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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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
precursor colloidal
alcoholic solution
colloidal sol
mixed
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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)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The present invention relates to a method for preparing processable bioactive glass ceramics material. At the ordinary temperature, an alcoholic solution of phosphorus pentoxide is dropwise added into an alcoholic solution of calcium nitrate to mix evenly, and a predecessor of hydroxyapatite is prepared. Tetraethyl orthosilicate, Al (NO3) 3*9H2O, Mg (NO3) 2*6H2O, MgF2 and KNO3 are mixed and stirred to prepare a phlogopite predecessor. The two predecessors are mixed and added with ZrO2 to stir evenly to prepare a mixed sol. Gels are dried by adopting a CO2 supercritical drying method to prepare xerogels which are processed through a crystallization way and are sintered to prepare the processable bioactive glass ceramics. The present invention is mixed with nanometer level ZrO2 particles which can be evenly dispersed in the mixed sol so as to achieve uniform mixing. Compared with the conventional method, the present invention has the advantages that material compositions are horizontally mixed in the gels in a molecular form, the adulterate quantity is easy to accurately control, the gel particle is small, the specific surface area is large, the sintering temperature is far lower than the glass melting temperature, the component volatilization can be avoided, raw material does not need to be melted by a crucible, and the sample purity is maintained.

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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