite of 8,12 soaks not rear sample weight loss figure on the same day in Tris-Hcl solution.
Detailed description of the invention
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only to explain the present invention,
Its content is not limited.
Embodiment 1
The preparation of wollastonite ceramics (CS):
Ethyl orthosilicate Si (OC is taken according to table 1 raw material dosage ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o; By ethyl orthosilicate under the catalytic action 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 formed limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol base silicon lime stone powder produced by table 1
Embodiment 2
The preparation of wollastonite ceramics (CS):
Ethyl orthosilicate Si (OC is taken according to table 2 raw material dosage ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o; By ethyl orthosilicate under the catalytic action 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 formed limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 2h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 1100 DEG C insulation 2h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol base silicon lime stone powder produced by table 2
Embodiment 3
Add Na
2the preparation of the wollastonite ceramics (CS-Na10) of O:
Ethyl orthosilicate Si (OC is taken according to table 3 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, Chile saltpeter NaNO
3; By ethyl orthosilicate under the catalytic action of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add four water-calcium nitrate and Chile saltpeter saturated solution and stir 1.0h fully dissolve formed limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 110 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 1000 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 3 produces 0.5mol containing Na
2the raw material dosage of the base silicon lime stone powder of O
Embodiment 4
Add the preparation of the wollastonite ceramics (CS-Mg10) of MgO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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 hermetic container, is formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, obtains xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 2h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 1000 DEG C insulation 2h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of MgO produced by table 4
Embodiment 5
Add the preparation of the wollastonite ceramics (CS-Zn10) of ZnO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 2h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 900 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of ZnO produced by table 5
Embodiment 6
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr10):
Ethyl orthosilicate Si (OC is taken according to table 6 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 6 produces 0.5mol containing ZrO
2the raw material dosage of base silicon lime stone powder
Embodiment 7
Add Na
2the preparation of the wollastonite ceramics (CS-Na5) of O:
Ethyl orthosilicate Si (OC is taken according to table 7 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, Chile saltpeter NaNO
3; By ethyl orthosilicate under the catalytic action 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 Chile saltpeter, and stir 1h and fully dissolve and form limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 7 produces 0.5mol containing Na
2the raw material dosage of the base silicon lime stone powder of O
Embodiment 8
Add Na
2the preparation of the wollastonite ceramics (CS-Na10) of O:
Ethyl orthosilicate Si (OC is taken according to table 8 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, Chile saltpeter NaNO
3; By ethyl orthosilicate under the catalytic action of 7.5ml salpeter solution (2mol/L) under 36ml deionized water for stirring prehydrolysis 30min, then add four water-calcium nitrate and Chile saltpeter saturated solution and stir 1.0h fully dissolve formed limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 8 produces 0.5mol containing Na
2the raw material dosage of the base silicon lime stone powder of O
Embodiment 9
Add Na
2the preparation of the wollastonite ceramics (CS-Na15) of O:
Ethyl orthosilicate Si (OC is taken according to table 9 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, Chile saltpeter NaNO
3; By ethyl orthosilicate under the catalytic action 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 Chile saltpeter, and stir 1h and fully dissolve and form limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 9 produces 0.5mol containing Na
2the raw material dosage of the base silicon lime stone powder of O
Embodiment 10
Add Na
2the preparation of the wollastonite ceramics (CS-Na20) of O:
Ethyl orthosilicate Si (OC is taken according to table 10 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, Chile saltpeter NaNO
3; By ethyl orthosilicate under the catalytic action 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 Chile saltpeter, and stir 1h and fully dissolve and form limpid colloidal sol; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 10 produces 0.5mol containing Na
2the raw material dosage of the base silicon lime stone powder of O
Embodiment 11
Add the preparation of the wollastonite ceramics (CS-Mg5) of MgO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of MgO produced by table 11
Embodiment 12
Add the preparation of the wollastonite ceramics (CS-Mg10) of MgO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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 hermetic container, is formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, obtains xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of MgO produced by table 12
Embodiment 13
Add the preparation of the wollastonite ceramics (CS-Mg15) of MgO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of MgO produced by table 13
Embodiment 14
Add the preparation of the wollastonite ceramics (CS-Mg20) of MgO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 700 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 950 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of MgO produced by table 14
Embodiment 15
Add the preparation of the wollastonite ceramics (CS-Zn5) of ZnO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of ZnO produced by table 15
Embodiment 16
Add the preparation of the wollastonite ceramics (CS-Zn10) of ZnO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of ZnO produced by table 16
Embodiment 17
Add the preparation of the wollastonite ceramics (CS-Zn15) of ZnO:
Ethyl orthosilicate Si (OC is taken 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 ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
The raw material dosage of 0.5mol containing the base silicon lime stone powder of ZnO produced by table 17
Embodiment 18
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr5):
Ethyl orthosilicate Si (OC is taken according to table 18 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 18 produces 0.5mol containing ZrO
2the raw material dosage of base silicon lime stone powder
Embodiment 19
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr10):
Ethyl orthosilicate Si (OC is taken according to table 19 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 19 produces 0.5mol containing ZrO
2the raw material dosage of base silicon lime stone powder
Embodiment 20
Add ZrO
2the preparation of wollastonite ceramics (CS-Zr15):
Ethyl orthosilicate Si (OC is taken according to table 20 ratio
2h
5)
4, four water-calcium nitrate Ca (NO
3)
24H
2o, zirconium oxychloride ZrOCl
28H
2o; By ethyl orthosilicate under the catalytic action 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; At room temperature placed 3 days in hermetic container by limpid colloidal sol, formed after gel until it and put into 60 DEG C of constant water bath box burin-in process 3 days, half dry state gel of gained is placed in drying baker dry, 120 DEG C of dry 24h, obtain xerogel; Gained xerogel is placed in ball mill ball milling and carries out 200 object screenings, obtain the precursor powder of wollastonite, then after 600 DEG C of stabilizing treatment 1h with the molding of poly-vinyl alcohol solution mixing granulation, compact specimen through 850 DEG C insulation 1h obtain wollastonite, the rate of heat addition is 5 DEG C/min.
Table 20 produces 0.5mol containing ZrO
2the raw material dosage of base silicon lime stone powder
Performance test is tested
Performance test experiment 1: wollastonite ceramics thermal coefficient of expansion is studied
Thermal coefficient of expansion tester is utilized to test the embodiment of the present invention 1,8,12,16, the thermal coefficient of expansion of the wollastonite ceramics of preparation in 19.
The linear expansion coefficient of bioactive ceramic layer should be close with the linear expansion coefficient of Ti6A14V as far as possible, and linear expansion coefficient difference therebetween should control 1.7 × 10
-6/ DEG C to be advisable.Therefore, be that the bioactive ceramics linear expansion coefficient of matrix should be (9.1 ~ 12.5) × 10 with Ti6Al4V
-6/ DEG C.Add the wollastonite of heterogeneity after Overheating Treatment, its 20 ~ 500 DEG C of linear expansion coefficients are shown in table 21 after tested.The size of thermal coefficient of expansion and the chemical composition of material, crystal content and kind relevant.The linear expansion coefficient of 20 ~ 500 DEG C, 5 kinds of samples is all in (9.28 ~ 11.97) × 10
-6/ DEG C between, therefore meet as the close requirement of titanium or titanium alloy coating material linear expansion coefficient.
Table 21 embodiment 1,8,12,16,19 wollastonite ceramicss are at the linear expansion coefficient of 20 ~ 500 DEG C
Performance test experiment 2: the mechanical property research of wollastonite ceramics
RGD-5 type electronic tensile machine is adopted to be tested bending strength and the elastic modelling quantity of the wollastonite ceramics of the embodiment of the present invention 1,8,12,16,19 by three-point bending method.
Embodiment 1,8, elastic mould value and the bending strength of the wollastonite ceramics of 12,16,19 are shown in table 22.After adding dopant, the elastic mould value of wollastonite is all improved.Elastic modelling quantity is at 5.75-6.57GPa, and the elastic modelling quantity of composite human body spongy bone (3.2-7.8GPa) and compact bone (3.9-11.7GPa), makes it can fill or substitution material as bone.The adjustment of the component bending strength of the wollastonite ceramics in the present invention is had very large change, namely sodium oxide, magnesium oxide, zinc oxide and zirconic interpolation all make the bending strength of wollastonite improve, and especially zirconic interpolation makes wollastonite bending strength obviously increase.Ceramic composition, crystalline phase granular size, shape, phase composition, content, pore size distribution and residual stress etc. all have impact to the mechanical property of wollastonite ceramics, and in addition, in pottery, the precipitation in 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 in simulated body fluid 1 day, 3 days, 7 days respectively to determine its biological activity.
(1) the phase structure change of wollastonite ceramics after soaking
Fig. 6 is embodiment 1, and 8,12,16,19 wollastonite ceramicss soak the XRD diffracting spectrum after 7 days in simulated body fluid.As can be seen from the figure, there is hydroxyapatite diffraction maximum in sample XRD after soaking 7d.All there is obvious amorphous bag in diffracting spectrum, illustrates that the deposit degree of crystallinity generated is not high.There is the diffraction maximum in matrix in sample, this may be that X-ray penetrates deposit and is irradiated on matrix because the wollastonite surface deposition after soaking 7d is compared thin.
Fig. 7 a and Fig. 7 b is embodiment 8, and 12 wollastonite ceramicss soak 1d respectively, the XRD diffracting spectrum after 3d and 7d.As can be seen from wollastonite soak in simulated body fluid not on the same day after XRD diffracting spectrum, along with the prolongation of soak time, in each embodiment, matrix peak weakens gradually, and apatite peak strengthens gradually, and the prolongation along with soak time is described, the degree of crystallinity of apatite increases.
(2) surface topography and the component analysis of rear wollastonite ceramics is soaked
Fig. 8 a to Fig. 8 f is embodiment 1, with the surface topography soaked after 7 days before 8,12 wollastonite ceramicss soak in simulated body fluid.Wollastonite ceramics rough surface before soaking, has a large amount of granule dense distribution on surface, have also appeared 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 fluid.Sample is after simulated body fluid soaks, and the sedimentary facies of its Surface Creation is comparatively obvious, and specimen surface is covered by spherical particle substantially, and Parts of deposits is reunited to together, forms larger-size aggregate.Soak rear surface and occurred that crackle may be that surface tension creates be full of cracks greatly because sample is in dry run.
(3) grown layer Surface energy spectrum analysis after soaking
Table 23 is embodiment 1, and 8,12 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 all containing O, P, Ca element in the grown layer after 7d, and be mainly this several element, in conjunction with XRD interpretation of result, can judge that surface deposits is apatite.
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, the weightless bar diagram after 8,12 wollastonite ceramicss soak different time in Tris-HCl buffer solution.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 rough surface prepared of the present invention, has a small amount of micropore and a large amount of spheroidal particle dense distribution on surface.After adding sodium oxide, surface becomes loose.After adding magnesium oxide, sample becomes more smooth densification, has a small amount of hole to occur.XRD result shows that the deposit soaking rear wollastonite ceramics Surface Creation is mainly hydroxyapatite.Along with the prolongation of soak time, the intensity of apatite diffraction maximum increases, and the diffracting spectrum after sample soaks 7d exists amorphous bag, illustrates that the degree of crystallinity of apatite is not high.After wollastonite ceramics soaks in simulated body fluid, sample surfaces has spherical particle to occur, deposit is reunited and is covered in wollastonite ceramics surface together.EDS result shows that deposit is formed primarily of O, P, Ca element.
(2) the biological active tabular spar ceramics linear expansion coefficient that prepared by the present invention meets the requirement of titanium alloy coating material linear expansion coefficient; The elastic modelling quantity of elastic modelling quantity composite human body spongy bone (3.2-7.8GPa) and compact bone (3.9-11.7GPa).Sodium oxide, magnesium oxide, zinc oxide and zirconic interpolation improve the intensity of wollastonite and have adjusted its linear expansion coefficient and elastic modelling quantity, make it not only can fill as bone or substitution material but also the requirement met as titanium alloy surface coating composition.
(3) each component pottery biodegradability and biological activity show greatly difference, can select the bioceramic material of different performance according to demand.
Claims (7)
1. a preparation method for biological active tabular spar ceramics, is characterized in that, comprises the following steps:
(1) by ethyl orthosilicate under the catalytic action 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 that step (1) is obtained is at room temperature positioned in hermetic container, formed after gel until it, 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 drying baker 110-130 DEG C of dry 18-30h, obtain xerogel;
(3) xerogel that step (2) is obtained is placed in ball mill ball milling, and carries out 200 object screenings, obtain the precursor powder of wollastonite, precursor powder is put into heat-treatment furnace, 550-750 DEG C of stabilizing treatment 1-3h, obtains basic powder;
(4) after the wollastonite briquetting prepared by step (3) in high temperature furnace sintering processes, sintering temperature is 800-1100 DEG C, and sintering time is 0.5-3h, obtains wollastonite ceramics after furnace cooling;
In step (1), the mol ratio of ethyl orthosilicate, nitric acid, deionized water, four water-calcium nitrate is 1:(0.02-0.04): (3-5): (0.6-1);
Dopant is zirconium oxychloride, accounts for the 5%-12% of ethyl orthosilicate 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), the concentration of salpeter solution is 2mol/L.
3. 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 mixing time is 1h.
4. 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 drying baker 120 DEG C of dry 24h, obtain xerogel.
5. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (3), the wollastonite stabilizing treatment temperature for wollastonite and doped with oxygen zirconium chloride is 600 DEG C, and the processing time is 1h.
6. the preparation method of a kind of biological active tabular spar ceramics as claimed in claim 1, is characterized in that, in step (4), the wollastonite sintering temperature of doped with oxygen zirconium chloride is 850 DEG C, and sintering time is 1h, and heating rate is 5 DEG C/min.
7. wollastonite ceramics prepared by the preparation method of the biological active tabular spar ceramics described in any one of claim 1 to 6.
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