CN102432182A - Method for preparing machinable microcrystal glass material with high bioactivity - Google Patents
Method for preparing machinable microcrystal glass material with high bioactivity Download PDFInfo
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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 sytull, be specifically related to a kind of machinable glass ceramics preparation methods of high biological activity.
Background technology
But machinable glass ceramics is also claimed the mechanical workout sytull; It is a kind of novel nucleated glass; Except that possessing the common excellent properties of general sytull, also possess the distinctive processability of the metallic substance of being similar to, the instrument that can use processing metal in various degree carries out cut; As can with lathe carry out car, mill, 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.Through in machinable glass ceramics, adding the biological activity that phosphatic rock increases material mutually, prepare the machinable glass ceramics of biologically active, can be applied to biomedical materials field.Because workability that it is good and biological activity, make its bone substitute and prosthodontics aspect receive much concern, its using value more and more receives people's attention, becomes one of research focus of biomedical materials field.
Traditional preparation process bio-medical microcrystal glass material often adopts scorification, sintering process and sol-gel method; Scorification is through high-temperature fusion with admixtion; Form homogeneous, do not have bubble, the glass metal of definite composition requirement is arranged; With the glass metal casting,, obtain finished-product material at last again through annealing, coring, crystallization process; The sintering rule is that melten glass liquid becomes earlier processes such as powder, compression moulding, the microcrystal glass material that obtains through the nucleus crystallization process more successively through shrend, ball milling; Sol-gel method is that the various metal alkoxide solutions of forming glass are successively added in the deionized water, forms transparent and homogeneous colloidal sol, and colloidal sol passes through gelation again, and high temperature is removed organism, sinters glass ceramic material at last into.But three kinds of methods all 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, expensive.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of machinable glass ceramics preparation methods of high biological activity is provided.
In order to achieve the above object, the present invention has adopted following technical scheme.
A kind of machinable glass ceramics preparation methods of high biological activity may further comprise the steps:
(1) preparation of hydroxy apatite powder: the 0.06mol primary ammonium phosphate is dissolved in the ethanolic soln, and adding ammoniacal liquor adjusting 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 the 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, on one side to wherein adding ca nitrate soln, adding pH value regulator adjusting pH value is 7; High speed centrifugation carries out lyophilize with the lower sediment that obtains after with washing with alcohol, obtains powder; At 700 ~ 800 ℃ of calcining 2 ~ 3h, cooling is ground, and crosses 200 mesh sieves with above-mentioned powder, obtains the hydroxy apatite powder of particle diameter≤75 micron;
The mol ratio of said primary ammonium phosphate and nitrocalcite is 6:7;
(2) fusion-water quenching prepares the fluorophlogopite glass powder: with mol ratio is that salt of wormwood, Natural manganese dioxide, aluminum oxide, silicon oxide and the Sellaite of 1:6:1:6:4 mixes and obtain mixed powder; And adding titanium oxide; Behind the mixing at 1450 ~ 1500 ℃ of fusion 2 ~ 3h; 250 mesh sieves are crossed in shrend, drying, grinding, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
The mass ratio of said titanium oxide and mixed powder is 1: (50～200);
(3) sol-gel method prepares the 45S5 bioactive glass powder: nitrocalcite and SODIUMNITRATE are added in the deionized water, under 65 ~ 70 ℃, be stirred to dissolving, dropwise add tetraethoxy again; Continue to be stirred to and be transparent and homogeneous solution; And then dropwise add triethyl phosphate, and continue to be stirred to and be transparent and homogeneous solution, using the salt acid for adjusting pH value is 4; Leave standstill and obtain gelatinous solid; Dry, calcining, cooling, grind, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron;
The mol ratio of said tetraethoxy, triethyl phosphate, nitrocalcite and SODIUMNITRATE is 46.1:2.6:26.9:24.4; The mol ratio of said 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) by mass ratio: (50～80): (5～30) are mixed and are obtained mixed powder; Add polyvinyl alcohol solution; Mix and obtain particle; Under 20MPa,, obtain shaped granule with particle compression moulding;
The mass ratio of said polyvinyl alcohol solution and mixed powder is 1: (8～15);
(5) crystallization is handled 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 the step of the present invention (1), the alcoholic acid massfraction is 25% in the said ethanolic soln.
In the step of the present invention (1), the rotating speed of said high-speed stirring is 270 ~ 400rpm, and said ultracentrifugal rotating speed is 4000 ~ 5000rpm, and the time is 5～10min; Said cryodesiccated temperature is-10～-5 ℃, and the time is 30～40h.
In the step of the present invention (2), said exsiccant temperature is 70 ~ 150 ℃, and the time is 48 ~ 72h.
In the step of the present invention (3), said exsiccant temperature is 70 ~ 150 ℃, and the time is 48 ~ 72h; Said incinerating temperature is 600 ~ 700 ℃, and the time is 2～3h.
In the step of the present invention (4), the massfraction of Z 150PH is 2% in the said polyvinyl alcohol solution.
The present invention compared with prior art has following unusual effect:
(1) crystal block section of the sytull of the present invention's preparation; A kind of is the fluorophlogopite crystal that crystallization produces, and provides material effective machinable performance, and another kind is to shift to an earlier date the good hydroxyapatite crystal of crystallization; Compare the fluorapatite of separating out in the existing machinable bioactive devitrified glass; More near the inorganic components of skeleton, biological activity is better for Win 40350, and Win 40350 also has the effect that increases the strength of materials;
(2) sytull 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 improved the biological activity of the machinable glass ceramics of the present invention's preparation greatly;
(3) the present invention adopts low temperature co-fired method, when guaranteeing that each uniform component distributes, through introducing the very low 45S5 glass powder of fusing point, has reduced sintering temperature significantly, has shortened sintering time;
(4) machinable performance, biological activity and the mechanical property of the machinable bioactive devitrified glass of the present invention's preparation can realize through the ratio of adjusting three kinds of presoma powders, are easy to control.
Description of drawings
Fig. 1 is the ESEM collection of illustrative plates of the machinable glass ceramics material of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but the scope that the present invention requires to protect 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 the ethanolic soln; Adding ammoniacal liquor adjusting 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, on one side to wherein adding ca nitrate soln, adding pH value regulator adjusting 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; At 700 ℃ of calcining 3h, cooling is ground, and crosses 200 mesh sieves with above-mentioned powder, obtains the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g Natural manganese dioxide, 10.2g aluminum oxide, 36.1g silicon oxide and the mixing of 14.9g Sellaite are obtained mixed powder; And adding 1.0g titanium oxide; Behind the mixing at 1500 ℃ of fusion 2h; 250 mesh sieves are crossed in shrend, 70 ℃ of dry 72h, grinding, 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, under 65 ℃, be stirred to dissolving, dropwise add the 16.7mL tetraethoxy again; Continue to be stirred to and be transparent and homogeneous solution; And then dropwise add the 1.44mL triethyl phosphate, and continue to be stirred to and be transparent and homogeneous solution, using 0.1mol/L salt acid for adjusting pH value is 4; Leave standstill 2h and obtain gelatinous solid; 70 ℃ of dry 72h, 600 ℃ of calcinings, coolings, 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, under 20MPa,, obtain shaped granule particle compression moulding;
(5) crystallization is handled and calcining: 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 the ethanolic soln; Adding ammoniacal liquor adjusting 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, on one side to wherein adding ca nitrate soln, adding pH value regulator adjusting 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; At 750 ℃ of calcining 2.5h, cooling is ground, and crosses 200 mesh sieves with above-mentioned powder, obtains the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g Natural manganese dioxide, 10.2g aluminum oxide, 36.1g silicon oxide and the mixing of 14.9g Sellaite are obtained mixed powder; And adding 1.984g titanium oxide; Behind the mixing at 1450 ℃ of fusion 3h; 250 mesh sieves are crossed in shrend, 150 ℃ of dry 48h, grinding, 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, under 70 ℃, be stirred to dissolving, dropwise add the 16.7mL tetraethoxy again; 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; Using 0.1mol/L salt acid for adjusting pH value is 4; Leave standstill 2h and obtain gelatinous solid, 100 ℃ of dry 60h, grind at 650 ℃ of calcinings, cooling; 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, under 20MPa,, obtain shaped granule particle compression moulding;
(5) crystallization is handled and calcining: 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 the ethanolic soln; Adding ammoniacal liquor adjusting 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, on one side to wherein adding ca nitrate soln, adding pH value regulator adjusting 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; At 800 ℃ of calcining 2h, cooling is ground, and crosses 200 mesh sieves with above-mentioned powder, obtains the hydroxy apatite powder of particle diameter≤75 micron;
(2) preparation of fluorophlogopite glass powder: 13.8g salt of wormwood, 24.2g Natural manganese dioxide, 10.2g aluminum oxide, 36.1g silicon oxide and the mixing of 14.9g Sellaite are obtained mixed powder; And adding 0.496g titanium oxide; Behind the mixing at 1500 ℃ of fusion 2h; 250 mesh sieves are crossed in shrend, 100 ℃ of dry 60h, grinding, 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, under 68 ℃, be stirred to dissolving, dropwise add the 16.7mL tetraethoxy again; Continue to be stirred to and be transparent and homogeneous solution; And then dropwise add the 1.44mL triethyl phosphate, and continue to be stirred to and be transparent and homogeneous solution, using 0.1mol/L salt acid for adjusting pH value is 4; Leave standstill 2h and obtain gelatinous solid; 150 ℃ of dry 48h, 700 ℃ of calcinings, coolings, 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, under 20MPa,, obtain shaped granule particle compression moulding;
(5) crystallization is handled and calcining: 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 ESEM collection of illustrative plates of the machinable glass ceramics material of the embodiment of the invention 1 preparation; Can find out; Machinable glass ceramics of the present invention contains multiple glassy phase, and mica crystal is stochastic distribution in machinable glass ceramics, and interlocking links to each other; Such microstructure helps stoping the destructive expansion of crackle, makes machinable glass ceramics of the present invention have good cutting ability.
Claims (6)
1. the machinable glass ceramics preparation methods of a high biological activity is characterized in that, may further comprise the steps:
(1) preparation of hydroxy apatite powder: primary ammonium phosphate is dissolved in the ethanolic soln, and adding ammoniacal liquor adjusting 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 the 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, on one side to wherein adding ca nitrate soln, adding ammoniacal liquor adjusting pH value is 7; High speed centrifugation carries out lyophilize with the lower sediment that obtains after with washing with alcohol, obtains powder; At 700 ~ 800 ℃ of calcining 2 ~ 3h, cooling is ground, and crosses 200 mesh sieves with above-mentioned powder, obtains the hydroxy apatite powder of particle diameter≤75 micron;
The mol ratio of said primary ammonium phosphate and nitrocalcite is 6:7;
(2) fusion-water quenching prepares the fluorophlogopite glass powder: with mol ratio is that salt of wormwood, Natural manganese dioxide, aluminum oxide, silicon oxide and the Sellaite of 1:6:1:6:4 mixes and obtain mixed powder; And adding titanium oxide; Behind the mixing at 1450 ~ 1500 ℃ of fusion 2 ~ 3h; 250 mesh sieves are crossed in shrend, drying, grinding, obtain the fluorophlogopite glass powder of particle diameter≤60 micron;
The mass ratio of said titanium oxide and mixed powder is 1: (50～200);
(3) sol-gel method prepares the 45S5 bioactive glass powder: nitrocalcite and SODIUMNITRATE are added in the deionized water, under 65 ~ 70 ℃, be stirred to dissolving, dropwise add tetraethoxy again; Continue to be stirred to and be transparent and homogeneous solution; And then dropwise add triethyl phosphate, and continue to be stirred to and be transparent and homogeneous solution, using the salt acid for adjusting pH value is 4; Leave standstill and obtain gelatinous solid; Dry, calcining, cooling, grind, cross 250 mesh sieves, obtain the 45S5 bioactive glass powder of particle diameter≤60 micron;
The mol ratio of said tetraethoxy, triethyl phosphate, nitrocalcite and SODIUMNITRATE is 46.1:2.6:26.9:24.4; The mol ratio of said 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) by mass ratio: (50～80): (5～30) are mixed and are obtained mixed powder; Add polyvinyl alcohol solution; Mix and obtain particle; Under 20MPa,, obtain shaped granule with particle compression moulding;
The mass ratio of said polyvinyl alcohol solution and mixed powder is 1: (8～15);
(5) crystallization is handled 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 the step (1), the alcoholic acid massfraction is 25% in the said ethanolic soln.
3. preparation method according to claim 2 is characterized in that, in the step (4), the massfraction of Z 150PH is 2% in the said polyvinyl alcohol solution.
4. according to the described preparation method of one of claim 1 ~ 3, it is characterized in that in the step (1), the rotating speed of said high-speed stirring is 270 ~ 400rpm, said ultracentrifugal rotating speed is 4000 ~ 5000rpm, and the time is 5～10min; Said cryodesiccated temperature is-10～-5 ℃, and the time is 30～40h.
5. preparation method according to claim 4 is characterized in that, in the step (2), said exsiccant temperature is 70 ~ 150 ℃, and the time is 48 ~ 72h.
6. preparation method according to claim 5 is characterized in that, in the step (3), said exsiccant temperature is 70 ~ 150 ℃, and the time is 48 ~ 72h; Said incinerating temperature 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 |
| CN106116162A (en) * | 2016-06-15 | 2016-11-16 | 山东智汇专利运营有限公司 | A kind of teaching mortar and preparation method thereof |
| CN106810079A (en) * | 2016-12-23 | 2017-06-09 | 四川名微晶科技股份有限公司 | The method that mica glass ceramic is prepared using granite waste residues |
| CN106986547A (en) * | 2017-04-18 | 2017-07-28 | 济南大学 | A kind of preparation method of nanometer of fluor-apatite glass ceramics |
| CN107673621A (en) * | 2017-09-29 | 2018-02-09 | 河南科技大学 | A kind of fluorophologopite/fluor-apatite glass ceramics and preparation method thereof |
| CN108585516A (en) * | 2018-03-19 | 2018-09-28 | 内蒙古科技大学 | A kind of founding tailing fluorophologopite glass ceramics and preparation method thereof |
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| CN111592229A (en) * | 2020-06-05 | 2020-08-28 | 中山市科信生物技术有限公司 | Process for preparing bioactive glass by salt loss method |
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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 |
| CN106116162A (en) * | 2016-06-15 | 2016-11-16 | 山东智汇专利运营有限公司 | A kind of teaching mortar and preparation method thereof |
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| CN108585516B (en) * | 2018-03-19 | 2021-05-28 | 内蒙古科技大学 | Fusion-cast tailing fluorophlogopite glass ceramic and preparation method thereof |
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