CN100408498C - Microcrystal glass with Li20-SiO2-P205 as main raw materials and production thereof - Google Patents

Microcrystal glass with Li20-SiO2-P205 as main raw materials and production thereof Download PDF

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Publication number
CN100408498C
CN100408498C CNB2005100104317A CN200510010431A CN100408498C CN 100408498 C CN100408498 C CN 100408498C CN B2005100104317 A CNB2005100104317 A CN B2005100104317A CN 200510010431 A CN200510010431 A CN 200510010431A CN 100408498 C CN100408498 C CN 100408498C
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raw material
glass
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zno
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CN1778747A (en
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温广武
郑欣
宋亮
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Harbin Institute of Technology
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Harbin Institute of 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Abstract

The present invention provides microcrystalline glass and a preparation method thereof, wherein the microcrystalline glass uses Li2O-SiO2-P2O5 as main raw materials. In order to solve the problems of low crystallization degree and poor mechanical property of the existing microcrystalline glass, the microcrystalline glass is composed of raw materials: 60 to 75 wt% of SiO2, 15 to 18 wt% of Li2O, 2 to 11 wt% of P2O5, 2.5 to 3.5 wt% of ZnO, 4 to 6.5 wt% K2O and 1 to 1.5 wt% of CaO. The preparation method comprises the following steps: 1, the raw materials are processed by ball milling and drying; 2, powder in step 1 is put in a crucible for fusion; 3, glass melting liquid obtained in step 2 is processed into blocky glass in a water quenching mode; 4, the glass in step 3 is processed into powder in a ball milling mode; 5, the powder in step 4 is put in a hot pressing sintering furnace, the powder is demoulded after being uniaxially pressurized and sintered, and the powder is cooled according to the temperature of the furnace; finally, the microcrystalline glass using lithium disilicate as a main crystal phase is prepared. The main crystal phase obtained by the method is a clavate lithium disilicate crystal, and the clavate lithium disilicate crystal has the advantages of high crystallization degree and good mechanical property.

Description

With Li 2O-SiO 2-P 2O 5Be devitrified glass of main raw material and preparation method thereof
Technical field
The present invention relates to devitrified glass and preparation method thereof.
Background technology
Devitrified glass has been obtained the achievement that attracts people's attention in fields such as mechano-electronic, space industry, biomedicines since late 1950s, the phase succeeded in developing.Especially as the bio-microcrystal glass of novel dental prosthetic material, has its special advantages.Full porcelain reparation has become one of main development trend of current oral cavity fixed and repaired.1986, Ivoclar company and University of Zurich developed white garnet (leucite) glass-ceramic IPS Empress jointly, and hot pressing is cast into preparation technology and has been widely used in preparation Dental Glass Ceramics material.But the flexural strength of white garnet system devitrified glass is lower, has only 160～180MPa, can not satisfy the reparation that is used for fixing bridge.The preparation technology that the said firm in 1998 still adopts hot pressing to be cast into releases IPS Empress2 type glass-ceramic, and intensity is improved.Controlling the needs that its microstructure reaches attractive in appearance, satisfies intensity and biocompatibility, is the subject matter that the Oral Repair field need solve.The preparation technology of devitrified glass is one of essential condition that obtains good mechanical property.Can adopt scorification preparation technology for the machinable glass ceramics system that contains the mica phase and other low-melting glass systems, carry out carrying out the crystallization processing again after the high temperature cast molding; And for adding ZrO 2Can cause the fusing point of this system to raise as the devitrified glass of wild phase, generally be cold isostatic compaction after, carry out pressureless sintering, but low, the poor mechanical property of devitrified glass crystallization degree, the relation between sintering temperature and the crystallization temperature is difficult to grasp.
Summary of the invention
Existing devitrified glass crystallization degree is low, the problem of poor mechanical property in order to solve in the present invention, has proposed a kind of with Li 2O-SiO 2-P 2O 5Be devitrified glass of main raw material and preparation method thereof, the concrete technical scheme that this method is dealt with problems is as follows:
Devitrified glass of the present invention is by SiO 2, Li 2O, P 2O 5, ZnO, K 2O, CaO are that raw material is formed, and the content of each material composition is SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt%.
The present invention is with Li 2O-SiO 2-P 2O 5For the preparation process of the devitrified glass of main raw material as follows:
Step 1, with SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt% are as raw material, and adopting medical alcohol is that medium ball milling in ball grinder was slowly dried in 100～200 ℃ sand bath after 4～8 hours;
Step 2, the starting powder after the step 1 oven dry is put into crucible, crucible is placed in the air atmosphere stove temperature rise rate with 2 ℃/min～10 ℃/min, be warming up to 1350～1450 ℃ and be incubated 0.5～3 hour, make the starting powder fusing obtain the glass melt of uniformity;
Step 3, will under 1350～1450 ℃ of temperature of fusion, carry out shrend rapidly through the glass melt that step 2 obtains and become block pristine glass;
Step 4, the pristine glass that will obtain through step 3 in ball grinder with 150 rev/mins～300 rev/mins rotating speed, the pristine glass powder that ball milling obtained after 10～30 hours, the granularity of powder is 0.5 μ m～2 μ m;
Step 5, will in packing the high temperature steel mould into, the pristine glass powder that step 4 obtains be placed in the hot-pressed sintering furnace, temperature rise rate with 3 ℃/min～10 ℃/min is warming up to 800 ℃～900 ℃, and adopt 10～40MPa to carry out single shaft and exert pressure, at 800 ℃～900 ℃ following sintering the high temperature demoulding and furnace cooling after 0.5～2 hour, promptly prepare with Li 2O-SiO 2-P 2O 5For two lithium silicates of main raw material are the devitrified glass of principal crystalline phase.
The present invention is with Li 2O-SiO 2-P 2O 5The principal crystalline phase that the method that adopts hot-pressing sintering technique to prepare devitrified glass for main raw material obtains devitrified glass is two bar-shaped lithium silicate crystal, this crystalline crystallization degree height can reach 80%～90%, and mechanical property is good, its bending strength is at 100～300MPa, and fracture toughness property is at 1.5MPa/m 1/2～3.0MPa/m 1/2, preparation technology is simple, does not need behind the hot pressed sintering to handle through crystallization.
Embodiment
Embodiment one: the devitrified glass of present embodiment is by SiO 2, Li 2O, P 2O 5, ZnO, K 2O, CaO are that raw material is formed, and the content of each material composition is SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt%.
Embodiment two: the devitrified glass of present embodiment is by SiO 2: 64.5wt%, Li 2O:18wt%, P 2O 5: 8wt%, ZnO:2wt%, K 2O:6.5wt%, CaO:1wt% form.
Embodiment three: the devitrified glass of present embodiment is by SiO 2: 71wt%, Li 2O:15wt%, P 2O 5: 6wt%, ZnO:2.5wt%, K 2O:4wt%, CaO:1.5wt% form.
Embodiment four: the devitrified glass of present embodiment is by containing SiO 2: 73.5wt%, Li 2O:15wt%, P 2O 5: 2.5wt%, ZnO 2: 3wt%, K 2O:5wt%, CaO:1wt% form.
Embodiment five: present embodiment is with Li 2O-SiO 2-P 2O 5For the following step is adopted in the preparation of the devitrified glass of main raw material:
Step 1, with SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt% are as raw material, and the employing medical alcohol is a medium, and ball milling was slowly dried in 100～200 ℃ sand bath after 4～8 hours in the agate jar; SiO 2: Li 2The mol ratio of O is 1.8～2.2: 1; Owing in raw material, add P 2O 5As nucleating agent, remarkable crystal grain thinning obtains two tiny, bar-shaped lithium silicate crystal of submicron order, and the crystal of separating out can be evenly distributed in the glass basis, thereby improves the mechanical property of devitrified glass;
Step 2, the starting powder after the step 1 oven dry is put into Al 2O 3In the crucible, crucible is placed in the air atmosphere stove temperature rise rate with 2 ℃/min～10 ℃/min, is warming up to 1350～1450 ℃ and be incubated 0.5～3 hour, make the starting powder fusing obtain the glass melt of uniformity;
Step 3, will under 1350～1450 ℃ of temperature of fusion, carry out shrend rapidly through the glass melt that step 2 obtains and become the fritter pristine glass;
Step 4, will through pristine glass that step 3 obtains in the agate jar with 150 rev/mins～300 rev/mins rotating speed, the pristine glass powder that ball milling obtained after 10～30 hours, the granularity of powder is 0.5 μ m～2 μ m;
Step 5, will in packing the high temperature steel mould into, the pristine glass powder that step 4 obtains be placed in the hot-pressed sintering furnace, temperature rise rate with 3 ℃/min～10 ℃/min is warming up to 800 ℃～900 ℃, and adopt 10～40MPa to carry out single shaft and exert pressure, at 800 ℃～900 ℃ sintering the high temperature demoulding and furnace cooling after 0.5～2 hour, promptly prepare with Li 2O-SiO 2-P 2O 5For two lithium silicates of main raw material are the devitrified glass of principal crystalline phase.
Embodiment six: the difference of present embodiment and embodiment five is that raw material is by Li 2O:17.57wt%; SiO 2: 70.3wt%; ZnO:3.1wt%; K 2O:5.3wt%; CaO:1.06wt%; P 2O 5: 2.7wt% forms, with the above-mentioned raw materials ball milling after 4 hours, after fusing and shrend under 1350 ℃, ball milling is 20 hours in the agate jar, pristine glass powder behind the ball milling packed into carry out hot pressed sintering in the high temperature steel mould, temperature rise rate with 3 ℃/min～10 ℃/min is heated to 840 ℃, and insulation high temperature demoulding after 1 hour under 32MPa, and the density of material is 2.50g/cm 3, three-point bending strength is 249.9MPa, fracture toughness property is 2.12MPam 1/2, Vickers' hardness is 5.9GPa.Other step is identical with embodiment five.
Embodiment seven: the difference of present embodiment and embodiment five is that raw material is by Li 2O:17wt%; SiO 2: 68.45wt%; ZnO:3wt%; K 2O:5.3wt%; CaO:1.0wt%; P 2O 5: 5.25wt% forms, with the above-mentioned raw materials ball milling after 6 hours, at 1400 ℃ down after fusing and the shrend, ball milling is 24 hours in the agate jar, temperature rise rate with 3 ℃/min～10 ℃/min is heated to 840 ℃, insulation high temperature demoulding after 1 hour under 32MPa, and the density of material is 2.49g/cm 3, three-point bending strength is 214.6MPa, fracture toughness property is 2.20MPam 1/2, Vickers' hardness is 6.0GPa.Other step is identical with embodiment five.
Embodiment eight: the difference of present embodiment and embodiment five is that raw material is by Li 2O:17wt%; SiO 2: 68.45wt%; ZnO:3wt%; K 2O:5.3wt%; CaO:1.0wt%; P 2O 5: 5.25wt% forms, with the above-mentioned raw materials ball milling after 8 hours at 1450 ℃ down after fusing and the shrend, ball milling is 30 hours in the agate jar, is heated to 850 ℃ with the temperature rise rate of 3 ℃/min～10 ℃/min, insulation high temperature demoulding after 1 hour under 25MPa, the density of material is 2.50g/cm 3, three-point bending strength is 241.1MPa, fracture toughness property is 2.09MPam 1/2, Vickers' hardness is 6.0GPa.Other step is identical with embodiment five.

Claims (9)

1. Li 2O-SiO 2-P 2O 5Be the devitrified glass of main raw material, it is characterized in that it is by SiO 2, Li 2O, P 2O 5, ZnO, K 2O, CaO are that raw material is formed, and the content of each material composition is SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt%.
2. Li according to claim 1 2O-SiO 2-P 2O 5Devitrified glass for main raw material is characterized in that SiO 2With Li 2The mol ratio of O is 1.8～2.2: 1.
3. Li according to claim 1 and 2 2O-SiO 2-P 2O 5Be the devitrified glass of main raw material, it is characterized in that raw material is by SiO 2: 64.5wt%, Li 2O:18wt%, P 2O 5: 8wt%, ZnO:2wt%, K 2O:6.5wt%, CaO:1wt% form.
4. Li according to claim 1 and 2 2O-SiO 2-P 2O 5Be the devitrified glass of main raw material, it is characterized in that raw material is by SiO 2: 71wt%, Li 2O:15wt%, P 2O 5: 6wt%, ZnO:2.5wt%, K 2O:4wt%, CaO:1.5wt% form.
5. Li according to claim 1 and 2 2O-SiO 2-P 2O 5Be the devitrified glass of main raw material, it is characterized in that raw material is by SiO 2: 73.5wt%, Li 2O:15wt%, P 2O 5: 2.5wt%, ZnO:3wt%, K 2O:5wt%, CaO:1wt% form.
6. with Li 2O-SiO 2-P 2O 5Be the preparation method of the devitrified glass of main raw material, it is characterized in that it is finished by the following step:
Step 1, with SiO 2: 60～75wt%, Li 2O:15～18wt%, P 2O 5: 2～11wt%, ZnO:2.5～3.5wt%, K 2O:4～6.5wt%, CaO:1～1.5wt% are as raw material, and adopting medical alcohol is that medium ball milling in ball grinder was slowly dried in 100～200 ℃ sand bath after 4～8 hours;
Step 2, the starting powder after the step 1 oven dry is put into crucible, crucible is placed in the air atmosphere stove temperature rise rate with 2 ℃/min～10 ℃/min, be warming up to 1350～1450 ℃ and be incubated 0.5～3 hour, make the starting powder fusing obtain the glass melt of uniformity;
Step 3, will under 1350～1450 ℃ of temperature of fusion, carry out shrend rapidly through the glass melt that step 2 obtains and become block pristine glass;
Step 4, the pristine glass that will obtain through step 3 in ball grinder with 150 rev/mins～300 rev/mins rotating speed, the pristine glass powder that ball milling obtained after 10～30 hours, the granularity of powder is 0.5 μ m～2 μ m;
Step 5, will in packing the high temperature steel mould into, the pristine glass powder that step 4 obtains be placed in the hot-pressed sintering furnace, temperature rise rate with 3 ℃/min～10 ℃/min is warming up to 800 ℃～900 ℃, and adopt 10～40MPa to carry out single shaft and exert pressure, at 800 ℃～900 ℃ following sintering the high temperature demoulding and furnace cooling after 0.5～2 hour, promptly prepare with Li 2O-SiO 2-P 2O 5For two lithium silicates of main raw material are the devitrified glass of principal crystalline phase.
7. according to claim 6 with Li 2O-SiO 2-P 2O 5Preparation method for the devitrified glass of main raw material is characterized in that SiO 2With Li 2The mol ratio of O is 1.8～2.2: 1.
8. according to claim 6 or 7 described with Li 2O-SiO 2-P 2O 5Preparation method for the devitrified glass of main raw material is characterized in that raw material is by Li 2O:17wt%; SiO 2: 68.45wt%; ZnO:3wt%; K 2O:5.3wt%; CaO:1.0wt%; P 2O 5: 5.25wt% forms, with the above-mentioned raw materials ball milling after 6 hours, at 1400 ℃ down after fusing and the shrend, ball milling is 24 hours in the agate jar, temperature rise rate with 3 ℃/min～10 ℃/min is heated to 840 ℃, insulation high temperature demoulding after 1 hour under 32MPa, and the density of material is 2.49g/cm 3, three-point bending strength is 214.6MPa, fracture toughness property is 2.20MPam 1/2, Vickers' hardness is 6.0GPa.
9. according to claim 6 or 7 described with Li 2O-SiO 2-P 2O 5Preparation method for the devitrified glass of main raw material is characterized in that raw material is by Li 2O:17wt%; SiO 2: 68.45wt%; ZnO:3wt%; K 2O:5.3wt%; CaO:1.0wt%; P 2O 5: 5.25wt% forms, with the above-mentioned raw materials ball milling after 8 hours at 1450 ℃ down after fusing and the shrend, ball milling is 30 hours in the agate jar, is heated to 850 ℃ with the temperature rise rate of 3 ℃/min～10 ℃/min, insulation high temperature demoulding after 1 hour under 25MPa, the density of material is 2.50g/cm 3, three-point bending strength is 241.1MPa, fracture toughness property is 2.09MPam 1/2, Vickers' hardness is 6.0GPa.
CNB2005100104317A 2005-10-14 2005-10-14 Microcrystal glass with Li20-SiO2-P205 as main raw materials and production thereof Expired - Fee Related CN100408498C (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139170B (en) * 2007-08-02 2010-10-20 哈尔滨工业大学 Lithium disilicate glass-ceramics composite material using ZrO2 as reinforcing phase and method for making same
CN103553339B (en) * 2013-09-30 2015-08-05 西安交通大学 Lithium bisilicate microcrystal glass material prepared by hybrid reaction sintering process and method thereof
CN107365083B (en) * 2017-07-31 2019-10-15 长春理工大学 High-intensitive antibacterial osteoacusis lithium bisilicate glass ceramics and preparation method thereof
CN107555801B (en) * 2017-08-24 2020-10-16 陕西科技大学 Method for preparing lithium disilicate glass ceramics
WO2020210956A1 (en) * 2019-04-15 2020-10-22 深圳爱尔创口腔技术有限公司 Pre-sintered porcelain block for dental restoration, preparation method therefor and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003050052A1 (en) * 2001-12-12 2003-06-19 Schott Glas Anti-microbial, anti-inflammatory glass-ceramic, which absorbs uv radiation
CN1433985A (en) * 2003-03-12 2003-08-06 戴长禄 Nucleated glass composite material and process for preparing same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003050052A1 (en) * 2001-12-12 2003-06-19 Schott Glas Anti-microbial, anti-inflammatory glass-ceramic, which absorbs uv radiation
CN1433985A (en) * 2003-03-12 2003-08-06 戴长禄 Nucleated glass composite material and process for preparing same

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