WO2021121404A1 - 一种多晶核复合透明玻璃陶瓷及其制备方法 - Google Patents

一种多晶核复合透明玻璃陶瓷及其制备方法 Download PDF

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Publication number
WO2021121404A1
WO2021121404A1 PCT/CN2020/137725 CN2020137725W WO2021121404A1 WO 2021121404 A1 WO2021121404 A1 WO 2021121404A1 CN 2020137725 W CN2020137725 W CN 2020137725W WO 2021121404 A1 WO2021121404 A1 WO 2021121404A1
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glass
glass ceramic
crystal
temperature
treatment
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PCT/CN2020/137725
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English (en)
French (fr)
Inventor
胡伟
谈宝权
黄昊
覃文城
张延起
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重庆鑫景特种玻璃有限公司
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Priority to KR1020227024938A priority Critical patent/KR20220117309A/ko
Priority to US17/786,771 priority patent/US20230031267A1/en
Priority to EP20903625.0A priority patent/EP4079698A4/en
Publication of WO2021121404A1 publication Critical patent/WO2021121404A1/zh

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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
    • 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
    • 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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • 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
    • C03C21/002—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 ion-exchange between alkali ions
    • 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
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the invention relates to the technical field of glass production and manufacturing, in particular to a polycrystalline core composite transparent glass ceramic and a preparation method thereof.
  • Glass ceramics is a kind of composite material that combines crystal phase and glass made by high temperature melting, forming and heat treatment. Generally, nucleation and devitrification are controlled during the heat treatment process by adding a nucleating agent to the glass raw material. , In order to obtain the overall devitrification containing a large number of microcrystals. Compared with glass, glass ceramics have uniform crystals that are generally less than 10 ⁇ m, and their strength is an order of magnitude higher than ordinary glass. Therefore, glass ceramics are widely used in large-area touch screen electronic products such as smart phones and tablet computers.
  • glass ceramic products on the market are based on adding a certain amount of a single type of crystal nucleating agent before glass melting, such as adding TiO 2 or ZrO 2 or P2O5.
  • the crystal nucleating agent is first dissolved in the glass during the melting process.
  • crystal nuclei are separated or directly precipitated and crystallized to prepare high-strength glass ceramics.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a polycrystalline core composite transparent glass ceramic and a preparation method thereof.
  • the glass ceramic contains a variety of crystal nuclei, and the number of crystal nuclei is large and the crystal size is small. Damage resistance and fracture toughness are strong; at the same time, the visible light transmittance of the glass ceramic is greater than 85%, which can be applied to the fields of electronic product cover, and has strong practicability; the crystal phase of the glass ceramic is lithium disilicate and lithium disilicate. In the permeable feldspar, different crystal phases are intertwined with each other to enhance its breaking strength, so that the breaking strength of the glass ceramic is more than double that of a single crystal phase glass ceramic.
  • the technical scheme of the present invention is as follows: a polycrystalline core composite transparent glass ceramic, the crystal core includes at least two of ZrO2, TiO2, P2O5, rare earth elements, gold, silver, and fluoride; the crystal phase includes lithium disilicate And permeable feldspar; the surface compressive stress on either side of the glass ceramic ranges from 400 MPa to 600 MPa, the depth range of the stress layer of the glass ceramic ranges from 10 um to 100 um, and the tensile stress linear density of the glass ceramic is greater than 30,000 Mpa/mm.
  • the fluoride in the crystal core is NaF and/or CaF2; the rare earth element in the crystal core is La series element and/or Tm series element.
  • the crystal nucleus includes at least three of ZrO2, TiO2, P2O5, rare earth elements, gold, silver, and fluoride.
  • the surface compressive stress of either side of the glass ceramic ranges from 500 MPa to 600 MPa, and the depth range of the stress layer of the glass ceramic ranges from 20 um to 90 um.
  • the average crystal size of the glass ceramic is 50 nm to 150 nm, and the crystal mass ratio is greater than or equal to 80%.
  • the average visible light transmittance of the glass ceramic with a thickness of 1 mm is 86% to 93%.
  • the average crystal size of the glass ceramic is controlled within 50nm ⁇ 150nm, the crystal size is small, and the 1mm thick glass ceramic has an average visible light transmittance of 86% to 93%, and the visible light transmittance is higher than that in the prior art.
  • the visible light transmittance of glass ceramics makes the application range of glass ceramics wider and improves its practicability.
  • the tensile stress linear density of the glass ceramic ranges from 30000Mpa/mm to 44000Mpa/mm.
  • the invention also provides a method for preparing the polycrystalline core composite transparent glass ceramic, which includes the following steps:
  • S2 Obtain plain glass with a certain external dimension from the glass obtained in S1.
  • S3 Put the plain glass obtained in S2 at a temperature of T1, and heat it for 1h ⁇ 6h for annealing treatment. After the annealing treatment is completed, place it at a temperature of T2 and heat it for 1h ⁇ 6h for nucleation treatment. After the chemical treatment is completed, it is placed under the condition of temperature T3 and heated for 0 to 3 hours for crystallization treatment to prepare glass ceramics; the temperature T1 ranges from 450°C to 550°C, and the temperature T2 ranges from 500°C to 500°C. 580°C, the temperature T3 ranges from 600°C to 800°C, and the T1 ⁇ T2.
  • the crystal nucleating agent added in the step S1 includes: at least two of ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm, and the content of the crystal nucleating agent added is: ZrO2: 1 mol% ⁇ 3mol%, TiO2: 0.5mol% ⁇ 1.5mol%, P2O5: 1mol% ⁇ 3mol%, NaF+CaF2: 0mol% ⁇ 4mol%, La+Tm: 0.1mol% ⁇ 1mol%.
  • At least two nucleating agents of ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm are added in the glass melting process, and the prepared glass ceramic contains multiple types of crystal nuclei, increasing the types of crystal nuclei, thereby Reduce the nucleation and crystallization energy required for crystal precipitation, and reduce the heat treatment temperature and time.
  • the glass in the step S1 includes: SiO 2 : 65 mol% to 75 mol%, Al 2 O 3 : 6 mol% to 13 mol%, B 2 O 3 : 1 mol% to 3 mol%, MgO 2 : 0 mol% to 7mol%, ZnO: 1mol% ⁇ 2mol%, K 2 O: 1mol% ⁇ 3mol%, Na 2 O: 1mol% ⁇ 7mol%, Li 2 O: 10mol% ⁇ 20mol%, CeO: 0.1mol% ⁇ 0.25mol% , SnO 2 : 0.2mol% ⁇ 0.3mol%.
  • the temperature T1 ranges from 500°C to 550°C
  • the temperature T2 ranges from 560°C to 580°C
  • the temperature T3 ranges from 700°C to 800°C. Said T1 ⁇ T2.
  • the method for preparing a polycrystalline core composite transparent glass ceramic after the step S3 further includes the step S4: placing the ceramic glass obtained in S3 in at least sodium nitrate, potassium nitrate, sodium carbonate, and potassium carbonate. At least one strengthening treatment is carried out in a salt bath to prepare strengthened glass ceramics.
  • the salt bath contains at least two of sodium nitrate, potassium nitrate, sodium carbonate, and potassium carbonate.
  • the temperature of the first strengthening treatment is 380°C to 450°C, and the strengthening time is 1h to 10h; the temperature of the second strengthening treatment is 380°C to 450°C, The strengthening time is 10min ⁇ 240min.
  • the present invention provides a polycrystalline core composite transparent glass ceramic and a preparation method thereof, by adding at least two of the crystal nucleating agents ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm during the glass melting process , So that there are multiple types of crystal nuclei in the glass, and they are respectively placed under the conditions of T1, T2, and T3, and respectively subjected to annealing, nucleation, and crystallization treatments, to prepare a variety of crystal nuclei, and the crystal nucleus A large number of glass ceramics with crystal phases of lithium disilicate and lithium feldspar.
  • the polycrystalline nucleus formed reduces the nucleation and crystallization energy required for crystal precipitation, reduces the heat treatment temperature and time, and adjusts the ratio of crystals ,
  • the small crystal size enhances the damage resistance and fracture toughness of glass ceramics.
  • the two crystal phases of lithium disilicate and lithosene are interwoven to enhance the destructive strength, thereby increasing the service life of glass ceramics;
  • the prepared glass ceramic has a large number of crystal nuclei, and multiple crystal nuclei can effectively reduce the crystallization energy of the crystal, which is conducive to the uniform distribution of the crystal phase in the glass ceramic, reduces the size of the crystal, improves the transmittance of visible light, and strengthens the glass ceramic Practicability:
  • the above preparation method can also be extended to other glass preparation methods. According to different components and different requirements, the corresponding conditions are changed to prepare different glass ceramics with strong versatility.
  • the present invention provides a polycrystalline core composite transparent glass ceramic, the crystal core includes at least two of ZrO2, TiO2, P2O5, rare earth elements, gold, silver, and fluoride; the crystal phase includes lithium disilicate and lithium permeable long Stone; the surface compressive stress of either side of the glass ceramic ranges from 400 MPa to 600 MPa, the depth range of the stress layer of the glass ceramic ranges from 10 um to 100 um, and the tensile stress linear density of the glass ceramic is greater than 30000Mpa/mm.
  • the crystal nucleus contains at least two of ZrO2, TiO2, P2O5, rare earth elements, gold, silver, and fluoride. At least two crystal nuclei exist.
  • the glass ceramic crystal phase is lithium disilicate and lapisite, which are different
  • the crystalline phases are intertwined to enhance its breaking strength, so that the breaking strength of the glass ceramic is more than twice that of a single crystal phase glass ceramic; the surface compressive stress of any side of the formed glass ceramic ranges from 400MPa to 400MPa. 600MPa, the tensile stress linear density is greater than 30000Mpa/mm, enhance the tensile strength and damage resistance of glass ceramics, and improve the service life of glass ceramics.
  • the fluorides in the crystal nucleus are NaF and CaF2
  • the rare earth elements in the crystal nucleus are La-based elements and Tm-based elements.
  • the crystal nucleus includes ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm.
  • the surface compressive stress of any surface of the glass ceramic ranges from 500 MPa to 600 MPa, and the tensile stress linear density of the glass ceramic ranges from 30000Mpa/mm to 44000Mpa/mm.
  • the depth of the stress layer ranges from 20um to 90um, the average crystal size of the glass-ceramic is 50nm-150nm, and the proportion of crystal mass is greater than or equal to 80%.
  • the average visible light transmittance of the glass-ceramic with a thickness of 1mm is 86% ⁇ 93%.
  • the average crystal size of glass ceramics is controlled at 50nm ⁇ 150nm, the crystal size is small, and the average visible light transmittance of the 1mm thick glass ceramic is 86% ⁇ 93%, and the visible light transmittance is higher than the existing ones.
  • the visible light transmittance of glass ceramics in technology makes glass ceramics have broad application prospects and improves their practicability.
  • the glass ceramic of the present invention has a variety of crystal nuclei, a large number of crystals, a small crystal size, and has higher mechanical properties than ordinary glass ceramics, especially in terms of damage resistance and fracture toughness, and improves the service life of the glass ceramics.
  • the invention also provides a method for preparing the polycrystalline core composite transparent glass ceramic, which includes the following steps:
  • S3 Put the plain glass obtained in S2 at a temperature of T1, and heat it for 1h ⁇ 6h for annealing treatment. After the annealing treatment is completed, place it at a temperature of T2 and heat it for 1h ⁇ 6h for nucleation treatment. After the chemical treatment is completed, it is placed under the condition of temperature T3 and heated for 0 to 3 hours for crystallization treatment to prepare glass ceramics; the temperature T1 ranges from 450°C to 550°C, and the temperature T2 ranges from 500°C to 500°C. 580°C, the temperature T3 ranges from 600°C to 800°C, and the T1 ⁇ T2.
  • the crystal nucleating agent added in the step S1 includes: ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm, and the content of the crystal nucleating agent added is: ZrO2: 1 mol% ⁇ 3mol%, TiO2: 0.5mol% ⁇ 1.5mol%, P2O5: 1mol% ⁇ 3mol%, NaF+CaF2: 0mol% ⁇ 4mol%, La+Tm: 0.1mol% ⁇ 1mol%.
  • the prepared glass ceramics contain various types of crystal nuclei, increasing the types of crystal nuclei, thereby reducing the nucleation and crystallization energy required for crystal precipitation, and lowering the heat treatment temperature and time.
  • the glass in the step S1 includes: SiO 2 : 65 mol% to 75 mol%, Al 2 O 3 : 6 mol% to 13 mol%, B 2 O 3 : 1 mol% to 3 mol%, MgO 2 : 0mol% ⁇ 7mol%, ZnO: 1mol% ⁇ 2mol%, K 2 O: 1mol% ⁇ 3mol%, Na 2 O: 1mol% ⁇ 7mol%, Li 2 O: 10mol% ⁇ 20mol%, CeO: 0.1mol% ⁇ 0.25 mol%, SnO 2 : 0.2 mol% to 0.3 mol%.
  • the present invention obtains glass for melting, and adds a variety of different crystal nucleating agents according to the needs of the actual production process.
  • the polycrystalline nucleus reduces the nucleation and crystallization energy required for crystal precipitation, reduces the heat treatment temperature and time, and adjusts the crystal
  • the ratio can effectively increase the number of crystal nuclei in the glass ceramic and reduce the crystal size, so that the damage resistance and fracture toughness of the glass ceramic are enhanced, thereby increasing the service life of the glass ceramic; on the other hand, due to the prepared glass ceramic inner crystal nucleus A large number and a variety of crystal nuclei can effectively reduce the crystallization energy of the crystal, which is conducive to the uniform distribution of the crystal phase in the glass ceramic, reduces the size of the crystal, improves the transmittance of visible light, and enhances the practicality of the glass ceramic; the above preparation method can also Extending to other glass preparation methods, according to the different components and requirements, the corresponding conditions are changed to prepare different glass ceramics with strong versatility.
  • the method for preparing a polycrystalline core composite transparent glass ceramics further includes step S4 after the step S3: placing the ceramic glass obtained in S3 in a glass containing at least one of sodium nitrate, potassium nitrate, sodium carbonate, and potassium carbonate At least one strengthening treatment is performed in the salt bath to prepare strengthened glass ceramics.
  • the salt bath for ion exchange in step S4 contains sodium nitrate, potassium nitrate, and sodium carbonate, and has undergone two strengthening treatments, and the temperature of the first strengthening treatment is 380 °C ⁇ 450°C, the strengthening time is 1h ⁇ 10h; the temperature of the second strengthening treatment is 380°C ⁇ 450°C, and the strengthening time is 10min ⁇ 240min.
  • the surface compressive stress of the strengthened glass ceramic in the present invention ranges from 400 MPa to 600 MPa, the depth of the stress layer ranges from 10 um to 100 um, and the tensile stress linear density is greater than 30,000 Mpa/mm.
  • Example 1 to Example 6 the preparation process conditions and related parameters of the preparation method of the polycrystalline core composite transparent glass ceramic contained in each example are as follows.
  • Example 1 The following takes Example 1 as an example for further analysis:
  • Step S1 According to the glass formula in Example 1, a crystal nucleating agent is added for melting to prepare glass.
  • Step S2 Obtain plain glass with a certain outer dimension from the glass obtained in S1, wherein the thickness D of the plain glass is 0.65 ⁇ m, and the Vickers hardness is 660 kgf/mm 2 .
  • Step S3 Place the obtained plain glass at a temperature of 473°C and heat it for 240 minutes for annealing treatment. After the annealing treatment, place the plain glass at a temperature of 523°C and heat it for 120 minutes for nucleation treatment. After the nucleation treatment is completed, it is further placed at a temperature of 620°C and heated for 60 minutes to prepare glass ceramics.
  • the Vickers hardness of the obtained glass ceramic is 785kgf/mm 2
  • the tensile stress linear density of the glass ceramic is 32528MPa/mm
  • the visible light transmittance is 92%
  • the crystal ratio in the glass ceramic is 72wt%
  • the average glass ceramic The crystal size is 35nm.
  • Step S4 in this embodiment, two strengthening treatments are performed on the glass ceramics.
  • the first strengthening treatment the prepared glass ceramics are placed with 90wt% NaNO 3 , 5wt% KNO 3 , 5wt% Na 2 CO
  • the first strengthening treatment process is carried out in the mixed salt bath of 3 , the strengthening temperature is 430°C, and the strengthening time is 4h;
  • the second strengthening treatment the glass ceramics that have undergone the first strengthening treatment process are placed in 5wt% NaNO 3 ,
  • the second strengthening treatment process is carried out in a mixed salt bath of 95wt% KNO 3 , the strengthening temperature is 440°C, and the strengthening time is 30 minutes.
  • the surface compressive stress of the strengthened glass ceramic is 468 MPa, the compressive stress depth is 89 ⁇ m, and the Vickers hardness is 789 kgf/mm 2 .
  • the glass in this embodiment is added with nucleating agents ZrO2, TiO2, P2O5, La+Tm during the melting process, so that ZrO2, TiO2, P2O5, La and Tm are formed in the obtained glass, and the polycrystalline nucleus reduces the crystallinity.
  • the nucleation and crystallization energy required for precipitation can reduce the heat treatment temperature and time, and adjust the ratio of crystals, which can effectively increase the number of crystal nuclei in glass ceramics.
  • a variety of crystal nuclei can effectively reduce the crystallization energy of crystals, which is beneficial to glass
  • the uniform distribution of the crystal phase in the ceramic reduces the crystal size.
  • the proportion of crystals in the prepared glass ceramic is 72wt%, and the average crystal size of the crystal is controlled at 35nm, which enhances the damage resistance and fracture toughness of the glass ceramic; due to the number of crystal nuclei
  • the glass ceramic has a small crystal size.
  • the visible light transmittance of glass ceramics is higher than 86% (92% in this embodiment), which improves the visible light transmittance.
  • the prepared glass ceramics can be applied to the cover plate of electronic products. Production to improve the practicability of glass ceramics.
  • step S1 according to the glass formula in Example 6, a crystal nucleating agent is added for melting, and glass is prepared.
  • Step S2 Obtain plain glass with a certain outer dimension from the glass obtained in S1, wherein the thickness D of the plain glass is 0.65 ⁇ m, and the Vickers hardness is 709 kgf/mm 2 .
  • Step S3 Place the obtained plain glass at a temperature of 547°C and heat it for 240 minutes for annealing treatment. After the annealing treatment, place the plain glass at a temperature of 580°C and heat it for 120 minutes for nucleation treatment. After the nucleation treatment is completed, it is further placed at a temperature of 620°C and heated for 60 minutes to prepare glass ceramics.
  • the Vickers hardness of the obtained glass ceramic is 823kgf/mm 2
  • the tensile stress linear density of the glass ceramic is 32528MPa/mm
  • the visible light transmittance is 87%
  • the crystal ratio in the glass ceramic is 59wt%
  • the average glass ceramic The crystal size is 67nm.
  • Step S4 in this embodiment, the glass ceramic is strengthened twice, the first strengthening treatment: the prepared glass ceramic is placed in a mixed salt bath containing 95wt% of NaNO 3 and 5wt% of KNO 3 for the second time.
  • the first strengthening treatment process the strengthening temperature is 430°C, and the strengthening time is 4h;
  • the second strengthening treatment the glass ceramics after the first strengthening treatment process are placed in a mixture of 5wt% NaNO 3 and 95wt% KNO 3
  • the second strengthening treatment process is carried out in the salt bath, the strengthening temperature is 440°C, and the strengthening time is 30 minutes.
  • the surface compressive stress of the strengthened glass ceramic is 584 MPa, the compressive stress depth is 63 ⁇ m, and the Vickers hardness is 823 kgf/mm 2 .
  • the glass in this embodiment is added with nucleating agents ZrO2, TiO2, P2O5, La+Tm during the melting process, so that ZrO2, TiO2, P2O5, La, Tm are formed in the obtained glass, and the polycrystalline nucleus reduces the crystallinity.
  • the nucleation and crystallization energy required for precipitation can reduce the heat treatment temperature and time, and adjust the ratio of crystals, which can effectively increase the number of crystal nuclei in glass ceramics.
  • a variety of crystal nuclei can effectively reduce the crystallization energy of crystals, which is beneficial to glass
  • the uniform distribution of the crystal phase in the ceramic reduces the crystal size.
  • the proportion of crystals in the prepared glass ceramic is 59wt%, and the average crystal size of the crystal is controlled at 67nm, which enhances the damage resistance and fracture toughness of the glass ceramic; due to the number of crystal nuclei
  • the crystal size is small, the visible light transmittance of glass ceramics is higher than 86% (87% in this embodiment), which improves the visible light transmittance, and the prepared glass ceramics can be applied to the cover plate of electronic products. Production to improve the practicability of glass ceramics.
  • Example 10 The following takes Example 10 as an example for further analysis:
  • Step S1 according to the glass formula in Example 10, a crystal nucleating agent is added for melting, and glass is prepared.
  • Step S2 Obtain plain glass with a certain outer dimension from the glass obtained in S1, wherein the thickness D of the plain glass is 0.65 ⁇ m, and the Vickers hardness is 708 kgf/mm 2 .
  • Step S3 Place the obtained plain glass at a temperature of 550°C and heat it for 240 minutes for annealing treatment. After the annealing treatment, place the plain glass at a temperature of 580°C and heat it for 240 minutes for nucleation treatment. After the nucleation treatment is completed, it is further placed at a temperature of 620°C and heated for 120 minutes to prepare glass ceramics.
  • the Vickers hardness of the obtained glass ceramic is 756kgf/mm 2
  • the tensile stress linear density of the glass ceramic is 34926MPa/mm
  • the visible light transmittance is 88%
  • the crystal ratio in the glass ceramic is 60wt%.
  • the crystal size is 65nm.
  • Step S4 in this embodiment, the glass ceramic is strengthened twice, the first strengthening treatment: the prepared glass ceramic is placed with 90wt% of NaNO 3 , 5wt% of KNO 3 and 5wt% of Na 2 CO The first strengthening treatment process is carried out in the mixed salt bath of 3 , the strengthening temperature is 430°C, and the strengthening time is 4h; the second strengthening treatment: the glass ceramics that have undergone the first strengthening treatment process are placed in 5wt% NaNO 3 , The second strengthening treatment process is carried out in a mixed salt bath of 95wt% KNO 3 , the strengthening temperature is 440°C, and the strengthening time is 30 minutes.
  • the surface compressive stress of the strengthened glass ceramic is 524 MPa, the compressive stress depth is 69 ⁇ m, and the Vickers hardness is 756 kgf/mm 2 .
  • the glass in this embodiment is added with nucleating agents ZrO2, TiO2, P2O5, La+Tm during the melting process, so that ZrO2, TiO2, P2O5, La, Tm are formed in the obtained glass, and the polycrystalline nucleus reduces the crystal
  • the nucleation and crystallization energy required for precipitation can reduce the heat treatment temperature and time, and adjust the ratio of crystals, which can effectively increase the number of crystal nuclei in glass ceramics.
  • a variety of crystal nuclei can effectively reduce the crystallization energy of crystals, which is beneficial to glass
  • the uniform distribution of the crystal phase in the ceramic reduces the crystal size.
  • the proportion of crystals in the prepared glass ceramic is 60wt%, and the average crystal size of the crystal is controlled at 65nm, which enhances the damage resistance and fracture toughness of the glass ceramic; due to the number of crystal nuclei The crystal size is small.
  • the visible light transmittance of glass ceramics is higher than 86% (88% in this embodiment), which improves the visible light transmittance.
  • the prepared glass ceramics can be applied to the cover plate of electronic products. Production to improve the practicability of glass ceramics.
  • the present invention provides a polycrystalline core composite transparent glass ceramic and a preparation method thereof, by adding at least two of the crystal nucleating agents ZrO2, TiO2, P2O5, NaF+CaF2, La+Tm during the glass melting process Therefore, there are multiple types of crystal nuclei in the glass, and they are respectively placed under the conditions of T1, T2, and T3, and then subjected to annealing treatment, nucleation treatment, and crystallization treatment respectively to prepare a variety of crystal nuclei and crystal nuclei.
  • the number of nuclei is large, and the crystal phase is glass-ceramic with lithium disilicate and lithium feldspar.
  • the polycrystalline nucleus formed reduces the nucleation and crystallization energy required for crystal precipitation, reduces the heat treatment temperature and time, and adjusts the crystal
  • the ratio and small crystal size enhance the damage resistance and fracture toughness of glass ceramics.
  • the two crystal phases of lithium disilicate and lapisite are interwoven to enhance the destructive strength, thereby increasing the service life of glass ceramics; Due to the large number of crystal nuclei in the prepared glass ceramic, a variety of crystal nuclei can effectively reduce the crystallization energy of the crystal, which is conducive to the uniform distribution of the crystal phase in the glass ceramic, reduces the size of the crystal, improves the transmittance of visible light, and strengthens the glass Practicality of ceramics.

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Abstract

本发明公开一种多晶核复合透明玻璃陶瓷及其制备方法，所述的多晶核复合透明玻璃陶瓷的制备方法包括以下步骤：在玻璃熔制时加入多种晶核剂，加工后获取具有一定外形尺寸的素玻璃；将S2中所得的素玻璃置于温度为T1的条件下，加热1h～6h进行退火处理，退火处理完成后置于温度为T2的条件下，加热1h～6h，做核化处理，核化处理完成后置于温度为T3的条件下，加热0～3h进行晶化处理，且所述T1<T2。本发明制备出含有多种晶核，晶相为二硅酸锂和透锂长石的玻璃陶瓷，多晶核降低了晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，通过该制备方法制备出的玻璃陶瓷耐损坏性增强，断裂韧度好，应用范围广。

Description

一种多晶核复合透明玻璃陶瓷及其制备方法 技术领域
本发明涉及玻璃生产制造技术领域，尤其涉及一种多晶核复合透明玻璃陶瓷及其制备方法。
背景技术
玻璃陶瓷是经过高温融化、成型、热处理而制成的一类晶相与玻璃相结合的复合材料，一般是通过在玻璃原料中添加晶核剂，并在热处理过程中进行控制成核和析晶，以获得含有大量微晶体的整体析晶。相比玻璃，玻璃陶瓷因为具有均匀的、一般小于10μm的晶体，它比普通玻璃的强度高出一个数量级，因此而被广泛用于用于智能手机、平板电脑等大面积触屏电子产品中。
目前，市面上玻璃陶瓷产品是基于在玻璃熔制前加入一定量的单一种类的晶核剂，如加入TiO 2或ZrO 2或P2O5等，晶核剂在熔制过程中先溶解在玻璃中，热处理过程中通过分相或直接析出晶核，并晶化，从而制备出高强度玻璃陶瓷。
已知的玻璃陶瓷材料，由于制备过程中只加入了单一种类的晶核剂，晶相单一，导致玻璃陶瓷的结构强度有限；同时由于陶瓷玻璃所具有的晶核数量较少，析出晶体的比例有限，常常呈现固有的脆性，抗拉强度较低，导致玻璃陶瓷材料耐损坏性和断裂韧度较差，且晶核数量少易导致晶体较大(大于100nm)，影响玻璃陶瓷的可见光透过率，从而限制了玻璃陶瓷的应用范围，降低其实用性，例如，现有的玻璃陶瓷可见光透过率低于85％，均不能用于电子产品的显示盖板。因此，急需对玻璃陶瓷材料的脆性、抗拉强度进行改进，以提高玻璃陶瓷的耐损坏性和断裂韧度及抗拉强度；另一方面，需要降低晶体的尺寸，提高可见光的透过率，从而提高玻璃陶瓷 的实用性。
因此，现有技术存在缺陷，需要改进。
发明内容
本发明的目的是克服现有技术的不足，提供一种多晶核复合透明玻璃陶瓷及其制备方法，所述玻璃陶瓷含有多种晶核，且晶核数量多，晶体尺寸小，玻璃陶瓷的耐损坏性、断裂韧度强；同时所述玻璃陶瓷的可见光的透过率大于85％，可应用与电子产品盖板等领域，实用性强；所述玻璃陶瓷晶相为二硅酸锂和透锂长石，不同晶相相互交织，增强其抗破坏强度，使得所述玻璃陶瓷的抗破坏强度为单一晶相玻璃陶瓷的抗破坏强度的一倍以上。
本发明的技术方案如下：一种多晶核复合透明玻璃陶瓷，所述晶核包括ZrO2、TiO2、P2O5、稀土元素、金、银、氟化物中的至少两种；晶相包括二硅酸锂和透锂长石；所述玻璃陶瓷任一面的表面压应力范围为400MPa～600MPa，所述玻璃陶瓷的应力层深度范围为10um～100um，所述玻璃陶瓷的张应力线密度大于30000Mpa/mm。
进一步地，所述晶核中的所述氟化物为NaF和/或CaF2；所述晶核中的所述稀土元素为La系元素和/或Tm系元素。
进一步地，所述晶核包括ZrO2、TiO2、P2O5、稀土元素、金、银、氟化物中的至少三种。
进一步地，所述玻璃陶瓷任一面的表面压应力范围为500MPa～600MPa，所述玻璃陶瓷的应力层深度范围为20um～90um。
进一步地，所述玻璃陶瓷的平均晶体尺寸为50nm～150nm，晶体质量占比大于或等于80％，此时1mm厚的所述玻璃陶瓷的可见光平均透过率为86％～93％。玻璃陶瓷的平均晶体尺寸控制在50nm～150nm，晶体尺寸较小，且1mm厚的所述玻璃陶瓷的可见光平均透过率为86％～93％，可见光的透过率高于现有技术中的玻璃陶瓷的可见光透过率，使得玻璃陶瓷的应用范 围更广，提高其实用性。
进一步地，所述玻璃陶瓷的张应力线密度的范围为30000Mpa/mm～44000Mpa/mm。
本发明还提供一种多晶核复合透明玻璃陶瓷的制备方法，包括以下步骤：
S1：熔制玻璃时，并加入晶核剂，制备出玻璃。
S2：从S1中所得的所述玻璃中，获取具有一定外形尺寸素玻璃。
S3：将S2中所得的素玻璃置于温度为T1的条件下，加热1h～6h进行退火处理，退火处理完成后置于温度为T2的条件下，加热1h～6h，做核化处理，核化处理完成后置于温度为T3的条件下，加热0～3h进行晶化处理，制备出玻璃陶瓷；所述温度T1的范围为450℃～550℃，所述温度T2的范围为500℃～580℃，所述温度T3的范围为600℃～800℃，且所述T1<T2。
进一步地，所述步骤S1中加入的晶核剂包括：ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm中的至少两种，且所加入晶核剂的含量分别为：ZrO2:1mol％～3mol％、TiO2：0.5mol％～1.5mol％、P2O5：1mol％～3mol％、NaF+CaF2：0mol％～4mol％、La+Tm：0.1mol％～1mol％。在玻璃的熔制过程中加入ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm中的至少两种晶核剂，制备出的玻璃陶瓷中含有多种类型的晶核，增加晶核种类，从而降低晶体析出所需的核化和晶化能，降低热处理温度和时间。
进一步地，所述步骤S1中所述玻璃包含：SiO 2：65mol％～75mol％、Al 2O 3：6mol％～13mol％、B 2O 3：1mol％～3mol％、MgO 2：0mol％～7mol％、ZnO：1mol％～2mol％、K 2O：1mol％～3mol％、Na 2O：1mol％～7mol％、Li 2O：10mol％～20mol％、CeO：0.1mol％～0.25mol％、SnO 2：0.2mol％～0.3mol％。
进一步地，所述步骤S3中，所述温度T1的范围为500℃～550℃，所述温度T2的范围为560℃～580℃，所述温度T3的范围为700℃～800℃，且 所述T1<T2。
进一步地，制备一种多晶核复合透明玻璃陶瓷的方法中在所述步骤S3之后还包括步骤S4：将S3中所得的陶瓷玻璃置于包含硝酸钠、硝酸钾、碳酸钠、碳酸钾中至少一种的盐浴中进行至少一次强化处理，从而制备出强化的玻璃陶瓷。
进一步地，所述盐浴中含有硝酸钠、硝酸钾、碳酸钠、碳酸钾中的至少两种。
进一步地，所述步骤S4中进行了两次强化处理，第一次强化处理的温度为380℃～450℃，强化时间为1h～10h；第二次强化处理的温度为380℃～450℃，强化时间为10min～240min。
采用上述方案，本发明提供一种多晶核复合透明玻璃陶瓷及其制备方法，通过在玻璃熔制过程中加入晶核剂ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm中的至少两种，使得玻璃中有多种类型的晶核，并分别置于温度为T1、T2、T3条件下，分别进行退火处理、核化处理、晶化处理，制备出含有多种晶核，且晶核数量多，晶相为二硅酸锂和透锂长石的玻璃陶瓷，形成的多晶核降低了晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，晶体尺寸小，使得玻璃陶瓷的耐损坏性、断裂韧度增强，同时由二硅酸锂和透锂长石两种晶相相互交织，增强抗破坏强度，从而提高玻璃陶瓷的使用寿命；由于制备出的玻璃陶瓷内晶核数量多，多种晶核能够有效降低晶体的晶化能，有利于玻璃陶瓷内晶体相的均匀分布，降低晶体的尺寸，提高可见光的透过率，增强玻璃陶瓷实用性；上述制备方法还可以延伸至其它玻璃的制备方法中，根据组分的不同，需求的差异，改变相应条件，从而制备出不同的玻璃陶瓷，通用性强。
具体实施方式
以下结合具体实施例，对本发明进行详细说明。
本发明提供一种多晶核复合透明玻璃陶瓷，所述晶核包括ZrO2、TiO2、 P2O5、稀土元素、金、银、氟化物中的至少两种；晶相包括二硅酸锂和透锂长石；所述玻璃陶瓷任一面的表面压应力范围为400MPa～600MPa，所述玻璃陶瓷的应力层深度范围为10um～100um，所述玻璃陶瓷的张应力线密度大于30000Mpa/mm。晶核中包含ZrO2、TiO2、P2O5、稀土元素、金、银、氟化物中的至少两种，至少存在两种晶核，同时由于玻璃陶瓷晶相为二硅酸锂和透锂长石，不同晶相相互交织，增强其抗破坏强度，使得所述玻璃陶瓷的抗破坏强度为单一晶相玻璃陶瓷的抗破坏强度的一倍以上；所形成的玻璃陶瓷任一面的表面压应力范围为400MPa～600MPa，张应力线密度大于30000Mpa/mm，增强玻璃陶瓷的抗拉强度、耐损坏性，提高玻璃陶瓷的使用寿命。具体地，本发明实施例中，所述晶核中的所述氟化物为NaF和CaF2，所述晶核中的所述稀土元素为La系元素和Tm系元素。优选地，所述晶核包括ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm。具体地，本发明实施例中，所述玻璃陶瓷任一面的表面压应力范围为500MPa～600MPa，所述玻璃陶瓷的张应力线密度的范围为30000Mpa/mm～44000Mpa/mm，所述玻璃陶瓷的应力层深度范围为20um～90um，所述玻璃陶瓷的平均晶体尺寸为50nm～150nm，晶体质量占比大于或等于80％，此时1mm厚的所述玻璃陶瓷的可见光平均透过率为86％～93％。本发明将玻璃陶瓷的平均晶体尺寸控制在50nm～150nm，晶体尺寸较小，且1mm厚的所述玻璃陶瓷的可见光平均透过率为86％～93％，可见光的透过率高于现有技术中的玻璃陶瓷的可见光透过率，使得玻璃陶瓷具有广阔的应用前景，提高其实用性。本发明的玻璃陶瓷具有多种晶核，晶体数量多，晶体尺寸小，相对普通玻璃陶瓷具有更高的机械性能，尤其是在耐损坏性、断裂韧度强，提高玻璃陶瓷的使用寿命。
本发明还提供一种多晶核复合透明玻璃陶瓷的制备方法，包括以下步骤：
S1：熔制玻璃时，并加入晶核剂，制备出玻璃；
S2：从S1中所得的所述玻璃中，获取具有一定外形尺寸素玻璃；
S3：将S2中所得的素玻璃置于温度为T1的条件下，加热1h～6h进行退火处理，退火处理完成后置于温度为T2的条件下，加热1h～6h，做核化处理，核化处理完成后置于温度为T3的条件下，加热0～3h进行晶化处理，制备出玻璃陶瓷；所述温度T1的范围为450℃～550℃，所述温度T2的范围为500℃～580℃，所述温度T3的范围为600℃～800℃，且所述T1<T2。
具体地，本发明实施例中，所述步骤S1中加入的晶核剂包括：ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm，且所加入晶核剂的含量分别为：ZrO2:1mol％～3mol％、TiO2：0.5mol％～1.5mol％、P2O5：1mol％～3mol％、NaF+CaF2：0mol％～4mol％、La+Tm：0.1mol％～1mol％。在玻璃的熔制过程中加入多种晶核剂，制备出的玻璃陶瓷中含有多种类型的晶核，增加晶核种类，从而降低晶体析出所需的核化和晶化能，降低热处理温度和时间。本发明实施例中，所述步骤S1中所述玻璃包含：SiO 2：65mol％～75mol％、Al 2O 3：6mol％～13mol％、B 2O 3：1mol％～3mol％、MgO 2：0mol％～7mol％、ZnO：1mol％～2mol％、K 2O：1mol％～3mol％、Na 2O：1mol％～7mol％、Li 2O：10mol％～20mol％、CeO：0.1mol％～0.25mol％、SnO 2：0.2mol％～0.3mol％。本发明获取玻璃进行熔制，并根据实际生产过程的需要，加入多种不同的晶核剂，经过该处理后，使得所得的玻璃中有多种晶核，获取具有一定外形尺寸的上述玻璃后，置于温度为T1条件下进行退火，完成退火处理后，将该玻璃置于T2条件下进行核化处理，经过核化处理后进一步将该玻璃置于T3条件下进行晶化处理，制备出含有多种晶核、晶相为二硅酸锂和透锂长石的玻璃陶瓷，多晶核降低了晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，可有效增加玻璃陶瓷内晶核数量，降低晶体尺寸，使得玻璃陶瓷的耐损坏性、断裂韧度增强，从而提高玻璃陶瓷的使用寿命；另一方面，由于制备出的玻璃陶瓷内晶核数量多，多种晶核能够有效降低晶体的晶化能，有利于玻璃陶瓷内晶体相 的均匀分布，降低晶体的尺寸，提高可见光的透过率，增强玻璃陶瓷实用性；上述制备方法还可以延伸至其它玻璃的制备方法中，根据组分的不同，需求的差异，改变相应条件，从而制备出不同的玻璃陶瓷，通用性强。
制备一种多晶核复合透明玻璃陶瓷的方法中在所述步骤S3之后还包括步骤S4：将S3中所得的陶瓷玻璃置于包含硝酸钠、硝酸钾、碳酸钠、碳酸钾中至少一种的盐浴中进行至少一次强化处理，从而制备出强化的玻璃陶瓷。具体地，本发明实施例中，所述步骤S4中进行离子交换的所述盐浴中含有硝酸钠、硝酸钾、碳酸钠，并进行了两次强化处理，第一次强化处理的温度为380℃～450℃，强化时间为1h～10h；第二次强化处理的温度为380℃～450℃，强化时间为10min～240min。具体地，本发明中强化后的所述玻璃陶瓷的表面压应力范围为400MPa～600MPa，应力层深度范围为10um～100um，张应力线密度大于30000Mpa/mm。
下面列举具体实施例对本发明提供的制备方法做进一步更详细的说明，但并不以任何方式限定发明的保护范围。
实施例1至实施例6中制备一种多晶核复合透明玻璃陶瓷的方法的步骤1中的所述玻璃及加入晶核剂的配方如下表：
Figure PCTCN2020137725-appb-000001
Figure PCTCN2020137725-appb-000002
实施例1至实施例6中，各个实施例含有的多晶核复合透明玻璃陶瓷的制备方法的制备工艺条件及相关参数如下表。
Figure PCTCN2020137725-appb-000003
Figure PCTCN2020137725-appb-000004
Figure PCTCN2020137725-appb-000005
实施例1至实施例6中玻璃、玻璃陶瓷及强化后的玻璃陶瓷的特性对比如下表。
Figure PCTCN2020137725-appb-000006
Figure PCTCN2020137725-appb-000007
以下以实施例1为例作进一步分析：
步骤S1，根据实施例1中的玻璃配方，添加晶核剂进行熔制，制备出玻璃。
步骤S2，从S1中所得的玻璃中获取具有一定外形尺寸的素玻璃，其中，所述素玻璃的厚度D为0.65μm，维氏硬度为660kgf/mm 2。
步骤S3，将获取的素玻璃置于温度为473℃条件下，加热240min进行退火处理，进行退火处理后，将所述素玻璃置于温度为523℃条件下，加热120min，进行核化处理，完成核化处理后，进一步置于温度为620℃条件下，加热60min，制备出玻璃陶瓷。所得到的玻璃陶瓷的维氏硬度为785kgf/mm 2，玻璃陶瓷的张应力线密度为32528MPa/mm，可见光的透过率为92％，玻璃陶瓷中的晶体比例为72wt％，玻璃陶瓷中平均晶体尺寸为35nm。
步骤S4，在本实施例中对玻璃陶瓷进行两次强化处理，第一次强化处理：将制得的玻璃陶瓷置于含有90wt％的NaNO 3、5wt％的KNO 3、5wt％的Na 2CO 3的混合盐浴中进行第一次强化处理工艺，强化温度为430℃，强化时间为4h；第二次强化处理：将经过第一次强化处理工艺的玻璃陶瓷置于含有5wt％的NaNO 3、95wt％的KNO 3的混合盐浴中进行第二次强化处理工艺，强化温度为440℃，强化时间为30min。强化后的玻璃陶瓷的表面压应力为468MPa，压应力深度89μm，维氏硬度为789kgf/mm 2。
本实施例中的玻璃在熔制过程中加入了晶核剂ZrO2、TiO2、P2O5、La+Tm，使得所得玻璃中形成ZrO2、TiO2、P2O5、La、Tm多种晶核，多晶核降低晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，可有效增加玻璃陶瓷内晶核数量，多种晶核能够有效降低晶体的晶化能，有利于玻璃陶瓷内晶体相的均匀分布，降低晶体尺寸，所制备出的玻璃陶瓷中的晶体比例为72wt％，晶体平均晶体尺寸控制在35nm，增强玻璃陶瓷的耐损坏性、断裂韧度；由于晶核数量多，晶体尺寸 小，玻璃陶瓷的可见光透过率高于86％(本实施例中为92％)，提高了可见光的透过率，可将制备所得的玻璃陶瓷应用于电子产品的盖板的生产，提高玻璃陶瓷的实用性。
以下以实施例6为例作进一步分析：
步骤S1，根据实施例6中的玻璃配方，添加晶核剂进行熔制，制备出玻璃。
步骤S2，从S1中所得的玻璃中获取具有一定外形尺寸的素玻璃，其中，所述素玻璃的厚度D为0.65μm，维氏硬度为709kgf/mm 2。
步骤S3，将获取的素玻璃置于温度为547℃条件下，加热240min进行退火处理，进行退火处理后，将所述素玻璃置于温度为580℃条件下，加热120min，进行核化处理，完成核化处理后，进一步置于温度为620℃条件下，加热60min，制备出玻璃陶瓷。所得到的玻璃陶瓷的维氏硬度为823kgf/mm 2，玻璃陶瓷的张应力线密度为32528MPa/mm，可见光的透过率为87％，玻璃陶瓷中的晶体比例为59wt％，玻璃陶瓷中平均晶体尺寸为67nm。
步骤S4，在本实施例中对玻璃陶瓷进行两次强化处理，第一次强化处理：将制得的玻璃陶瓷置于含有95wt％的NaNO 3、5wt％的KNO 3的混合盐浴中进行第一次强化处理工艺，强化温度为430℃，强化时间为4h；第二次强化处理：将经过第一次强化处理工艺的玻璃陶瓷置于含有5wt％的NaNO 3、95wt％的KNO 3的混合盐浴中进行第二次强化处理工艺，强化温度为440℃，强化时间为30min。强化后的玻璃陶瓷的表面压应力为584MPa，压应力深度63μm，维氏硬度为823kgf/mm 2。
本实施例中的玻璃在熔制过程中加入了晶核剂ZrO2、TiO2、P2O5、La+Tm，使得所得玻璃中形成ZrO2、TiO2、P2O5、La、Tm多种晶核，多晶核降低晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，可有效增加玻璃陶瓷内晶核数量，多种晶核能够有效 降低晶体的晶化能，有利于玻璃陶瓷内晶体相的均匀分布，降低晶体尺寸，所制备出的玻璃陶瓷中的晶体比例为59wt％，晶体平均晶体尺寸控制在67nm，增强玻璃陶瓷的耐损坏性、断裂韧度；由于晶核数量多，晶体尺寸小，玻璃陶瓷的可见光透过率高于86％(本实施例中为87％)，提高了可见光的透过率，可将制备所得的玻璃陶瓷应用于电子产品的盖板的生产，提高玻璃陶瓷的实用性。
以下以实施例10为例作进一步分析：
步骤S1，根据实施例10中的玻璃配方，添加晶核剂进行熔制，制备出玻璃。
步骤S2，从S1中所得的玻璃中获取具有一定外形尺寸的素玻璃，其中，所述素玻璃的厚度D为0.65μm，维氏硬度为708kgf/mm 2。
步骤S3，将获取的素玻璃置于温度为550℃条件下，加热240min进行退火处理，进行退火处理后，将所述素玻璃置于温度为580℃条件下，加热240min，进行核化处理，完成核化处理后，进一步置于温度为620℃条件下，加热120min，制备出玻璃陶瓷。所得到的玻璃陶瓷的维氏硬度为756kgf/mm 2，玻璃陶瓷的张应力线密度为34926MPa/mm，可见光的透过率为88％，玻璃陶瓷中的晶体比例为60wt％，玻璃陶瓷中平均晶体尺寸为65nm。
步骤S4，在本实施例中对玻璃陶瓷进行两次强化处理，第一次强化处理：将制得的玻璃陶瓷置于含有90wt％的NaNO 3、5wt％的KNO 3和5wt％的Na 2CO 3的混合盐浴中进行第一次强化处理工艺，强化温度为430℃，强化时间为4h；第二次强化处理：将经过第一次强化处理工艺的玻璃陶瓷置于含有5wt％的NaNO 3、95wt％的KNO 3的混合盐浴中进行第二次强化处理工艺，强化温度为440℃，强化时间为30min。强化后的玻璃陶瓷的表面压应力为524MPa，压应力深度69μm，维氏硬度为756kgf/mm 2。
本实施例中的玻璃在熔制过程中加入了晶核剂ZrO2、TiO2、P2O5、 La+Tm，使得所得玻璃中形成ZrO2、TiO2、P2O5、La、Tm多种晶核，多晶核降低晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，可有效增加玻璃陶瓷内晶核数量，多种晶核能够有效降低晶体的晶化能，有利于玻璃陶瓷内晶体相的均匀分布，降低晶体尺寸，所制备出的玻璃陶瓷中的晶体比例为60wt％，晶体平均晶体尺寸控制在65nm，增强玻璃陶瓷的耐损坏性、断裂韧度；由于晶核数量多，晶体尺寸小，玻璃陶瓷的可见光透过率高于86％(本实施例中为88％)，提高了可见光的透过率，可将制备所得的玻璃陶瓷应用于电子产品的盖板的生产，提高玻璃陶瓷的实用性。
综上所述，本发明提供一种多晶核复合透明玻璃陶瓷及其制备方法，通过在玻璃熔制过程中加入晶核剂ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm中的至少两种，使得玻璃中有多种类型的晶核，并分别置于温度为T1、T2、T3条件下，分别进行退火处理、核化处理、晶化处理，制备出含有多种晶核，且晶核数量多，晶相为二硅酸锂和透锂长石的玻璃陶瓷，形成的多晶核降低了晶体析出所需的核化和晶化能，能够降低热处理温度和时间，并且调整晶体的比例，晶体尺寸小，使得玻璃陶瓷的耐损坏性、断裂韧度增强，同时由二硅酸锂和透锂长石两种晶相相互交织，增强抗破坏强度，从而提高玻璃陶瓷的使用寿命；由于制备出的玻璃陶瓷内晶核数量多，多种晶核能够有效降低晶体的晶化能，有利于玻璃陶瓷内晶体相的均匀分布，降低晶体的尺寸，提高可见光的透过率，增强玻璃陶瓷实用性。
以上仅为本发明的较佳实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种多晶核复合透明玻璃陶瓷，其特征在于，所述晶核包括ZrO2、TiO2、P2O5、稀土元素、金、银、氟化物中的至少两种；晶相包括二硅酸锂和透锂长石；所述玻璃陶瓷任一面的表面压应力范围为400MPa～600MPa，所述玻璃陶瓷的应力层深度范围为10um～100um，所述玻璃陶瓷的张应力线密度大于30000Mpa/mm。
  2. 根据权利要求1所述的一种多晶核复合透明玻璃陶瓷，其特征在于，所述晶核中的所述氟化物为NaF和/或CaF2；所述晶核中的所述稀土元素为La系元素和/或Tm系元素。
  3. 根据权利要求1所述的一种多晶核复合透明玻璃陶瓷，其特征在于，所述晶核包括ZrO2、TiO2、P2O5、稀土元素、金、银、氟化物中的至少三种。
  4. 根据权利要求1所述的一种多晶核复合透明玻璃陶瓷，其特征在于，所述玻璃陶瓷任一面的表面压应力范围为500MPa～600MPa，所述玻璃陶瓷的应力层深度范围为20um～90um。
  5. 根据权利要求1所述的一种多晶核复合透明玻璃陶瓷，其特征在于，所述玻璃陶瓷的平均晶体尺寸为50nm～150nm，晶体质量占比大于或等于80％，此时1mm厚的所述玻璃陶瓷的可见光平均透过率为86％～93％。
  6. 根据权利要求1所述的一种多晶核复合透明玻璃陶瓷，其特征在于，所述玻璃陶瓷的张应力线密度的范围为30000Mpa/mm～44000Mpa/mm。
  7. 一种制备如权利要求1-6所述的多晶核复合透明玻璃陶瓷的方法， 其特征在于，包括以下步骤：
    S1：熔制玻璃时，加入晶核剂，制备出玻璃；
    S2：从S1中所得的所述玻璃中，获取具有一定外形尺寸素玻璃；
    S3：将S2中所得的素玻璃置于温度为T1的条件下，加热1h～6h进行退火处理，退火处理完成后置于温度为T2的条件下，加热1h～6h，做核化处理，核化处理完成后置于温度为T3的条件下，加热0～3h进行晶化处理，制备出玻璃陶瓷；
    所述温度T1的范围为450℃～550℃，所述温度T2的范围为500℃～580℃，所述温度T3的范围为600℃～800℃，且所述T1<T2。
  8. 根据权利要求7所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述步骤S1中加入的晶核剂包括：ZrO2、TiO2、P2O5、NaF+CaF2、La+Tm中的至少两种，且所加入晶核剂的含量分别为：ZrO2:1mol％～3mol％、TiO2：0.5mol％～1.5mol％、P2O5：1mol％～3mol％、NaF+CaF2：0mol％～4mol％、La+Tm：0.1mol％～1mol％。
  9. 根据权利要求7所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述步骤S1中所述玻璃包含：SiO 2：65mol％～75mol％、Al 2O 3：6mol％～13mol％、B 2O 3：1mol％～3mol％、MgO 2：0mol％～7mol％、ZnO：1mol％～2mol％、K 2O：1mol％～3mol％、Na 2O：1mol％～7mol％、Li 2O：10mol％～20mol％、CeO：0.1mol％～0.25mol％、SnO 2：0.2mol％～0.3mol％。
  10. 根据权利要求7所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述步骤S3中，所述温度T1的范围为500℃～550℃，所述温度T2的范围为560℃～580℃，所述温度T3的范围为700℃～800℃， 且所述T1<T2。
  11. 根据权利要求7所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述步骤S3之后还包括：
    S4：将S3中所得的陶瓷玻璃置于包含硝酸钠、硝酸钾、碳酸钠、碳酸钾中至少一种的盐浴中进行至少一次强化处理，从而制备出强化的玻璃陶瓷。
  12. 根据权利要求11所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述盐浴中含有硝酸钠、硝酸钾、碳酸钠、碳酸钾中的至少两种。
  13. 根据权利要求11所述的一种多晶核复合透明玻璃陶瓷的制备方法，其特征在于，所述步骤S4中进行了两次强化处理，第一强化处理的温度为380℃～450℃，强化时间为1h～10h；第二次强化处理的温度为380℃～450℃，强化时间为10min～240min。
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