Detailed Description
The invention provides 3D glass ceramics which are characterized in that the crystallinity of the 3D glass ceramics is 14-100 wt%; the average grain diameter of the crystals of the 3D glass ceramics is 10-100 nm.
Preferably, the crystallinity of the 3D glass ceramics is 14-30 wt%, or the crystallinity of the 3D glass ceramics is 50-100 wt%; or the crystallinity of the 3D glass ceramics is 31-49 wt%; or the crystallinity of the 3D glass ceramics is 10-20 wt%; 21-30 wt%; 31-40 wt%; 41-50 wt%; 51-60 wt%; 61-70 wt%; 71-80 wt%; 81-90 wt%; 91-100 wt%.
Or the average grain diameter of the crystals of the 3D glass ceramics is 15-30 nm;
or the thickness of the 3D glass ceramics is 0.02-5mm, and preferably, the thickness of the 3D glass ceramics is 0.35-1.2 mm.
Preferably, the average transmittance of the 3D glass ceramics for light with wavelength of 380-780nm is 88-93%, preferably 90-91.5%;
or the average transmittance of the 3D glass ceramics at the wavelength of 360-400nm is 65-91.5%, preferably 79-91%, and more preferably 85-91%.
Preferably, the absolute value of the b value (yellow-blue value) of the 3D glass ceramics with the thickness of 0.7mm is 0.1-3.5, preferably 0.3-1.5;
alternatively, the haze of the 3D glass ceramics is 0.07-1.0%, preferably 0.07-0.5%.
Preferably, the crystalline phase of the 3D glass ceramics is one or more of lithium silicate, lithium disilicate, β -quartz solid solution, petalite, β -spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesium aluminate spinel and rutile.
Preferably, the 3D glass ceramics contain oxides in mol% in the following proportions:
wherein the rare earth oxide is selected from La 2 O 3 ,Eu 2 O 3 ,Pr 6 O 11 ,Nd 2 O 3 ,Er 2 O 3 And Dy 2 O 3 One or more than two of them.
Preferably, wherein, theThe 3D glass ceramics contains SiO in mol% 2 And Al 2 O 3 The total amount is more than 60 percent; preferably 68-80%;
or, contain Na 2 O+Li 2 The content of O in mol% is 7-30%, preferably 10-26%.
Preferably, the 3D glass ceramics comprise nucleating agents, and the nucleating agents comprise P in terms of oxides, fluorides or simple substances 2 O 5 ,TiO 2 ,ZrO 2 ,Cr 2 O 3 ,CaF 2 ,LiF,NaF,KF,Y 2 O 3 One or more of Au, Ag and Cu; preferably P 2 O 5 ,TiO 2 And ZrO 2 One or more than two of them.
Preferably, the 3D glass ceramics comprise a clarifying agent, and the clarifying agent comprises NaCl and Na 2 SO 4 ,SnO 2 ,As 2 O 3 ,Sb 2 O 3 ,NaNO 3 ,KNO 3 ,CeO 2 And (NH) 4 ) 2 SO 4 One or more than two of the above; preferably NaCl, SnO 2 ,NaNO 3 And CeO 2 One or more than two of them.
Preferably, the crystallized glass original sheet of the 3D glass ceramic is a glass sheet which is subjected to nucleation and crystallization and has crystals with an average grain diameter of 5-50 nm.
Preferably, the crystallized glass original sheet of the 3D glass ceramics is a glass sheet having a crystallinity of 5 to 90 wt% after nucleation and crystallization, and preferably, the crystallinity is 5 to 10 wt%, 11 to 15 wt%, 16 to 20 wt%, 21 to 25 wt%, 26 to 30 wt%, 31 to 35 wt%, 36 to 40 wt%, 41 to 45 wt%, 46 to 50 wt%, 51 to 55 wt%, 56 to 60 wt%, 61 to 65 wt%, 66 to 70 wt%, 71 to 75 wt%, 76 to 80 wt%, 81 to 85 wt%, 86 to 90 wt%, 91 to 95 wt%, 96 to 100 wt%, 15 to 29 wt%, 30 to 75 wt%, 76 to 90 wt%, and/or 30 to 55 wt%.
Preferably, the drop height of the 3D glass ceramics after chemical strengthening is more than 1.5m, and the Vickers hardness of 300N force load 10s is more than 650.
When the thickness of the 3D glass ceramics is 0.65mm, after chemical strengthening, the falling height of the complete machine which bears the load of 160g and falls on the bottom plate with the medium made of marble is more than 1.5m, and preferably, the Vickers hardness of the 3D glass ceramics under the load of 300N force of 10s is more than 650.
The invention also provides a preparation method of the 3D glass ceramics, wherein the preparation method comprises the following steps:
step 1: mixing the preparation raw materials of the 3D glass ceramics, melting, cooling and annealing to obtain a glass substrate;
step 2: carrying out nucleation treatment on the glass substrate obtained in the step 1; wherein cutting can be carried out according to the requirements before and after the nucleation treatment;
and step 3: crystallizing the nucleated glass substrate obtained in the step 2;
and 4, step 4: cutting the crystallized glass substrate according to the requirement to obtain a crystallized glass raw material;
and 5: 3D hot bending treatment is carried out on the crystallized glass raw material to obtain a 3D microcrystalline glass sample;
wherein the 3D hot bending treatment process in the step 5 is also accompanied by a crystallization treatment process.
Wherein, in steps 4 and 5, the crystallized glass material may be a partially crystallized glass material.
Preferably, the method further comprises the step of subjecting the 3D glass ceramic sample to chemical strengthening treatment to obtain a 3D glass ceramic finished product.
Preferably, wherein, in the step 1, the melting temperature is 1350-; preferably, the melting temperature is 1400-1650 ℃; more preferably, the melt is cooled to 500-.
Preferably, in the step 1, the melting time is 1 to 5 hours; preferably, the crystallization treatment is carried out after the temperature is preserved for 5-300min at the temperature of 500-900 ℃ in the step 3; preferably, in the step 3, one or more of trimming, CNC machine processing, rough grinding and/or polishing treatment is performed to obtain the crystallized glass raw material.
Preferably, the amount of the added nucleating agent in the step 1 is 1 to 9mol percent of the total amount of the nucleating agent and the microcrystalline glass oxide, and the amount of the nucleating agent is 2 to 5mol percent.
Preferably, the amount of the added refining agent in the step 1 is 0-4 wt%, preferably 0.1-2 wt% of the total mass of the nucleating agent and the microcrystalline glass oxide.
Preferably, in the step 2, the temperature of the nucleation treatment is 450-800 ℃, and the time of the nucleation treatment is 30-360 min; more preferably, the temperature of the nucleation treatment is 520-570 ℃, and the time of the nucleation treatment is 120-300 min.
Preferably, in the step 3, the temperature of the crystallization treatment is 550-;
preferably, the temperature of the crystallization treatment is 600-850 ℃, the time of the crystallization treatment is 10-240min,
further preferably, the temperature of the crystallization treatment is 600-750 ℃, and the time of the crystallization treatment is 10-150 min.
Preferably, the hot bending process in step 5 includes a preheating station, a hot pressing station and a cooling station.
Preferably, the number of preheating stations is 1-30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30; preferably 2 to 4; the number of the hot pressing stations is 1-30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 and 30; preferably 1 to 3; the cooling stations comprise 1 to 30, preferably 1,2,3,4,5,6,7,8,9,10,11,1,2,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29, 30; preferably 2-4.
Preferably, wherein the temperature of the preheating station is 300-850 ℃; the temperature of the hot pressing station is 600-920 ℃, and the pressure is 0-6 MPa; the temperature of the cooling station is 200-650 ℃.
Preferably, the working time of the preheating work station is 20-800 seconds; the working time of the hot-pressing work station is 20-800 seconds, and the working time of the cooling work station is 20-800 seconds;
preferably, the working time of the preheating work station is 60-600 seconds; the working time of the hot-pressing work station is 60-480 seconds, and the working time of the cooling work station is 60-600 seconds.
The invention also provides the 3D glass ceramics prepared by the preparation method.
Preferably, the 3D glass-ceramic is characterized in that the 3D glass-ceramic is transparent or opaque; preferably, the 3D glass ceramics are curved or planar.
The invention also provides application of the 3D glass ceramics or the 3D glass ceramics of claim 24 or claim 25 in mobile phone display screens, tablet computer display screens, handheld game machines, electronic terminals, portable digital devices, vehicle-mounted central control screens, electronic white board glasses, smart home touch screens, vehicle windshield glasses, aircraft windshield glasses or aircraft windshield glasses.
The noun explains:
3D glass ceramics: the upper surface and the lower surface are non-planar microcrystalline glass;
2D glass ceramics: the upper surface and the lower surface are both plane microcrystalline glass;
2.5D glass ceramics: one surface is a plane, and the other surface is non-planar microcrystalline glass;
degree of crystallinity: the microcrystalline glass contains a crystal phase and a glass phase, and the mass of the crystal phase accounts for the percentage of the total mass of the microcrystalline glass and is the crystallinity;
transmittance: the ratio of radiant energy projected through and through the object to total radiant energy projected onto the object during the course of an incident flux exiting from the illuminated or medium incident face to the other;
average transmittance: the transmittance at each wavelength is measured at intervals of 10nm in a predetermined wavelength range, and the sum of the measured transmittances at each wavelength is divided by the number of the measured transmittances at each wavelength. For example, the average transmittance at the wavelength of 360-400nm is calculated as follows: respectively measuring the transmittances of 360nm, 370nm, 380nm, 390nm and 400nm, wherein the number of the measured transmittances of 360 and 400nm is 5, and the sum of the transmittances is divided by 5 to obtain the average transmittance of 360 and 400 nm;
nucleation: the nucleating substances in the glass grow into crystal nuclei with the length of about 5nm through heat treatment;
crystallization: the glass grows a certain crystal on the basis of the crystal nucleus through heat treatment;
average crystal particle diameter: based on the average value of the grain lengths in the glass ceramics observed at a magnification of 10 ten thousand to 100 ten thousand times. Measured by observation using a transmission electron microscope (model: ThermoFisher Scientific (original FEI) Talos F200S). During measurement, the method is equivalent to taking a magnified picture of the crystal grains at a certain position, limited crystal grains are in the magnified picture area, the sizes of the limited crystal grains are marked according to a scale, and then the average value is calculated. The magnification in the measurement in the example of the present invention was 50 ten thousand times.
b value: the yellow-blue value of the material is represented, the b value in the invention is the b value of transmitted light, and the b value is positive, so that the material is blue; measured using a chromatograph (model CM-3600A).
Haze: the transmitted light intensity above an angle of 2.5 ° from the incident light is a percentage of the total transmitted light intensity. Measured using a chromatograph (model CM-3600A).
The optical performance of the 3D glass ceramics when the thickness is 0.65mm is that the absolute value of the b value under a D65 light source is 0.1-3.5, and the preferred absolute value of the b value under a D65 light source is 0.3-1.5; the light transmittance at a wavelength of 360nm is 80% or more, preferably 85% or more.
Nucleating agents include, but are not limited to, P 2 O 5 ,TiO 2 ,ZrO 2 ,Cr 2 O 3 ,CaF 2 ,LiF,NaF,KF,Y 2 O 3 Au, Ag, Cu, etc.
When the partially crystallized microcrystalline glass is crystallized by hot bending, the crystallization speed is controllable, which is beneficial to growing crystals with the grain diameter of less than 100nm, and the average grain diameter of the precipitated crystals can be ensured to be 10-100nm by controlling the process, so that the optical performance of the 3D microcrystalline glass is improved;
in other specific embodiments, the partially crystallized glass ceramic is subjected to crystallization and 3D bending simultaneously in a 3D bending process, the bending time is generally within 30min, and some examples show that the partially crystallized glass ceramic can reach a crystallinity of 80 wt% or more by 10-20min of 3D bending in a suitable process, and the optical properties meet the requirements.
The crystalline phase of the 3D glass ceramics comprises lithium silicate, lithium disilicate, beta-quartz, a beta-quartz solid solution, petalite, beta-spodumene, a beta-spodumene solid solution, nepheline, cordierite, mullite, apatite, zirconium dioxide, gahnite, magnesia-alumina spinel, rutile and the like.
In order that the invention may be better understood, reference will now be made to the following examples which illustrate the invention.
The following description will be made of the manufacturers of raw materials and equipment used in this example, and the equipment and analysis method used in the product analysis, wherein the chemical substances are not labeled as being of the chemical purity grade of conventional reagents.
Wherein, the information of the raw materials used in the examples and comparative examples is shown in the following table 1.
TABLE 1 information on materials and instruments used in the present invention
Examples
The hot bending process in the examples is shown in table 2 below, for example, when the process number is 1, the hot bending process includes 4 preheating stations, 3 hot pressing stations, and 2 cooling stations. The temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, and the temperature of the fourth preheating station is 680 ℃. The temperature of the first hot pressing station is 800 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the second hot pressing station is 810 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 20 s.
For example, the hot bending process with serial number 12 is as follows: the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 700 ℃, and the temperature of the fourth preheating station is 850 ℃. The temperature of the first hot pressing station is 780 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot-pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. To cite this.
TABLE 2 Hot bending Process tables in examples and comparative examples
Example 13D method of making microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 62.00%;Al 2 O 3 17.00%;MgO 2.50%;Na 2 O 2.50%;Li 2 O 10.00%;B 2 O 3 2.00% of rare earth oxide La 2 O 3 0.8% of nucleating agent (containing 2.00% of P) 2 O 5 (ii) a 1.20% of ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g), the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1650 ℃, the melting time is 5h, and the raw materials are poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 620 ℃, then the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 760 ℃, and the time of the nucleation treatment is 120 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at 790 ℃ for 10min to obtain a partially crystallized glass brick;
and 4, step 4: and (3) trimming the partially crystallized glass brick by using a grinding and polishing machine, cutting the trimmed glass brick into pieces by using a multi-wire cutting machine, processing the glass pieces into glass pieces with the length, width and thickness of 158 x 75 x 0.65mm by using a CNC machine tool, and respectively performing coarse grinding and polishing treatment by using a flat grinder and a polishing machine to obtain partially crystallized glass raw pieces, wherein the crystallinity of the partially crystallized glass raw pieces is 10 wt% according to determination.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, and the temperature of the fourth preheating station is 680 ℃. The temperature of the first hot pressing station is 800 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the second hot pressing station is 810 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0.4MPa, and the lower pressure is 0.4 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 20 s. (i.e., the thermal bending process with the number 1 in table 2 is adopted), and a 3D glass ceramic sample 1 is obtained.
And (3) detecting the 3D microcrystalline glass sample 1, and analyzing the detected X-ray diffraction data by using a ray diffractometer and setting the instrument setting voltage to be 40mV, the current to be 30mA, the test range to be 10-50 degrees, the scanning speed to be 1 degree/min and the step length to be 0.02 degree/step, wherein the crystallinity of the 3D microcrystalline glass sample 1 is 15 wt%, the precipitated crystalline phase is beta-spodumene and the average grain size of the crystal is 37 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 1 is 2.30; the light transmittance at the wavelength of 360nm is 76.30%, the light average transmittance at the wavelength of 380-780nm is 88.20%, the light average transmittance at the wavelength of 360-400nm is 80.10%, and the haze is 0.40%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% NaNO at the temperature of 430 DEG C 3 And (5) the solution is kept for 8 hours, and finally the 3D glass ceramics finished product 1 is obtained.
Example 23D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 64.00%;Al 2 O 3 17.00%;Na 2 O 2.50%;Li 2 O 12.5%;B 2 O 3 2.00%, nucleating agent (0.80% P) 2 O 5 ;1.20%ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1650 ℃, the melting time is 5h, and the melting and forming treatment is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 1;
step 4 trimming, cutting into pieces, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 13 wt% by determination;
and 5: and (3) carrying out 3D hot bending treatment on the partially crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 2 by adopting a hot bending process (referring to example 1) with the number 1 in the table 2.
The 3D glass ceramics sample 2 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 2 had a crystallinity of 24 wt% after hot bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 27 nm. When the light source is limited to D65, the absolute value of the b value of the 3D microcrystalline glass sample 2 is measured to be 3.10; the light transmittance at the wavelength of 360nm is 76.00%, the light average transmittance at the wavelength of 380-780nm is 88.00%, the light average transmittance at the wavelength of 360-400nm is 78.00%, and the haze is 0.43%.
And 6: and (5) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the embodiment 1 to finally obtain a 3D glass ceramics finished product 2.
Example 33D method for making microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 63.64%;Al 2 O 3 16.03%;Li 2 O 16.03%;B 2 O 3 2.00%, nucleating agent (0.80% P) 2 O 5 ;1.50%ZrO 2 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 610 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 705 ℃, and the time of the nucleation treatment is 120 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 775 ℃, and the crystallization treatment time is 10min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 9 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 3 was obtained by the hot bending process (refer to example 1) with number 1 in table 2.
The 3D glass ceramics sample 3 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 3 had a crystallinity of 18 wt% after thermal bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 3 is 1.21 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 83.71 percent, the light average transmission rate at the wavelength of 380-780nm is 90.22 percent, the light average transmission rate at the wavelength of 360-400nm is 84.56 percent, and the haze is 0.16 percent.
Example 43D method for making microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.63%;Al 2 O 3 15.13%;MgO 4.76%;Na 2 O 1.55%;Li 2 8.65 percent of O; rare earth oxide La 2 O 3 0.81%, nucleating agent (0.67% P) 2 O 5 ;1.30%ZrO 2 ,Y 2 O 3 0.50 percent) and NaCl accounting for 0.8 percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace), the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the melting and forming treatment is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is to preserve the temperature for 5 hours at the temperature of 610 ℃, and reduce the temperature to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 720 ℃, and the time of the nucleation treatment is 120 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 780 ℃, and the crystallization treatment time is 10min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was measured to be 11 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 4 was obtained by the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 4 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 4 had a crystallinity of 23 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 27 nm. The absolute value of the b value of the 3D microcrystalline glass sample 4 is 1.48 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 80.06%, the light average transmission rate at the wavelength of 380-780nm is 89.5%, the light average transmission rate at the wavelength of 360-400nm is 83.50%, and the haze is 0.25%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 450 DEG C 3 And (5) the solution is subjected to 7 hours, and a 3D glass ceramic finished product 4 is finally obtained.
Example 53D method for making microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.96%;Al 2 O 3 14.20%;MgO 4.79%;Na 2 O 0.56%;Li 2 9.70 percent of O; rare earth oxide Er 2 O 3 0.81%, nucleating agent (1.68% P) 2 O 5 ;1.30%ZrO 2 ) And 0.4 wt% of NaCl and 0.4 wt% of SnO based on the total mass of the nucleating agent and the preparation raw materials 2 1713.6g of total weight of the raw materials serving as a clarifying agent are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 4;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 16% by weight.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; a 3D glass ceramics sample 5 was obtained by the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 5 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 5 had a crystallinity of 33 wt% after hot bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle size of the crystals was 22 nm. When the light source is limited to D65, the absolute value of the 5b value of the 3D microcrystalline glass sample is 3.24; the light transmission rate at the wavelength of 360nm is 72.00 percent, the light average transmission rate at the wavelength of 380-780nm is 88.90 percent, the light average transmission rate at the wavelength of 360-400nm is 78.60 percent, and the haze is 0.54 percent.
Example 63D method of making a microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.95%;Al 2 O 3 14.20%;MgO 2.29%;Na 2 O 1.56%;ZnO 1.00%,Li 2 9.70 percent of O; rare earth oxide La 2 O 3 0.81%, nucleating agent (1.68% P) 2 O 5 ;1.31%ZrO 2 ;0.5%Y 2 O 3 ) And a clarifier NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1713.6g of the total weight of the raw materials are fully mixed, then the mixture is melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 765 ℃, and the crystallization treatment time is 20min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 12 wt%.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and a 3D glass ceramic sample 6 was obtained by using the hot bending process (refer to example 1) with the number 1 in table 2.
The 3D glass-ceramic sample 6 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 6 had a crystallinity of 23 wt% after hot bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle diameter of the crystals was 30 nm. The absolute value of the b value is 3.4 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 66.30%, the light average transmission rate at the wavelength of 380-780nm is 88.30%, the light average transmission rate at the wavelength of 360-400nm is 76.20%, and the haze is 0.96%.
Example 73D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.42%;Al 2 O 3 14.09%;MgO 4.75%;Na 2 O 1.55%;Li 2 O9.62%, nucleating agent (0.67% P) 2 O 5 ;1.3%ZrO 2 ;1.6%TiO 2 ) And NaCl accounting for 0.8 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and molded in a high-temperature lifting furnace, the temperature of the melting and molding treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 750 ℃, and the time of the crystallization treatment is 20min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 17% by weight.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 1 in table 2 (refer to example 1) was employed to obtain a 3D glass ceramic sample 7.
The 3D glass ceramics sample 7 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 7 had a crystallinity of 34 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 7 is measured to be 1.20 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 83.10 percent, the light average transmittance at the wavelength of 380-780nm is 90.28 percent, the light average transmittance at the wavelength of 360-400nm is 84.62 percent, and the haze is 0.15 percent.
And 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 430 DEG C 3 And (5) the solution is subjected to 9 hours, and a 3D glass ceramic finished product 7 is finally obtained.
Example 83D microcrystalline glass manufacturing method:
step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mole: SiO 2 2 66.95%;Al 2 O 3 13.20%;CaO 1.0%;MgO3.79%;Na 2 O 1.56%;Li 2 9.70 percent of O; nucleating agent (1.68% P) 2 O 5 ;1.51%ZrO 2 ,0.61%Ti 2 O and NaCl which accounts for 0.7 wt% of the total mass of the nucleating agent and the preparation raw material, wherein 1711.9g of the total weight of the raw materials are fully mixed, then the mixture is melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 715 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 820 ℃, and the time of the crystallization treatment is 10min to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 28 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating work station is 480 ℃, the temperature of the second preheating work station is 635 ℃, the temperature of the third preheating work station is 685 ℃, and the temperature of the fourth preheating work station is 715 ℃. The temperature of the first hot pressing station is 745 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.6 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0MPa, and the lower pressure is 0. MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 80 s. (i.e., the thermal bending process with serial number 8 in table 2) was used to obtain 3D glass ceramics sample 8.
The 3D glass ceramics sample 8 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 8 had a crystallinity of 45 wt% after thermal bending, precipitated crystal phases of β -quartz solid solution and β -spodumene, and an average particle diameter of the crystals was 37 nm. When the light source is defined as D65, the absolute value of the b value of the 3D glass ceramic sample 8 is 2.90; the light transmission rate at the wavelength of 360nm is 76.11 percent, the light average transmission rate at the wavelength of 380-780nm is 88.10 percent, the light average transmission rate at the wavelength of 360-400nm is 78.80 percent, and the haze is 0.63 percent.
Example 93D method for producing microcrystalline glass:
step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mole: SiO 2 2 66.96%;Al 2 O 3 13.20%;MgO 5.79%;Na 2 O 1.26%;Li 2 O 8.00%;B 2 O 3 1.00 percent; rare earth oxide Er 2 O 3 0.9% of nucleating agent (1.68% of P) 2 O 5 ;1.21%ZrO 2 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the glass brick;
step 2 and step 3 are the same as in example 8;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was measured to be 19 wt%.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 9.
The 3D glass-ceramic sample 9 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 9 had a crystallinity of 32 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 24 nm. The absolute value of the b value of the 3D microcrystalline glass sample 9 is measured to be 1.30 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 82.10%, the light average transmittance at the wavelength of 380-780nm is 89.40%, the light average transmittance at the wavelength of 360-400nm is 85.20%, and the haze is 0.21%.
Example 103D method for producing microcrystalline glass:
step 1: preparing and weighing glass preparation raw materials, wherein the glass preparation raw materials comprise the following components in percentage by mol: SiO 2 2 71.65%;Al 2 O 3 13.20%;MgO 2.79%;Na 2 O 0.56%;Li 2 O8.00 percent; rare earth oxide Er 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ;1.51%ZrO 2 ) And a clarifying agent NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, and the raw materials are fully mixed and then placed in a high-temperature lifting furnacePerforming medium melting molding, wherein the temperature of the melting molding treatment is 1630 ℃, the melting time is 5 hours, and pouring the glass brick into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 was the same as in example 8;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 800 ℃ for 10min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 20% by weight.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 10.
The 3D glass-ceramic sample 10 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 10 had a crystallinity of 37 wt% after hot bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 27 nm. The absolute value of b is 1.60 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 81.13%, the light average transmission rate at the wavelength of 380-780nm is 89.60%, the light average transmission rate at the wavelength of 360-400nm is 82.80%, and the haze is 0.19%.
Example 113D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.65%;Al 2 O 3 13.20%;MgO 2.79%;Na 2 O 1.56%;Li 2 O8.00 percent; rare earth oxide La 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ;1.51%ZrO 2 ) And a clarifier NaCl accounting for 0.7 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1711.9g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into ASTM SA213/TP310S austenitic chromium nickelObtaining a glass brick in a stainless steel mold;
step 2 and step 3 were the same as in example 10;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 21 wt%.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 8 in table 2 (refer to example 8) was used to obtain a 3D glass ceramic sample 11.
The 3D glass ceramics sample 11 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 11 had a crystallinity of 41 wt% after thermal bending, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 22 nm. When the light source is defined as D65, the absolute value of the b value is 1.10; the light transmittance at the wavelength of 360nm is 82.40%, the light average transmittance at the wavelength of 380-780nm is 90.60%, the light average transmittance at the wavelength of 360-400nm is 85.30%, and the haze is 0.13%.
Example 123D method of making a microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.65%;Al 2 O 3 12.92%;MgO 2.42%;ZnO 0.80%;Na 2 O 1.05%;Li 2 O8.25 percent; rare earth oxide La 2 O 3 1.22%, nucleating agent (1.37% P) 2 O 5 ;1.32%Y 2 O 3 ) And NaNO accounting for 0.3 wt% of the total mass of the nucleating agent and the preparation raw materials 3 And 0.4 wt% of As 2 O 3 As a clarifying agent, 1711.9g of the total weight of the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 700 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as example 5;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 25 wt%.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 12.
The 3D glass ceramics sample 12 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 12 had a crystallinity of 43 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 24 nm. When the light source is defined as D65, the absolute value of the b value is 1.15; the light transmittance at the wavelength of 360nm is 83.68%, the light average transmittance at the wavelength of 380-780nm is 90.56%, the light average transmittance at the wavelength of 360-400nm is 86.30%, and the haze is 0.17%.
Step 6: and (4) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5), wherein the chemical strengthening conditions are the same as those in the embodiment 7, and finally obtaining a 3D glass ceramics finished product 12.
Example 133D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 71.15%;Al 2 O 3 12.70%;MgO 2.79%;Na 2 O 0.56%;Li 2 O 8.00%;B 2 O 3 1.00% of rare earth oxide Nd 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ;1.51%CaF 2 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 570 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 710 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as in example 10;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 18% by weight.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process numbered 8 in table 2 (refer to example 8) was used to obtain a 3D glass ceramic sample 13.
The 3D glass ceramics sample 13 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 13 had a crystallinity of 34 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 35 nm. The absolute value of the b value is 1.75 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 81.03 percent, the light average transmittance at the wavelength of 380-780nm is 89.00 percent, the light average transmittance at the wavelength of 360-400nm is 82.30 percent, and the haze is 0.23 percent.
Example 143D microcrystalline glass manufacturing method:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 68.00%;Al 2 O 3 12.00%;MgO 3.5%;Na 2 O 0.50%;Li 2 O 10.00%;B 2 O 3 3.00%, nucleating agent (2.00% P) 2 O 5 ;1.00%Y 2 O 3 ) NaCl accounting for 0.2 wt% of the total mass of the nucleating agent and the preparation raw materials and SnO accounting for 0.2 wt% of the total mass of the nucleating agent and the preparation raw materials 2 And 0.2 wt% of CeO 2 The clarifier is prepared by mixing above raw materials 1711.9g, melting in high temperature furnace at 1630 deg.C for 5 hr, and pouring into ASTM SA213/TP310S austenitic chromium-nickel stainless steelObtaining a glass brick in the mould;
step 2 is the same as in example 13;
step 3 is the same as in example 1;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 35 wt%.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 14.
The 3D glass-ceramic sample 14 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the crystallinity of the 3D glass-ceramic sample 14 after hot bending was 62 wt%, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 27 nm. When the light source is defined as D65, the absolute value of the b value is 1.11; the light transmission rate at the wavelength of 360nm is 84.20 percent, the light average transmission rate at the wavelength of 380-780nm is 90.90 percent, the light average transmission rate at the wavelength of 360-400nm is 85.80 percent, and the haze is 0.22 percent.
Example 153D microcrystalline glass production method:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.95%;Al 2 O 3 11.20%;CaO 1.20%;MgO 4.59%;Na 2 O 1.26%;Li 2 O 9.00%;B 2 O 3 2.00% of rare earth oxide Nd 2 O 3 0.61%, nucleating agent (1.68% P) 2 O 5 ;1.51%ZrO 2 ) 1710.2g of the total weight of the raw materials, namely fully mixing, then melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at 550 ℃, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 690 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 750 ℃, and the time of the crystallization treatment is 30min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 32% by weight.
And 5: 3D hot bending treatment is carried out on the partially crystallized glass original sheet, and a hot bending process with the serial number of 8 in the table 2 (refer to example 8) is adopted to obtain a 3D microcrystalline glass sample 15.
The 3D glass-ceramic sample 15 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 15 had a crystallinity of 53 wt% after being thermally bent, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 24 nm. The absolute value of b is measured to be 0.70 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 85.22%, the light average transmittance at the wavelength of 380-780nm is 91.20%, the light average transmittance at the wavelength of 360-400nm is 87.50%, and the haze is 0.16%.
Example 163D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 65.10%;Al 2 O 3 8.51%;Na 2 O 1.00%;Li 2 O 20.83%;B 2 O 3 1.52%, nucleating agent (0.82% P) 2 O 5 ;1.72%ZrO 2 (ii) a 0.5 percent of NaF), and NaNO accounting for 0.3 percent of the total mass of the nucleating agent and the preparation raw materials by weight 3 And 0.3 wt% of As 2 O 3 1710.2g of the raw materials are fully mixed as a clarifying agent, then the mixture is melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1620 ℃, the melting time is 5 hours, and the mixture is poured into a mold made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at 550 ℃, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 670 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 710 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 40 wt%.
And 5: 3D hot bending treatment is carried out on a part of crystallized glass sheet, the hot bending process adopts a hot bending process with the sequence number of 6 in the table 2, and the hot bending treatment comprises 4 preheating work stations, 3 hot pressing work stations and 2 cooling work stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 710 ℃. The temperature of the first hot pressing station is 730 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.3 MPa; the temperature of the second hot pressing station is 740 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 60 s. A 3D glass ceramic sample 16 was obtained.
The 3D glass-ceramic sample 16 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 16 had a crystallinity of 60 wt% after hot bending, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 21 nm. The absolute value of b is 0.62 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 86.02%, the light average transmission rate at the wavelength of 380-780nm is 91.10%, the light average transmission rate at the wavelength of 360-400nm is 88.10%, and the haze is 0.17%.
And 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% NaNO at the temperature of 430 DEG C 3 And (5) the solution is kept for 11 hours, and finally the 3D glass ceramics finished product 16 is obtained.
Example 173D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 68.00%;Al 2 O 3 5.50%;CaO 0.50%;Na 2 O 1.00%;Li 2 O 21.00%;B 2 O 3 1.50%, nucleating agent (0.80% P) 2 O 5 ;1.70%ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1708.5g, the raw materials are fully mixed and then are melted and formed in a high-temperature lifting furnace, the melting and forming treatment temperature is 1630 ℃, the melting time is 5 hours, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 500 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 570 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 640 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 78 wt%.
And 5: the 3D hot bending process is performed on the partially crystallized glass original sheet, and the hot bending process with serial number 6 in table 2 (refer to example 16) is employed to obtain a 3D microcrystalline glass sample 17.
The 3D glass-ceramic sample 17 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 17 had a crystallinity of 91 wt% after hot bending, the precipitated crystal phase was β -quartz solid solution + petalite, and the average particle size of the crystal was 21 nm. When the light source is defined as D65, the absolute value of the b value is 1.0; the light transmittance at the wavelength of 360nm is 84.32 percent, the light average transmittance at the wavelength of 380-780nm is 90.80 percent, the light average transmittance at the wavelength of 360-400nm is 86.40 percent, and the haze is 0.16 percent.
Example 183D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 69.14%;Al 2 O 3 5.21%;Na 2 O 0.46%;Li 2 O 21.13%;B 2 O 3 1.52%, nucleating agent (0.82% P) 2 O 5 ;1.72%ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1708.5g of the total weight of the raw materials are fully mixed, then are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 490 ℃ for 5 hours, and the temperature is reduced to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 530 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 640 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 72 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts the hot bending process with the serial number of 13 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 710 ℃. The temperature of the first hot pressing station is 720 ℃, the upper pressure is 0.3MPa, and the lower pressure is 0.3 MPa; the temperature of the second hot pressing station is 720 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 18 was obtained.
And (3) detecting the 3D glass-ceramic sample 18, and analyzing the detected X-ray diffraction data by using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the crystallinity of the 3D glass-ceramic sample 18 after being subjected to thermal bending is 92 wt%, the precipitated crystal phase is lithium disilicate and petalite, and the average grain size of the crystal is 18 nm. The absolute value of b is measured to be 0.43 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 87.17 percent, the light average transmittance at the wavelength of 380-780nm is 92.10 percent, the light average transmittance at the wavelength of 360-400nm is 90.30 percent, and the haze is 0.11 percent.
Example 193D method for making a microcrystalline glass:
steps 1-2 are the same as those of example 18;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 630 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 60 wt% by determination;
and 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 19 was obtained by the hot bending process (see example 18) with number 13 in table 2.
The 3D glass ceramics sample 19 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 19 had a crystallinity of 86 wt% after thermal bending, and the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystal was 19 nm. The absolute value of b is measured to be 0.44 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 87.31 percent, the light average transmission rate at the wavelength of 380-780nm is 92.30 percent, the light average transmission rate at the wavelength of 360-400nm is 89.50 percent, and the haze is 0.11 percent.
Example 203D method for producing microcrystalline glass:
steps 1-2 are identical to those of example 18;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 625 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, and performing coarse grinding and polishing treatment in the same process as in example 1, wherein the crystallinity is 51 wt% after determination;
and 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process (see example 18) numbered 13 in table 2 was used to obtain a 3D glass ceramic sample 20.
The 3D glass-ceramic sample 20 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 20 had a crystallinity of 73 wt% after hot bending, the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 23 nm. The absolute value of b is 0.58 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 86.20 percent, the light average transmittance at the wavelength of 380-780nm is 92.10 percent, the light average transmittance at the wavelength of 360-400nm is 87.80 percent, and the haze is 0.10 percent.
Example 213D method for producing microcrystalline glass:
steps 1-2 are identical to those of example 18;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the crystallization treatment temperature is 620 ℃, and the crystallization treatment time is 120min, so as to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing were carried out in the same manner as in example 1, and then the degree of crystallinity was determined to be 30% by weight,
and 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 21 was obtained by the hot bending process (see example 18) with number 13 in table 2.
The 3D glass-ceramic sample 21 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 21 had a crystallinity of 65 wt% after hot bending, the precipitated crystal phase was lithium disilicate + petalite, and the average particle size of the crystals was 25 nm. The absolute value of b is measured to be 0.62 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 85.14%, the light average transmittance at the wavelength of 380-780nm is 91.60%, the light average transmittance at the wavelength of 360-400nm is 88.10%, and the haze is 0.15%.
Example 223D method for making microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 69.5%;Al 2 O 3 5.3%;Na 2 O 1.60%;Li 2 O 20.5%;B 2 O 3 0.55% of nucleating agent (0.8% of P) 2 O 5 ;1.75%ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1708.5g of the total weight of the raw materials are fully mixed, then are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, the temperature is kept for 5 hours, and the temperature is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 560 ℃, and the time of the nucleation treatment is 200 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 630 ℃, and the crystallization treatment time is 100min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 39 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 15 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 740 ℃. The temperature of the first hot pressing station is 770 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 22 was obtained.
The 3D glass ceramics sample 22 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 22 had a crystallinity of 85 wt% after thermal bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystals was 19 nm. The absolute value of b is measured to be 0.42 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 88.23%, the light average transmittance at the wavelength of 380-780nm is 92.10%, the light average transmittance at the wavelength of 360-400nm is 89.30%, and the haze is 0.15%.
Step 6: performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 5, and soaking the glass in molten 100 wt% of NaNO at the temperature of 450 DEG C 3 And (5) the solution is kept for 9 hours, and finally the 3D glass ceramics finished product 22 is obtained.
Example 233D method for producing microcrystalline glass:
step 1: preparation of glass weighing raw materials (molar percentage comprising the following group)Dividing into: SiO 2 2 71.80%;Al 2 O 3 4.80%;MgO 1.40%;Na 2 O 1.00%;Li 2 18.80 percent of O; ZnO 0.3%, nucleating agent (0.8% P) 2 O 5 ;1.1%ZrO 2 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.5 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1550 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, the temperature is kept for 5 hours, and the temperature is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 545 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 610 ℃ for 200min to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 45 wt%.
And 5: 3D hot bending treatment is carried out on a part of crystallized glass original sheets, and a hot bending process (refer to example 22) with the serial number of 15 in Table 2 is adopted to obtain a 3D microcrystalline glass sample 23;
the 3D glass ceramics sample 23 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 23 had a crystallinity of 92 wt% after thermal bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystals was 20 nm. The absolute value of b is 0.61 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 85.82 percent, the light average transmittance at the wavelength of 380-780nm is 91.50 percent, the light average transmittance at the wavelength of 360-400nm is 88.00 percent, and the haze is 0.15 percent.
Step 6: and (3) carrying out chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the example 22 to finally obtain a 3D glass ceramics finished product 23.
Example 243D method for making microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 69.50%;Al 2 O 3 4.25%;Na 2 O 1.60%;Li 2 O 20.5%;B 2 O 3 1.60%, nucleating agent (0.8% P) 2 O 5 ;1.75%ZrO 2 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.5 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1550 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, the temperature is kept for 5 hours, and the temperature is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 538 ℃, and the time of the nucleation treatment is 200 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 620 ℃, and the time of the crystallization treatment is 100min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 43 wt%.
And 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts a hot bending process with the serial number of 14 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 720 ℃. The temperature of the first hot pressing station is 750 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot-pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramic sample 24 was obtained.
And b, detecting the 3D glass-ceramic sample 24 by using light with the absolute value of a wavelength of 360nm, and analyzing the detected X-ray diffraction data by using a ray diffractometer under the same instrument setting conditions as in example 1, wherein the crystallinity of the 3D glass-ceramic sample 24 after being subjected to thermal bending is 82 wt%, the precipitated crystal phase is petalite + lithium disilicate, and the average particle size of the crystal is 22 nm. The absolute value of b is measured to be 0.43 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.17%, the light average transmittance at the wavelength of 380-780nm is 92.60%, the light average transmittance at the wavelength of 360-400nm is 89.60%, and the haze is 0.11%.
Step 6: and (4) performing chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step (5) under the same treatment conditions as those in the example 22 to finally obtain a 3D glass ceramics finished product 24.
Example 253D method of making a microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 68.76%;Al 2 O 3 4.13%;MgO 0.98%,ZnO 0.98%,Na 2 O 0.45%;Li 2 O 20.71%;B 2 O 3 1.49%, nucleating agent (0.81% P) 2 O 5 ;1.69%ZrO 2 ) And a clarifier NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein 1708.5g of the total weight of the raw materials are fully mixed, then are melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1550 ℃, the melting time is 5 hours, and the mixture is poured into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is 480 ℃, keeping the temperature for 5 hours, and reducing the temperature to 30 ℃ at 1 ℃/min), and carrying out XRD test on the obtained annealed glass brick to obtain a figure 1, wherein the glass brick is in a glass state, and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 540 ℃, and the time of the nucleation treatment is 200 min;
step 3 is the same as in example 24;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 47 wt%. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 2, which was seen to be in a partially crystallized state.
And 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a 3D microcrystalline glass sample 25 was obtained by the hot bending process (see example 24) with reference number 14 in table 2.
And (3) detecting the 3D glass-ceramic sample 25, and analyzing the detected X-ray diffraction data by using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass-ceramic sample 25 has a crystallinity after being thermally bent, the crystallinity after being thermally bent is 87 wt%, the precipitated crystal phase is a solid solution of lithium disilicate, petalite and beta-quartz, and the average particle size of the crystal is 18 nm. The absolute value of b is 0.39 when the light source is defined as D65; the light transmission rate at the wavelength of 360nm is 88.80%, the light average transmission rate at the wavelength of 380-780nm is 92.70%, the light average transmission rate at the wavelength of 360-400nm is 89.80%, and the haze is 0.09%.
And 5: carrying out chemical strengthening treatment on the hot-bent 3D glass ceramics obtained in the step 4, and soaking the glass in molten 100 wt% of NaNO at the temperature of 450 DEG C 3 And (5) the solution is subjected to the treatment for 10 hours, and finally a 3D glass ceramic finished product 25 is obtained.
Example 263D microcrystalline glass production method:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 68.73%;Al 2 O 3 4.13%;MgO 0.98%,ZnO1.68%,Na 2 O 0.45%;Li 2 O 20.01%;B 2 O 3 1.49%, nucleating agent (0.81% P) 2 O 5 ;1.72%ZrO 2 ) And a clarifying agent NaCl accounting for 0.5 wt% of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is1708.5g, fully mixing, melting and molding in a high-temperature lifting furnace, wherein the temperature of the melting and molding treatment is 1550 ℃, the melting time is 5 hours, and pouring into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 is the same as in example 25;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 615 ℃, and the time of the crystallization treatment is 120min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 55 wt%. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 3, which was seen to be in a partially crystallized state.
And 5: the partially crystallized glass original piece was subjected to 3D hot bending treatment, and a hot bending process (see example 22) numbered 15 in table 2 was used to obtain a 3D microcrystalline glass sample 26.
The 3D glass ceramics sample 26 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 30 had a crystallinity of 91 wt% after thermal bending, the precipitated crystal phase was petalite, and the average particle size of the crystal was 23 nm. The absolute value of b is measured to be 0.42 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 88.13%, the light average transmittance at the wavelength of 380-780nm is 92.80%, the light average transmittance at the wavelength of 360-400nm is 89.90%, and the haze is 0.11%.
Example 273D method of making microcrystalline glass:
step 1: the same as in example 18, except for the temperature of the melt molding treatment; the temperature of the melting and forming treatment in the embodiment is 1610 ℃;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is to preserve heat at 460 ℃ for 5 hours and reduce the temperature to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 480 ℃, and the time of the nucleation treatment is 360 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace at the temperature of 550 ℃ for 300min to obtain a partially crystallized glass brick;
step 4 trimming, cutting into pieces, rough grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 6% by weight.
And 5: the 3D hot bending process was performed on the partially crystallized glass original piece, and the hot bending process with the number 1 in table 2 (the same as in example 1) was used to obtain a 3D microcrystalline glass sample 27.
The 3D glass ceramics sample 27 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 27 had a crystallinity of 14 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 10 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 27 is 0.15; the light transmittance at the wavelength of 360nm is 90.60%, the light average transmittance at the wavelength of 380-780nm is 93.00%, the light average transmittance at the wavelength of 360-400nm is 91.40%, and the haze is 0.07%.
Example 283D method of making microcrystalline glass:
step 1 is the same as in example 27;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is to keep the temperature at 460 ℃ for 5 hours and reduce the temperature to 30 ℃ at 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 500 ℃, and the time of the nucleation treatment is 300 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 570 ℃, and the time of the crystallization treatment is 280min, so as to obtain a partially crystallized glass brick;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was measured to be 8 wt%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 28 by adopting a hot bending process with the sequence number 1 in the table 2.
The above 3D glass ceramics sample 28 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 28 had a crystallinity of 16 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 15 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 28 is 0.25; the light transmission rate at the wavelength of 360nm is 90.10 percent, the light average transmission rate at the wavelength of 380-780nm is 92.80 percent, the light average transmission rate at the wavelength of 360-400nm is 91.20 percent, and the haze is 0.09 percent.
Example 293D microcrystalline glass preparation method:
step 1 is the same as in example 27;
step 2 was the same as in example 28;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 560 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was measured to be 9 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the sequence number of 1 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 28.
The 3D glass ceramics sample 29 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 29 had a crystallinity of 17 wt%, a precipitated crystal phase was lithium silicate, and an average particle diameter of the crystal was 13 nm. When the light source is defined as D65, the absolute value of the b value of the 3D microcrystalline glass sample 29 is 0.23; the light transmission rate at the wavelength of 360nm is 90.50 percent, the light average transmission rate at the wavelength of 380-780nm is 92.70 percent, the light average transmission rate at the wavelength of 360-400nm is 91.50 percent, and the haze is 0.08 percent.
Example 303D method for producing microcrystalline glass:
step 1 is the same as in example 17;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept at 500 ℃ for 5 hours, and is reduced to 30 ℃ at a speed of 1 ℃/min), and transferring the glass brick to a precise annealing furnace for nucleation; the temperature of the nucleation treatment is 600 ℃, and the time of the nucleation treatment is 80 min;
and step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the crystallization treatment temperature is 610 ℃, and the crystallization treatment time is 180min, so as to obtain a partially crystallized glass brick;
step 4 the process of trimming, cutting into pieces, rough grinding and polishing was the same as in example 1, and then the crystallinity was determined to be 37 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the sequence number of 3 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 30. The obtained partially crystallized glass original piece was subjected to XRD test to obtain FIG. 4, which was seen to be in a partially crystallized state.
And (3) detecting the 3D microcrystalline glass sample 30, and analyzing the detected X-ray diffraction data by using a ray diffractometer under the same instrument setting conditions as in example 1, wherein the crystallinity of the 3D microcrystalline glass sample 30 after being subjected to hot bending is 75 wt%, the precipitated crystal phase is petalite + beta-quartz solid solution, and the average grain size of the crystal is 18 nm. The absolute value of b is measured to be 0.35 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 88.20 percent, the light average transmittance at the wavelength of 380-780nm is 92.60 percent, the light average transmittance at the wavelength of 360-400nm is 90.00 percent, and the haze is 0.11 percent.
Example 313D method for producing a crystallized glass:
step 1 is the same as example 2;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept for 5 hours at the temperature of 600 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 800 ℃, and the time of the nucleation treatment is 30 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 870 ℃, and the time of the crystallization treatment is 15min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were performed in the same manner as in example 1, and then the crystallinity was determined to be 88 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 4 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 31.
The 3D glass ceramics sample 31 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 31 had a crystallinity of 99 wt% after thermal bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 48 nm. The absolute value of the b value is measured to be 2.60 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 74.10%, the light average transmittance at the wavelength of 380-780nm is 89.30%, the light average transmittance at the wavelength of 360-400nm is 80.50%, and the haze is 0.78%.
Example 323D method for producing microcrystalline glass:
step 1 is the same as example 2;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is that the temperature is kept for 5 hours at the temperature of 600 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 780 ℃, and the time of the nucleation treatment is 60 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precision annealing furnace, wherein the temperature of the crystallization treatment is 900 ℃, and the time of the crystallization treatment is 5min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 58 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 7 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 32.
The 3D glass ceramics sample 32 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 32 had a crystallinity of 98 wt% after hot bending, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 81 nm. The absolute value of b is 2.80 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 62.00 percent, the light average transmittance at the wavelength of 380-780nm is 88.60 percent, the light average transmittance at the wavelength of 360-400nm is 65.80 percent, and the haze is 0.72 percent.
Example 333D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 67.45%;Al 2 O 3 14.20%;CaO 0.50%;MgO 1.79%;Na 2 O 1.56%;Li 2 9.70 percent of O; nucleating agent (2.18% P) 2 O 5 ;0.81%TiO 2 ;1.31%ZrO 2 ;0.5%Y 2 O 3 ) The glass brick is prepared by the following steps of mixing 1713.5g of raw materials, melting and molding in a high-temperature lifting furnace at 1650 ℃ for 5h after fully mixing, and pouring the mixture into a die made of an ASTM SA213/TP310S austenitic chromium nickel stainless steel material to obtain a glass brick, wherein NaCl accounts for 0.8 wt% of the total mass of the nucleating agent and the prepared raw materials;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 500 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 650 ℃, and the time of the nucleation treatment is 160 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 820 ℃, and the time of the crystallization treatment is 30min, so as to obtain the glass brick after partial crystallization treatment;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 90 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 6 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 33.
The 3D glass ceramics sample 33 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 33 had a crystallinity of 100 wt% after being thermally bent, a precipitated crystal phase was β -spodumene, and an average particle diameter of the crystal was 98 nm. When the light source is defined as D65, the absolute value of the b value is 3.8; the light transmittance at the wavelength of 360nm is 63.10 percent, the light average transmittance at the wavelength of 380-780nm is 88.20 percent, the light average transmittance at the wavelength of 360-400nm is 65.40 percent, and the haze is 0.98 percent.
Example 343D microcrystalline glass production method:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 66.65%;Al 2 O 3 10.87%;MgO 2.44%;ZnO 2.82%;Na 2 O 0.21%;K 2 O 0.21%;Li 2 O 9.88%;B 2 O 3 0.94 percent; nucleating agent (1.85% P) 2 O 5 ;2.00%ZrO 2 ;2.13%CaF 2 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 4h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 500 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 620 ℃, and the time of the nucleation treatment is 240 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 650 ℃, and the time of the crystallization treatment is 40min, so as to obtain a partially crystallized glass brick;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 68 wt%.
And 5: and 3D hot bending treatment is carried out on the partial crystallized glass original sheet, and a hot bending process with the serial number of 7 in the table 2 is adopted to obtain a 3D microcrystalline glass sample 34.
The 3D glass ceramics sample 34 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 34 had a crystallinity of 79 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 65 nm. The absolute value of b is measured to be 0.76 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 84.22 percent, the light average transmission rate at the wavelength of 380-780nm is 91.00 percent, the light average transmission rate at the wavelength of 360-400nm is 87.50 percent, and the haze is 0.16 percent.
Example 353D method of producing a crystallized glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 64.55%;Al 2 O 3 10.45%;MgO 2.37%;ZnO 2.73%;Na 2 O 0.21%;K 2 O 0.20%;Li 2 O 9.58%;B 2 O 3 0.91 percent; nucleating agent (1.94% P) 2 O 5 ;2.91%TiO 2 ;2.02%ZrO 2 ;2.13%CaF 2 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 4h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 35;
step 4 trimming, dicing, coarse grinding and polishing were carried out in the same manner as in example 1, and then the crystallinity was determined to be 82 wt%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 35 by adopting a hot bending process with the serial number 6 in the table 2.
The 3D glass ceramics sample 35 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same setting conditions as in example 1, wherein the 3D glass ceramics sample 35 had a crystallinity of 86 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystal was 42 nm. The absolute value of b is measured to be 0.68 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 85.42%, the light average transmittance at the wavelength of 380-780nm is 91.10%, the light average transmittance at the wavelength of 360-400nm is 87.20%, and the haze is 0.19%.
Example 363D method of making microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.13%;Al 2 O 3 11.50%;MgO 2.57%;ZnO 2.97%;Na 2 O 0.22%;K 2 O 0.22%;Li 2 O 10.40%;B 2 O 3 0.99 percent; nucleating agent (0.84% P) 2 O 5 ;0.16%CaF 2 ) The glass brick is prepared by the following steps of mixing 1711.9g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.7 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1640 ℃ for 3h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium-nickel stainless steel to obtain a glass brick;
step 2 and step 3 were the same as in example 34;
step 4 trimming, cutting into pieces, rough grinding and polishing were carried out in the same manner as in example 1, and then the degree of crystallinity was measured to be 63 wt%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 36 by adopting a hot bending process with the serial number 5 in the table 2.
The 3D glass-ceramic sample 36 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 36 had a crystallinity of 70 wt% after being thermally bent, a precipitated crystal phase was β -quartz solid solution, and an average particle size of the crystals was 37 nm. It was determined that when the illuminant was defined as D65, the absolute value of b was 0.53; the light transmittance at the wavelength of 360nm is 86.00%, the light average transmittance at the wavelength of 380-780nm is 92.20%, the light average transmittance at the wavelength of 360-400nm is 88.60%, and the haze is 0.10%.
Example 373D microcrystalline glass production method:
step 1: the same as in example 17, except for the temperature and melting time of the melt molding process. The temperature of the melting and forming treatment in the embodiment is 1650 ℃, and the melting time is 2 h;
and 2, step: cooling the glass brick obtained in the step 1 to 800 ℃, transferring the glass brick to an annealing furnace for annealing (the annealing process is carried out for 5 hours at the temperature of 500 ℃, and the temperature is reduced to 30 ℃ at the speed of 1 ℃/min), and transferring the glass brick to a precision annealing furnace for nucleation; the temperature of the nucleation treatment is 600 ℃, and the time of the nucleation treatment is 80 min;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 600 ℃, and the time of the crystallization treatment is 240min, so as to obtain a partially crystallized glass brick;
step 4 the processes of trimming, cutting into pieces, rough grinding and polishing were the same as in example 1, and then the crystallinity was determined to be 75 wt%.
And 5: and (3) carrying out 3D hot bending treatment on the partial crystallized glass original sheet, and obtaining a 3D microcrystalline glass sample 37 by adopting a hot bending process with the serial number 6 in the table 2.
The 3D glass-ceramic sample 37 was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass-ceramic sample 37 had a crystallinity of 88 wt% after hot bending, the precipitated crystal phase was petalite + β -quartz solid solution, and the average particle size of the crystal was 57 nm. It was determined that when the illuminant was defined as D65, the absolute value of b was 0.38; the light transmission rate at the wavelength of 360nm is 88.40%, the light average transmission rate at the wavelength of 380-780nm is 92.80%, the light average transmission rate at the wavelength of 360-400nm is 90.10%, and the haze is 0.12%.
Example 383D method of making microcrystalline glass:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass sheet, and the hot bending process adopts the hot bending process with the serial number of 20 in the table 2; the hot bending treatment comprises 3 preheating work stations, 4 hot pressing work stations and 2 cooling work stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, and the temperature of the third preheating station is 650 ℃. The temperature of the first hot-pressing station is 760 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 750 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 720 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the fourth hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating work station, the hot pressing work station and the cooling work station is the same and is 140s, and the 3D microcrystalline glass sample 22F is obtained.
The 3D glass ceramics sample 22F was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 22F had a crystallinity of 84 wt% after hot bending, the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystal was 18 nm. The absolute value of b is 0.43 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 88.15 percent, the light average transmittance at the wavelength of 380-780nm is 92.77 percent, the light average transmittance at the wavelength of 360-400nm is 89.45 percent, and the haze is 0.11 percent.
Example 393D microcrystalline glass manufacturing method:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 21 in the table 3; the hot bending treatment comprises 5 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 430 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 600 ℃, the temperature of the fourth preheating station is 680 ℃, and the temperature of the fifth preheating station is 720 ℃. The temperature of the first hot pressing station is 745 ℃, the upper pressure is 0.5MPa, and the lower pressure is 0.5 MPa; the temperature of the second hot pressing station is 760 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating work station, the hot pressing work station and the cooling work station is the same and is 140s, and the 3D microcrystalline glass sample 22G is obtained.
The 3D glass ceramics sample 22G was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setting conditions as in example 1, wherein the 3D glass ceramics sample 22G had a crystallinity of 90 wt% after thermal bending, and the precipitated crystal phase was petalite + lithium disilicate, and the average particle size of the crystal was 22 nm. The absolute value of b is measured to be 0.55 when the light source is limited to D65; the light transmittance at the wavelength of 360nm is 86.12%, the light average transmittance at the wavelength of 380-780nm is 92.40%, the light average transmittance at the wavelength of 360-400nm is 88.40%, and the haze is 0.10%.
Comparative example
Comparative example 13D method for producing crystallized glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 62.40%;Al 2 O 3 13.24%;MgO 4.46%;Na 2 O 1.46%;Li 2 O9.04%, nucleating agent (0.94% P) 2 O 5 ;6.58%ZrO 2 ;1.88%TiO 2 9.40 percent of nucleating agent in total), and NaCl accounting for 0.8 weight percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2 is the same as example 4; it can be seen that the nucleated glass sheet has precipitated crystals and is in a ceramic state, which does not meet the conditions of the subsequent hot bending process.
Comparative example 23D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 60.70%;Al 2 O 3 12.87%;MgO 4.34%;Na 2 O 1.42%;Li 2 O8.79%, nucleating agent (0.91% P) 2 O 5 ;9.14%ZrO 2 ;1.83%TiO 2 11.88 percent of nucleating agent in total), and NaCl accounting for 0.8wt percent of the total mass of the nucleating agent and the preparation raw materials, wherein the total weight of the raw materials is 1713.6g, the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chrome-nickel stainless steel to obtain a glass brick;
step 2: crystals are separated out from the central part of the glass brick obtained in the step 1 in the process of cooling to 800 ℃, and the glass brick is cracked and cannot be machined due to the stress difference inside the glass brick.
Comparative example 33D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 67.45%;Al 2 O 3 14.20%;CaO 0.50%;MgO 1.79%;Na 2 O 1.56%;Li 2 9.70 percent of O; nucleating agent (2.18% P) 2 O 5 ;1.31%ZrO 2 ;0.81%TiO 2 And 0.5% Y 2 O 3 ) The glass brick is prepared by the following steps of mixing 1708.5g of total weight of a nucleating agent and a clarifying agent NaCl accounting for 0.8 wt% of the total weight of the nucleating agent and the preparation raw materials, melting and molding in a high-temperature lifting furnace at 1630 ℃ for 5h, and pouring the mixture into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain the glass brick;
step 2 is the same as example 4;
and 3, step 3: continuously carrying out crystallization treatment on the nucleated glass brick in a precise annealing furnace, wherein the temperature of the crystallization treatment is 930 ℃, and the time of the crystallization treatment is 30 min; uncontrollable crystallization occurs in the glass brick after crystallization treatment due to overhigh crystallization temperature, and stress difference occurs in the glass brick, so that the glass brick is cracked and cannot be machined.
Comparative example 43D method for producing microcrystalline glass:
step 1: preparing and weighing raw materials for preparing glass (comprising the following components in percentage by mol: SiO) 2 70.33%;Al 2 O 3 14.82%;Na 2 O 1.63%;Li 2 10.11 percent of O; 1.34 percent of MgO; ZnO 1.04%, nucleating agent (0.52% P) 2 O 5 ;0.21%ZrO 2 ) And clarifying agents NaCl and SnO accounting for 0.4 wt% and 0.4 wt% of the total mass of the nucleating agent and the preparation raw materials respectively 2 1708.5g of the total weight of the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
the conditions of step 2 and step 3 are the same as those of example 33, and XRD test is performed on the glass brick after nucleation, so that it can be seen that no crystal nucleus appears due to too little nucleating agent, uncontrollable crystallization appears during crystallization treatment, and stress difference appears inside the glass, which causes breakage of the hot-bent glass.
Comparative example 53D method for producing microcrystalline glass:
step 1: preparing raw materials for preparing the glass (comprising the following components in percentage by mol: SiO) 2 70.45%;Al 2 O 3 13.16%;MgO 2.78%;Na 2 O 0.56%;Li 2 O 7.98%;B 2 O 3 1.00 percent; nucleating agent (1.67% P) 2 O 5 ;1.30%ZrO 2 ;0.60%TiO 2 And 0.5% Y 2 O 3 ) And clarifying agents NaCl and CeO accounting for 0.4 wt% and 0.3 wt% of the total mass of the nucleating agent and the preparation raw materials 2 1711.9g of the total weight of the raw materials are fully mixed and then melted and formed in a high-temperature lifting furnace, the temperature of the melting and forming treatment is 1630 ℃, the melting time is 5h, and the mixture is poured into a die made of ASTM SA213/TP310S austenitic chromium nickel stainless steel to obtain a glass brick;
step 2: cooling the glass brick obtained in the step 1 to 900 ℃, and transferring the glass brick to a precision annealing furnace for nucleation treatment; the temperature of the nucleation treatment is 850 ℃, and the time of the nucleation treatment is 120 min; the uncontrollable crystallization of the glass brick after the nucleation treatment due to the over-high nucleation temperature and the stress difference in the glass brick cause the glass brick to break and the subsequent treatment and processing can not be carried out.
Comparative example 63D method for producing microcrystalline glass:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 16 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 480 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 720 ℃. The temperature of the first hot pressing station is 940 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 920 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 90 s. A 3D glass ceramics sample 22B was obtained.
The 3D glass ceramics sample 22B was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same instrument setup conditions as in example 1, wherein the 3D glass ceramics sample 22B had a crystallinity of 100 wt% after hot bending, a precipitated crystal phase of β -spodumene + lithium disilicate, and an average particle diameter of the crystal was 111 nm. The absolute value of b is 7.45 when the light source is defined as D65; the light transmittance at the wavelength of 360nm is 64.10%, the light average transmittance at the wavelength of 380-780nm is 86.50%, the light average transmittance at the wavelength of 360-400nm is 69.20%, and the haze is 0.99%. Due to the fact that the hot pressing temperature is too high, the average grain size of crystals of the finally prepared microcrystalline glass is too high, the b value is increased, the light transmittance is reduced, the b value is too high, the microcrystalline glass is bluish, and imaging is affected.
Comparative example 73D method for producing microcrystalline glass:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 17 in the table 2; the hot bending process comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. Wherein the temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 600 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 720 ℃. The temperature of the first hot pressing station is 930 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 920 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramics sample 22C was obtained.
The 3D glass ceramics sample 22C was examined, and the X-ray diffraction data after examination was analyzed using a radiation diffractometer under the same apparatus setting conditions as in example 1, wherein the 3D glass ceramics sample 22C had a crystallinity of 100 wt% after thermal bending, a precipitated crystal phase of β -spodumene + lithium disilicate, and an average particle diameter of the crystals was 124 nm. The absolute value of b is 7.86 when the light source is limited to D65; the light transmission rate at the wavelength of 360nm is 62.40 percent, the light average transmission rate at the wavelength of 380-780nm is 87.30 percent, the light average transmission rate at the wavelength of 360-400nm is 68.20 percent, and the haze is 1.10 percent. Due to the fact that the hot pressing temperature is too high, the average grain size of crystals of the finally prepared microcrystalline glass is too high, the b value is increased, the light transmittance is reduced, the b value is too high, the microcrystalline glass is bluish, and imaging is affected.
Comparative example 83D method for producing microcrystalline glass:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts the hot bending process with the serial number of 18 in the table 2; the hot bending treatment comprises 4 preheating stations, 3 hot pressing stations and 2 cooling stations. The temperature of the first preheating station is 450 ℃, the temperature of the second preheating station is 500 ℃, the temperature of the third preheating station is 650 ℃, and the temperature of the fourth preheating station is 650 ℃. The temperature of the first hot pressing station is 580 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 600 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein, the working time of each work station in the preheating work station, the hot pressing work station and the cooling work station is the same and is 90 s. A 3D glass ceramics sample 22D was obtained. Due to the excessively low hot pressing temperature, the 3D glass ceramic sample 22D cannot be hot-bent into the target shape.
Comparative example 93D method for producing microcrystalline glass:
step 1, step 2, step 3 and step 4 were the same as in example 22;
and 5: 3D hot bending treatment is carried out on part of the crystallized glass original sheet, and the hot bending process adopts a hot bending process with the serial number of 19 in Table 2; the hot bending treatment comprises 3 preheating work stations, 3 hot pressing work stations and 2 cooling work stations. The temperature of the first preheating station is 500 ℃, the temperature of the second preheating station is 550 ℃, and the temperature of the third preheating station is 600 ℃. The temperature of the first hot pressing station is 600 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the second hot-pressing station is 580 ℃, the upper pressure is 0.1MPa, and the lower pressure is 0.1 MPa; the temperature of the third hot pressing station is 550 ℃, the upper pressure is 0MPa, and the lower pressure is 0 MPa. The temperature of the first cooling station is 450 ℃, and the temperature of the second cooling station is 300 ℃. Wherein the working time of each of the preheating station, the hot-pressing station and the cooling station is the same and is 90s, and the 3D microcrystalline glass sample 22E is obtained. Since the hot pressing temperature was too low, the 3D glass ceramic sample 22E could not be hot-bent into the target shape.
Application example
Mechanical parameters were measured on 3D glass ceramics obtained by chemically strengthening the above-described examples 1,2, 4, 7, 12, 16, 22,23,24 and 25, and the test glass thickness was 0.65, and the results of the tests are shown in table 3.
The test result comprises surface compressive stress, compressive stress depth and average tensile stress, the linear density of the tensile stress is a calculated value, and the sum of the tensile stress measured by the SLP-2000 stress meter is divided by the thickness of the glass.
Surface compressive stress (MPa): after the glass is chemically strengthened, the alkali metal ions with smaller radius on the surface are replaced by the alkali metal ions with larger radius, and the surface of the glass generates compressive stress due to the squeezing effect of the alkali metal ions with larger radius, which is called surface compressive stress;
depth of compressive stress (μm): the distance from the surface of the chemically strengthened glass to a position where the compressive stress is zero;
average tensile stress CT-AV (MPa): the ratio of the sum of tensile stress and the thickness of a tensile stress area obtained by testing according to an SLP-2000 stress meter;
tensile stress linear density CT-LD: according to SLP-2000 stress meter test, the ratio of tensile stress integral and glass thickness of the chemically strengthened glass under the thickness section is obtained;
and (3) complete machine drop test: a method for testing the strength of strengthened glass includes sticking the strengthened glass to the specimen of electronic equipment such as mobile telephone, falling down from high position, recording the broken height of glass, and testing the whole falling test. The testing method is characterized in that a mobile phone with 180g of tempered glass sheet load freely falls on 120-mesh abrasive paper, and the abrasive paper is tightly attached to a marble bottom plate;
vickers hardness (Hv) (300N pressure hold 10 s): pressing a diamond regular pyramid pressure head with an included angle of 136 degrees between opposite surfaces into the surface of the tested sample under the action of a load of 300N, removing the load after keeping for 10s, measuring the diagonal length d of the indentation, further calculating the surface area of the indentation, and finally solving the average pressure on the surface area of the indentation, namely the Vickers hardness value of the glass, which is represented by a symbol HV.
TABLE 3 determination of mechanical parameters
As can be seen from the above table, in the embodiment, the surface compressive stress of the chemically strengthened 3D glass ceramic finished product is 108-514MPa, the depth of the compressive stress is 109-121 μm, the average tensile stress CT-AV is 42-93MPa, the linear density CT-LD of the tensile stress is 30145-43157, the total machine drop test height is 1.51-1.82m, and the Vickers hardness (300N pressure retention for 10s) of the chemically strengthened 3D glass ceramic finished product is 712-741 Hv.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.