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.