WO2023125005A1 - Glass product processing method and glass ceramic mold - Google Patents
Glass product processing method and glass ceramic mold Download PDFInfo
- Publication number
- WO2023125005A1 WO2023125005A1 PCT/CN2022/138936 CN2022138936W WO2023125005A1 WO 2023125005 A1 WO2023125005 A1 WO 2023125005A1 CN 2022138936 W CN2022138936 W CN 2022138936W WO 2023125005 A1 WO2023125005 A1 WO 2023125005A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- weight
- mold
- thermal expansion
- hot bending
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 183
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 93
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- 238000013003 hot bending Methods 0.000 claims abstract description 115
- 239000013078 crystal Substances 0.000 claims description 30
- 229910000500 β-quartz Inorganic materials 0.000 claims description 30
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052644 β-spodumene Inorganic materials 0.000 claims description 17
- 229910000174 eucryptite Inorganic materials 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 13
- 229910020068 MgAl Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 87
- 238000002425 crystallisation Methods 0.000 description 33
- 230000008025 crystallization Effects 0.000 description 33
- 238000000034 method Methods 0.000 description 32
- 238000000137 annealing Methods 0.000 description 28
- 230000008569 process Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 238000010899 nucleation Methods 0.000 description 12
- 230000006911 nucleation Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000006121 base glass Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007507 annealing of glass Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/0066—Re-forming shaped glass by bending
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
-
- 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
-
- 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
- C03C10/0045—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 containing SiO2, Al2O3 and MgO as main constituents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Definitions
- the present application relates to the technical field of molding and processing mold preparation, in particular to a glass product processing method and a glass ceramic mold.
- Hot bending glass is a curved glass made of flat glass or glass-ceramic glass products heated and softened in a mold, and then annealed.
- the glass needs to transfer heat and force from the mold without affecting the precision and characteristics of the glass. Therefore, the material of the mold needs to have the characteristics of easy processing, high thermal conductivity, high temperature resistance, low expansion, high softening point and high thermal shock resistance.
- the application discloses a glass product processing method, which controls the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product,
- the average roughness of the glass product after hot bending is higher than that before hot bending 12% to 40%.
- the average The roughness is increased by 15% to 30% compared with that before hot bending.
- the average The roughness is increased by 70% to 95% compared with that before hot bending.
- the present application also discloses a glass ceramic mold used in the glass product processing method, the main crystal phase of the glass ceramic mold includes MgAl 2 Si 3 O 10 , MgAl 2 O 4 , ZnAl One or more of 2 O 4 , mullite, ⁇ -quartz, ⁇ -quartz solid solution, ⁇ -spodumene, ⁇ -eucryptite and cordierite.
- the thermal expansion coefficient of the glass-ceramic mold is greater than -1.0 ⁇ 10 -6 /K and less than or equal to 3.0 ⁇ 10 -5 /K in the temperature range of 25-1000°C.
- the components include Li 2 O, in the range of 0.50-10% by mass fraction, the mass of the ⁇ -quartz, the ⁇ -spodumene and the ⁇ -natcryptite Scores range from 0.1% to 70.0%.
- the components also include Na 2 O and K 2 O, and the mass ratio of Na 2 O, K 2 O and Li 2 O is required as follows: (Na 2 O+K 2 O)/Li 2 O ⁇ 1.00, and the total mass fraction of Na 2 O and K 2 O is ⁇ 8.00%.
- the following raw materials are included in parts by weight: SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts Na 2 O: 0.00-2.00 parts; B 2 O 3 : 0.00-5.00 parts; K 2 O: 0.00-5.00 parts; MgO: 0.00-20.00 parts; CaO: 0.00-5.00 parts; P 2 O 5 : 0.00 ⁇ 5.00 parts; TiO 2 : 0.00 ⁇ 5.00 parts; BaO: 0.00 ⁇ 2.00 parts; ZnO: 0.00 ⁇ 10.00 parts.
- the glass transition temperature of the glass ceramic mold is greater than or equal to 700°C.
- the thermal conductivity of the glass-ceramic mold is greater than or equal to 1 W/(m ⁇ k) within the temperature range of 25-1000°C.
- This application provides a specific processing control parameter relationship to match glass products with different thermal expansion coefficients, and can obtain hot-bent glass products with different roughness improvement effects, reduce the surface roughness of glass products after hot bending, and improve It ensures the dimensional stability of glass products after hot bending.
- the application provides a processing method for glass products:
- the average roughness of the glass product after hot bending is higher than that before hot bending 12% to 40%.
- the glass product to be bent when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.3 and 0.7, the glass product to be bent The average roughness is 15%-30% higher than that before hot bending.
- the average value of the glass product after hot bending is increased by 70% to 95% compared with that before hot bending.
- the glass product is the blank to be hot-bent, and its material is glass or glass ceramics, and its coefficient of thermal expansion has a large range.
- the roughness of the glass product is greatly increased, so the hot bending mold is required to have a wide range and adjustable thermal expansion coefficient.
- the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.2 and 1.4
- the average roughness of the glass product after hot bending is only 12% to 40% higher than that before hot bending.
- the average roughness of the glass product after hot bending is increased by 15% to 30% compared with that before hot bending.
- the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product When it is between 0 and 0.2, the average roughness of the glass products after hot bending is only 70% to 95% higher than that before hot bending, and it is 400% higher than that of glass products after hot bending applied in metal molds or graphite molds Compared with the increase of the average roughness, the increase of the average roughness has been greatly improved, and the problem of a large increase in the roughness caused by the difference in expansion coefficient between the hot bending mold and the glass product has also been solved.
- the hot bending mold since the hot bending mold has a wide adjustable coefficient of thermal expansion, it can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and avoid the problem of a large increase in roughness. On this basis, by controlling A1/A2, it can be further taught how to control the degree of roughness improvement by adjusting the difference range of thermal expansion coefficient.
- the coefficient of thermal expansion is tested with a Lindsay DIL-L76 thermal dilatometer at 25-1000°C for the glass-ceramic mold, and the sample size for the glass-ceramic mold test is 5mm*5mm*50mm.
- the present application also provides a glass ceramic mold applied to the above processing method
- the main crystal phase of the glass ceramic mold includes MgAl 2 Si 3 O 10 , MgAl 2 O 4 , ZnAl 2 O 4 , mullite, ⁇ -quartz, ⁇ -quartz solid solution, ⁇ -spodumene, ⁇ -eucryptite and cordierite, and the mass fraction of ⁇ -quartz+
- the mass fraction of the ⁇ -spodumene + the mass fraction of the ⁇ -eucryptite is in the range of 0.1% to 70.0%.
- the instrument is set to a voltage of 40mV, a current of 30mA, a test range of 10-50°, a scanning speed of 1°/min, and a step size of 0.02°/step to analyze the X-ray diffraction data after detection. Confirm the ratio of each crystal phase.
- the glass ceramic mold includes the following raw materials in parts by weight: SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts; Na 2 O: 0.00 ⁇ 2.00 parts; B 2 O 3 : 0.00 ⁇ 5.00 parts; K 2 O: 0.00 ⁇ 5.00 parts; MgO: 0.00 ⁇ 20.00 parts; CaO: 0.00 ⁇ 5.00 parts; P 2 O 5 : 0.00 ⁇ 5.00 parts; TiO 2 : 0.00-5.00 parts; BaO: 0.00-2.00 parts; ZnO: 0.00-10.00 parts.
- Li 2 O will speed up the precipitation of ⁇ -quartz, ⁇ -quartz solid solution crystals, ⁇ -spodumene and ⁇ -eucryptite with low thermal expansion coefficient, and significantly reduce the thermal expansion coefficient of glass ceramics. It is also possible to control the mass fractions of negative expansion coefficient crystals ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite in the glass ceramic mold after crystallization of the basic glass. However, too much lithium will lead to the transformation of the precipitated crystal phase, which will increase the thermal expansion coefficient of the glass ceramics.
- the mass fraction of Li 2 O is controlled at 0.5% to 10%, which is convenient for controlling the glass ceramic mold to obtain a suitable range of thermal expansion coefficients.
- the mass fraction of Li 2 O includes 0.50% by weight to 10.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.50% by weight to 7.50% by weight, 0.50% by weight to 5.00% by weight, 0.50% by weight - 2.50% by weight, 2.00% by weight - 10.00% by weight, 2.00% by weight - 7.50% by weight, 2.00% by weight - 5.00% by weight, 5.00% by weight - 10.00% by weight, 5.00% by weight - 7.50% by weight, 7.50% by weight %-10.00% by weight etc.
- the content of Li2O can be controlled at 0.00 wt%, 0.50 wt%, 1.00 wt%, 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, 6.00 wt%, 7.00 wt%, 8.00% by weight, 9.00% by weight, 10.00% by weight, etc.
- Na 2 O and K 2 O can reduce the crystallization upper limit temperature of glass-ceramics, thereby reducing the difficulty of production and molding of the base glass (uncrystallized glass ceramics, called base glass).
- Na and K are generally present in the base glass. After crystallization, it is enriched in the glass phase. Too much Na 2 O and K 2 O will significantly increase the thermal expansion coefficient and reduce the glass transition temperature of glass ceramics.
- the mass ratio of Na 2 O, K 2 O and Li 2 O is required as follows: (Na 2 O+K 2 O)/Li 2 O ⁇ 1.00, and Na 2 O and K The total mass fraction of 2 O is ⁇ 8.00%.
- the mass fraction of Na 2 O includes 0.00% by weight to 2.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.25% by weight to 2.00% by weight, 0.25% by weight to 1.50% by weight, 0.25% by weight-1.00% by weight, 1.00% by weight-2.00% by weight, 1.00% by weight-1.50% by weight, etc.
- the content of Na 2 O can be controlled at 0.00% by weight, 0.25% by weight, 1.00% by weight, 1.25% by weight, 1.50% by weight, 1.75% by weight, 2.00% by weight and so on.
- the mass fraction of K 2 O includes 0.00% by weight to 5.00% by weight and all ranges and subranges therebetween, for example, it can be controlled at 0.80% by weight to 5.00% by weight, 0.80% by weight to 4.00% by weight, 0.80 wt%-3.00 wt%, 0.80 wt%-2.00 wt%, 0.80 wt%-1.00 wt%, 1.00 wt%-5.00 wt%, 2.00 wt%-5.00 wt%, 3.00 wt%-5.00 wt%, 4.00 wt% %-5.00% by weight, 2.00%-4.00% by weight, 2.00%-3.00% by weight, etc.
- the content of K2O can be controlled at 0.00 wt%, 0.80 wt%, 1.00 wt%, 1.50 wt%, 2.00 wt%, 2.50 wt%, 3.00 wt%, 3.50 wt%, 4.00 wt%, 4.50% by weight, 5.00% by weight, etc.
- B 2 O 3 can reduce the thermal expansion coefficient of the glass phase in glass ceramics (there are glass phase and crystal phase in glass ceramics), but too much B 2 O 3 will reduce the strength of glass ceramics.
- the mass fraction of B 2 O 3 includes 0.00% by weight to 5.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.75% by weight to 5.00% by weight, and 0.75% by weight to 4.00% by weight , 0.75% by weight-3.00% by weight, 0.75% by weight-2.00% by weight, 0.75% by weight-1.00% by weight, 1.00% by weight-5.00% by weight, 2.00% by weight-5.00% by weight, 3.00% by weight-5.00% by weight, 4.00 % by weight-5.00% by weight, 2.00% by weight-4.00% by weight, 2.00% by weight-3.00% by weight, etc.
- the mass fraction of B2O3 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight %, 4.00% by weight, 4.50% by weight, 5.00% by weight, etc.
- MgO and ZnO participate in glass ceramics MgAl 2 Si 3 O 10 , ZnAl 2 O 4 , MgAl 2 O 4 , mullite, cordierite, ⁇ -quartz, ⁇ -quartz solid solution, ⁇ -spodumene and ⁇ -eucryptite formation of magnesium-containing crystals.
- the mass fraction of MgO includes 0.00% by weight to 20.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.00% by weight to 19.00% by weight, 0.00% by weight to 18.70% by weight, and 0.00% by weight %-16.00% by weight, 0.00% by weight-14.00% by weight, 0.00% by weight-13.30% by weight, 0.00% by weight-11.00% by weight, 0.00% by weight-9.00% by weight, 10.00% by weight-20.00% by weight, 13.30% by weight -20.00 wt%, 15.00 wt%-20.00 wt%, 17.00 wt%-20.00 wt%, 18.70 wt%-20.00 wt%, etc.
- the mass fraction of MgO can be controlled at 0.00% by weight, 1.00% by weight, 2.00% by weight, 3.00% by weight, 4.00% by weight, 5.00% by weight, 6.00% by weight, 7.00% by weight, 8.00% by weight, 9.00% by weight % by weight, 10.00% by weight, 11.00% by weight, 12.00% by weight, 13.00% by weight, 14.00% by weight, 15.00% by weight, 16.00% by weight, 17.00% by weight, 18.00% by weight, 19.00% by weight, 20.00% by weight, etc.
- ZrO 2 and P 2 O 5 are mainly used to control the crystal growth rate on the surface and inside of the basic glass.
- the mass fraction of ZrO 2 should be controlled between 0.5 and 10%, and the mass fraction of P 2 O 5
- the score should be controlled between 0 and 5%.
- the mass fraction of ZrO 2 includes 0.5% by weight to 10% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.50% by weight to 10.00% by weight, 0.50% by weight to 7.50% by weight, 0.50% by weight % by weight-4.00% by weight, 0.80% by weight-10.00% by weight, 0.80% by weight-4.00% by weight, 4.00% by weight-10.00% by weight, 4.00% by weight-8.00% by weight, 4.00% by weight-6.00% by weight, etc.
- the content of ZrO2 can be controlled at 0.00% by weight, 0.50% by weight, 0.80% by weight, 1.00% by weight, 2.00% by weight, 3.00% by weight, 4.00% by weight, 5.00% by weight, 6.00% by weight, 7.00% by weight % by weight, 8.00% by weight, 9.00% by weight, 10.00% by weight, etc.
- the mass fraction of P 2 O 5 includes 0% by weight to 5% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, or 1.00% by weight to 4.00% by weight , 1.00% by weight-3.00% by weight, 1.00% by weight-2.00% by weight, 2.00% by weight-5.00% by weight, 3.00% by weight-5.00% by weight, 4.00% by weight-5.00% by weight, 2.00% by weight-4.00% by weight, 2.00 % by weight - 3.00% by weight, etc.
- the mass fraction of P2O5 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight %, 4.00% by weight, 4.50% by weight, 5.00% by weight, etc.
- TiO 2 as an effective nucleating agent can control the precipitated crystal size of the base glass to less than 2 ⁇ m, reducing the risk of cracks in the base glass due to the formation of large crystals.
- the mass fraction of TiO 2 includes 0% by weight to 5% by weight and all ranges and subranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, 1.00% by weight to 4.70% by weight, 1.00% by weight % by weight - 4.60% by weight, 1.00% by weight - 4.00% by weight, 1.00% by weight - 3.00% by weight, 1.00% by weight - 2.00% by weight, 2.00% by weight - 5.00% by weight, 2.00% by weight - 4.00% by weight, 3.00% by weight -5.00 wt%, 3.00 wt%-4.00 wt%, 2.00 wt%-3.00 wt%, etc.
- the mass fraction of TiO2 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight, 4.00% by weight, 4.60% by weight, 4.70% by weight, 5.00% by weight, etc.
- the addition of CaO can effectively reduce the liquidus viscosity of the basic glass, thereby reducing the difficulty of forming, but too much CaO will cause crystallization during the forming process of the basic glass.
- the mass fraction of CaO in this application is 0-5%.
- the mass fraction of CaO includes 0% by weight to 5% by weight and all ranges and subranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, 1.50% by weight to 5.00% by weight, and 2.00% by weight %-5.00 wt%, 3.00 wt%-5.00 wt%, 4.00 wt%-5.00 wt%, 2.00 wt%-4.00 wt%, 2.00 wt%-3.00 wt%, etc.
- the content of K2O can be controlled at 0.00% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight, 4.00% by weight, 4.50% by weight, 5.00% by weight etc.
- the mass fraction of Li 2 O is controlled at 0.50-10.00%, and the mass ratio of Na 2 O, K 2 O, and Li 2 O in the raw material satisfies: (Na 2 O+K 2 O)/Li 2 O ⁇ 1.00, the total mass fraction of Na 2 O and K 2 O is ⁇ 8.00%, Na and K are generally enriched in the glass phase after crystallization of the basic glass, too much Na2O and K2O will significantly increase the thermal expansion coefficient and reduce The glass transition temperature of glass ceramics, while controlling the mass fraction of the sum of ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite at 0.1% to 70.0%, ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite They are three types of crystals with low thermal expansion coefficients.
- Controlling their total mass proportion can contribute to the adjustment of the overall thermal expansion coefficient of the glass-ceramic mold, thus realizing the thermal expansion coefficient of the glass-ceramic mold within the temperature range of 25-1000°C Adjustable, the adjustment range is -1.0 ⁇ 10-6 ⁇ 3.0 ⁇ 10-5/K.
- the glass ceramic mold of the present application also has a wide adjustable range of thermal expansion coefficient, so that the mold has a wider application range and improves the applicability of the mold.
- the glass transition temperature of the glass-ceramic mold of the present application is greater than or equal to 700°C.
- the glass transition temperature of the glass-ceramic mold is higher, that is, the softening point is higher, which can adapt to the high temperature during the hot bending process, and avoid the deformation of the hot-bent glass product and the reduction of dimensional accuracy.
- the transition temperature of the residual glass phase after the crystallization of the mold will also increase, which can reduce the deformation of the glass phase of the mold when the mold is in use.
- ⁇ -quartz includes ⁇ -quartz solid solution and ⁇ -quartz.
- mass fraction of the sum of ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite in glass ceramics is greater than 70.0%, it will significantly reduce the overall thermal expansion coefficient of the glass ceramic mold, resulting in a temperature range of 25 to 1000 °C for the glass ceramic mold.
- the range of the coefficient of thermal expansion within the range is narrowed to a greater extent, especially the upper limit of the range of the coefficient of thermal expansion is weakened.
- the sum of the mass fractions of ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite in the glass ceramics of the present application includes the range of 0.1% to 70.0% and all ranges and sub-ranges therebetween, such as Controlled at 0.1%-70.0%, 5.0%-70.0%, 5.0%-60.0%, 5.0%-50.0%, 5.0%-47.0%, 5.0%-37.0%, 5.0%-35.0%, 5.0%-33.0%, 5.0%-30.0%, 5.0%-25.0%, 5.0%-16.0%, 16.0%-60.0%, 16.0%-50.0%, 16.0%-47.0%, 16.0%-35.0%, 16.0%-20.0%, 33.0% -70.0%, 33.0%-60.0%, 33.0%-50.0%, 33.0%-47.0%, etc.
- the sum of the mass fractions of ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite in the glass ceramics of the present application can be controlled at 10.0% by weight, 11.0% by weight, 12.0% by weight, 13.0% by weight, 14.0 wt%, 15.0 wt%, 16.0 wt%, 17.0 wt%, 18.0 wt%, 19.0 wt%, 20.0 wt%, 21.0 wt%, 22.0 wt%, 23.0 wt%, 24.0 wt%, 25.0 wt%, 26.0 wt% %, 27.0 wt%, 28.0 wt%, 29.0 wt%, 30.0 wt%, 31.0 wt%, 32.0 wt%, 33.0 wt%, 34.0 wt%, 35.0 wt%, 36.0 wt%, 37.0 wt%, 38.0 wt%, 39.0 wt
- the glass transition temperature is tested with a Mettler-Toledo DSC-3 differential scanning calorimeter to test the glass transition temperature of the glass-ceramic mold.
- the glass-ceramic mold is pulverized with an agate mortar in advance, and then passed through a 200-mesh sieve. Take the sifted powder for testing.
- the thermal conductivity of the glass-ceramic mold provided by the present application is greater than or equal to 1 W/(m ⁇ k) within the temperature range of 25-1000°C. In this way, the temperature of the mold can be raised quickly, and the heat can be better transferred to the hot-bending glass product, so that the temperature of the mold and the glass product can quickly reach the same temperature, and the temperature consistency of each part of the mold can be ensured.
- the preparation method of the glass-ceramic mold provided by the application is as follows:
- Step S100 a mixing process, weighing and mixing each raw material uniformly to form a basic mixture, and each raw material includes the following parts by weight:
- SiO 2 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts; Na 2 O: 0.00-2.00 parts; B 2 O 3 : 0.00 ⁇ 5.00 parts; K 2 O: 0.00 ⁇ 5.00 parts; MgO: 0.00 ⁇ 20.00 parts; CaO: 0.00 ⁇ 5.00 parts; P 2 O 5 : 0.00 ⁇ 5.00 parts; TiO 2 : 0.00 ⁇ 5.00 parts; BaO: 0.00 ⁇ 2.00 parts parts; ZnO: 0.00 to 10.00 parts.
- the above-mentioned raw materials and clarifying agent are accurately weighed and fully mixed evenly, and put into a corundum crucible.
- the clarifying agent is selected from As 2 O 3 , Sb 2 O 3 , SnO 2 , chloride, fluoride, SO 3 - compound, and more than one compound containing NO 3- , preferably one or more selected from SnO 2 , compound containing SO 3- , chloride, and compound containing NO 3- ; preferably the clarification
- the additive content is 0-2% by weight.
- Step S200 a melting process, melting the basic mixture and pouring it into a mold to generate a basic glass piece.
- the above-mentioned corundum crucible with uniformly mixed raw materials is placed in a silicon-molybdenum rod electric furnace, and melted at 1500-1700° C. for 3-16 hours. After the glass liquid is clarified and homogenized, it is poured into a mold to form a basic glass piece.
- the mold described here is a molten mixture containing glass raw materials, which is cooled to obtain a basic glass piece.
- Step S300 forming process, making the basic glass part into a glass mold part of desired shape.
- the forming process is cold engraving or hot bending.
- a 3D hot bending machine on the market to perform hot bending to obtain a glass mold part, such as a commercially available model from DTK, a commercially available model from Mengli, and the like.
- DTK-DGP-3D12S3D hot bending machine, or Mengli CG07-4222 hot bending machine can be used.
- an annealing process is also included before the forming process, and the annealing process is to anneal the basic glass piece and cool it to room temperature.
- the annealing of glass is to reheat the glass product with permanent stress to the temperature where the particles inside the glass can move, and use the displacement of the particle to disperse the stress to eliminate or weaken the permanent stress, thereby improving the thermal expansion uniformity and mechanical strength of the glass product.
- the annealing range of glass is generally between the annealing point and the strain point, and the corresponding glass viscosity is 1013dPa ⁇ s to 1014.7dPa ⁇ s.
- the glass will soften and deform; when it is lower than the lower limit of the annealing temperature, the glass structure can actually be considered fixed, and the internal particles can no longer move, so it is impossible to disperse or eliminate stress.
- the internal stress of the glass can be eliminated within a few hours near the strain point.
- the longer the annealing time the smaller the stress of the glass and the higher the uniformity.
- new stress will be newly generated during the annealing and cooling process of the glass. The slower the cooling rate, the smaller the stress generated, the higher the stress uniformity of the inner and outer glass, and the higher the uniformity of the thermal expansion coefficient of the glass.
- the obtained basic glass parts are annealed at 600-900°C for 30-1200 hours. Further, in order to control the consistency of the expansion coefficient of different parts of the mold, the annealing time is preferably more than 120 hours.
- the strain point is determined by extrapolation of the annealing point data, the strain point is the temperature when the viscous deflection velocity is 0.0316 times the annealing viscous deflection velocity, the annealing of this application
- the temperature is the temperature at which the annealing viscous deflection velocity of the glass is 0.02 to 0.0316 times. In this temperature range, a better annealing effect can be obtained, that is, the higher the uniformity of the thermal expansion coefficient.
- the glass mold parts are obtained.
- Step S400 a microcrystallization treatment process, performing nucleation and crystallization treatments on the glass mold part in sequence to make the microcrystallization mold part;
- the nucleation temperature is 650-1000°C, and the nucleation time is 1-6 hours; the crystallization temperature is 900-1400°C, and the crystallization time is 0-15 hours.
- the microcrystallization treatment process can be performed simultaneously with the hot bending forming, specifically, the microcrystallization treatment is performed while the glass mold part is hot bending forming.
- the process of nucleation treatment by introducing an appropriate crystal nucleating agent into the glass component, the viscosity of the glass will decrease during the subsequent heat treatment, and a large number of uniform tiny crystals will be precipitated (nucleated and grown) in the glass, that is crystal nucleus.
- the process of crystallization treatment the required crystals are grown on the surface of the precipitated crystal nuclei, so that the internal composition of the glass changes into a crystal phase and a glass phase.
- Appropriate nucleation temperature and time are conducive to the precipitation of uniform and fine crystal nuclei, and further growth of uniform and fine crystals during the crystallization process.
- Crystallization is the growth of crystals through heat treatment in glass ceramics or glasses that have formed crystal nuclei.
- thermal shock resistance when cracks propagate along the boundaries of different particles with greatly different thermal expansion coefficients, the thermal resistance of the material can be improved due to the bending, passivation and branching of the cleavage plane in the crystal. Vibration has been improved. Therefore, glass ceramics with high thermal shock resistance can be obtained by adjusting the raw material composition, crystallization temperature and crystallization time.
- the glass mold part is nucleated at 650-1000°C for 1-6h, and then crystallized at 900-1400°C for 0-15h, further, the crystallization time includes 0-15h and all ranges and sub-ranges therebetween , such as 1h ⁇ 2h, 1h ⁇ 3h, 1h ⁇ 4h, 1h ⁇ 5h, 2h ⁇ 3h, 2h ⁇ 4h, 2h ⁇ 5h, 5h ⁇ 15h, 10h ⁇ 11h, 10h ⁇ 12h, 10h ⁇ 13h, 10h ⁇ 14h, 10h ⁇ 15h, 14h ⁇ 15, etc., preferably 5h ⁇ 15h, including 6h ⁇ 15h, 7h ⁇ 12h, 7h ⁇ 13h, 7h ⁇ 14h, etc.
- Step S500 cooling process, annealing and cooling the microcrystallized mold part to room temperature to form a glass ceramic mold.
- a polishing process for the glass-ceramic mold is also included. After the mold is prepared, put the blank to be bent into the above-mentioned mold when the blank is to be bent, then put it into the bending machine, set the bending process, and take it out after cooling.
- the hot bending mold has the advantages of high thermal conductivity, high temperature resistance, high softening point and high thermal shock resistance, and the dimensional accuracy of the glass after hot bending has not changed. It is also resistant to oxidation at high temperatures and has a long service life, suitable for mass production of 2.5D or 3D glass.
- the method for testing the uniformity of the coefficient of expansion is as follows: on the prepared basic mold, take samples A and B with a diameter of 6 mm and a thickness of 10 mm, and test the coefficient of thermal expansion respectively, A/B is 0.995-1.005, That is to meet the uniformity requirements of the annealing expansion coefficient.
- the test instrument is Germany NETZSCH-DIL402C high temperature thermal expansion coefficient meter.
- the thermal conductivity test method of the glass ceramic mold is: the size of the test sample is 100mm*100*1mm in length, width and thickness.
- the test instrument is the heat flow method thermal conductivity tester HFM436.
- the average roughness test method is as follows: use the Huakuang TR200 roughness meter to test the surface of the sample three times, each sampling length is 20mm, and the average roughness of the three times is taken as the average roughness of the sample.
- table 1-1 is the raw material composition table of each glass-ceramic mold base glass in embodiment 1-6 and comparative example 1
- table 1-2 is the concrete of each glass-ceramic mold preparation process of embodiment 1-6 and comparative example 1
- Process parameter table table 1-3 is the main crystal phase and performance parameter table of each glass ceramic mold prepared in embodiment 1-6 and comparative example 1.
- Example 1 the preparation process of the glass-ceramic mold is specifically described according to the data in Table 1-1 and 1-2:
- Examples 2-6 and Comparative Example 1 also refer to the data requirements of Table 1-1 and Table 1-2, and the preparation process is the same as that of Example 1, and will not be repeated here.
- Table 1-3 is a table of main crystal phases and performance parameters of glass hot bending molds prepared based on Table 1-1 and Table 1-2.
- Example 1 describe the prepared hot bending mold according to Table 1-3:
- the main crystal phase of the prepared glass ceramic hot bending mold includes: cordierite, ⁇ -quartz solid solution, ⁇ -quartz, and the ⁇ -quartz solid solution, ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite in the crystal phase
- the mass fraction of and is 16wt%, and the glass transition temperature of the crystallized glass-ceramic hot-bending mold is 760°C; the coefficient of thermal expansion at 25-1000°C is 2.2 ⁇ 10 -6 /K; on the prepared basic mold, Take A and B samples with a diameter of 6mm and a thickness of 10mm, and use the German NETZSCH-DIL402C high-temperature thermal expansion coefficient meter to test the thermal expansion coefficients of A and B samples respectively, and the A/B is 0.996, which meets the uniformity requirements of the annealing expansion coefficient;
- thermo conductivity tester HFM436 When testing the thermal conductivity, a sample with a length, width, and thickness of 100mm*100*1mm is obtained on a glass ceramic hot bending mold, and the heat flow method thermal conductivity tester HFM436 is used for testing.
- the thermal conductivity is 2.81W/(m ⁇ k), and the test glass
- each sampling length is 20mm, and the average value of the roughness measured three times is used as the average value of the sample.
- Roughness the measured average roughness of the glass-ceramic hot-bending mold of Example 1 is 0.008 ⁇ m.
- Embodiments 2-6 are the same as above, and will not be repeated here.
- comparative example 1 and embodiment 3 have the same raw material composition
- the crystallization temperature in the preparation process is 1450 degrees, greater than 1400 degrees
- the crystallization time is 30, greater than 15h
- the main crystal phase of the prepared hot bending mold is ⁇ - Quartz solid solution
- the mass fraction of the sum of ⁇ -quartz solid solution, ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite of the prepared hot-bending mold is 73wt%, greater than 70wt%, which reduces the overall weight of the glass-ceramic mold Thermal expansion coefficient.
- the glass ceramic hot bending molds prepared in the above Examples 1-6 were used to hot bend the glass products, and five glass products A-E were selected.
- the raw material composition and performance parameters of each glass product are shown in Table 1-4.
- glass product B and glass product C are glass
- glass product A, glass product D and glass product E are glass ceramics
- glass products A of different batches are firstly selected and prepared using Examples 1-6
- the roughness of the glass product A produced in different batches is different.
- the performance of the glass product after hot bending is shown in Table 1-5.
- the glass product A of the same system with different roughness is subjected to hot bending by using the hot bending mold prepared in Example 1-6.
- the average roughness The roughness is in the range of 12% to 40%.
- the average roughness of the glass product after hot bending is in the range of 15% to 30%.
- the average roughness of the glass product is The average roughness after hot bending is in the range of 70% to 95%.
- the glass ceramic mold of the present application has good applicability. Not only has a wide adjustable thermal expansion coefficient, but also can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and thus avoid the problem of a large increase in roughness. It further teaches how to control the degree of roughness improvement by adjusting the range of differences in thermal expansion coefficients.
- Example 1 the glass-ceramic hot-bending mold prepared in Example 1 was selected to perform hot-bending processing on the glass products A to E listed in Tables 1-4 above, and the properties of the processed glass products are shown in Tables 1-6.
- Example 1 For the range of process parameters provided in Example 1, a set of comparative examples is provided for the annealing time, nucleation time, crystallization time and annealing temperature respectively.
- the performance of the hot bending mold and the conditions of the glass products after hot bending are shown in Table 1- 7 shows:
- the application also provides a pair of ratios, which are common graphite hot bending molds on the market.
- the graphite mold of ratio 1 and the glass ceramic hot bending mold of Example 1 are used to hot bend the same glass products.
- Example 1 comparison see the table below:
- the glass ceramic hot bending molds prepared have good performance.
- the thermal expansion coefficient of glass ceramics is controlled at -1.0 ⁇ 10 -6 ⁇ 3.0 ⁇ 10 -5 /K, and its The glass transition temperature is greater than or equal to 700 ° C, and the mass fraction of Li 2 O in the raw material is controlled at 0.50-10.00%, so that the mass fraction of the sum of ⁇ -quartz, ⁇ -spodumene and ⁇ -eucryptite after crystallization is In the range of 0.1% to 70.0%, the thermal expansion coefficient of the glass ceramic mold can be adjusted in the temperature range of 25 to 1000°C (the adjustment range is -1.0 ⁇ 10-6 to 3.0 ⁇ 10-5).
- the glass ceramic mold since the glass ceramic mold has a wide adjustable coefficient of thermal expansion, it can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and avoid the problem of a large increase in roughness.
- the glass transition temperature of the glass-ceramic mold is higher, that is, the softening point is higher, which can adapt to the high temperature during the hot bending process, and avoid the deformation of hot-bent glass products and the reduction of dimensional accuracy.
- the thermal conductivity of the prepared glass-ceramic hot bending mold is greater than or equal to 1W/(m ⁇ k) in the temperature range of 25-1000°C, which has good thermal conductivity and can realize rapid heat transfer. Further, by controlling The annealing time, annealing temperature, nucleation time and crystallization time in the process parameters are within a reasonable range to control the uniformity of the expansion coefficient of different parts of the glass ceramic hot bending mold and to ensure the low roughness of the glass product after hot bending.
- the glass-ceramic hot-bending mold provided by this application overcomes the shortcomings of traditional graphite molds such as low oxidation resistance, short service life, and low operating temperature, and realizes easy processing, high thermal conductivity, high temperature resistance, low expansion, high softening point, and high resistance to corrosion. Thermal shock resistance and other advantages, and the dimensional accuracy of the glass after hot bending has not changed.
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Abstract
The present application discloses a glass product processing method and a glass ceramic mold. The absolute value of the ratio of the thermal expansion coefficient A1 of a mold to the thermal expansion coefficient A2 of a glass product is controlled so that when the absolute value of the ratio of the thermal expansion coefficient A1 of the mold to the thermal expansion coefficient A2 of the glass product is 0.2-1.5, the average roughness of the glass product after hot bending is increased by 0%-40% compared with that before hot bending. In the present application, a specific processing control parameter relationship is provided to fit glass products having different thermal expansion coefficients, so that hot-bent glass products having different roughness improvement effects can be obtained, the surface roughness of the glass product after hot bending is reduced, and the dimensional stability of the glass product after hot bending is improved.
Description
本申请涉及成型加工模具制备技术领域，特别涉及一种玻璃制品的加工方法及玻璃陶瓷模具。The present application relates to the technical field of molding and processing mold preparation, in particular to a glass product processing method and a glass ceramic mold.
热弯玻璃是由平板玻璃或玻璃陶瓷玻璃制品加热软化在模具中成型，再经退火制成的曲面玻璃。玻璃在热弯过程中需要由模具传热传力，而且不影响玻璃的精度和特性。因此，模具的材质需要具备易加工、高热导率、耐高温、低膨胀、高软化点和高抗热震性等特点。且玻璃制品热弯过程中对其粗糙度的控制有较高的要求，不同热膨胀系数的玻璃制品在热弯成型时，如果模具热膨胀系数与玻璃制品热膨胀系数差异过大，会造成玻璃制品表面的粗糙度大幅增加，进一步降低热弯后玻璃或玻璃陶瓷的尺寸稳定性。Hot bending glass is a curved glass made of flat glass or glass-ceramic glass products heated and softened in a mold, and then annealed. During the hot bending process, the glass needs to transfer heat and force from the mold without affecting the precision and characteristics of the glass. Therefore, the material of the mold needs to have the characteristics of easy processing, high thermal conductivity, high temperature resistance, low expansion, high softening point and high thermal shock resistance. In addition, there are high requirements for the roughness control of glass products during hot bending. When glass products with different thermal expansion coefficients are hot bent and formed, if the thermal expansion coefficient of the mold is too different from that of the glass product, the surface of the glass product will be warped. The roughness increases considerably, further reducing the dimensional stability of the glass or glass-ceramic after hot bending.
发明内容Contents of the invention
(一)申请目的(1) Purpose of application
基于此，为了提供一种具体的加工控制参数关系，来匹配不同热膨胀系数的玻璃制品，进一步获得不同粗糙度改进效果的热弯后玻璃制品产品，降低玻璃制品热弯后的表面粗糙度，提高玻璃制品热弯后的尺寸稳定性，本申请公开了以下技术方案。Based on this, in order to provide a specific processing control parameter relationship to match glass products with different thermal expansion coefficients, further obtain hot-bent glass products with different roughness improvement effects, reduce the surface roughness of glass products after hot bending, and improve For the dimensional stability of glass products after heat bending, the present application discloses the following technical solutions.
(二)技术方案(2) Technical solution
本申请公开了一种玻璃制品的加工方法，控制热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值，The application discloses a glass product processing method, which controls the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product,
当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.2～1.4之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高12％～40％。When the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.2 and 1.4, the average roughness of the glass product after hot bending is higher than that before hot bending 12% to 40%.
在一种可能的实施方式中，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.3～0.7之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高15％～30％。In a possible implementation manner, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.3 and 0.7, the average The roughness is increased by 15% to 30% compared with that before hot bending.
在一种可能的实施方式中，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0～0.2之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高70％～95％。In a possible implementation manner, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0 and 0.2, the average The roughness is increased by 70% to 95% compared with that before hot bending.
作为本申请的第二方面，本申请还公开了一种应用在玻璃制品加工方法上的玻璃陶瓷模具，所述玻璃陶瓷模具的主晶相包括MgAl
2Si
3O
10、MgAl
2O
4、ZnAl
2O
4、莫来石、β-石英、β-石英固溶体、β-锂辉石、β-锂霞石和堇青石中的一种或多种。
As the second aspect of the present application, the present application also discloses a glass ceramic mold used in the glass product processing method, the main crystal phase of the glass ceramic mold includes MgAl 2 Si 3 O 10 , MgAl 2 O 4 , ZnAl One or more of 2 O 4 , mullite, β-quartz, β-quartz solid solution, β-spodumene, β-eucryptite and cordierite.
在一种可能的实施方式中，所述玻璃陶瓷模具的热膨胀系数在25～1000℃的温度范围内为大于-1.0×10
-6/K且小于或等于3.0×10
-5/K。
In a possible implementation manner, the thermal expansion coefficient of the glass-ceramic mold is greater than -1.0×10 -6 /K and less than or equal to 3.0×10 -5 /K in the temperature range of 25-1000°C.
在一种可能的实施方式中，组分包括Li
2O，以质量分数计在0.50～10％范围内，所述β-石英、所述β-锂辉石和所述β-钠霞石的质量分数在0.1％～70.0％范围内。
In a possible implementation manner, the components include Li 2 O, in the range of 0.50-10% by mass fraction, the mass of the β-quartz, the β-spodumene and the β-natcryptite Scores range from 0.1% to 70.0%.
在一种可能的实施方式中，组分还包括Na
2O和K
2O，Na
2O、K
2O和Li
2O的质量比要求如下：(Na
2O+K
2O)/Li
2O＜1.00，且Na
2O和K
2O总质量分数≤8.00％。
In a possible implementation, the components also include Na 2 O and K 2 O, and the mass ratio of Na 2 O, K 2 O and Li 2 O is required as follows: (Na 2 O+K 2 O)/Li 2 O<1.00, and the total mass fraction of Na 2 O and K 2 O is ≤8.00%.
在一种可能的实施方式中，包括以下重量份的各原料：SiO
2：40.00～80.00份；Al
2O
3：18.00～40.00份；ZrO
2：0.50～10.00份；Li
2O：0.50～10.00份；Na
2O：0.00～2.00份；B
2O
3：0.00～5.00份；K
2O：0.00～5.00份；MgO：0.00～20.00份；CaO：0.00～5.00份；P
2O
5：0.00～5.00份；TiO
2：0.00～5.00份；BaO：0.00～2.00份；ZnO：0.00～10.00份。
In a possible implementation, the following raw materials are included in parts by weight: SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts Na 2 O: 0.00-2.00 parts; B 2 O 3 : 0.00-5.00 parts; K 2 O: 0.00-5.00 parts; MgO: 0.00-20.00 parts; CaO: 0.00-5.00 parts; P 2 O 5 : 0.00 ～5.00 parts; TiO 2 : 0.00～5.00 parts; BaO: 0.00～2.00 parts; ZnO: 0.00～10.00 parts.
在一种可能的实施方式中，所述玻璃陶瓷模具的玻璃化转变温度大于或等于700℃。In a possible implementation manner, the glass transition temperature of the glass ceramic mold is greater than or equal to 700°C.
在一种可能的实施方式中，所述玻璃陶瓷模具的热导率在25～1000℃的温度范围内大于或等于1W/(m·k)。In a possible implementation manner, the thermal conductivity of the glass-ceramic mold is greater than or equal to 1 W/(m·k) within the temperature range of 25-1000°C.
本申请提供了一种具体的加工控制参数关系，来匹配不同热膨胀系数的玻璃制品，可以获得不同粗糙度改进效果的热弯后玻璃制品产品，降低了玻璃制品热弯后的表面粗糙度，提高了玻璃制品热弯后的尺寸稳定性。This application provides a specific processing control parameter relationship to match glass products with different thermal expansion coefficients, and can obtain hot-bent glass products with different roughness improvement effects, reduce the surface roughness of glass products after hot bending, and improve It ensures the dimensional stability of glass products after hot bending.
为使本申请实施的目的、技术方案和优点更加清楚，下面对本申请实施例中的技术方案进行更加详细的描述。In order to make the objectives, technical solutions and advantages of the application more clear, the technical solutions in the embodiments of the application are described in more detail below.
本申请提供一种玻璃制品的加工方法：The application provides a processing method for glass products:
控制热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值，Control the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product,
当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.2～1.4之间时，所述玻璃制品热弯后的平均 粗糙度相对于热弯前升高12％～40％。When the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.2 and 1.4, the average roughness of the glass product after hot bending is higher than that before hot bending 12% to 40%.
进一步，在一种实施方式中，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.3～0.7之间时，所述待玻璃制品热弯后的平均粗糙度相对于热弯前升高15％～30％。Further, in one embodiment, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.3 and 0.7, the glass product to be bent The average roughness is 15%-30% higher than that before hot bending.
然而，在一种实施方式中，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0～0.2之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高70％～95％。However, in one embodiment, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0 and 0.2, the average value of the glass product after hot bending The roughness is increased by 70% to 95% compared with that before hot bending.
本申请中，玻璃制品即待热弯坯件，其材质为玻璃或者玻璃陶瓷，其热膨胀系数范围较大，若热弯模具与玻璃制品的热膨胀系数差异较大，会使热弯后的玻璃制品的粗糙度大幅增加，所以要求热弯模具具有较宽范围的且可调的热膨胀系数，当热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值在0.2～1.4之间时，热弯后的玻璃制品的平均粗糙度相对于热弯前仅升高12％～40％，进一步，当热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值在0.3～0.7之间时，热弯后的玻璃制品的平均粗糙度相对于热弯前升高15％～30％，然而，当热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值在0～0.2之间时，热弯后的玻璃制品的平均粗糙度相对于热弯前也仅仅升高70％～95％，与应用在金属模具或石墨模具中的热弯后玻璃制品400％的平均粗糙度的涨幅相比，平均粗糙度的涨幅大大改善，热弯模具与玻璃制品膨胀系数差导致的粗糙度大幅增加的问题也得到了解决。In this application, the glass product is the blank to be hot-bent, and its material is glass or glass ceramics, and its coefficient of thermal expansion has a large range. The roughness of the glass product is greatly increased, so the hot bending mold is required to have a wide range and adjustable thermal expansion coefficient. When the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.2 and 1.4 The average roughness of the glass product after hot bending is only 12% to 40% higher than that before hot bending. Further, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.3 and 0.7, the average roughness of the glass product after hot bending is increased by 15% to 30% compared with that before hot bending. However, when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product When it is between 0 and 0.2, the average roughness of the glass products after hot bending is only 70% to 95% higher than that before hot bending, and it is 400% higher than that of glass products after hot bending applied in metal molds or graphite molds Compared with the increase of the average roughness, the increase of the average roughness has been greatly improved, and the problem of a large increase in the roughness caused by the difference in expansion coefficient between the hot bending mold and the glass product has also been solved.
本申请中，由于热弯模具有宽泛可调的热膨胀系数，能适配玻璃 制品的热膨胀系数，改进较大的热膨胀系数差异，进而避免粗糙度提升较大的问题。在此基础上，还可以通过控制A1/A2，进一步教导如何通过调节热膨胀系数差异范围控制粗糙度提升幅度的情况。In this application, since the hot bending mold has a wide adjustable coefficient of thermal expansion, it can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and avoid the problem of a large increase in roughness. On this basis, by controlling A1/A2, it can be further taught how to control the degree of roughness improvement by adjusting the difference range of thermal expansion coefficient.
本申请中，热膨胀系数使用林赛斯DIL-L76热膨胀仪测试玻璃陶瓷模具的25～1000℃的热膨胀系数，玻璃陶瓷模具测试制样尺寸为5mm*5mm*50mm。In this application, the coefficient of thermal expansion is tested with a Lindsay DIL-L76 thermal dilatometer at 25-1000°C for the glass-ceramic mold, and the sample size for the glass-ceramic mold test is 5mm*5mm*50mm.
基于此，本申请还提供一种应用于上述加工方法的玻璃陶瓷模具，所述玻璃陶瓷模具的主晶相包括所述玻璃陶瓷模具的主晶相包括MgAl
2Si
3O
10、MgAl
2O
4、ZnAl
2O
4、莫来石、β-石英、β-石英固溶体、β-锂辉石、β-锂霞石和堇青石中的一种或多种，且所述β-石英的质量分数+所述β-锂辉石的质量分数+所述β-锂霞石的质量分数在0.1％～70.0％的范围内。
Based on this, the present application also provides a glass ceramic mold applied to the above processing method, the main crystal phase of the glass ceramic mold includes MgAl 2 Si 3 O 10 , MgAl 2 O 4 , ZnAl 2 O 4 , mullite, β-quartz, β-quartz solid solution, β-spodumene, β-eucryptite and cordierite, and the mass fraction of β-quartz+ The mass fraction of the β-spodumene + the mass fraction of the β-eucryptite is in the range of 0.1% to 70.0%.
具体的，使用射线衍射仪，仪器设置电压40mV，电流30mA，测试范围10-50°，扫描速度1°/min，步长设置0.02°/步，对检测后的X射线衍射数据进行分析，从而确认各晶相的比例。Specifically, using a ray diffractometer, the instrument is set to a voltage of 40mV, a current of 30mA, a test range of 10-50°, a scanning speed of 1°/min, and a step size of 0.02°/step to analyze the X-ray diffraction data after detection. Confirm the ratio of each crystal phase.
玻璃陶瓷模具包括以下重量份的各原料：SiO
2：40.00～80.00份；Al
2O
3：18.00～40.00份；ZrO
2：0.50～10.00份；Li
2O：0.50～10.00份；Na
2O：0.00～2.00份；B
2O
3：0.00～5.00份；K
2O：0.00～5.00份；MgO：0.00～20.00份；CaO：0.00～5.00份；P
2O
5：0.00～5.00份；TiO
2：0.00～5.00份；BaO：0.00～2.00份；ZnO：0.00～10.00份。
The glass ceramic mold includes the following raw materials in parts by weight: SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts; Na 2 O: 0.00～2.00 parts; B 2 O 3 : 0.00～5.00 parts; K 2 O: 0.00～5.00 parts; MgO: 0.00～20.00 parts; CaO: 0.00～5.00 parts; P 2 O 5 : 0.00～5.00 parts; TiO 2 : 0.00-5.00 parts; BaO: 0.00-2.00 parts; ZnO: 0.00-10.00 parts.
本申请提供的玻璃陶瓷模具各原料的作用如下：The effect of each raw material of the glass-ceramic mold provided by the application is as follows:
Li
2O的加入会加快析出热膨胀系数较低的β-石英、β-石英固溶 体晶体、β-锂辉石和β-锂霞石，显著降低玻璃陶瓷的热膨胀系数。还可以控制基础玻璃晶化后玻璃陶瓷模具中负膨胀系数晶体β-石英、β-锂辉石和β-锂霞石的质量分数。但是过多的锂会导致析出晶相的转变，反而升高玻璃陶瓷的热膨胀系数，将Li
2O的质量分数控制在0.5％～10％，便于控制玻璃陶瓷模具获取合适范围的热膨胀系数
The addition of Li 2 O will speed up the precipitation of β-quartz, β-quartz solid solution crystals, β-spodumene and β-eucryptite with low thermal expansion coefficient, and significantly reduce the thermal expansion coefficient of glass ceramics. It is also possible to control the mass fractions of negative expansion coefficient crystals β-quartz, β-spodumene and β-eucryptite in the glass ceramic mold after crystallization of the basic glass. However, too much lithium will lead to the transformation of the precipitated crystal phase, which will increase the thermal expansion coefficient of the glass ceramics. The mass fraction of Li 2 O is controlled at 0.5% to 10%, which is convenient for controlling the glass ceramic mold to obtain a suitable range of thermal expansion coefficients.
在一些实施方式中，Li
2O的质量分数包括0.50重量％～10.00重量％及其之间的所有范围和子范围，比如可以控制在0.50重量％-7.50重量％，0.50重量％-5.00重量％，0.50重量％-2.50重量％，2.00重量％-10.00重量％，2.00重量％-7.50重量％，2.00重量％-5.00重量％，5.00重量％-10.00重量％，5.00重量％-7.50重量％，7.50重量％-10.00重量％等。在一些实施方式中，Li
2O的含量可控制在0.00重量％，0.50重量％，1.00重量％，2.00重量％，3.00重量％，4.00重量％，5.00重量％，6.00重量％，7.00重量％，8.00重量％，9.00重量％，10.00重量％等。
In some embodiments, the mass fraction of Li 2 O includes 0.50% by weight to 10.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.50% by weight to 7.50% by weight, 0.50% by weight to 5.00% by weight, 0.50% by weight - 2.50% by weight, 2.00% by weight - 10.00% by weight, 2.00% by weight - 7.50% by weight, 2.00% by weight - 5.00% by weight, 5.00% by weight - 10.00% by weight, 5.00% by weight - 7.50% by weight, 7.50% by weight %-10.00% by weight etc. In some embodiments, the content of Li2O can be controlled at 0.00 wt%, 0.50 wt%, 1.00 wt%, 2.00 wt%, 3.00 wt%, 4.00 wt%, 5.00 wt%, 6.00 wt%, 7.00 wt%, 8.00% by weight, 9.00% by weight, 10.00% by weight, etc.
Na
2O和K
2O的加入可以降低微晶玻璃的析晶上限温度，从而降低基础玻璃(未晶化的玻璃陶瓷，称为基础玻璃)的生产和成型难度，Na和K一般在基础玻璃晶化后富集于玻璃相内，过多的Na
2O和K
2O会显著升高热膨胀系数，降低玻璃陶瓷的玻璃化转化温度，为控制热膨胀系数及降低玻璃陶瓷的玻璃化转化温度，控制所述Na
2O和K
2O，Na
2O、K
2O和Li
2O的质量比要求如下：(Na
2O+K
2O)/Li
2O＜1.00，且Na
2O和K
2O总质量分数≤8.00％。
The addition of Na 2 O and K 2 O can reduce the crystallization upper limit temperature of glass-ceramics, thereby reducing the difficulty of production and molding of the base glass (uncrystallized glass ceramics, called base glass). Na and K are generally present in the base glass. After crystallization, it is enriched in the glass phase. Too much Na 2 O and K 2 O will significantly increase the thermal expansion coefficient and reduce the glass transition temperature of glass ceramics. In order to control the thermal expansion coefficient and reduce the glass transition temperature of glass ceramics, To control the Na 2 O and K 2 O, the mass ratio of Na 2 O, K 2 O and Li 2 O is required as follows: (Na 2 O+K 2 O)/Li 2 O<1.00, and Na 2 O and K The total mass fraction of 2 O is ≤8.00%.
在一些实施方式中，Na
2O的质量分数包括0.00重量％～2.00重 量％及其之间的所有范围和子范围，比如可以控制在0.25重量％-2.00重量％，0.25重量％-1.50重量％，0.25重量％-1.00重量％，1.00重量％-2.00重量％，1.00重量％-1.50重量％等。在一些实施方式中，Na
2O的含量可控制在0.00重量％，0.25重量％，1.00重量％，1.25重量％，1.50重量％,1.75重量％，2.00重量％等。
In some embodiments, the mass fraction of Na 2 O includes 0.00% by weight to 2.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.25% by weight to 2.00% by weight, 0.25% by weight to 1.50% by weight, 0.25% by weight-1.00% by weight, 1.00% by weight-2.00% by weight, 1.00% by weight-1.50% by weight, etc. In some embodiments, the content of Na 2 O can be controlled at 0.00% by weight, 0.25% by weight, 1.00% by weight, 1.25% by weight, 1.50% by weight, 1.75% by weight, 2.00% by weight and so on.
在一些实施方式中，K
2O的质量分数包括0.00重量％～5.00重量％及其之间的所有范围和子范围，比如可以控制在0.80重量％-5.00重量％，0.80重量％-4.00重量％，0.80重量％-3.00重量％，0.80重量％-2.00重量％，0.80重量％-1.00重量％，1.00重量％-5.00重量％，2.00重量％-5.00重量％，3.00重量％-5.00重量％，4.00重量％-5.00重量％，2.00重量％-4.00重量％，2.00重量％-3.00重量％等。在一些实施方式中，K
2O的含量可控制在0.00重量％，0.80重量％，1.00重量％，1.50重量％，2.00重量％，2.50重量％，3.00重量％，3.50重量％，4.00重量％，4.50重量％，5.00重量％等。
In some embodiments, the mass fraction of K 2 O includes 0.00% by weight to 5.00% by weight and all ranges and subranges therebetween, for example, it can be controlled at 0.80% by weight to 5.00% by weight, 0.80% by weight to 4.00% by weight, 0.80 wt%-3.00 wt%, 0.80 wt%-2.00 wt%, 0.80 wt%-1.00 wt%, 1.00 wt%-5.00 wt%, 2.00 wt%-5.00 wt%, 3.00 wt%-5.00 wt%, 4.00 wt% %-5.00% by weight, 2.00%-4.00% by weight, 2.00%-3.00% by weight, etc. In some embodiments, the content of K2O can be controlled at 0.00 wt%, 0.80 wt%, 1.00 wt%, 1.50 wt%, 2.00 wt%, 2.50 wt%, 3.00 wt%, 3.50 wt%, 4.00 wt%, 4.50% by weight, 5.00% by weight, etc.
B
2O
3的加入可以降低玻璃陶瓷中玻璃相(玻璃陶瓷中存在玻璃相和晶体相)的热膨胀系数，但是过多的B
2O
3会降低玻璃陶瓷的强度。
The addition of B 2 O 3 can reduce the thermal expansion coefficient of the glass phase in glass ceramics (there are glass phase and crystal phase in glass ceramics), but too much B 2 O 3 will reduce the strength of glass ceramics.
在一些实施方式中，B
2O
3的质量分数包括0.00重量％～5.00重量％及其之间的所有范围和子范围，比如可以控制在0.75重量％-5.00重量％，0.75重量％-4.00重量％，0.75重量％-3.00重量％，0.75重量％-2.00重量％，0.75重量％-1.00重量％，1.00重量％-5.00重量％，2.00重量％-5.00重量％，3.00重量％-5.00重量％，4.00重量％-5.00 重量％，2.00重量％-4.00重量％，2.00重量％-3.00重量％等。在一些实施方式中，B
2O
3的质量分数可控制在0.00重量％，0.50重量％，0.75重量％，1.00重量％，1.50重量％，2.00重量％，2.50重量％，3.00重量％，3.50重量％，4.00重量％，4.50重量％，5.00重量％等。
In some embodiments, the mass fraction of B 2 O 3 includes 0.00% by weight to 5.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.75% by weight to 5.00% by weight, and 0.75% by weight to 4.00% by weight , 0.75% by weight-3.00% by weight, 0.75% by weight-2.00% by weight, 0.75% by weight-1.00% by weight, 1.00% by weight-5.00% by weight, 2.00% by weight-5.00% by weight, 3.00% by weight-5.00% by weight, 4.00 % by weight-5.00% by weight, 2.00% by weight-4.00% by weight, 2.00% by weight-3.00% by weight, etc. In some embodiments, the mass fraction of B2O3 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight %, 4.00% by weight, 4.50% by weight, 5.00% by weight, etc.
MgO和ZnO参与了玻璃陶瓷MgAl
2Si
3O
10、ZnAl
2O
4、MgAl
2O
4、莫来石、堇青石、β-石英、β-石英固溶体、β-锂辉石和β-锂霞石等含镁晶体的形成。
MgO and ZnO participate in glass ceramics MgAl 2 Si 3 O 10 , ZnAl 2 O 4 , MgAl 2 O 4 , mullite, cordierite, β-quartz, β-quartz solid solution, β-spodumene and β-eucryptite formation of magnesium-containing crystals.
在一些实施方式中，MgO的质量分数包括0.00重量％～20.00重量％及其之间的所有范围和子范围，比如可以控制在0.00重量％-19.00重量％，0.00重量％-18.70重量％，0.00重量％-16.00重量％，0.00重量％-14.00重量％％，0.00重量％-13.30重量％，0.00重量％-11.00重量％，0.00重量％-9.00重量％，10.00重量％-20.00重量％，13.30重量％-20.00重量％，15.00重量％-20.00重量％，17.00重量％-20.00重量％，18.70重量％-20.00重量％等。在一些实施方式中，MgO的质量分数可控制在0.00重量％，1.00重量％，2.00重量％，3.00重量％，4.00重量％，5.00重量％，6.00重量％，7.00重量％，8.00重量％，9.00重量％，10.00重量％，11.00重量％，12.00重量％，13.00重量％，14.00重量％，15.00重量％，16.00重量％，17.00重量％，18.00重量％，19.00重量％，20.00重量％等。In some embodiments, the mass fraction of MgO includes 0.00% by weight to 20.00% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.00% by weight to 19.00% by weight, 0.00% by weight to 18.70% by weight, and 0.00% by weight %-16.00% by weight, 0.00% by weight-14.00% by weight, 0.00% by weight-13.30% by weight, 0.00% by weight-11.00% by weight, 0.00% by weight-9.00% by weight, 10.00% by weight-20.00% by weight, 13.30% by weight -20.00 wt%, 15.00 wt%-20.00 wt%, 17.00 wt%-20.00 wt%, 18.70 wt%-20.00 wt%, etc. In some embodiments, the mass fraction of MgO can be controlled at 0.00% by weight, 1.00% by weight, 2.00% by weight, 3.00% by weight, 4.00% by weight, 5.00% by weight, 6.00% by weight, 7.00% by weight, 8.00% by weight, 9.00% by weight % by weight, 10.00% by weight, 11.00% by weight, 12.00% by weight, 13.00% by weight, 14.00% by weight, 15.00% by weight, 16.00% by weight, 17.00% by weight, 18.00% by weight, 19.00% by weight, 20.00% by weight, etc.
ZrO
2和P
2O
5作为有效的成核剂，主要用于控制基础玻璃表面和内部的晶体生长速度一致，ZrO
2的质量分数应控制在0.5～10％之间，P
2O
5的质量分数应控制在0～5％。
As effective nucleating agents, ZrO 2 and P 2 O 5 are mainly used to control the crystal growth rate on the surface and inside of the basic glass. The mass fraction of ZrO 2 should be controlled between 0.5 and 10%, and the mass fraction of P 2 O 5 The score should be controlled between 0 and 5%.
在一些实施方式中，ZrO
2的质量分数包括0.5重量％～10重量％及其之间的所有范围和子范围，比如可以控制在0.50重量％-10.00重量％，0.50重量％-7.50重量％，0.50重量％-4.00重量％，0.80重量％-10.00重量％，0.80重量％-4.00重量％，4.00重量％-10.00重量％，4.00重量％-8.00重量％，4.00重量％-6.00重量％等。在一些实施方式中，ZrO
2的含量可控制在0.00重量％，0.50重量％，0.80重量％，1.00重量％，2.00重量％，3.00重量％，4.00重量％，5.00重量％，6.00重量％，7.00重量％，8.00重量％，9.00重量％，10.00重量％等。
In some embodiments, the mass fraction of ZrO 2 includes 0.5% by weight to 10% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 0.50% by weight to 10.00% by weight, 0.50% by weight to 7.50% by weight, 0.50% by weight % by weight-4.00% by weight, 0.80% by weight-10.00% by weight, 0.80% by weight-4.00% by weight, 4.00% by weight-10.00% by weight, 4.00% by weight-8.00% by weight, 4.00% by weight-6.00% by weight, etc. In some embodiments, the content of ZrO2 can be controlled at 0.00% by weight, 0.50% by weight, 0.80% by weight, 1.00% by weight, 2.00% by weight, 3.00% by weight, 4.00% by weight, 5.00% by weight, 6.00% by weight, 7.00% by weight % by weight, 8.00% by weight, 9.00% by weight, 10.00% by weight, etc.
在一些实施方式中，P
2O
5的质量分数包括0重量％～5重量％及其之间的所有范围和子范围，比如可以控制在1.00重量％-5.00重量％，1.00重量％-4.00重量％，1.00重量％-3.00重量％，1.00重量％-2.00重量％，2.00重量％-5.00重量％，3.00重量％-5.00重量％，4.00重量％-5.00重量％，2.00重量％-4.00重量％，2.00重量％-3.00重量％等。在一些实施方式中，P
2O
5的质量分数可控制在0.00重量％，0.50重量％，0.75重量％，1.00重量％，1.50重量％，2.00重量％，2.50重量％，3.00重量％，3.50重量％，4.00重量％，4.50重量％，5.00重量％等。
In some embodiments, the mass fraction of P 2 O 5 includes 0% by weight to 5% by weight and all ranges and sub-ranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, or 1.00% by weight to 4.00% by weight , 1.00% by weight-3.00% by weight, 1.00% by weight-2.00% by weight, 2.00% by weight-5.00% by weight, 3.00% by weight-5.00% by weight, 4.00% by weight-5.00% by weight, 2.00% by weight-4.00% by weight, 2.00 % by weight - 3.00% by weight, etc. In some embodiments, the mass fraction of P2O5 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight %, 4.00% by weight, 4.50% by weight, 5.00% by weight, etc.
TiO
2作为有效的成核剂加入能控制基础玻璃的析出晶体尺寸小于2μm，减小基础玻璃因生成大晶体产生裂纹的风险。
The addition of TiO 2 as an effective nucleating agent can control the precipitated crystal size of the base glass to less than 2 μm, reducing the risk of cracks in the base glass due to the formation of large crystals.
在一些实施方式中，TiO
2的质量分数包括0重量％～5重量％及其之间的所有范围和子范围，比如可以控制在1.00重量％-5.00重量％，1.00重量％-4.70重量％，1.00重量％-4.60重量％，1.00重量％-4.00重量％，1.00重量％-3.00重量％，1.00重量％-2.00重量％，2.00重 量％-5.00重量％，2.00重量％-4.00重量％，3.00重量％-5.00重量％，3.00重量％-4.00重量％，2.00重量％-3.00重量％等。在一些实施方式中，TiO
2的质量分数可控制在0.00重量％，0.50重量％，0.75重量％，1.00重量％，1.50重量％，2.00重量％，2.50重量％，3.00重量％，3.50重量％，4.00重量％，4.60重量％，4.70重量％，5.00重量％等。
In some embodiments, the mass fraction of TiO 2 includes 0% by weight to 5% by weight and all ranges and subranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, 1.00% by weight to 4.70% by weight, 1.00% by weight % by weight - 4.60% by weight, 1.00% by weight - 4.00% by weight, 1.00% by weight - 3.00% by weight, 1.00% by weight - 2.00% by weight, 2.00% by weight - 5.00% by weight, 2.00% by weight - 4.00% by weight, 3.00% by weight -5.00 wt%, 3.00 wt%-4.00 wt%, 2.00 wt%-3.00 wt%, etc. In some embodiments, the mass fraction of TiO2 can be controlled at 0.00% by weight, 0.50% by weight, 0.75% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight, 4.00% by weight, 4.60% by weight, 4.70% by weight, 5.00% by weight, etc.
CaO的加入能有效降低基础玻璃的液相线粘度，从而降低成型难度，但是过多的CaO会造成基础玻璃成型过程中的析晶，本申请中CaO的质量分数为0～5％。The addition of CaO can effectively reduce the liquidus viscosity of the basic glass, thereby reducing the difficulty of forming, but too much CaO will cause crystallization during the forming process of the basic glass. The mass fraction of CaO in this application is 0-5%.
在一些实施方式中，CaO的质量分数包括0重量％～5重量％及其之间的所有范围和子范围，比如可以控制在1.00重量％-5.00重量％，1.50重量％-5.00重量％，2.00重量％-5.00重量％，3.00重量％-5.00重量％，4.00重量％-5.00重量％，2.00重量％-4.00重量％，2.00重量％-3.00重量％等。在一些实施方式中，K
2O的含量可控制在0.00重量％，1.00重量％，1.50重量％，2.00重量％，2.50重量％，3.00重量％，3.50重量％，4.00重量％，4.50重量％，5.00重量％等。
In some embodiments, the mass fraction of CaO includes 0% by weight to 5% by weight and all ranges and subranges therebetween, for example, it can be controlled at 1.00% by weight to 5.00% by weight, 1.50% by weight to 5.00% by weight, and 2.00% by weight %-5.00 wt%, 3.00 wt%-5.00 wt%, 4.00 wt%-5.00 wt%, 2.00 wt%-4.00 wt%, 2.00 wt%-3.00 wt%, etc. In some embodiments, the content of K2O can be controlled at 0.00% by weight, 1.00% by weight, 1.50% by weight, 2.00% by weight, 2.50% by weight, 3.00% by weight, 3.50% by weight, 4.00% by weight, 4.50% by weight, 5.00% by weight etc.
由此，本申请中Li
2O的质量分数控制在0.50～10.00％，且原料中的Na
2O、K
2O、Li
2O的质量比满足：(Na
2O+K
2O)/Li
2O＜1.00，Na
2O和K
2O总质量分数≤8.00％，Na和K一般在基础玻璃晶化后富集于玻璃相内，过多的Na2O和K2O会显著升高热膨胀系数，降低玻璃陶瓷的玻璃化转变温度，同时控制β-石英、β-锂辉石和β-锂霞石的和的质量分数在0.1％～70.0％，β-石英、β-锂辉石和β-锂霞石是三种热膨胀系数较低的晶体，控制它们的总质量占比，能够对玻璃陶瓷 模具整体的热膨胀系数的调节作出贡献，从而实现了玻璃陶瓷模具的热膨胀系数在25～1000℃的温度范围内可调，调节范围为-1.0×10-6～3.0×10-5/K。
Therefore, in this application, the mass fraction of Li 2 O is controlled at 0.50-10.00%, and the mass ratio of Na 2 O, K 2 O, and Li 2 O in the raw material satisfies: (Na 2 O+K 2 O)/Li 2 O<1.00, the total mass fraction of Na 2 O and K 2 O is ≤8.00%, Na and K are generally enriched in the glass phase after crystallization of the basic glass, too much Na2O and K2O will significantly increase the thermal expansion coefficient and reduce The glass transition temperature of glass ceramics, while controlling the mass fraction of the sum of β-quartz, β-spodumene and β-eucryptite at 0.1% to 70.0%, β-quartz, β-spodumene and β-eucryptite They are three types of crystals with low thermal expansion coefficients. Controlling their total mass proportion can contribute to the adjustment of the overall thermal expansion coefficient of the glass-ceramic mold, thus realizing the thermal expansion coefficient of the glass-ceramic mold within the temperature range of 25-1000°C Adjustable, the adjustment range is -1.0×10-6～3.0×10-5/K.
在满足低热膨胀系数要求的情况下，本申请的玻璃陶瓷模具还具有宽泛可调的热膨胀系数范围，使得模具具有较宽的适用范围，提升了模具的适用性。Under the condition of meeting the requirement of low thermal expansion coefficient, the glass ceramic mold of the present application also has a wide adjustable range of thermal expansion coefficient, so that the mold has a wider application range and improves the applicability of the mold.
本申请玻璃陶瓷模具的玻璃化转变温度大于或等于700℃。玻璃陶瓷模具的玻璃化转变温度较高，即软化点较高，可适应热弯过程中的高温，避免热弯玻璃制品变形及尺寸精确度降低等现象发生。同时模具晶化后残余玻璃相的转变温度也会升高，可以减少模具在使用时模具玻璃相的形变。The glass transition temperature of the glass-ceramic mold of the present application is greater than or equal to 700°C. The glass transition temperature of the glass-ceramic mold is higher, that is, the softening point is higher, which can adapt to the high temperature during the hot bending process, and avoid the deformation of the hot-bent glass product and the reduction of dimensional accuracy. At the same time, the transition temperature of the residual glass phase after the crystallization of the mold will also increase, which can reduce the deformation of the glass phase of the mold when the mold is in use.
需要说明的是，β-石英包括β-石英固溶体和β-石英两种类型。玻璃陶瓷中β-石英、β-锂辉石和β-锂霞石的和的质量分数大于70.0％时，会显著降低玻璃陶瓷模具整体的热膨胀系数，导致玻璃陶瓷模具在25～1000℃的温度范围内的热膨胀系数范围较大程度的缩减变窄，特别是减弱其热膨胀系数范围的上限值。It should be noted that β-quartz includes β-quartz solid solution and β-quartz. When the mass fraction of the sum of β-quartz, β-spodumene and β-eucryptite in glass ceramics is greater than 70.0%, it will significantly reduce the overall thermal expansion coefficient of the glass ceramic mold, resulting in a temperature range of 25 to 1000 °C for the glass ceramic mold. The range of the coefficient of thermal expansion within the range is narrowed to a greater extent, especially the upper limit of the range of the coefficient of thermal expansion is weakened.
在一些实施方式中，本申请玻璃陶瓷中的β-石英、β-锂辉石和β-锂霞石的质量分数之和包括0.1％～70.0％范围及其之间的所有范围和子范围，比如可以控制在0.1％-70.0％，5.0％-70.0％，5.0％-60.0％，5.0％-50.0％，5.0％-47.0％，5.0％-37.0％，5.0％-35.0％，5.0％-33.0％，5.0％-30.0％，5.0％-25.0％，5.0％-16.0％，16.0％-60.0％，16.0％-50.0％，16.0％-47.0％，16.0％-35.0％，16.0％-20.0％，33.0％-70.0％，33.0％-60.0％， 33.0％-50.0％，33.0％-47.0％等。在一些实施方式中，本申请玻璃陶瓷中的β-石英、β-锂辉石和β-锂霞石的质量分数之和可控制在10.0重量％，11.0重量％，12.0重量％，13.0重量％，14.0重量％，15.0重量％，16.0重量％，17.0重量％，18.0重量％，19.0重量％，20.0重量％，21.0重量％，22.0重量％，23.0重量％，24.0重量％，25.0重量％，26.0重量％，27.0重量％，28.0重量％，29.0重量％，30.0重量％，31.0重量％，32.0重量％，33.0重量％，34.0重量％，35.0重量％，36.0重量％，37.0重量％，38.0重量％，39.0重量％，40.0重量％，41.0重量％，42.0重量％，43.0重量％，44.0重量％，45.0重量％，46.0重量％，47.0重量％，48.0重量％，49.0重量％，50.0重量％，51.0重量％，52.0重量％，53.0重量％，54.0重量％，55.0重量％，56.0重量％，57.0重量％，58.0重量％，59.0重量％，60.0重量％，61.0重量％，62.0重量％，63.0重量％，64.0重量％，65.0重量％，66.0重量％，67.0重量％，68.0重量％，69.0重量％，70.0重量％等。In some embodiments, the sum of the mass fractions of β-quartz, β-spodumene and β-eucryptite in the glass ceramics of the present application includes the range of 0.1% to 70.0% and all ranges and sub-ranges therebetween, such as Controlled at 0.1%-70.0%, 5.0%-70.0%, 5.0%-60.0%, 5.0%-50.0%, 5.0%-47.0%, 5.0%-37.0%, 5.0%-35.0%, 5.0%-33.0%, 5.0%-30.0%, 5.0%-25.0%, 5.0%-16.0%, 16.0%-60.0%, 16.0%-50.0%, 16.0%-47.0%, 16.0%-35.0%, 16.0%-20.0%, 33.0% -70.0%, 33.0%-60.0%, 33.0%-50.0%, 33.0%-47.0%, etc. In some embodiments, the sum of the mass fractions of β-quartz, β-spodumene and β-eucryptite in the glass ceramics of the present application can be controlled at 10.0% by weight, 11.0% by weight, 12.0% by weight, 13.0% by weight, 14.0 wt%, 15.0 wt%, 16.0 wt%, 17.0 wt%, 18.0 wt%, 19.0 wt%, 20.0 wt%, 21.0 wt%, 22.0 wt%, 23.0 wt%, 24.0 wt%, 25.0 wt%, 26.0 wt% %, 27.0 wt%, 28.0 wt%, 29.0 wt%, 30.0 wt%, 31.0 wt%, 32.0 wt%, 33.0 wt%, 34.0 wt%, 35.0 wt%, 36.0 wt%, 37.0 wt%, 38.0 wt%, 39.0 wt%, 40.0 wt%, 41.0 wt%, 42.0 wt%, 43.0 wt%, 44.0 wt%, 45.0 wt%, 46.0 wt%, 47.0 wt%, 48.0 wt%, 49.0 wt%, 50.0 wt%, 51.0 wt% %, 52.0 wt%, 53.0 wt%, 54.0 wt%, 55.0 wt%, 56.0 wt%, 57.0 wt%, 58.0 wt%, 59.0 wt%, 60.0 wt%, 61.0 wt%, 62.0 wt%, 63.0 wt%, 64.0% by weight, 65.0% by weight, 66.0% by weight, 67.0% by weight, 68.0% by weight, 69.0% by weight, 70.0% by weight, etc.
本申请中，玻璃化转变温度使用梅特勒-托利多DSC-3差示扫描热仪测试玻璃陶瓷模具的玻璃化转变温度，玻璃陶瓷模具提前使用玛瑙碾钵磨粉，之后过200目筛，取过筛后粉末测试。In the present application, the glass transition temperature is tested with a Mettler-Toledo DSC-3 differential scanning calorimeter to test the glass transition temperature of the glass-ceramic mold. The glass-ceramic mold is pulverized with an agate mortar in advance, and then passed through a 200-mesh sieve. Take the sifted powder for testing.
在至少一种实施方式中，本申请提供的玻璃陶瓷模具的热导率在25～1000℃的温度范围内大于等于1W/(m·k)。这样，能够使得模具的温度升高快，能更好的将热量传递到热弯玻璃制品，保证模具和玻璃制品温度快速达到一致，另外保证模具各部位温度的一致性。In at least one embodiment, the thermal conductivity of the glass-ceramic mold provided by the present application is greater than or equal to 1 W/(m·k) within the temperature range of 25-1000°C. In this way, the temperature of the mold can be raised quickly, and the heat can be better transferred to the hot-bending glass product, so that the temperature of the mold and the glass product can quickly reach the same temperature, and the temperature consistency of each part of the mold can be ensured.
本申请提供的玻璃陶瓷模具的制备方法如下：The preparation method of the glass-ceramic mold provided by the application is as follows:
步骤S100，混合工序，将各原料称量并混合均匀，制成基础混合物，所述各原料包括以下重量份：Step S100, a mixing process, weighing and mixing each raw material uniformly to form a basic mixture, and each raw material includes the following parts by weight:
SiO
2：40.00～80.00份；Al
2O
3：18.00～40.00份；ZrO
2：0.50～10.00份；Li
2O：0.50～10.00份；Na
2O：0.00～2.00份；B
2O
3：0.00～5.00份；K
2O：0.00～5.00份；MgO：0.00～20.00份；CaO：0.00～5.00份；P
2O
5：0.00～5.00份；TiO
2：0.00～5.00份；BaO：0.00～2.00份；ZnO：0.00～10.00份。
SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts; Na 2 O: 0.00-2.00 parts; B 2 O 3 : 0.00 ～5.00 parts; K 2 O: 0.00～5.00 parts; MgO: 0.00～20.00 parts; CaO: 0.00～5.00 parts; P 2 O 5 : 0.00～5.00 parts; TiO 2 : 0.00～5.00 parts; BaO: 0.00～2.00 parts parts; ZnO: 0.00 to 10.00 parts.
具体的，将上述各原料与澄清剂准确称量后充分混合均匀，装入刚玉坩埚内，澄清剂选自As
2O
3、Sb
2O
3、SnO
2、氯化物、氟化物、含SO
3-的化合物、和含NO
3-的化合物中的一种以上，优选选自SnO
2、含SO
3-的化合物、氯化物、和含NO
3-的化合物中的一种以上；优选所述澄清剂含量为0-2重量％。
Specifically, the above-mentioned raw materials and clarifying agent are accurately weighed and fully mixed evenly, and put into a corundum crucible. The clarifying agent is selected from As 2 O 3 , Sb 2 O 3 , SnO 2 , chloride, fluoride, SO 3 - compound, and more than one compound containing NO 3- , preferably one or more selected from SnO 2 , compound containing SO 3- , chloride, and compound containing NO 3- ; preferably the clarification The additive content is 0-2% by weight.
步骤S200，熔制工序，将所述基础混合物进行熔制并浇注至模具中，生成基础玻璃件。Step S200, a melting process, melting the basic mixture and pouring it into a mold to generate a basic glass piece.
具体的，将上述装有混合均匀的原料的刚玉坩埚置于硅钼棒电炉中，于1500～1700℃下熔制3～16h。待玻璃液澄清均化后，浇注到模具中，生成基础玻璃件。Specifically, the above-mentioned corundum crucible with uniformly mixed raw materials is placed in a silicon-molybdenum rod electric furnace, and melted at 1500-1700° C. for 3-16 hours. After the glass liquid is clarified and homogenized, it is poured into a mold to form a basic glass piece.
需要说明的是，此处所述的模具为盛放玻璃原料的熔化混合物，并进行降温冷却得到基础玻璃件。It should be noted that the mold described here is a molten mixture containing glass raw materials, which is cooled to obtain a basic glass piece.
步骤S300，成型工序，将所述基础玻璃件制成所需形状的玻璃模具件。Step S300, forming process, making the basic glass part into a glass mold part of desired shape.
具体的，成型工序为冷雕加工或为热弯成型。Specifically, the forming process is cold engraving or hot bending.
进一步地，成型工序为热弯成型时，采用市面上的3D热弯机进行热弯成型得到玻璃模具件，如DTK市售机型，盟立市售机型等。在一些实施方式中可选用DTK-DGP-3D12S3D热弯机，或者盟立CG07-4222热弯机等。Furthermore, when the forming process is hot bending, use a 3D hot bending machine on the market to perform hot bending to obtain a glass mold part, such as a commercially available model from DTK, a commercially available model from Mengli, and the like. In some embodiments, DTK-DGP-3D12S3D hot bending machine, or Mengli CG07-4222 hot bending machine can be used.
进一步地，成型工序为冷雕加工时，在所述成型工序前还包括退火工序，所述退火工序为将所述基础玻璃件退火，冷却至室温。玻璃的退火，就是把具有永久应力的玻璃制品重新加热到玻璃内部质点可以移动的温度，利用质点的位移使应力分散来消除或减弱永久应力，从而提高玻璃制品的热膨胀均匀性和机械强度。Further, when the forming process is cold engraving, an annealing process is also included before the forming process, and the annealing process is to anneal the basic glass piece and cool it to room temperature. The annealing of glass is to reheat the glass product with permanent stress to the temperature where the particles inside the glass can move, and use the displacement of the particle to disperse the stress to eliminate or weaken the permanent stress, thereby improving the thermal expansion uniformity and mechanical strength of the glass product.
玻璃的退火范围一般为退火点和应变点之间，对应的玻璃粘度为1013dPa·s至1014.7dPa·s。高于退火点温度时，玻璃会软化变形；低于退火温度下限时，玻璃结构实际上可认为已固定，内部质点已不能移动，也就无法分散或消除应力。在应变点附近可在数小时内消除玻璃内部应力，理论上退火时间越长玻璃的应力越小，均匀性越高。另外，新的应力会在玻璃退火降温过程中新产生，降温速率越慢，所产生的应力越小，内外玻璃的应力均匀性越高，玻璃的热膨胀系数均匀性也越高。The annealing range of glass is generally between the annealing point and the strain point, and the corresponding glass viscosity is 1013dPa·s to 1014.7dPa·s. When the temperature is higher than the annealing temperature, the glass will soften and deform; when it is lower than the lower limit of the annealing temperature, the glass structure can actually be considered fixed, and the internal particles can no longer move, so it is impossible to disperse or eliminate stress. The internal stress of the glass can be eliminated within a few hours near the strain point. Theoretically, the longer the annealing time, the smaller the stress of the glass and the higher the uniformity. In addition, new stress will be newly generated during the annealing and cooling process of the glass. The slower the cooling rate, the smaller the stress generated, the higher the stress uniformity of the inner and outer glass, and the higher the uniformity of the thermal expansion coefficient of the glass.
具体地，将获取的基础玻璃件于600～900℃退火30～1200h，进一步，为控制模具不同部位膨胀系数的一致性，优选120h以上退火时间，本申请中依照标准GB/T 28196-2011《玻璃退火点和应变点测试方法》确认玻璃的退火点，应变点由退火点数据外推确定，应变点 是粘滞挠曲速度为退火粘滞挠曲速度0.0316倍时的温度，本申请的退火温度为玻璃退火粘滞挠曲速度0.02～0.0316倍时的温度，在此温度范围内可获得更好的退火效果，即热膨胀系数均匀性越高。Specifically, the obtained basic glass parts are annealed at 600-900°C for 30-1200 hours. Further, in order to control the consistency of the expansion coefficient of different parts of the mold, the annealing time is preferably more than 120 hours. In this application, according to the standard GB/T 28196-2011 " Glass annealing point and strain point test method "Confirm the annealing point of the glass, the strain point is determined by extrapolation of the annealing point data, the strain point is the temperature when the viscous deflection velocity is 0.0316 times the annealing viscous deflection velocity, the annealing of this application The temperature is the temperature at which the annealing viscous deflection velocity of the glass is 0.02 to 0.0316 times. In this temperature range, a better annealing effect can be obtained, that is, the higher the uniformity of the thermal expansion coefficient.
进而再以5～20℃/h的降温速度冷却到室温，随后通过CNC冷雕，对基础玻璃进行磨边，去除余量，并通过钻头将基础玻璃进行倒边和钻孔等工序，以满足终成品要求，得到玻璃模具件。Then cool down to room temperature at a cooling rate of 5-20°C/h, and then use CNC cold engraving to grind the edges of the basic glass to remove the excess, and use the drill to chamfer and drill the basic glass to meet the According to the requirements of the final product, the glass mold parts are obtained.
步骤S400，微晶化处理工序，将所述玻璃模具件依次进行核化、晶化处理，制成所述微晶化模具件；Step S400, a microcrystallization treatment process, performing nucleation and crystallization treatments on the glass mold part in sequence to make the microcrystallization mold part;
具体的，所述核化的温度为650～1000℃，核化的时间为1～6小时；晶化的温度为900～1400℃，晶化的时间为0～15小时。Specifically, the nucleation temperature is 650-1000°C, and the nucleation time is 1-6 hours; the crystallization temperature is 900-1400°C, and the crystallization time is 0-15 hours.
在一种实施方式中，当成型工序为热弯成型时，微晶化处理工序能够与热弯成型同时进行，具体地，在对玻璃模具件热弯成型的同时，进行微晶化处理。In one embodiment, when the forming process is hot bending forming, the microcrystallization treatment process can be performed simultaneously with the hot bending forming, specifically, the microcrystallization treatment is performed while the glass mold part is hot bending forming.
其中，核化处理的过程：通过在玻璃组分中引入适当的晶核剂，在随后的热处理过程中，玻璃的粘度降低，玻璃中会析出(成核和生长)大量均匀的微小晶体，即晶核。Among them, the process of nucleation treatment: by introducing an appropriate crystal nucleating agent into the glass component, the viscosity of the glass will decrease during the subsequent heat treatment, and a large number of uniform tiny crystals will be precipitated (nucleated and grown) in the glass, that is crystal nucleus.
晶化处理的过程：在析出的晶核表面生长出所需的晶体，使玻璃内部组成变为晶体相和玻璃相。The process of crystallization treatment: the required crystals are grown on the surface of the precipitated crystal nuclei, so that the internal composition of the glass changes into a crystal phase and a glass phase.
合适的核化温度和时间有利于析出尺寸均匀和细小的晶核，进一步在晶化处理过程中生长出尺寸均匀和细小的晶体。Appropriate nucleation temperature and time are conducive to the precipitation of uniform and fine crystal nuclei, and further growth of uniform and fine crystals during the crystallization process.
本申请中核化温度的确认：使用差示扫描量热法(DSC)测试玻璃的玻璃化转变温度Tg，核化温度为(Tg-20)～(Tg+130)℃。具 体的测试条件为玻璃退火后磨粉，过200目筛，过筛后玻璃粉经300℃烘干60min后，取玻璃粉20mg烘干以10℃/min的升温速率，测试室温～1500℃的DSC数据，以DSC曲线的第一个吸热峰的斜率最大处为Tg点。Confirmation of the nucleation temperature in this application: use differential scanning calorimetry (DSC) to test the glass transition temperature Tg of the glass, and the nucleation temperature is (Tg-20)～(Tg+130)°C. The specific test conditions are that the glass powder is ground after annealing, passed through a 200-mesh sieve, and after sieving, the glass powder is dried at 300°C for 60 minutes, then 20 mg of glass powder is taken and dried at a heating rate of 10°C/min, and the temperature of the room temperature to 1500°C is tested. For DSC data, the point where the slope of the first endothermic peak of the DSC curve is the largest is the Tg point.
晶化即为在已形成晶核的玻璃陶瓷或玻璃中通过热处理生长出晶体。Crystallization is the growth of crystals through heat treatment in glass ceramics or glasses that have formed crystal nuclei.
本申请中晶化温度的确认：使用差示扫描量热法(DSC)测试玻璃的首个析晶峰值温度Tc，晶化温度为(Tc-50)～(Tc+50)℃。具体的测试条件为玻璃退火后磨粉，过200目筛，过筛后玻璃粉经300℃烘干60min后，取玻璃粉20mg烘干以10℃/min的升温速率，测试室温～1500℃的DSC数据，以DSC曲线的第一个放热峰的斜率最小处为Tc点。Confirmation of the crystallization temperature in this application: use differential scanning calorimetry (DSC) to test the first crystallization peak temperature Tc of the glass, and the crystallization temperature is (Tc-50)～(Tc+50)°C. The specific test conditions are that the glass powder is ground after annealing, passed through a 200-mesh sieve, and after sieving, the glass powder is dried at 300°C for 60 minutes, then 20 mg of glass powder is taken and dried at a heating rate of 10°C/min, and the temperature of the room temperature to 1500°C is tested. For DSC data, the point where the slope of the first exothermic peak of the DSC curve is the smallest is the Tc point.
晶化对热膨胀系数的影响：通过控制坯件的晶化温度和晶化时间可获得不同结晶度，不同晶相的玻璃陶瓷的热膨胀系数差异较大，因此，可以通过调整组成、晶化温度和晶化时间来调控玻璃陶瓷的热膨胀系数。The influence of crystallization on the thermal expansion coefficient: different crystallinity can be obtained by controlling the crystallization temperature and crystallization time of the blank, and the thermal expansion coefficients of glass ceramics with different crystal phases are quite different. Therefore, it is possible to adjust the composition, crystallization temperature and The crystallization time is used to control the thermal expansion coefficient of glass ceramics.
晶化对抗热震性的影响：当裂纹沿着热膨胀系数相差很大的不同颗粒的边界进行扩展时，由于可通过晶内的解理面发生弯曲、钝化和分支，从而使得材料的抗热震性得到改善。因此，可以通过调整原料组成、晶化温度和晶化时间来获得抗热震性高的玻璃陶瓷。The effect of crystallization on thermal shock resistance: when cracks propagate along the boundaries of different particles with greatly different thermal expansion coefficients, the thermal resistance of the material can be improved due to the bending, passivation and branching of the cleavage plane in the crystal. Vibration has been improved. Therefore, glass ceramics with high thermal shock resistance can be obtained by adjusting the raw material composition, crystallization temperature and crystallization time.
具体的，将所述玻璃模具件在650～1000℃核化1～6h，然后在900～1400℃晶化0～15h，进一步，晶化时间包括0～15h及其之间所有 的范围和子范围，例如1h～2h、1h～3h、1h～4h、1h～5h、2h～3h、2h～4h、2h～5h、5h～15h、10h～11h、10h～12h、10h～13h、10h～14h、10h～15h、14h～15等，优选为5h～15h，包括6h～15h、7h～12h、7h～13h、7h～14h等。Specifically, the glass mold part is nucleated at 650-1000°C for 1-6h, and then crystallized at 900-1400°C for 0-15h, further, the crystallization time includes 0-15h and all ranges and sub-ranges therebetween , such as 1h～2h, 1h～3h, 1h～4h, 1h～5h, 2h～3h, 2h～4h, 2h～5h, 5h～15h, 10h～11h, 10h～12h, 10h～13h, 10h～14h, 10h~15h, 14h~15, etc., preferably 5h~15h, including 6h~15h, 7h~12h, 7h~13h, 7h~14h, etc.
步骤S500，冷却工序，将所述微晶化模具件退火冷却至室温后生成玻璃陶瓷模具。Step S500, cooling process, annealing and cooling the microcrystallized mold part to room temperature to form a glass ceramic mold.
具体的，以5～40℃/h的降温速度冷却到室温，为控制模具不同部位膨胀系数的均匀性，优选5～20℃/h的冷却速度。Specifically, it is cooled to room temperature at a cooling rate of 5-40 °C/h. In order to control the uniformity of the expansion coefficient of different parts of the mold, a cooling rate of 5-20 °C/h is preferred.
在至少一种实施方式中，所述冷却工序后，还包括对所述玻璃陶瓷模具的抛光工序。模具制备完成后，在待热弯坯件进行热弯时，将待热弯坯件放入上述模具中，然后放入热弯机中，设置热弯工艺，待冷却后取出。该热弯模具具备高热导率、耐高温、高软化点和高抗热震性等优点，且玻璃热弯后的尺寸精度并未发生改变。并且高温下抗氧化，使用寿命长，适合2.5D或3D玻璃批量生产。In at least one embodiment, after the cooling process, a polishing process for the glass-ceramic mold is also included. After the mold is prepared, put the blank to be bent into the above-mentioned mold when the blank is to be bent, then put it into the bending machine, set the bending process, and take it out after cooling. The hot bending mold has the advantages of high thermal conductivity, high temperature resistance, high softening point and high thermal shock resistance, and the dimensional accuracy of the glass after hot bending has not changed. It is also resistant to oxidation at high temperatures and has a long service life, suitable for mass production of 2.5D or 3D glass.
在至少一种实施方式中，膨胀系数均匀性测试方法为：在所制备基础模具上，取直径为6mm，厚度10mm的的A、B样品，分别测试热膨胀系数，A/B在0.995～1.005，即满足退火膨胀系数的均匀性要求。测试仪器为德国NETZSCH-DIL402C高温热膨胀系数仪。In at least one embodiment, the method for testing the uniformity of the coefficient of expansion is as follows: on the prepared basic mold, take samples A and B with a diameter of 6 mm and a thickness of 10 mm, and test the coefficient of thermal expansion respectively, A/B is 0.995-1.005, That is to meet the uniformity requirements of the annealing expansion coefficient. The test instrument is Germany NETZSCH-DIL402C high temperature thermal expansion coefficient meter.
玻璃陶瓷模具的热导率测试方法为：测试样品尺寸长宽厚为100mm*100*1mm。测试仪器为热流法导热测试仪HFM436。The thermal conductivity test method of the glass ceramic mold is: the size of the test sample is 100mm*100*1mm in length, width and thickness. The test instrument is the heat flow method thermal conductivity tester HFM436.
平均粗糙度测试的方法为：使用化矿TR200粗糙度仪在样品表面分别测试三次，每次取样长度20mm，以三次所测粗糙的平均值作 为样品的平均粗糙度。The average roughness test method is as follows: use the Huakuang TR200 roughness meter to test the surface of the sample three times, each sampling length is 20mm, and the average roughness of the three times is taken as the average roughness of the sample.
下面通过具体实施例来说明本申请制备的玻璃陶瓷热弯模具的性能参数。The performance parameters of the glass-ceramic hot-bending mold prepared in the present application are illustrated below through specific examples.
下述表1-1为实施例1-6及对比例1中各玻璃陶瓷模具基础玻璃的原料组成表，表1-2为实施例1-6及对比例1各玻璃陶瓷模具制备过程的具体工艺参数表，表1-3为实施例1-6及对比例1制备好的各玻璃陶瓷模具的主晶相及性能参数表。Following table 1-1 is the raw material composition table of each glass-ceramic mold base glass in embodiment 1-6 and comparative example 1, and table 1-2 is the concrete of each glass-ceramic mold preparation process of embodiment 1-6 and comparative example 1 Process parameter table, table 1-3 is the main crystal phase and performance parameter table of each glass ceramic mold prepared in embodiment 1-6 and comparative example 1.
表1-1玻璃陶瓷模具基础玻璃组成表Table 1-1 Basic glass composition of glass ceramic mold
表1-2玻璃陶瓷模具制备工艺参数表Table 1-2 Glass ceramic mold preparation process parameter table
下面以实施例1为例，根据表1-1、和1-2的数据具体描述玻璃陶瓷模具的制备流程：Taking Example 1 as an example below, the preparation process of the glass-ceramic mold is specifically described according to the data in Table 1-1 and 1-2:
准确称取各原料：SiO
2：47.10份；Al
2O
3：28.50份；ZrO
2：0.80份；Li
2O：2.50份；Na
2O：0.00份，B
2O
3：0.00份，K
2O：0.80份，MgO：13.30份，CaO：0.00份，P
2O
5：0.00份，TiO
2：4.70份，BaO：0.00份，ZnO：2.30份。将各原料充分混合均匀，装入刚玉坩埚内，加入澄清剂，将刚玉坩埚置于硅钼棒电炉中于1640℃下熔制5h，待玻璃液澄清均化后，浇注到模具中生成基础玻璃件。将获取的基础玻璃件于720℃退火120h，再以6℃/h的降温速度冷却到室温，随后进行CNC冷雕，并对基础玻璃进行磨边，去除余量，通过钻头将基础玻璃进行倒边和钻孔等工序，以满足终成品要求，得到玻璃模具件。将所述玻璃模具件在830℃温度下核化2h，然后在1200℃温度下晶化3h，再以7℃/h的降温速度冷却到室温，然后进行抛光工序，即完成玻璃陶瓷模具的制备过程。
Accurately weigh each raw material: SiO 2 : 47.10 parts; Al 2 O 3 : 28.50 parts; ZrO 2 : 0.80 parts; Li 2 O: 2.50 parts; Na 2 O: 0.00 parts, B 2 O 3 : 0.00 parts, K 2 O: 0.80 parts, MgO: 13.30 parts, CaO: 0.00 parts, P 2 O 5 : 0.00 parts, TiO 2 : 4.70 parts, BaO: 0.00 parts, ZnO: 2.30 parts. Mix all raw materials well, put them into a corundum crucible, add clarifier, put the corundum crucible in a silicon-molybdenum rod electric furnace and melt at 1640°C for 5 hours, after the glass liquid is clarified and homogenized, pour it into a mold to form a basic glass pieces. Anneal the acquired basic glass at 720°C for 120h, then cool it down to room temperature at a cooling rate of 6°C/h, then carry out CNC cold carving, and grind the edge of the basic glass to remove the excess, and pour the basic glass through a drill Edge and drilling processes to meet the requirements of the final product to obtain glass mold parts. The glass mold parts were nucleated at 830°C for 2 hours, then crystallized at 1200°C for 3 hours, then cooled to room temperature at a cooling rate of 7°C/h, and then polished to complete the preparation of the glass ceramic mold process.
实施例2-6及对比例1同样参照表1-1和表1-2的数据要求并与实施例1的制备流程相同，此处不再赘述。表1-3为基于表1-1和表1-2制备的玻璃热弯模具的主晶相及性能参数表。Examples 2-6 and Comparative Example 1 also refer to the data requirements of Table 1-1 and Table 1-2, and the preparation process is the same as that of Example 1, and will not be repeated here. Table 1-3 is a table of main crystal phases and performance parameters of glass hot bending molds prepared based on Table 1-1 and Table 1-2.
表1-3玻璃陶瓷模具晶相及性能参数表Table 1-3 Crystal phase and performance parameters of glass ceramic mold
下面以实施例1为例，根据表格1-3描述制备完成的热弯模具：Taking Example 1 as an example, describe the prepared hot bending mold according to Table 1-3:
制备完成的玻璃陶瓷热弯模具的主晶相包括：堇青石、β-石英固溶体、β-石英，且晶相中β-石英固溶体、β-石英、β-锂辉石和β-锂霞石的和的质量分数为16wt％，晶化后的玻璃陶瓷热弯模具的玻璃化转变温度为760℃；25～1000℃的热膨胀系数为2.2×10
-6/K； 在所制备的基础模具上，取直径为6mm，厚度10mm的A、B样品，利用德国NETZSCH-DIL402C高温热膨胀系数仪分别测试A、B样品热膨胀系数，得出A/B为0.996，满足退火膨胀系数的均匀性要求；
The main crystal phase of the prepared glass ceramic hot bending mold includes: cordierite, β-quartz solid solution, β-quartz, and the β-quartz solid solution, β-quartz, β-spodumene and β-eucryptite in the crystal phase The mass fraction of and is 16wt%, and the glass transition temperature of the crystallized glass-ceramic hot-bending mold is 760°C; the coefficient of thermal expansion at 25-1000°C is 2.2×10 -6 /K; on the prepared basic mold, Take A and B samples with a diameter of 6mm and a thickness of 10mm, and use the German NETZSCH-DIL402C high-temperature thermal expansion coefficient meter to test the thermal expansion coefficients of A and B samples respectively, and the A/B is 0.996, which meets the uniformity requirements of the annealing expansion coefficient;
测试热导率时，在玻璃陶瓷热弯模具上获取长宽厚为100mm*100*1mm的样品，利用热流法导热测试仪HFM436进行测试，热导率为2.81W/(m·k)，测试玻璃陶瓷热弯模具的平均粗糙度时，使用化矿TR200粗糙度仪在实施例1的玻璃陶瓷热弯模具表面分别测试三次，每次取样长度20mm，以三次所测粗糙的平均值作为样品的平均粗糙度，测得的实施例1的玻璃陶瓷热弯模具的平均粗糙度为0.008μm。实施例2-6同上，此处不再赘述。When testing the thermal conductivity, a sample with a length, width, and thickness of 100mm*100*1mm is obtained on a glass ceramic hot bending mold, and the heat flow method thermal conductivity tester HFM436 is used for testing. The thermal conductivity is 2.81W/(m·k), and the test glass When the average roughness of the ceramic hot bending mold is tested three times on the surface of the glass ceramic hot bending mold in Example 1 using the Huashen TR200 roughness meter, each sampling length is 20mm, and the average value of the roughness measured three times is used as the average value of the sample. Roughness, the measured average roughness of the glass-ceramic hot-bending mold of Example 1 is 0.008 μm. Embodiments 2-6 are the same as above, and will not be repeated here.
其中，对比例1与实施例3的原料组成相同，制备过程中的晶化温度为1450度，大于1400度，晶化时间为30，大于15h，制备的热弯模具的主晶相为β-石英固溶体，且制备的热弯模具的的β-石英固溶体、β-石英、β-锂辉石和β-锂霞石的和的质量分数为73wt％，大于70wt％，降低了玻璃陶瓷模具整体的热膨胀系数。Wherein, comparative example 1 and embodiment 3 have the same raw material composition, the crystallization temperature in the preparation process is 1450 degrees, greater than 1400 degrees, the crystallization time is 30, greater than 15h, the main crystal phase of the prepared hot bending mold is β- Quartz solid solution, and the mass fraction of the sum of β-quartz solid solution, β-quartz, β-spodumene and β-eucryptite of the prepared hot-bending mold is 73wt%, greater than 70wt%, which reduces the overall weight of the glass-ceramic mold Thermal expansion coefficient.
利用以上实施例1-6中制备的各玻璃陶瓷热弯模具对玻璃制品进行热弯，选取A-E五件玻璃制品，各玻璃制品的原料组成及性能参数见表1-4。The glass ceramic hot bending molds prepared in the above Examples 1-6 were used to hot bend the glass products, and five glass products A-E were selected. The raw material composition and performance parameters of each glass product are shown in Table 1-4.
表1-4玻璃制品原料组成及性能表Table 1-4 Raw material composition and properties of glass products
根据表1-4可知，其中，玻璃制品B和玻璃制品C为玻璃，玻璃制品A、玻璃制品D和玻璃制品E为玻璃陶瓷，首先选取不同批次的玻璃制品A利用实施例1-6制备的热弯模具进行热弯，不同批次生产的玻璃制品A的粗糙度不同，热弯后的玻璃制品的性能见表1-5。According to Table 1-4, it can be seen that glass product B and glass product C are glass, glass product A, glass product D and glass product E are glass ceramics, and glass products A of different batches are firstly selected and prepared using Examples 1-6 The roughness of the glass product A produced in different batches is different. The performance of the glass product after hot bending is shown in Table 1-5.
表1-5玻璃制品A热弯后性能参数表Table 1-5 Performance parameters of glass product A after hot bending
根据表1-5可知，利用实施例1-6制备的热弯模具对不同粗糙度的同体系的玻璃制品A进行热弯，当在0.2～1.4范围内时，玻璃制品热弯后的平均粗糙度在12％～40％范围内，进一步，当在0.3～0.7范围内时，玻璃制品热弯后的平均粗糙度在15％～30％范围内，当在0～0.2范围内时，玻璃制品热弯后的平均粗糙度在70％～95％范围内，然而当为3.06时，玻璃制品热弯后的平均粗糙度为132％，相比金属或石墨模具中的热弯后玻璃制品400％的平均粗糙度的涨幅相比，依然有较大改善。According to Table 1-5, it can be known that the glass product A of the same system with different roughness is subjected to hot bending by using the hot bending mold prepared in Example 1-6. When it is in the range of 0.2 to 1.4, the average roughness The roughness is in the range of 12% to 40%. Further, when it is in the range of 0.3 to 0.7, the average roughness of the glass product after hot bending is in the range of 15% to 30%. When it is in the range of 0 to 0.2, the average roughness of the glass product is The average roughness after hot bending is in the range of 70% to 95%. However, when it is 3.06, the average roughness of glass products after hot bending is 132%, which is 400% compared with the hot bending glass products in metal or graphite molds. Compared with the increase in the average roughness of , there is still a big improvement.
如上，针对同一个玻璃体系但不同粗糙度的玻璃制品，本申请玻璃陶瓷模具有着良好的适用性。不仅具有宽泛可调的热膨胀系数，能适配玻璃制品的热膨胀系数，改进较大的热膨胀系数差异，进而避免粗糙度提升较大的问题。还进一步教导如何通过调节热膨胀系数差异 范围控制粗糙度提升幅度的情况。As above, for glass products with the same glass system but different roughness, the glass ceramic mold of the present application has good applicability. Not only has a wide adjustable thermal expansion coefficient, but also can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and thus avoid the problem of a large increase in roughness. It further teaches how to control the degree of roughness improvement by adjusting the range of differences in thermal expansion coefficients.
进一步，选取实施例1制备的玻璃陶瓷热弯模具对上述表1-4中的玻璃制品A～玻璃制品E分别进行热弯加工，加工后的玻璃制品的性能见表1-6。Further, the glass-ceramic hot-bending mold prepared in Example 1 was selected to perform hot-bending processing on the glass products A to E listed in Tables 1-4 above, and the properties of the processed glass products are shown in Tables 1-6.
表1-6玻璃制品A-E热弯后性能参数表Table 1-6 Performance parameters of glass products A-E after hot bending
根据表1-6可知，利用实施例1制备的热弯模具对不同体系的玻璃制品A-玻璃制品E分别进行热弯，热弯后的玻璃制品体系不会发生改变，且当在0.3～0.7范围内时，玻璃制品热弯后的平均粗糙度在15％～30％范围内。可见，针对不同玻璃体系的玻璃制品，本申请玻璃陶瓷模具有着良好的适用性。According to Tables 1-6, it can be seen that using the hot bending mold prepared in Example 1 to heat bend glass products A-glass product E of different systems, the glass product system after hot bending will not change, and when the temperature is between 0.3 and 0.7 When it is within the range, the average roughness of the glass product after hot bending is within the range of 15% to 30%. It can be seen that for glass products of different glass systems, the glass ceramic mold of the present application has good applicability.
针对实施例1提供的工艺参数范围，分别针对退火时间、核化时间、晶化时间和退火温度各提供一组对比例，得到的热弯模具性能及 热弯后的玻璃制品情况见表1-7所示：For the range of process parameters provided in Example 1, a set of comparative examples is provided for the annealing time, nucleation time, crystallization time and annealing temperature respectively. The performance of the hot bending mold and the conditions of the glass products after hot bending are shown in Table 1- 7 shows:
表1-7工艺参数对比例表Table 1-7 Comparison table of process parameters
根据表1-7可知，当退火时间小于30h时，25-1000℃热膨胀系数较大，且热膨胀系数均匀性较不稳定，玻璃制品热弯后的平均粗糙度大幅提升；当核化时间小于1h时，由于核化时间过短，玻璃在晶化时发生非均匀的析晶，晶化后玻璃破裂，无法使用；当晶化时间大于15h时，25-1000℃热膨胀系数较大，且热膨胀系数均匀性较不稳定，玻璃制品热弯后的平均粗糙度大幅提升；当退火温度25-1000℃热膨胀系数较大，且热膨胀系数均匀性较不稳定，玻璃制品热弯后的平均粗糙度大幅提升；由此可见，利用本申请限定的退火时间、核化时间、晶化时间和退火温度才能制得热膨胀系数合适、均匀性较好，且玻璃制品热弯后平均粗糙度低的玻璃陶瓷热弯模具。According to Table 1-7, it can be seen that when the annealing time is less than 30h, the thermal expansion coefficient at 25-1000°C is relatively large, and the uniformity of the thermal expansion coefficient is relatively unstable, and the average roughness of the glass product after hot bending is greatly improved; when the nucleation time is less than 1h When the nucleation time is too short, non-uniform crystallization occurs in the glass during crystallization, and the glass breaks after crystallization and cannot be used; The uniformity is relatively unstable, and the average roughness of glass products after hot bending is greatly improved; when the annealing temperature is 25-1000°C, the thermal expansion coefficient is relatively large, and the uniformity of thermal expansion coefficient is relatively unstable, and the average roughness of glass products after hot bending is greatly improved It can be seen that only the annealing time, nucleation time, crystallization time and annealing temperature defined in the present application can be used to produce glass ceramics with suitable thermal expansion coefficient, good uniformity, and low average roughness after glass products are bent. mold.
本申请还提供一对比例，该对比例为市面上常见的石墨热弯模具，利用比例1的石墨模具与实施例1的玻璃陶瓷热弯模具对相同的玻璃制品进行热弯，其性能与实施例1对比，见下表：The application also provides a pair of ratios, which are common graphite hot bending molds on the market. The graphite mold of ratio 1 and the glass ceramic hot bending mold of Example 1 are used to hot bend the same glass products. Example 1 comparison, see the table below:
表1-8性能参数对比表Table 1-8 Performance parameter comparison table
| 性能参数performance parameter | 实施例1Example 1 | 石墨模具graphite mold |
| 热膨胀系数(25～1000℃)/(×10 -6/K) Coefficient of thermal expansion (25～1000℃)/(×10 -6 /K) | 2.22.2 | 4.04.0 |
| 热导率(25～1000℃)/[W/(m·k)]Thermal conductivity (25～1000℃)/[W/(m·k)] | 2.812.81 | 4.184.18 |
| 热弯温度(℃，空气气氛)Bending temperature (°C, air atmosphere) | 760760 | 760760 |
| 正常热弯使用温度(℃，空气气氛)Normal bending temperature (°C, air atmosphere) | 700-1100700-1100 | ＜350<350 |
| 模具的平均粗糙度(μm)Average roughness of mold (μm) | 0.0080.008 | 0.0090.009 |
| 玻璃制品热弯前的平均粗糙度(μm)Average roughness of glass products before hot bending (μm) | 0.00760.0076 | 0.00760.0076 |
| 玻璃制品热弯后的平均粗糙度提升Increased average roughness of glass products after hot bending | 23％twenty three% | 320％320% |
| 热弯后模具粗糙度增加百分比Percent increase in mold roughness after hot bending | 4％4% | 450％450% |
| 热弯后模具质量减少量Die mass reduction after hot bending | 00 | 12％12% |
根据上述表格1-1至1-8可知，通过原料比例的配合和调整，以及制备工艺的严格控制，制备出的玻璃陶瓷热弯模具具备良好的性能，通过控制原料中(Na
2O+K
2O)/Li
2O＜1.00，且Na
2O和K
2O总质量分数≤8.00％，使得玻璃陶瓷的热膨胀系数控制在-1.0×10
-6～3.0×10
-5/K，且其玻璃化转变温度大于等于700℃，而原料中Li
2O的质量分数控制在0.50～10.00％，使得晶化后的β-石英、β-锂辉石和β-锂霞石的和的质量分数在0.1％～70.0％范围内，从而实现玻璃陶瓷模具的热膨胀系数在25～1000℃的温度范围内可调节(调节范围为-1.0×10-6～ 3.0×10-5)。
According to the above tables 1-1 to 1-8, it can be seen that through the combination and adjustment of raw material ratios and strict control of the preparation process, the glass ceramic hot bending molds prepared have good performance. By controlling the (Na 2 O+K 2 O)/Li 2 O<1.00, and the total mass fraction of Na 2 O and K 2 O is ≤8.00%, so that the thermal expansion coefficient of glass ceramics is controlled at -1.0×10 -6 ~ 3.0×10 -5 /K, and its The glass transition temperature is greater than or equal to 700 ° C, and the mass fraction of Li 2 O in the raw material is controlled at 0.50-10.00%, so that the mass fraction of the sum of β-quartz, β-spodumene and β-eucryptite after crystallization is In the range of 0.1% to 70.0%, the thermal expansion coefficient of the glass ceramic mold can be adjusted in the temperature range of 25 to 1000°C (the adjustment range is -1.0×10-6 to 3.0×10-5).
由此，由于玻璃陶瓷模具有宽泛可调的热膨胀系数，能适配玻璃制品的热膨胀系数，改进较大的热膨胀系数差异，进而避免粗糙度提升较大的问题。Therefore, since the glass ceramic mold has a wide adjustable coefficient of thermal expansion, it can adapt to the thermal expansion coefficient of glass products, improve the large difference in thermal expansion coefficient, and avoid the problem of a large increase in roughness.
且玻璃陶瓷模具的玻璃化转变温度较高，即软化点较高，可适应热弯过程中的高温，避免热弯玻璃制品变形及尺寸精确度降低等现象发生。Moreover, the glass transition temperature of the glass-ceramic mold is higher, that is, the softening point is higher, which can adapt to the high temperature during the hot bending process, and avoid the deformation of hot-bent glass products and the reduction of dimensional accuracy.
另一方面，制备的玻璃陶瓷热弯模具的热导率在25～1000℃的温度范围内大于等于1W/(m·k)，具有良好的导热性，能够实现快速传热，进一步，通过控制工艺参数中的退火时间、退火温度、核化时间和晶化时间在合理范围内，来控制玻璃陶瓷热弯模具不同部位膨胀系数的均匀性、以及保证热弯后玻璃制品的低粗糙度。On the other hand, the thermal conductivity of the prepared glass-ceramic hot bending mold is greater than or equal to 1W/(m·k) in the temperature range of 25-1000°C, which has good thermal conductivity and can realize rapid heat transfer. Further, by controlling The annealing time, annealing temperature, nucleation time and crystallization time in the process parameters are within a reasonable range to control the uniformity of the expansion coefficient of different parts of the glass ceramic hot bending mold and to ensure the low roughness of the glass product after hot bending.
进一步，根据表1-8中对比例与实施例1对比可知，在热弯温度均为760℃、玻璃制品热弯前的平均粗糙度均为0.0076μm，且模具的平均粗糙度相近的条件下，本申请提供的玻璃陶瓷热弯模具热弯玻璃制品后平均粗糙度的提升远小于传统的石墨模具，且玻璃陶瓷热弯模具热弯玻璃制品后模具质量减少量为0％，而石墨模具减少量为12％，以及本申请提供的玻璃陶瓷热弯模具的使用温度远远高于传统石墨模具。Further, according to the comparison between the comparative examples in Tables 1-8 and Example 1, it can be seen that under the conditions that the bending temperature is 760°C, the average roughness of glass products before bending is 0.0076 μm, and the average roughness of the mold is similar , the improvement of the average roughness of the glass-ceramic hot-bending mold provided by the application after hot-bending glass products is much smaller than that of traditional graphite molds, and the reduction in mold mass after hot-bending glass products by the glass-ceramic hot-bending mold is 0%, while graphite molds reduce The amount is 12%, and the service temperature of the glass-ceramic hot-bending mold provided by the application is much higher than that of the traditional graphite mold.
由此，本申请提供的玻璃陶瓷热弯模具克服传统石墨模具不耐氧化，寿命短，使用温度低的缺点，实现了易加工、高热导率、耐高温、低膨胀、高软化点和高抗热震性等优点，且玻璃热弯后的尺寸精度并 未发生改变。Thus, the glass-ceramic hot-bending mold provided by this application overcomes the shortcomings of traditional graphite molds such as low oxidation resistance, short service life, and low operating temperature, and realizes easy processing, high thermal conductivity, high temperature resistance, low expansion, high softening point, and high resistance to corrosion. Thermal shock resistance and other advantages, and the dimensional accuracy of the glass after hot bending has not changed.
以上所述，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以所述权利要求的保护范围为准。The above is only a specific embodiment of the application, but the scope of protection of the application is not limited thereto. Any person familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the application. All should be covered within the scope of protection of this application. Therefore, the protection scope of the present application should be determined by the protection scope of the claims.
Claims (10)
- 一种玻璃制品的加工方法，其特征在于，控制热弯模具的热膨胀系数A1和玻璃制品的热膨胀系数A2的比值的绝对值，A glass product processing method, characterized in that the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is controlled,当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.2～1.4之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高12％～40％。When the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.2 and 1.4, the average roughness of the glass product after hot bending is higher than that before hot bending 12% to 40%.
- 如权利要求1所述的加工方法，其特征在于，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0.3～0.7之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高15％～30％。The processing method according to claim 1, wherein when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0.3 and 0.7, the glass product The average roughness after hot bending is 15%-30% higher than that before hot bending.
- 如权利要求1所述的加工方法，其特征在于，当所述热弯模具的热膨胀系数A1和所述玻璃制品的热膨胀系数A2的比值的绝对值在0～0.2之间时，所述玻璃制品热弯后的平均粗糙度相对于热弯前升高70％～95％。The processing method according to claim 1, wherein when the absolute value of the ratio of the thermal expansion coefficient A1 of the hot bending mold to the thermal expansion coefficient A2 of the glass product is between 0 and 0.2, the glass product The average roughness after hot bending is 70%-95% higher than that before hot bending.
- 一种应用在权利要求1所述的加工方法的玻璃陶瓷模具，其特征在于，A kind of glass-ceramic mold that is applied in the processing method described in claim 1, is characterized in that,所述玻璃陶瓷模具的主晶相包括MgAl 2Si 3O 10、MgAl 2O 4、ZnAl 2O 4、莫来石、β-石英、β-石英固溶体、β-锂辉石、β-锂霞石和堇青石中的一种或多种。 The main crystal phase of the glass ceramic mold includes MgAl 2 Si 3 O 10 , MgAl 2 O 4 , ZnAl 2 O 4 , mullite, β-quartz, β-quartz solid solution, β-spodumene, β-eucryptite One or more of stone and cordierite.
- 如权利要求4所述的玻璃陶瓷模具，其特征在于，所述玻璃陶瓷模具的热膨胀系数在25～1000℃的温度范围内为大于-1.0×10 -6/K且小于或等于3.0×10 -5/K。 The glass-ceramic mold according to claim 4, wherein the coefficient of thermal expansion of the glass-ceramic mold is greater than -1.0×10 -6 /K and less than or equal to 3.0×10 - in the temperature range of 25 to 1000°C 5 /K.
- 如权利要求4所述的玻璃热弯模具，其特征在于，组分包括 Li 2O，以质量分数计在0.50～10％范围内，所述β-石英、所述β-锂辉石和所述β-钠霞石的质量分数在0.1％～70.0％范围内。 The hot bending mold for glass according to claim 4, wherein the components include Li 2 O, in the range of 0.50-10% by mass fraction, the β-quartz, the β-spodumene and the The mass fraction of β-Nacryptite is in the range of 0.1% to 70.0%.
- 如权利要求6所述的玻璃热弯模具，其特征在于，组分还包括Na 2O和K 2O，Na 2O、K 2O和Li 2O的质量比要求如下：(Na 2O+K 2O)/Li 2O＜1.00，且Na 2O和K 2O总质量分数≤8.00％。 The hot bending mold for glass according to claim 6, wherein the components also include Na 2 O and K 2 O, and the mass ratio requirements of Na 2 O, K 2 O and Li 2 O are as follows: (Na 2 O+ K 2 O)/Li 2 O<1.00, and the total mass fraction of Na 2 O and K 2 O is ≤8.00%.
- 如权利要求4所述的玻璃陶瓷模具，其特征在于，包括以下重量份的各原料：SiO 2：40.00～80.00份；Al 2O 3：18.00～40.00份；ZrO 2：0.50～10.00份；Li 2O：0.50～10.00份；Na 2O：0.00～2.00份；B 2O 3：0.00～5.00份；K 2O：0.00～5.00份；MgO：0.00～20.00份；CaO：0.00～5.00份；P 2O 5：0.00～5.00份；TiO 2：0.00～5.00份；BaO：0.00～2.00份；ZnO：0.00～10.00份。 The glass-ceramic mold according to claim 4, characterized in that it comprises the following raw materials in parts by weight: SiO 2 : 40.00-80.00 parts; Al 2 O 3 : 18.00-40.00 parts; ZrO 2 : 0.50-10.00 parts; Li 2 O: 0.50-10.00 parts; Na 2 O: 0.00-2.00 parts; B 2 O 3 : 0.00-5.00 parts; K 2 O: 0.00-5.00 parts; MgO: 0.00-20.00 parts; CaO: 0.00-5.00 parts; P 2 O 5 : 0.00-5.00 parts; TiO 2 : 0.00-5.00 parts; BaO: 0.00-2.00 parts; ZnO: 0.00-10.00 parts.
- 如权利要求8所述的玻璃陶瓷模具，其特征在于，所述玻璃陶瓷模具的玻璃化转变温度大于或等于700℃。The glass ceramic mold according to claim 8, wherein the glass transition temperature of the glass ceramic mold is greater than or equal to 700°C.
- 如权利要求4-9任一项所述的玻璃陶瓷模具，其特征在于，所述玻璃陶瓷模具的热导率在25～1000℃的温度范围内大于或等于1W/(m·k)。The glass-ceramic mold according to any one of claims 4-9, characterized in that the thermal conductivity of the glass-ceramic mold is greater than or equal to 1 W/(m·k) within the temperature range of 25-1000°C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111676529.1 | 2021-12-31 | ||
| CN202111676529.1A CN116409916B (en) | 2021-12-31 | 2021-12-31 | Glass product processing method and glass ceramic mold |
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| WO2023125005A1 true WO2023125005A1 (en) | 2023-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/CN2022/138936 WO2023125005A1 (en) | 2021-12-31 | 2022-12-14 | Glass product processing method and glass ceramic mold |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059428A (en) * | 1976-02-20 | 1977-11-22 | Corning Glass Works | Method of forming sagging mold from a glass ceramic |
| US4246207A (en) * | 1979-05-14 | 1981-01-20 | Corning Glass Works | Method for casting glass-plastic lenses comprising allyl diglycol carbonate plastic |
| JP2001150452A (en) * | 1999-11-25 | 2001-06-05 | Ohara Inc | Mold for molding resin and method of manufacturing the same |
| CN1495134A (en) * | 2002-08-16 | 2004-05-12 | Ф�ز�����˾ | Forming method for glass and glass-ceramic |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62182134A (en) * | 1986-02-05 | 1987-08-10 | Koumei:Kk | Class ceramic mold for resin lens |
| US4938802A (en) * | 1989-01-19 | 1990-07-03 | Corning Incorporated | Reusable ceramic mold |
-
2021
- 2021-12-31 CN CN202111676529.1A patent/CN116409916B/en active Active
-
2022
- 2022-12-14 WO PCT/CN2022/138936 patent/WO2023125005A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059428A (en) * | 1976-02-20 | 1977-11-22 | Corning Glass Works | Method of forming sagging mold from a glass ceramic |
| US4246207A (en) * | 1979-05-14 | 1981-01-20 | Corning Glass Works | Method for casting glass-plastic lenses comprising allyl diglycol carbonate plastic |
| JP2001150452A (en) * | 1999-11-25 | 2001-06-05 | Ohara Inc | Mold for molding resin and method of manufacturing the same |
| CN1495134A (en) * | 2002-08-16 | 2004-05-12 | Ф�ز�����˾ | Forming method for glass and glass-ceramic |
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| CN116409916A (en) | 2023-07-11 |
| CN116409916B (en) | 2024-07-26 |
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