WO2019080422A1 - Procédé d'amélioration des propriétés physiques et chimiques d'une vitrocéramique dentaire - Google Patents

Procédé d'amélioration des propriétés physiques et chimiques d'une vitrocéramique dentaire

Info

Publication number
WO2019080422A1
WO2019080422A1 PCT/CN2018/077001 CN2018077001W WO2019080422A1 WO 2019080422 A1 WO2019080422 A1 WO 2019080422A1 CN 2018077001 W CN2018077001 W CN 2018077001W WO 2019080422 A1 WO2019080422 A1 WO 2019080422A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
ceramic
nitrate
chemical properties
enhancing
Prior art date
Application number
PCT/CN2018/077001
Other languages
English (en)
Chinese (zh)
Inventor
刘鸿琳
张腾
傅宇宏
杨晓丹
林城
季景仲
Original Assignee
福州瑞克布朗医药科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福州瑞克布朗医药科技有限公司 filed Critical 福州瑞克布朗医药科技有限公司
Publication of WO2019080422A1 publication Critical patent/WO2019080422A1/fr

Links

Classifications

    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/006—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform an exchange of the type Xn+ ----> nH+
    • 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
    • C03C10/0027—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 containing SiO2, Al2O3, Li2O as main constituents

Definitions

  • the invention belongs to the field of glass-ceramics, and in particular relates to a method for enhancing the physical and chemical properties of dental glass-ceramics.
  • dental silicate glass-ceramic materials such as lithium disilicate Li 2 Si 2 O 5 , Li 2 O ⁇ 2SiO 2
  • the indicators and semi-transparency are closer to the advantages of natural teeth and easy machining, which are favored by everyone.
  • Most of the dental blocks used in China today are imported, mainly because the physical and chemical properties (such as breaking strength and hardness rate) of domestic products are not as good as those of foreign products. Therefore, the method for enhancing the physical and chemical properties of dental glass ceramics provided by the patent is of great practical significance.
  • the object of the present invention is to provide a method for enhancing the physical and chemical properties of dental glass-ceramics in view of the deficiencies of the prior art.
  • the physical and chemical properties (including various mechanical properties, chemical stability, etc.) of the glass ceramics are further improved by surface ion exchange treatment of the finished glass ceramics having Li 2 Si 2 O 5 as the main crystal phase and having a partial glass body.
  • a method for enhancing the physical and chemical properties of dental glass-ceramics using a molten divalent metal nitrate to ion-exchange a monovalent ion in a Li-containing dental glass-ceramic having a relatively high characteristic temperature to make a divalent radius
  • the metal ions occupy the position of monovalent ions in the glass ceramic, and enhance the physical and chemical properties of the glass ceramic.
  • the molten divalent metal nitrate has a melting point of 550 to 600 ° C and a boiling point of not lower than 600 ° C, including but not limited to one or more of calcium nitrate, cerium nitrate and cerium nitrate. More preferably, the molten divalent metal nitrate is a mixture of calcium nitrate and cerium nitrate.
  • the Li-containing dental glass-ceramic having a higher characteristic temperature has an initial crystallization temperature of ⁇ 600 ° C and a softening temperature of ⁇ 900 ° C.
  • the main raw materials of the Li-containing dental glass-ceramic having a higher characteristic temperature are SiO 2 , Li 2 CO 3 , K 2 CO 3 , Na 2 CO 3 , Al 2 O 3 , P 2 O 5 and ZrO 2 .
  • the method for enhancing the physical and chemical properties of the dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in the nitrate in the crucible to be buried;
  • step 1) the crystallizing treatment method of the glass ceramics is determined according to the specific glass component and its thermal properties, and is required to be in a state of easy cutting and defect-free; the final crystallizing heat treatment of the glass ceramic is based on the specific glass. Depending on the composition and its thermal properties, it is required to be the final heat treatment step, after which no further heat treatment is required and the sample has no significant defects.
  • the washing water used is deionized water to exclude the introduction of other impurity ions during the washing process.
  • the heating rate of the nitrate is 1 ⁇ 10 ° C / min, preferably 4 ⁇ 8 ° C / min;
  • the holding temperature is 550 ⁇ 600 ° C, preferably 560 ⁇ 590 ° C;
  • the holding time is 1 ⁇ 12 h, preferably It is 2 ⁇ 8h.
  • the molten salt is required to completely cover the surface of the sample, and the surface of the crucible is covered to prevent contamination and volatilization.
  • the cooling of the sample taken out may be performed by different cooling methods such as furnace cooling, air cooling, air cooling, water cooling, etc., and the cooling rate is selected to be fast under the premise of ensuring that the sample does not have cracks, caving and the like. method.
  • the method can also be used for the surface treatment of dental all-ceramic restoration materials.
  • the present invention designs a glass ceramic rich in Al 2 O 3 and ZrO 2 to make the glass ceramic have a higher characteristic temperature and expand the ion exchange temperature and reagent (such as calcium nitrate, melting point 560 ° C). Increase the ion exchange rate;
  • Ca, Sr, Ba are essential elements of the human body, and Ca is the main component of human bones and teeth, which can improve the compatibility of dentures and periodontal;
  • the field strength and radius of the divalent metal ion are higher than that of the monovalent ion, and the surface of the divalent metal ion is concentrated on the surface of the glass, which is also beneficial to the improvement of the chemical stability of the surface of the glass ceramic;
  • the preparation material of the invention is simple and easy to obtain, the process is stable, and the conditions of practicalization and industrialization are achieved.
  • Example 1 is a surface XRD test chart of Example 1.
  • a method for enhancing the physical and chemical properties of dental glass-ceramics using a molten divalent metal nitrate to ion-exchange a monovalent ion in a Li-containing dental glass-ceramic having a relatively high characteristic temperature to make a larger radius
  • the divalent metal ions occupy the position of monovalent ions in the glass ceramic and enhance the physical and chemical properties of the glass ceramic.
  • the molten divalent metal nitrate has a melting point of 550 to 600 ° C and a boiling point of not lower than 600 ° C, including but not limited to one or more of calcium nitrate, cerium nitrate and cerium nitrate. More preferably, the molten divalent metal nitrate is a mixture of calcium nitrate and cerium nitrate.
  • the Li-containing dental glass-ceramic having a higher characteristic temperature has an initial crystallization temperature of ⁇ 600 ° C and a softening temperature of ⁇ 900 ° C.
  • the main raw materials of the Li-containing dental glass-ceramic having a higher characteristic temperature are SiO 2 , Li 2 CO 3 , K 2 CO 3 , Na 2 CO 3 , Al 2 O 3 , P 2 O 5 and ZrO 2 .
  • the method for enhancing the physical and chemical properties of the dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in the nitrate in the crucible to be buried;
  • step 1) the crystallizing treatment method of the glass ceramics is determined according to the specific glass component and its thermal properties, and is required to be in a state of easy cutting and defect-free; the final crystallizing heat treatment of the glass ceramic is based on the specific glass. Depending on the composition and its thermal properties, it is required to be the final heat treatment step, after which no further heat treatment is required and the sample has no significant defects.
  • the washing water used is deionized water to exclude the introduction of other impurity ions during the washing process.
  • the heating rate of the nitrate is 1 ⁇ 10 ° C / min, preferably 4 ⁇ 8 ° C / min;
  • the holding temperature is 550 ⁇ 600 ° C, preferably 560 ⁇ 590 ° C;
  • the holding time is 1 ⁇ 12 h, preferably It is 2 ⁇ 8h.
  • the molten salt is required to completely cover the surface of the sample, and the surface of the crucible is covered to prevent contamination and volatilization.
  • the cooling of the sample taken out may be performed by different cooling methods such as furnace cooling, air cooling, air cooling, water cooling, etc., and the cooling rate is selected to be fast under the premise of ensuring that the sample does not have cracks, caving and the like. method.
  • the method can also be used for the surface treatment of dental all-ceramic restoration materials.
  • Table 1 is the ion exchange selection reagents in Examples 1-5 and the exchange temperature table (mass percentage)
  • the present invention selects the main raw materials for SiO 2 50 ⁇ 65wt%, Li 2 CO 3 20 ⁇ 30 wt%, K 2 CO 3 0 ⁇ 4 wt%, Na 2 CO 3 0.5 ⁇ 5 wt %, Al 2 O 3 2 ⁇ 10 wt%, P 2 O 5 1 ⁇ 4 wt%, and ZrO 2 1 ⁇ 4 wt% glass-ceramics are tested; it should be noted that the glass-ceramics are also suitable for the method of the invention. .
  • the method for enhancing the physical and chemical properties of dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in the calcium nitrate in the crucible to be buried;
  • Fig. 1 is a XRD pattern of the surface of the sample of this example, from which it can be seen that crystals containing Ca on the surface of the sample are precipitated.
  • the method for enhancing the physical and chemical properties of dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in the cerium nitrate in the crucible to be buried;
  • the glass ceramics were washed and subjected to various performance tests. The results obtained are shown in Table 2.
  • the three-point bending strength value was 457 MPa
  • the fracture toughness was 3.8 MPa ⁇ m 0.5
  • the HV1 Vickers hardness value was 611. Enhanced.
  • the method for enhancing the physical and chemical properties of dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in the cerium nitrate in the crucible to be buried;
  • the glass ceramics were washed and subjected to various performance tests. The results obtained are shown in Table 2.
  • the three-point bending strength value was 445 MPa
  • the fracture toughness was 3.7 MPa ⁇ m 0.5
  • the HV1 Vickers hardness value was 581. Enhanced.
  • the method for enhancing the physical and chemical properties of dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in calcium nitrate and cerium nitrate in the crucible to be buried;
  • the glass ceramics were washed and subjected to various performance tests, and the results obtained are shown in Table 2.
  • the three-point bending strength value is 466 MPa
  • the fracture toughness is 3.8 MPa ⁇ m 0.5
  • the HV1 Vickers hardness value is 621, and each performance is enhanced, and the performance enhancement of this embodiment is most remarkable, which is a preferred embodiment.
  • the method for enhancing the physical and chemical properties of dental glass ceramics is as follows:
  • the glass ceramic obtained in the step 1) is washed with deionized water and dried, and then buried in calcium nitrate, barium nitrate and barium nitrate in the crucible to be buried;
  • the glass ceramics were washed and subjected to various performance tests. The results obtained are shown in Table 2.
  • the three-point bending strength value was 455 MPa
  • the fracture toughness was 3.7 MPa ⁇ m 0.5
  • the HV1 Vickers hardness value was 588. Enhanced.
  • the present invention achieves a method for enhancing the physical and chemical properties of dental glass-ceramics by the above implementation. Its remarkable effects are concentrated in excellent fracture toughness and flexural strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne un procédé d'amélioration des propriétés physiques et chimiques de la vitrocéramique dentaire. Une vitrocéramique dentaire contenant du Li et un sel fondu de métal divalent ayant une température caractéristique élevée sont conçus, un échange d'ions est favorisé par la température élevée, et les ions monovalents peuvent en conséquence être remplacés par des ions divalents avec des rayons ioniques plus grands. Étant donné que les positions des ions monovalents (comme K+ et Li+) sont occupées par les ions divalents (comme Ca2+, Sr2+, et Ba2+) avec des rayons plus grands, une contrainte de compression se forme sur une surface de verre dans un processus de refroidissement ultérieur, et les propriétés physiques et chimiques de la vitrocéramique sont ainsi améliorées.
PCT/CN2018/077001 2017-10-27 2018-02-23 Procédé d'amélioration des propriétés physiques et chimiques d'une vitrocéramique dentaire WO2019080422A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711021050.8A CN107721195A (zh) 2017-10-27 2017-10-27 一种增强齿科微晶玻璃理化性能的方法
CN201711021050.8 2017-10-27

Publications (1)

Publication Number Publication Date
WO2019080422A1 true WO2019080422A1 (fr) 2019-05-02

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019232003A2 (fr) * 2018-05-31 2019-12-05 Corning Incorporated Processus d'échange d'ions inverse pour verre contenant du lithium
CN113979647B (zh) * 2021-11-19 2022-09-23 西北有色金属研究院 一种利用离子交换对二硅酸锂玻璃陶瓷强韧化及表面活化的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105837031A (zh) * 2016-03-03 2016-08-10 深圳市力沣实业有限公司 高强度化学强化玻璃、玻璃强化方法
WO2016124486A1 (fr) * 2015-02-05 2016-08-11 Dentsply International Inc. Procédé pour la production d'un corps de formage comprenant ou contenant une vitrocéramique à base de silicate de lithium ainsi que corps de formage
WO2016137916A2 (fr) * 2015-02-27 2016-09-01 Corning Incorporated Procédé de renforcement chimique à basse température pour le verre
CN107207332A (zh) * 2014-11-26 2017-09-26 康宁股份有限公司 强化玻璃、玻璃陶瓷和陶瓷制品以及通过加压离子交换制造其的方法

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
NL303028A (fr) * 1963-01-07
JPS6487534A (en) * 1987-09-29 1989-03-31 Hoya Corp Method for improving chemical durability of glass body
US5741944A (en) * 1995-12-06 1998-04-21 Union Carbide Chemicals & Plastics Technology Corporation Hydroformaylation processes
DE102015108169A1 (de) * 2015-05-22 2016-11-24 Degudent Gmbh Verfahren zur Erhöhung der Festigkeit eines aus Lithiumsilikat-Glaskeramik bestehenden Formkörpers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107207332A (zh) * 2014-11-26 2017-09-26 康宁股份有限公司 强化玻璃、玻璃陶瓷和陶瓷制品以及通过加压离子交换制造其的方法
WO2016124486A1 (fr) * 2015-02-05 2016-08-11 Dentsply International Inc. Procédé pour la production d'un corps de formage comprenant ou contenant une vitrocéramique à base de silicate de lithium ainsi que corps de formage
WO2016137916A2 (fr) * 2015-02-27 2016-09-01 Corning Incorporated Procédé de renforcement chimique à basse température pour le verre
CN105837031A (zh) * 2016-03-03 2016-08-10 深圳市力沣实业有限公司 高强度化学强化玻璃、玻璃强化方法

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