CN102432182B - Method for preparing machinable microcrystal glass material with high bioactivity - Google Patents
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Abstract
The invention discloses a method for preparing a machinable microcrystal glass material with high bioactivity, which comprises the steps of: preparing hydroxyapatite powder by using ammonium dihydrogen phosphate and calcium nitrate as raw materials; preparing fluorophlogopite powder by the melting-water quenching method; preparing 45S5 bioactive glass powder by the sol-gel method; uniformly mixing the three precursor powders and adding the polyvinyl alcohol used as a binding agent, compression moulding and then crystallizing and sintering to obtain the machinable microcrystal glass material with high bioactivity. The microcrystal glass prepared by the invention has good bioactivity, machinability and mechanical properties and performances can be realized by adjusting the ratio of the three precursor powders and are easy to control. With adoption of co-firing at low temperature, the invention greatly reduces the sintering temperature, shortens the sintering time and lowers the cost while ensuring that components are uniformly distributed at the same time.
Description
Technical field
The invention belongs to the biological active materials field, relate to a kind of preparation method of devitrified glass, be specifically related to a kind of preparation method of machinable glass ceramics material of high biological activity.
Background technology
But machinable glass ceramics also claims the mechanical workout devitrified glass, it is a kind of novel nucleated glass, except possessing the common excellent properties of general devitrified glass, also possesses the distinctive processability of the metallic substance of being similar to, the instrument that can use in various degree processing metal carries out machining, as can with lathe carry out car, mill, the precise measure processing such as plane, mill, saw, boring or tapping, to make precise measure component and complex shaped components, this is that other glass or microcrystal glass material are not available, has wide future in engineering applications.By adding phosphatic rock to increase mutually the biological activity of material in machinable glass ceramics, prepare and have bioactive machinable glass ceramics, can be applied to biomedical materials field.Because the workability that it is good and biological activity, make its bone substitute and prosthodontics aspect receive much concern, its using value more and more is subject to people's attention, and becomes one of study hotspot of biomedical materials field.
Tradition prepares the bio-medical microcrystal glass material and often adopts scorification, sintering process and sol-gel method, scorification is through high-temperature fusion with admixtion, form homogeneous, without bubble, the glass metal of definite composition requirement is arranged, with the glass metal casting,, through annealing, coring, crystallization process, obtain finally finished-product material again; The sintering rule be melten glass liquid first successively through processes such as shrend, ball grinds, compression mouldings, then the microcrystal glass material that obtains through the nucleus crystallization process; Sol-gel method is that the various metal alkoxide solutions that form glass are successively added in deionized water, forms transparent and homogeneous colloidal sol, and colloidal sol passes through gelation again, and high temperature is removed organism, sinters finally glass ceramic material into.But three kinds of methods have its weak point, and scorification and sintering process sintering temperature are high, and are active low; Collosol and gel rule complex procedures, ingredient requirement is high, price.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of machinable glass ceramics material of high biological activity is provided.
In order to achieve the above object, the present invention has adopted following technical scheme.
A kind of preparation method of machinable glass ceramics material of high biological activity comprises the following steps:
(1) preparation of hydroxy apatite powder: the 0.06mol primary ammonium phosphate is dissolved in ethanolic soln, and adding ammoniacal liquor to regulate the pH value is 10～11, and the preparation volumetric molar concentration is the primary ammonium phosphate ethanolic soln of 0.12mol/L; 0.07mol nitrocalcite is dissolved in deionized water, and the preparation volumetric molar concentration is the ca nitrate soln of 3.5mol/L; The primary ammonium phosphate ethanolic soln is carried out high-speed stirring on one side, Yi Bian add wherein ca nitrate soln, adding pH value conditioning agent to regulate the pH value is 7; High speed centrifugation, carry out lyophilize with the lower sediment that obtains after with washing with alcohol, obtains powder; Above-mentioned powder is at 700 ~ 800 ℃ of calcining 2 ~ 3h, cooling, grind, cross 200 mesh sieves, obtain the hydroxy apatite powder of particle diameter≤75 micron;
The mol ratio of described primary ammonium phosphate and nitrocalcite is 6:7;
(2) melting-water quenching prepares the fluorophlogopite glass powder: the salt of wormwood, magnesium oxide, aluminum oxide, silicon oxide and the magnesium fluoride that are 1:6:1:6:4 with mol ratio are mixed to get mixed powder, and add titanium dioxide, mix rear at 1450 ~ 1500 ℃ of melting 2 ~ 3h, shrend, drying, grinding, cross 250 mesh sieves, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
The mass ratio of described titanium dioxide and mixed powder is 1:(50～200);
(3) sol-gel method prepares the 45S5 bioactive glass powder: nitrocalcite and SODIUMNITRATE are added in deionized water, be stirred to dissolving under 65 ~ 70 ℃, dropwise add again tetraethoxy, continue to be stirred to and be transparent and homogeneous solution, and then dropwise add triethyl phosphate, continue to be stirred to and be transparent and homogeneous solution, be 4 with the salt acid for adjusting pH value, the standing gelatinous solid that obtains, drying, calcining, cooling, grinding, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron;
The mol ratio of described tetraethoxy, triethyl phosphate, nitrocalcite and SODIUMNITRATE is 46.1:2.6:26.9:24.4; The mol ratio of described nitrocalcite and deionized water is 1:(14～17.5);
(4) grain forming: the 45S5 bioactive glass powder that the hydroxy apatite powder that step (1) is obtained, the fluorophlogopite glass powder that step (2) obtains and step (3) obtain is (15～20) in mass ratio: (50～80): (5～30) are mixed to get mixed powder, add polyvinyl alcohol solution, mix and obtain particle,, with particle compression moulding, obtain shaped granule under 20MPa;
The mass ratio of described polyvinyl alcohol solution and mixed powder is 1:(8～15);
(5) crystallization is processed and sintering: the shaped granule that step (4) is obtained is incubated 3 ~ 5h at 900 ℃,, at 900 ℃～1000 ℃ sintering 1 ~ 2h, obtains the machinable glass ceramics material of high biological activity.
In step of the present invention (1), in described ethanolic soln, the massfraction of ethanol is 25%.
In step of the present invention (1), the rotating speed of described high-speed stirring is 270 ~ 400rpm, and described ultracentrifugal rotating speed is 4000 ~ 5000rpm, and the time is 5～10min; Described cryodesiccated temperature is-10～-5 ℃, and the time is 30～40h.
In step of the present invention (2), the temperature of described drying is 70 ~ 150 ℃, and the time is 48 ~ 72h.
In step of the present invention (3), the temperature of described drying is 70 ~ 150 ℃, and the time is 48 ~ 72h; The temperature of described calcining is 600 ~ 700 ℃, and the time is 2～3h.
In step of the present invention (4), in described polyvinyl alcohol solution, the massfraction of polyvinyl alcohol is 2%.
The present invention compared with prior art, has following unusual effect:
(1) crystal block section of the devitrified glass of the present invention's preparation, a kind of is the fluorophlogopite crystal that crystallization produces, provide material effective machinability, another kind is to shift to an earlier date the good hydroxyapatite crystal of crystallization, compare the fluorapatite of separating out in existing Review of Machinable Bioactive Glass-ceramics, hydroxyapatite is more near the inorganic components of skeleton, and biological activity is better, and hydroxyapatite also has the effect that increases the strength of materials;
(2) devitrified glass of the present invention preparation has been introduced 45S5 bioactivity glass powder as fusing assistant, and the 45S5 very high artificial inorganic bio that is biological activity, has greatly improved the biological activity of the machinable glass ceramics of the present invention's preparation;
(3) the present invention adopts low temperature co-fired method, when guaranteeing that each uniform component distributes, by introducing the very low 45S5 glass powder of fusing point, decrease sintering temperature, shortened sintering time;
(4) machinability, biological activity and the mechanical property of the Review of Machinable Bioactive Glass-ceramics of the present invention's preparation, can realize by the ratio of adjusting three kinds of presoma powders, is easy to control.
Description of drawings
Fig. 1 is the scanning electron microscope collection of illustrative plates of the machinable glass ceramics material of the embodiment of the present invention 1 preparation.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but the scope of protection of present invention is not limited to this.
Embodiment 1
(1) preparation of hydroxy apatite powder: 125mL ethanol is dissolved in the 375mL deionized water, the preparation quality mark is 25% ethanolic soln, the 6.84g primary ammonium phosphate is dissolved in ethanolic soln, adding ammoniacal liquor to regulate the pH value is 10～11, and the preparation volumetric molar concentration is the primary ammonium phosphate ethanolic soln of 0.12mol/L; 16.27g nitrocalcite is dissolved in the 20mL deionized water, and the preparation volumetric molar concentration is the ca nitrate soln of 3.5mol/L; The primary ammonium phosphate ethanolic soln is carried out high-speed stirring with 270rpm on one side, Yi Bian add wherein ca nitrate soln, adding pH value conditioning agent to regulate the pH value is 7; With 4000rpm high speed centrifugation 10min, with the lower sediment that obtains with washing with alcohol after in-10 ℃ of lyophilize 30h, obtain powder; Above-mentioned powder is at 700 ℃ of calcining 3h, cooling, grind, cross 200 mesh sieves, obtain the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g magnesium oxide, 10.2g aluminum oxide, 36.1g silicon oxide and 14.9g magnesium fluoride are mixed to get mixed powder, and add 1.0g titanium dioxide, mix rear at 1500 ℃ of melting 2h, shrend, 70 ℃ of dry 72h, grinding, cross 250 mesh sieves, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
(3) preparation of 45S5 bioactive glass powder: 10.3g nitrocalcite and 6.7g SODIUMNITRATE are added in the 11.0mL deionized water, be stirred to dissolving under 65 ℃, dropwise add again the 16.7mL tetraethoxy, continue to be stirred to and be transparent and homogeneous solution, and then dropwise add the 1.44mL triethyl phosphate, continue to be stirred to and be transparent and homogeneous solution, be 4 with 0.1mol/L salt acid for adjusting pH value, standing 2h obtains gelatinous solid, 70 ℃ of dry 72h, 600 ℃ of calcinings, cooling, grind, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron;
(4) grain forming: 2.0g hydroxy apatite powder, 6.5g fluorophlogopite glass powder and 1.5g 45S5 bioactive glass powder are mixed, add 1mL 2%(wt.) polyvinyl alcohol solution, mix and obtain particle,, with particle compression moulding, obtain shaped granule under 20MPa;
(5) crystallization is processed and calcined: the shaped granule that step (4) is obtained is incubated 4h at 850 ℃,, at 900 ℃ of calcining 2h, obtains the machinable glass ceramics of high biological activity.
Embodiment 2
(1) preparation of hydroxy apatite powder: 125mL ethanol is dissolved in the 375mL deionized water, the preparation quality mark is 25% ethanolic soln, the 6.84g primary ammonium phosphate is dissolved in ethanolic soln, adding ammoniacal liquor to regulate the pH value is 10～11, and the preparation volumetric molar concentration is the primary ammonium phosphate ethanolic soln of 0.12mol/L; 16.27g nitrocalcite is dissolved in the 20mL deionized water, and the preparation volumetric molar concentration is the ca nitrate soln of 3.5mol/L; The primary ammonium phosphate ethanolic soln is carried out high-speed stirring with 400rpm on one side, Yi Bian add wherein ca nitrate soln, adding pH value conditioning agent to regulate the pH value is 7; With 5000rpm high speed centrifugation 5min, with the lower sediment that obtains with washing with alcohol after in-5 ℃ of lyophilize 40h, obtain powder; Above-mentioned powder is at 750 ℃ of calcining 2.5h, cooling, grind, cross 200 mesh sieves, obtain the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g magnesium oxide, 10.2g aluminum oxide, 36.1g silicon oxide and 14.9g magnesium fluoride are mixed to get mixed powder, and add 1.984g titanium dioxide, mix rear at 1450 ℃ of melting 3h, shrend, 150 ℃ of dry 48h, grinding, cross 250 mesh sieves, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
(3) preparation of 45S5 bioactive glass powder: 10.3g nitrocalcite and 6.7g SODIUMNITRATE are added in the 13.74mL deionized water, be stirred to dissolving under 70 ℃, dropwise add again the 16.7mL tetraethoxy, continue to be stirred to and be transparent and homogeneous solution, and then dropwise add the 1.44mL triethyl phosphate, continue to be stirred to and be transparent and homogeneous solution, be 4 with 0.1mol/L salt acid for adjusting pH value, standing 2h obtains gelatinous solid, 100 ℃ of dry 60h, 650 ℃ of calcinings, cooling, grind, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron,
(4) grain forming: 2.0g hydroxy apatite powder, 5.0g fluorophlogopite glass powder and 3.0g 45S5 bioactive glass powder are mixed, add 1.25mL 2%(wt.) polyvinyl alcohol solution, mix and obtain particle,, with particle compression moulding, obtain shaped granule under 20MPa;
(5) crystallization is processed and calcined: the shaped granule that step (4) is obtained is incubated 5h at 800 ℃,, at 950 ℃ of calcining 1.5h, obtains the machinable glass ceramics of high biological activity.
Embodiment 3
(1) preparation of hydroxy apatite powder: 125mL ethanol is dissolved in the 375mL deionized water, the preparation quality mark is 25% ethanolic soln, the 6.84g primary ammonium phosphate is dissolved in ethanolic soln, adding ammoniacal liquor to regulate the pH value is 10～11, and the preparation volumetric molar concentration is the primary ammonium phosphate ethanolic soln of 0.12mol/L; 16.27g nitrocalcite is dissolved in the 20mL deionized water, and the preparation volumetric molar concentration is the ca nitrate soln of 3.5mol/L; The primary ammonium phosphate ethanolic soln is carried out high-speed stirring with 350rpm on one side, Yi Bian add wherein ca nitrate soln, adding pH value conditioning agent to regulate the pH value is 7; With 4500rpm high speed centrifugation 8min, with the lower sediment that obtains with washing with alcohol after in-8 ℃ of lyophilize 35h, obtain powder; Above-mentioned powder is at 800 ℃ of calcining 2h, cooling, grind, cross 200 mesh sieves, obtain the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g magnesium oxide, 10.2g aluminum oxide, 36.1g silicon oxide and 14.9g magnesium fluoride are mixed to get mixed powder, and add 0.496g titanium dioxide, mix rear at 1500 ℃ of melting 2h, shrend, 100 ℃ of dry 60h, grinding, cross 250 mesh sieves, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
(3) preparation of 45S5 bioactive glass powder: 10.3g nitrocalcite and 6.7g SODIUMNITRATE are added in the 12.56mL deionized water, be stirred to dissolving under 68 ℃, dropwise add again the 16.7mL tetraethoxy, continue to be stirred to and be transparent and homogeneous solution, and then dropwise add the 1.44mL triethyl phosphate, continue to be stirred to and be transparent and homogeneous solution, be 4 with 0.1mol/L salt acid for adjusting pH value, standing 2h obtains gelatinous solid, 150 ℃ of dry 48h, 700 ℃ of calcinings, cooling, grind, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron,
(4) grain forming: 8.0g hydroxy apatite powder, 1.5g fluorophlogopite glass powder and 0.5g 45S5 bioactive glass powder are mixed, add 0.67mL 2%(wt.) polyvinyl alcohol solution, mix and obtain particle,, with particle compression moulding, obtain shaped granule under 20MPa;
(5) crystallization is processed and calcined: the shaped granule that step (4) is obtained is incubated 3h at 900 ℃,, at 1000 ℃ of calcining 1h, obtains the machinable glass ceramics of high biological activity.
Fig. 1 is the scanning electron microscope collection of illustrative plates of the machinable glass ceramics material of the embodiment of the present invention 1 preparation, can find out, machinable glass ceramics of the present invention contains multiple glassy phase, mica crystal is stochastic distribution in machinable glass ceramics, interlocking is connected, such microstructure is conducive to stop the destructive expansion of crackle, makes machinable glass ceramics of the present invention have good cutting ability.
Claims (5)
1. the preparation method of the machinable glass ceramics material of a high biological activity, is characterized in that, comprises the following steps:
(1) preparation of hydroxy apatite powder: primary ammonium phosphate is dissolved in ethanolic soln, and adding ammoniacal liquor to regulate the pH value is 10～11, and the preparation volumetric molar concentration is the primary ammonium phosphate ethanolic soln of 0.12mol/L; Nitrocalcite is dissolved in deionized water, and the preparation volumetric molar concentration is the ca nitrate soln of 3.5mol/L; The primary ammonium phosphate ethanolic soln is carried out high-speed stirring on one side, Yi Bian add wherein ca nitrate soln, adding ammoniacal liquor to regulate the pH value is 7; High speed centrifugation, carry out lyophilize with the lower sediment that obtains after with washing with alcohol, obtains powder; Above-mentioned powder is at 700～800 ℃ of calcining 2～3h, cooling, grind, cross 200 mesh sieves, obtain the hydroxy apatite powder of particle diameter≤75 micron;
The mol ratio of described primary ammonium phosphate and nitrocalcite is 6:7;
(2) melting-water quenching prepares the fluorophlogopite glass powder: the salt of wormwood, magnesium oxide, aluminum oxide, silicon oxide and the magnesium fluoride that are 1:6:1:6:4 with mol ratio are mixed to get mixed powder, and add titanium dioxide, mix rear at 1450～1500 ℃ of melting 2～3h, shrend, drying, grinding, cross 250 mesh sieves, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
The mass ratio of described titanium dioxide and mixed powder is 1:(50～200);
(3) sol-gel method prepares the 45S5 bioactive glass powder: nitrocalcite and SODIUMNITRATE are added in deionized water, be stirred to dissolving under 65～70 ℃, dropwise add again tetraethoxy, continue to be stirred to and be transparent and homogeneous solution, and then dropwise add triethyl phosphate, continue to be stirred to and be transparent and homogeneous solution, be 4 with the salt acid for adjusting pH value, the standing gelatinous solid that obtains, drying, calcining, cooling, grinding, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron;
The mol ratio of described tetraethoxy, triethyl phosphate, nitrocalcite and SODIUMNITRATE is 46.1:2.6:26.9:24.4; The mol ratio of described nitrocalcite and deionized water is 1:(14～17.5);
(4) grain forming: the 45S5 bioactive glass powder that the hydroxy apatite powder that step (1) is obtained, the fluorophlogopite glass powder that step (2) obtains and step (3) obtain is (15～20) in mass ratio: (50～80): (5～30) are mixed to get mixed powder, add polyvinyl alcohol solution, mix and obtain particle,, with particle compression moulding, obtain shaped granule under 20MPa; In described polyvinyl alcohol solution, the massfraction of polyvinyl alcohol is 2%;
The mass ratio of described polyvinyl alcohol solution and mixed powder is 1:(8～15);
(5) crystallization is processed and sintering: the shaped granule that step (4) is obtained is incubated 3～5h at 800～900 ℃,, at 900 ℃～1000 ℃ sintering 1～2h, obtains the machinable glass ceramics material of high biological activity.
2. preparation method according to claim 1, is characterized in that, in step (1), in described ethanolic soln, the massfraction of ethanol is 25%.
3. one of according to claim 1～2 described preparation methods, is characterized in that, in step (1), the rotating speed of described high-speed stirring is 270～400rpm, and described ultracentrifugal rotating speed is 4000～5000rpm, and the time is 5～10min; Described cryodesiccated temperature is-10～-5 ℃, and the time is 30～40h.
4. preparation method according to claim 3, is characterized in that, in step (2), the temperature of described drying is 70～150 ℃, and the time is 48～72h.
5. preparation method according to claim 4, is characterized in that, in step (3), the temperature of described drying is 70～150 ℃, and the time is 48～72h; The temperature of described calcining is 600～700 ℃, and the time is 2～3h.
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| CN104785198A (en) * | 2015-04-08 | 2015-07-22 | 陕西科技大学 | Carbonate hydroxyapatite/glass powder composite material as well as preparation method and application thereof |
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| JP3793532B2 (en) * | 2003-10-14 | 2006-07-05 | ペンタックス株式会社 | CaO-MgO-SiO2 bioactive glass and sintered calcium phosphate using the same |
| CN100348525C (en) * | 2004-09-28 | 2007-11-14 | 中南大学 | Biological activity glass ceramics capable of cutting and its preparation method |
| CN1724431A (en) * | 2005-06-29 | 2006-01-25 | 四川大学 | Preparation of wollastonite/phosphatic rock (AW) biological activity glass ceramic by sol-gel method |
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