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CN100340511C - Process for preparing processable biological active glass ceramic material - Google Patents

Process for preparing processable biological active glass ceramic material Download PDF

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Publication number
CN100340511C
CN100340511C CNB2005100963043A CN200510096304A CN100340511C CN 100340511 C CN100340511 C CN 100340511C CN B2005100963043 A CNB2005100963043 A CN B2005100963043A CN 200510096304 A CN200510096304 A CN 200510096304A CN 100340511 C CN100340511 C CN 100340511C
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gel
make
precursor colloidal
colloidal sol
alcoholic solution
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CN1792924A (en
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孙晓明
宁青菊
史永胜
王秀峰
于成龙
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

一种可加工生物活性玻璃陶瓷材料的制备方法，在常温下，将五氧化二磷的醇溶液滴加到硝酸钙的醇溶液中均匀混合，制成羟基磷灰石前驱物；将正硅酸乙酯、Al(NO3)3·9H2O、Mg(NO3)2·6H2O、MgF2和KNO3混合搅拌制成金云母前驱物；将上述两种前驱物混合并加入ZrO2搅拌均匀制成混合溶胶，采用CO2超临界干燥法对凝胶进行干燥制成干凝胶，对干凝胶进行晶化处理，并烧结即可制得可加工生物活性玻璃陶瓷。本发明掺入了纳米级的ZrO2粒子，该粒子可以均匀地分散在混合溶胶中，从而达到均匀混合。与传统方法相比：各原料成分在凝胶中以分子水平混合，容易准确控制掺杂量；凝胶颗粒小，比表面积大，其烧结温度远低于玻璃的熔融温度，可以避免成分的挥发；不需使用坩埚融化原料，保持样品纯度。A method for preparing a processable bioactive glass-ceramic material. At normal temperature, the alcohol solution of phosphorus pentoxide is added dropwise to the alcohol solution of calcium nitrate and mixed uniformly to prepare a hydroxyapatite precursor; orthosilicate Ethyl ester, Al(NO 3 ) 3 9H 2 O, Mg(NO 3 ) 2 6H 2 O, MgF 2 and KNO 3 are mixed and stirred to make a phlogopite precursor; mix the above two precursors and add ZrO 2 Stir evenly to make a mixed sol, dry the gel by CO2 supercritical drying method to make a xerogel, crystallize the xerogel, and sinter it to make a processable bioactive glass ceramic. The present invention incorporates nanoscale ZrO2 particles, which can be uniformly dispersed in the mixed sol to achieve uniform mixing. Compared with the traditional method: the raw material components are mixed at the molecular level in the gel, which is easy to accurately control the doping amount; the gel particles are small, the specific surface area is large, and its sintering temperature is much lower than the melting temperature of the glass, which can avoid the volatilization of components ; There is no need to use a crucible to melt the raw material to maintain the purity of the sample.

Description

A kind of preparation method of processable biological active glass ceramic material
Technical field
The present invention relates to a kind of preparation method of biological activated glass ceramic material, particularly a kind of preparation method of processable biological active glass ceramic material.
Background technology
Traditional preparation process biological glass ceramic material often adopts scorification, be about to admixtion and place crucible, the process heat forms uniformly, no bubble, and meet the glass metal of forming requirements, then with its shrend, adopt sintering process to prepare biological glass ceramic, or pour glass metal into mould, adopt casting to prepare biological glass ceramic.When the tradition scorification prepares biological glass ceramic, have following shortcoming: (1) melt temperature is generally higher, more than 1500 ℃, some component is volatilized when high temperature easily in the preparing glass charge, thereby makes the glass-ceramic composition of preparing can not be in strict conformity with design requirements; (2) because the use of crucible causes component to pollute easily; (3) when cast or shrend, separate out more unwanted crystalline phases easily; (4) when heat treatment process, be difficult to realize desired thing phase composite, and separate out multiple crystalline phase easily, be difficult to realize the design of microtexture; When (5) mixing, impurity particle at high temperature exists with the lewis' acid state, and therefore easy and other components formation dephasigns are unfavorable for the introducing of nanoparticle when crystallization is handled.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of processable biological active glass ceramic material is provided, according to said method Zhi Bei biological glass ceramic material has good cutting ability.
For achieving the above object, the technical solution used in the present invention is:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3～1: 4 and 1: 4～1: 5 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 2-xF x, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 6-x: x: 2, x=1～2 wherein are with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55～65 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 10wt%～20wt%, then with water: dehydrated alcohol=2～4: 1 mol ratio adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3～4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3～1: 5 mixed, add the ZrO of the granularity of 8～16wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 5～8 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 2～4 days, after the replacement completion, is that 30～50 ℃, pressure are to make CO under the condition of 7.0～9.5MPa in temperature 2Change supercritical state into, and after keeping 3～6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel.
5) under 750 ℃ and 900 ℃, be incubated 2～3 hours respectively xerogel is carried out the crystallization processing, be incubated 3～5 hours down at 1000 ℃～1100 ℃ and can make processable biological active glass ceramic.
Because the present invention has mixed nano level ZrO 2Particle, this particle can be evenly dispersed in the mixed sols, thereby reaches uniform mixing.Compare with traditional method: each material composition mixes with molecular level in gel, easily accurate controlled doping amount; Gel particle is little, and specific surface area is big, and its sintering temperature has been avoided the volatilization of some composition far below the glass melting temperature; Need not use crucible to melt raw material, can avoid polluting, keep sample purity.
Embodiment
Embodiment 1:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3 and 1: 5 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10F 2, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4: 2: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 65 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 18wt%, then with water: the mol ratio of dehydrated alcohol=4: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3 mixed, add the ZrO of the granularity of 12wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 6 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 2 days, after the replacement completion, is that 45 ℃, pressure are to make CO under the condition of 8.2MPa in temperature 2Change supercritical state into, and after keeping 6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 3 hours respectively xerogel is carried out the crystallization processing, be incubated 5 hours down at 1020 ℃ and can make processable biological active glass ceramic.
Embodiment 2:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.6 and 1: 4.3 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 1F 1, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 5: 1: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 58 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 12wt%, then with water: the mol ratio of dehydrated alcohol=2: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4 mixed, add the ZrO of the granularity of 15wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 8 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 3 days, after the replacement completion, is that 36 ℃, pressure are to make CO under the condition of 7.0MPa in temperature 2Change supercritical state into, and after keeping 3 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2 hours respectively xerogel is carried out the crystallization processing, be incubated 4 hours down at 1080 ℃ and can make processable biological active glass ceramic.
Embodiment 3:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.2 and 1: 4.6 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.5F 1.5, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.5: 1.5: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 10wt%, then with water: the mol ratio of dehydrated alcohol=3: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.5, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) above-mentioned two kinds of precursor colloidal sols are mixed by 15 mass ratio, add the ZrO of the granularity of 10wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 5 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 4 days, after the replacement completion, is that 48 ℃, pressure are to make CO under the condition of 9.5MPa in temperature 2Change supercritical state into, and after keeping 5 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.6 hours respectively xerogel is carried out the crystallization processing, be incubated 3 hours down at 1050 ℃ and can make processable biological active glass ceramic.
Embodiment 4:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 4 and 1: 4.1 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.8F 12, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.8: 1.2: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 60 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 15wt%, then with water: the mol ratio of dehydrated alcohol=2.5: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.7, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3.6 mixed, add the ZrO of the granularity of 8wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 7 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 4 days, after the replacement completion, is that 30 ℃, pressure are to make CO under the condition of 9.0MPa in temperature 2Change supercritical state into, and after keeping 4 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.2 hours respectively xerogel is carried out the crystallization processing, be incubated 4 hours down at 1000 ℃ and can make processable biological active glass ceramic.
Embodiment 5:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.5 and 1: 4.8 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.2F 1.8, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.2: 1.8: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 63 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 20wt%, then with water: the mol ratio of dehydrated alcohol=3.8: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.2, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4.2 mixed, add the ZrO of the granularity of 16wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 6.5 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 2 days, after the replacement completion, is that 50 ℃, pressure are to make CO under the condition of 8.0MPa in temperature 2Change supercritical state into, and after keeping 6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.5 hours respectively xerogel is carried out the crystallization processing, be incubated 5 hours down at 1060 ℃ and can make processable biological active glass ceramic.
Embodiment 6:1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.8 and 1: 4 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.6F 1.4, determine tetraethoxy (TEOS), Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.6: 1.4: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 13wt%, then with water: the mol ratio of dehydrated alcohol=3.2: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy (TEOS) again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4.7 mixed, add the ZrO of the granularity of 14wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 7.4 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is about 3 days, after the replacement completion, is that 40 ℃, pressure are to make CO under the condition of 7.5MPa in temperature 2Change supercritical state into, and after keeping 5 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.7 hours respectively xerogel is carried out the crystallization processing, be incubated 3 hours down at 1100 ℃ and can make processable biological active glass ceramic.
Material by the present invention's preparation contains the phlogopite phase, the hydroxyapatite phase, glassy phase and zirconium white phase, the sheet mica crystal is multidirectional stochastic distribution, and overlap mutually, has good interlocking capability, such microstructure is under the effect of tangential force, crackle is delivered to another crystal along the cleavage surface of mica crystal from a crystal easily, can effectively control the expansion approach of crackle, make crackle all the time tangentially the direction of power develop, therefore has good cutting ability, and material toughness is preferably given in the existence of zirconium white phase, and its bending strength is about 160～180MPa, fracture toughness property K IC=2.3～2.6.Make this material biologically active mutually owing to containing hydroxyapatite simultaneously.

Claims (7)

1, a kind of preparation method of processable biological active glass ceramic material is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3～1: 4 and 1: 4～1: 5 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 2-xF x, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 6-x: x: 2, x=1～2 wherein are with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55～65 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 10wt%～20wt%, then with water: dehydrated alcohol=2～4: 1 mol ratio adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3～4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3～1: 5 mixed, add the ZrO of the granularity of 8～16wt% simultaneously less than 100nm 2Particle stirs and makes uniform mixed sols, and mixed sols 25 ℃ of ageings 5～8 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 2～4 days, after the replacement completion, is that 30～50 ℃, pressure are to make CO under the condition of 7.0～9.5MPa in temperature 2Change supercritical state into, and after keeping 3～6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2～3 hours respectively xerogel is carried out the crystallization processing, be incubated 3～5 hours down at 1000 ℃～1100 ℃ and can make processable biological active glass ceramic.
2, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3 and 1: 5 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10F 2, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4: 2: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 65 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 18wt%, then with water: the mol ratio of dehydrated alcohol=4: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3 mixed, add the ZrO of the granularity of 12wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 6 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 2 days, after the replacement completion, is that 45 ℃, pressure are to make CO under the condition of 8.2MPa in temperature 2Change supercritical state into, and after keeping 6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 3 hours respectively xerogel is carried out the crystallization processing, be incubated 5 hours down at 1020 ℃ and can make processable biological active glass ceramic.
3, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.6 and 1: 4.3 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 1F 1, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 5: 1: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 58 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 12wt%, then with water: the mol ratio of dehydrated alcohol=2: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4 mixed, add the ZrO of the granularity of 15wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 8 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 3 days, after the replacement completion, is that 36 ℃, pressure are to make CO under the condition of 7.0MPa in temperature 2Change supercritical state into, and after keeping 3 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2 hours respectively to xerogel carry out crystallization handle 1080 ℃ down insulation can make processable biological active glass ceramic in 4 hours.
4, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.2 and 1: 4.6 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.5F 1.5, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.5: 1.5: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 10wt%, then with water: the mol ratio of dehydrated alcohol=3: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.5, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 5 mixed, add the ZrO of the granularity of 10wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 5 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 4 days, after the replacement completion, is that 48 ℃, pressure are to make CO under the condition of 9.5MPa in temperature 2Change supercritical state into, and after keeping 5 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.6 hours respectively xerogel is carried out the crystallization processing, be incubated 3 hours down at 1050 ℃ and can make processable biological active glass ceramic.
5, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 4 and 1: 4.1 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.8F 1.2, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.8: 1.2: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 60 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 15wt%, then with water: the mol ratio of dehydrated alcohol=2.5: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.7, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 3.6 mixed, add the ZrO of the granularity of 8wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 7 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 4 days, after the replacement completion, is that 30 ℃, pressure are to make CO under the condition of 9.0MPa in temperature 2Change supercritical state into, and after keeping 4 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.2 hours respectively xerogel is carried out the crystallization processing, be incubated 4 hours down at 1000 ℃ and can make processable biological active glass ceramic.
6, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.5 and 1: 4.8 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.2F 1.8, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.2: 1.8: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 63 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 20wt%, then with water: the mol ratio of dehydrated alcohol=3.8: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.2, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4.2 mixed, add the ZrO of the granularity of 16wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 6.5 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 2 days, after the replacement completion, is that 50 ℃, pressure are to make CO under the condition of 8.0MPa in temperature 2Change supercritical state into, and after keeping 6 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.5 hours respectively xerogel is carried out the crystallization processing, be incubated 5 hours down at 1060 ℃ and can make processable biological active glass ceramic.
7, the preparation method of processable biological active glass ceramic material according to claim 1 is characterized in that:
1) preparation of hydroxyapatite precursor colloidal sol
Respectively nitrocalcite and Vanadium Pentoxide in FLAKES are dissolved in dehydrated alcohol by the mass ratio of 1: 3.8 and 1: 4 and make the alcoholic solution of nitrocalcite and the alcoholic solution of Vanadium Pentoxide in FLAKES, then, at normal temperatures, the alcoholic solution of Vanadium Pentoxide in FLAKES is added drop-wise to uniform mixing in the alcoholic solution of nitrocalcite by the Ca/P=1.67 mol ratio, mixed solution is left standstill, obtain water white hydroxyapatite precursor colloidal sol;
2) preparation of phlogopite precursor colloidal sol
Molecular formula KMg according to phlogopite 3(Si 3Al) O 10(OH) 0.6F 1.4, determine tetraethoxy, Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Mol ratio be 6: 2: 4.6: 1.4: 2, with Al (NO 3) 39H 2O, Mg (NO 3) 26H 2O, MgF 2And KNO 3Add in the deionized water successively, stir at 55 ℃ of following constant temperature, after treating that it dissolves fully, be configured to the solution that concentration is 13wt%, then with water: the mol ratio of dehydrated alcohol=3.2: 1 adds dehydrated alcohol, stir after 5 minutes, add tetraethoxy again, stirred 2 minutes, the HCl adjusting pH value that adds 0.1mol/l at last is 3.4, by magnetic stirrer 30 minutes, leave standstill and obtain even, transparent phlogopite precursor colloidal sol;
3) mass ratio of above-mentioned two kinds of precursor colloidal sols by 1: 4.7 mixed, add the ZrO of the granularity of 14wt% simultaneously less than 100nm 2Particle, and stir and make uniform mixed sols, mixed sols 25 ℃ of ageings 7.4 hours, is formed even, transparent wet gel;
4) with the soaked in absolute ethyl alcohol gel moisture in the gel is all replaced, adopt CO 2Supercritical drying carries out drying to gel, uses liquid CO in autoclave 2The ethanol of displacement in the gel, time swap is 3 days, after the replacement completion, is that 40 ℃, pressure are to make CO under the condition of 7.5MPa in temperature 2Change supercritical state into, and after keeping 5 hours, discharge CO 2, when pressure reduces to zero, stop heating, take out xerogel;
5) under 750 ℃ and 900 ℃, be incubated 2.7 hours respectively xerogel is carried out the crystallization processing, be incubated 3 hours down at 1100 ℃ and can make processable biological active glass ceramic.
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