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CN100348525C - Biological activity glass ceramics capable of cutting and its preparation method - Google Patents

Biological activity glass ceramics capable of cutting and its preparation method Download PDF

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CN100348525C
CN100348525C CNB2004100792789A CN200410079278A CN100348525C CN 100348525 C CN100348525 C CN 100348525C CN B2004100792789 A CNB2004100792789 A CN B2004100792789A CN 200410079278 A CN200410079278 A CN 200410079278A CN 100348525 C CN100348525 C CN 100348525C
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furnace
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CN1754852A (en
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刘咏
向其军
单小宏
盛小娴
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/0007Compositions for glass with special properties for biologically-compatible glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C10/00Devitrified 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

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Abstract

本发明涉及硅酸盐材料领域,该材料应用于骨、齿缺损的修复与替代。其特征在于:将按重量百分比配制好的原料装入氧化铝球磨罐中混合均匀;接着倒入氧化铝坩埚中,在硅钼棒炉中高温熔炼;然后将熔融的玻璃浇于水中淬冷、烘干后磨碎;将这些玻璃粉再进行重熔后浇铸到石墨模具中,在500~700℃保温1h,随炉冷却至室温,得到成分均匀的玻璃母体;再升温至800~1100℃保温4~24h,使母体玻璃受控析出含有氟金云母和氟磷灰石两种主晶相的玻璃陶瓷。本发明制备的医用可切削生物活性玻璃陶瓷,其抗弯强度、弹性模量符合人体骨、齿的力学性能要求,能与人体骨组织直接产生强的化学键合;其色泽与人体牙釉质十分相近,适合用于齿科替代材料;且其制备工艺简单,技术成熟,易于操作。The invention relates to the field of silicate materials, which are applied to the repair and replacement of bone and tooth defects. It is characterized in that: the raw materials prepared according to the weight percentage are put into an alumina ball mill jar and mixed evenly; then poured into an alumina crucible and smelted at a high temperature in a silicon-molybdenum rod furnace; then the molten glass is poured into water to quench, Grind after drying; remelt the glass powder and cast it into a graphite mold, keep it at 500-700°C for 1 hour, and cool it to room temperature with the furnace to obtain a glass matrix with uniform composition; then heat it up to 800-1100°C and keep it warm 4 to 24 hours, the matrix glass is controlled to precipitate glass ceramics containing two main crystal phases of fluorphlogopite and fluoroapatite. The medical machinable bioactive glass-ceramic prepared by the present invention has the flexural strength and elastic modulus in line with the mechanical performance requirements of human bones and teeth, and can directly produce strong chemical bonds with human bone tissue; its color is very similar to human enamel , suitable for dental substitute materials; and its preparation process is simple, mature and easy to operate.

Description

A kind of biological activity glass ceramics capable of cutting and preparation method thereof
Technical field:
The present invention relates to especially a kind of biological activity glass ceramics capable of cutting in silicate material field and preparation method thereof, this material is applied to the damaged reparation of bone, tooth and substitutes.
Background technology:
Traditional biomaterial for medical purpose mostly is titanium alloy, stainless steel, vitallium, macromolecular material PMMA etc., these materials are because biocompatibility is poor, as in bone, the tooth equivalent material implant into body time, easily form the fibering packing, can not produce chemical bonding closely with osseous tissue, be easy to loose or dislocation.In recent years, biological ceramics is as a kind of novel biomaterial for medical purpose, and is subjected to extensive concern.But the ceramic-like materials difficulty of processing is big, and the profile of human body bone, tooth different and widely different because of individual and concrete position, thereby the processing difficulties of biological ceramics has limited its application in bone, tooth repair materials.
Summary of the invention:
The purpose of this invention is to provide a kind of have good machinability and bioactive medical glass stupalith and preparation method.
Biological activity glass ceramics capable of cutting of the present invention is (wt%) SiO by weight percentage 252-28%, Al 2O 311-5%, MgO 14-7%, NaF 15-8%, CaHPO 46-32%, CaCO 32-14%, CaF 2The 1-5% preparation is respectively 50~90% and 10~50% in the hope of fluorophlogopite and fluorapatite two-phase in the final glass-ceramic.
Biological activity glass ceramics capable of cutting preparation method of the present invention is: at first with raw materials by weight (wt%) SiO 252-28%, Al 2O 311-5%, MgO 14-7%, NaF 15-8%, CaHPO 46-32%, CaCO 32-14%, CaF 21-5% prepares, and mixes in the aluminum oxide ball milling jar of packing into; Then pour in the alumina crucible high melt in the Si-Mo rod stove into; Then fused glass is watered in water and grind after quenching, the oven dry.These glass powder are carried out being cast in the graphite jig after the remelting again,,, cool to room temperature with the furnace, obtain the uniform glass matrix of composition at 500~700 ℃ of insulation 1h before this with mold heated to 400~600 ℃; Determine suitable heat treating regime through the DTA differential thermal analysis, be warming up to 800~1100 ℃ of insulation 4~24h again, make the controlled glass-ceramic that contains fluorophlogopite and two kinds of principal crystalline phases of fluorapatite of separating out of mother glass.Owing to form by phosphatic rock more than 70% in the bone of human body, the tooth, therefore, fluorapatite has given glass-ceramic good biological activity and biocompatibility, the fluorophlogopite of laminate structure is owing to have very strong divisibility along (001) crystal face simultaneously, have good machinable performance, thereby make this glass-ceramic have machinability and biological activity concurrently.
The present invention is used for each ionic concn (10 of simulated body fluid of biological activity glass ceramics capable of cutting -3Mol/L) be: Na +142.0, K +5.0, Mg 2+1.5, Ca 2+2.5, Cl -147.8, HCO 3 -4.2, HPO 4 2-1.0, SO 4 2-0.5.
Advantage of the present invention and positively effect demonstrate fully in following several respects:
The medical machinable biological active glass ceramic of the present invention's preparation, its bending strength, Young's modulus meet the performance requriements of human body bone, tooth, have good biological activity and biocompatibility simultaneously, can directly produce strong chemical bonding with body bone tissue, and tissue is not had any toxic action, it is a kind of ideal novel biomaterial, its color and luster and human body enamel are very close, especially be suitable for tooth section equivalent material, and its preparation technology are simple, technology maturation, easy handling.
Embodiment:
Embodiment 1: press SiO 245.9%, Al 2O 39.2%, MgO 11.8%, and NaF 13.1%, CaHPO 412.6%, CaCO 35.4%, CaF 22.0% batching mixing; Pour in the alumina crucible, 1500 ℃ of following meltings are 2 hours in the Si-Mo rod stove, and heat-up rate is 5 ℃/min, and fused glass is watered quenching in water, below ball milling to the 74 μ m of oven dry back; These glass powders are carried out being cast in the graphite jig after the remelting under identical condition again,, immediately graphite jig is moved in the process furnace, obtain glass matrix at 650 ℃ of insulations furnace cooling after 1 hour before this with mold heated to 500~600 ℃; Then glass matrix is warmed up to 925 ℃ of insulations 6 hours from room temperature, heat-up rate is 10 ℃/min, takes out after cooling to room temperature with the furnace.After the glass-ceramic sample processing polishing that makes, be of a size of 3 * 4 * 35mm, adopting three-point bending method test bending strength on CSS-44100 type electronic universal tester is 134MPa, Young's modulus is 12GPa.
Perhaps be incubated 20 hours at 925 ℃ after obtaining glass matrix, recording its bending strength under same condition is 153MPa, and Young's modulus is 15GPa.
Sample is soaked in constant temperature in 37 ℃, pH value transfer to 7.4 simulated body fluid, take out after 3 days, the surface is carried out microscopic appearance behind the metal spraying and is observed, the resultant of sample surfaces is carried out X-ray analysis and in conjunction with EDAX micro-area composition analytical results at D/max-2500 type superpower X-ray diffractometer on JSM-5600LV type scanning electron microscope, discovery has a large amount of fluorapatites to generate at sample surfaces, shows that this kind glass-ceramic has high biological activity.
The method that employing is holed on drilling machine is weighed the cutting ability of glass-ceramic, the boring processing conditions is: constant axial power is 392N, and High Speed Steel Bit, bit diameter are Φ 3mm, rotating speed is 400r/min, drilling time is 15s, and a drill bit is changed in hole of every brill, and the result shows, 925 ℃ the insulation 6 hours or 20 hours after, the mean depth of glass-ceramic boring is respectively 2.6mm and 2.8mm, and the no visual crackle of hole periphery, does not have and be out of shape, and has shown the good machinability of this glass-ceramic.
Embodiment 2: press SiO 234.4%, Al 2O 36.9%, MgO 8.9%, and NaF 9.8%, CaHPO 425.3%, CaCO 310.7%, CaF 24.0% batching mixing; Pour in the alumina crucible, 1500 ℃ of following meltings are 2 hours in the Si-Mo rod stove, and heat-up rate is 5 ℃/min, and fused glass is watered quenching in water, below ball milling to the 74 μ m of oven dry back; These glass powders are carried out being cast in the graphite jig after the remelting under identical condition again,, immediately graphite jig is moved in the process furnace, obtain glass matrix at 650 ℃ of insulations furnace cooling after 1 hour before this with mold heated to 500~600 ℃; Then glass matrix is warmed up to 925 ℃ of insulations 6 hours from room temperature, heat-up rate is 10 ℃/min, takes out after cooling to room temperature with the furnace.After the glass-ceramic sample processing polishing that makes, be of a size of 3 * 4 * 35mm, adopting three-point bending method test bending strength on CSS-44100 type electronic universal tester is 168MPa, Young's modulus is 21GPa.
Perhaps be incubated 20 hours at 925 ℃ after obtaining glass matrix, recording its bending strength under same condition is 190MPa, and Young's modulus is 23GPa.
Sample is soaked in constant temperature in 37 ℃, pH value transfer to 7.4 simulated body fluid, take out after 3 days, the surface is carried out microscopic appearance behind the metal spraying and is observed, the resultant of sample surfaces is carried out X-ray analysis and in conjunction with EDAX micro-area composition analytical results at D/max-2500 type superpower X-ray diffractometer on JSM-5600LV type scanning electron microscope, discovery has a large amount of fluorapatites to generate at sample surfaces, shows that this kind glass-ceramic has high biological activity.
The method that employing is holed on drilling machine is weighed the cutting ability of glass-ceramic, the boring processing conditions is: constant axial power is 392N, and High Speed Steel Bit, bit diameter are Φ 3mm, rotating speed is 400r/min, drilling time is 15s, and a drill bit is changed in hole of every brill, and the result shows, 925 ℃ the insulation 6 hours or 20 hours after, the mean depth of glass-ceramic boring is respectively 2.2mm and 2.3mm, and the no visual crackle of hole periphery, does not have and be out of shape, and has shown the good machinability of this glass-ceramic.
Embodiment 3: press SiO 245.9%, Al 2O 39.2%, MgO 11.8%, and NaF 13.1%, CaHPO 412.6%, CaCO 35.4%, CaF 22.0% batching mixing; Pour in the alumina crucible, 1500 ℃ of following meltings are 2 hours in the Si-Mo rod stove, and heat-up rate is 5 ℃/min, and fused glass is watered quenching in water, below ball milling to the 74 μ m of oven dry back; These glass powders are carried out being cast in the graphite jig after the remelting under identical condition again,, immediately graphite jig is moved in the process furnace, obtain glass matrix at 650 ℃ of insulations furnace cooling after 1 hour before this with mold heated to 500~600 ℃; Then glass matrix is warmed up to 925 ℃ of insulations 6 hours from room temperature, heat-up rate is 10 ℃/min, takes out after cooling to room temperature with the furnace.After the glass-ceramic sample processing polishing that makes, be of a size of 3 * 4 * 35mm, adopting three-point bending method test bending strength on CSS-44100 type electronic universal tester is 134MPa, Young's modulus is 12GPa.
Perhaps after obtaining glass matrix, be incubated 20 hours at 925 ℃, recording its bending strength under same condition is 153MPa, Young's modulus is 15GPa, and the glass-ceramic for preparing under the heat-treat condition is compared similarly to Example 1, and its mechanical property is further enhanced.
Sample is soaked in constant temperature in 37 ℃, pH value transfer to 7.4 simulated body fluid, take out after 3 days, the surface is carried out microscopic appearance behind the metal spraying and is observed, the resultant of sample surfaces is carried out X-ray analysis and in conjunction with EDAX micro-area composition analytical results at D/max-2500 type superpower X-ray diffractometer on JSM-5600LV type scanning electron microscope, discovery has a large amount of fluorapatites to generate at sample surfaces, shows that this kind glass-ceramic has high biological activity.
The method that employing is holed on drilling machine is weighed the cutting ability of glass-ceramic, the boring processing conditions is: constant axial power is 392N, and High Speed Steel Bit, bit diameter are Φ 3mm, rotating speed is 400r/min, drilling time is 15s, and a drill bit is changed in hole of every brill, and the result shows, 925 ℃ the insulation 6 hours or 20 hours after, the mean depth of glass-ceramic boring is respectively 2.6mm and 2.8mm, and the no visual crackle of hole periphery, does not have and be out of shape, and has shown the good machinability of this glass-ceramic.
Embodiment 4: press SiO 234.4%, Al 2O 36.9%, MgO 8.9%, and NaF 9.8%, CaHPO 425.3%, CaCO 310.7%, CaF 24.0% batching mixing; Pour in the alumina crucible, 1500 ℃ of following meltings are 2 hours in the Si-Mo rod stove, and heat-up rate is 5 ℃/min, and fused glass is watered quenching in water, below ball milling to the 74 μ m of oven dry back; These glass powders are carried out being cast in the graphite jig after the remelting under identical condition again,, immediately graphite jig is moved in the process furnace, obtain glass matrix at 650 ℃ of insulations furnace cooling after 1 hour before this with mold heated to 500~600 ℃; Then glass matrix is warmed up to 925 ℃ of insulations 6 hours from room temperature, heat-up rate is 10 ℃/min, takes out after cooling to room temperature with the furnace.After the glass-ceramic sample processing polishing that makes, be of a size of 3 * 4 * 35mm, adopting three-point bending method test bending strength on CSS-44100 type electronic universal tester is 168MPa, Young's modulus is 21GPa.
Perhaps after obtaining glass matrix, be incubated 20 hours at 925 ℃, recording its bending strength under same condition is 190MPa, Young's modulus is 23GPa, compares with the glass-ceramic of embodiment 3 preparations with embodiment 1, embodiment 2, and its mechanical property is further enhanced.
Sample is soaked in constant temperature in 37 ℃, pH value transfer to 7.4 simulated body fluid, take out after 3 days, the surface is carried out microscopic appearance behind the metal spraying and is observed, the resultant of sample surfaces is carried out X-ray analysis and in conjunction with EDAX micro-area composition analytical results at D/max-2500 type superpower X-ray diffractometer on JSM-5600LV type scanning electron microscope, discovery has a large amount of fluorapatites to generate at sample surfaces, shows that this kind glass-ceramic has high biological activity.
The method that employing is holed on drilling machine is weighed the cutting ability of glass-ceramic, the boring processing conditions is: constant axial power is 392N, and High Speed Steel Bit, bit diameter are Φ 3mm, rotating speed is 400r/min, drilling time is 15s, and a drill bit is changed in hole of every brill, and the result shows, 925 ℃ the insulation 6 hours or 20 hours after, the mean depth of glass-ceramic boring is respectively 2.2mm and 2.3mm, and the no visual crackle of hole periphery, does not have and be out of shape, and has shown the good machinability of this glass-ceramic.
Embodiment 5: press SiO 228.6%, Al 2O 35.8%, MgO 7.4%, and NaF 8.2%, CaHPO 431.6%, CaCO 313.4%, CaF 25.0% batching mixing; Pour in the alumina crucible, 1500 ℃ of following meltings are 2 hours in the Si-Mo rod stove, and heat-up rate is 5 ℃/min, and fused glass is watered quenching in water, below ball milling to the 74 μ m of oven dry back; These glass powders are carried out being cast in the graphite jig after the remelting under identical condition again,, immediately graphite jig is moved in the process furnace, obtain glass matrix at 650 ℃ of insulations furnace cooling after 1 hour before this with mold heated to 500~600 ℃; Then glass matrix is warmed up to 925 ℃ of insulations 6 hours from room temperature, heat-up rate is 10 ℃/min, takes out after cooling to room temperature with the furnace.After the glass-ceramic sample processing polishing that makes, be of a size of 3 * 4 * 35mm, adopting three-point bending method test bending strength on CSS-44100 type electronic universal tester is 191MPa, Young's modulus is 26GPa.
Perhaps after obtaining glass matrix, be incubated 20 hours at 925 ℃, recording its bending strength under same condition is 215MPa, Young's modulus is 30GPa, compares with embodiment 1, embodiment 2, embodiment 3 and the glass-ceramic of embodiment 4 preparations, and its mechanical property is further enhanced.
Sample is soaked in constant temperature in 37 ℃, pH value transfer to 7.4 simulated body fluid, take out after 3 days, the surface is carried out microscopic appearance behind the metal spraying and is observed, the resultant of sample surfaces is carried out X-ray analysis and in conjunction with EDAX micro-area composition analytical results at D/max-2500 type superpower X-ray diffractometer on JSM-5600LV type scanning electron microscope, discovery has a large amount of fluorapatites to generate at sample surfaces, as shown in Figure 3, show that this kind glass-ceramic has high biological activity.
The method that employing is holed on drilling machine is weighed the cutting ability of glass-ceramic, the boring processing conditions is: constant axial power is 392N, and High Speed Steel Bit, bit diameter are Φ 3mm, rotating speed is 400r/min, drilling time is 15s, and a drill bit is changed in hole of every brill, and the result shows, 925 ℃ the insulation 6 hours or 20 hours after, the mean depth of glass-ceramic boring is respectively 2.0mm and 2.2mm, and the no visual crackle of hole periphery, does not have and be out of shape, and has shown the good machinability of this glass-ceramic.

Claims (4)

1.一种可切削的生物活性玻璃陶瓷,其特征在于:按重量百分比:SiO252-28%,Al2O311-5%,MgO14-7%,NaF15-8%,CaHPO46-32%,CaCO32-14%,CaF21-5%配制。1. A machinable bioactive glass-ceramic, characterized in that: by weight percentage: SiO 2 52-28%, Al 2 O 3 11-5%, MgO14-7%, NaF15-8%, CaHPO 4 6- 32%, CaCO 3 2-14%, CaF 2 1-5%. 2.根据权利要求1所述的一种可切削的生物活性玻璃陶瓷,其特征在于:配料成分为SiO2 45.9%,Al2O39.2%,MgO11.8%,NaF13.1%,CaHPO412.6%,CaCO35.4%,CaF22.0%。2. A machinable bioactive glass-ceramic according to claim 1, characterized in that: the ingredients are SiO 2 45.9%, Al 2 O 3 9.2%, MgO 11.8%, NaF 13.1%, CaHPO 4 12.6%, CaCO 3 5.4%, CaF 2 2.0%. 3.根据权利要求1所述的一种可切削的生物活性玻璃陶瓷,其特征在于:配料成分为SiO234.4%,Al2O36.9%,MgO8.9%,NaF9.8%,CaHPO425.3%,CaCO310.7%,CaF24.0%。3. A machinable bioactive glass-ceramic according to claim 1, characterized in that: the ingredients are SiO 2 34.4%, Al 2 O 3 6.9%, MgO 8.9%, NaF 9.8%, CaHPO 4 25.3%, CaCO 3 10.7%, CaF 2 4.0%. 4.一种根据权利要求1所述的可切削的生物活性玻璃陶瓷的制备方法,其特征在于:首先将配制好的原料,装入氧化铝球磨罐中混合均匀;接着倒入氧化铝坩锅中,在硅钼棒炉中高温熔炼;然后将熔融的玻璃浇于水中淬冷、烘干后磨碎;对这些玻璃粉再进行重熔后浇铸到石墨模具中,此前将模具加热到400~600℃,在500~700℃保温1h,随炉冷却至室温,得到成分均匀的玻璃母体;经DTA差热分析确定适当的热处理制度,再升温至800~1100℃保温4~24h,使母体玻璃受控析出含有氟金云母和氟磷灰石两种主晶相的玻璃陶瓷。4. A preparation method of a machinable bioactive glass-ceramic according to claim 1, characterized in that: at first the prepared raw materials are mixed uniformly in an alumina ball mill jar; then poured into an alumina crucible In the silicon-molybdenum rod furnace, it is smelted at a high temperature; then the molten glass is poured in water to quench, dried and ground; the glass powder is remelted and cast into a graphite mold, which was previously heated to 400~ 600°C, hold at 500-700°C for 1 hour, cool down to room temperature with the furnace, and obtain a glass matrix with uniform composition; determine the appropriate heat treatment system through DTA differential thermal analysis, and then raise the temperature to 800-1100°C for 4-24 hours to make the matrix glass Controlled precipitation of glass ceramics containing two main crystal phases of fluorphlogopite and fluoroapatite.
CNB2004100792789A 2004-09-28 2004-09-28 Biological activity glass ceramics capable of cutting and its preparation method Expired - Fee Related CN100348525C (en)

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CN102432182B (en) * 2011-09-28 2013-11-13 华南理工大学 Method for preparing machinable microcrystal glass material with high bioactivity
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