CN112624618B - Colored glass ceramics and preparation method thereof - Google Patents
Colored glass ceramics and preparation method thereof Download PDFInfo
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- CN112624618B CN112624618B CN202110033312.2A CN202110033312A CN112624618B CN 112624618 B CN112624618 B CN 112624618B CN 202110033312 A CN202110033312 A CN 202110033312A CN 112624618 B CN112624618 B CN 112624618B
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 126
- 238000004040 coloring Methods 0.000 claims abstract description 61
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- -1 lithium-aluminum-silicon Chemical compound 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 239000003086 colorant Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 description 26
- 150000002500 ions Chemical class 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 239000006121 base glass Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 3
- 239000005354 aluminosilicate glass Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- 230000009970 fire resistant effect Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 231100000021 irritant Toxicity 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000006060 molten glass Substances 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/10—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce uniformly-coloured transparent products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Crystallography & Structural Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a preparation method of colored glass ceramics, which comprises the following steps: carrying out microcrystallization heat treatment on the lithium-aluminum-silicon glass precursor to obtain microcrystalline glass; preheating the glass ceramics, and then putting the glass ceramics into coloring molten salt for coloring treatment, wherein the coloring temperature is controlled to be 500-650 ℃, and the coloring time is 10-120 min, so as to obtain the colored glass ceramics; the coloring molten salt is Cu-containing 2+ Sulfate of (a); the glass base composition of the microcrystalline glass comprises the following components in percentage by mass: SiO 2 2 68％‑75％、Al 2 O 3 7％‑12％、P 2 O 5 1.5％‑4％，Li 2 O 7％‑12％、Na 2 O 0％‑1％、ZrO 2 4％‑6％、BaO 0‑1.2％、SnO 2 0.05% -0.1%; the microcrystallization heat treatment comprises the following three-stage step heating treatment steps to realize the colored glass ceramics with light green, yellow, brownish green, red and colorful colors and patterns, wherein the L value is between 18 and 68, and the colored glass ceramics have better color saturation and aesthetic degree.
Description
Technical Field
The invention relates to the field of glass products, in particular to colored glass ceramics and a preparation method thereof.
Background
With the continuous improvement of the living standard of people, the pursuit of personalized products is more and more favored. For mass consumer smart phones, people tend to differentiate the appearance of the phones. The high-end mobile phone protection screen mainly based on the glass rear cover has no transparency requirement and cost reduction requirements, and becomes a hot spot for various manufacturers to research colored or multicolor glass.
At present, the common preparation method of colored glass is the bulk coloring of the glass formulation and the surface coloring of the glass. The mass coloring of the glass formula body needs to add coloring ions in the glass melting process, and the method is suitable for mass production of single color and is lack of mass production for the production of products with different color requirements. The glass surface is colored, and the surface coating (such as ink-jet printing, screen printing and the like) is commonly adopted, the colorant is adhered to the glass surface, and then the glass is colored through high-temperature sintering. The method has high requirements on the granularity of the colorant and the uniformity of coating, has high requirements on the temperature control of sintering, and has a complex process. The other surface coloring is high-temperature ion coloring, which realizes mutual replacement of ions by putting glass into high-temperature coloring molten salt to realize the surface coloring of the glass. The method has simple process, is very suitable for mass production, and can realize different color effects by changing the type or proportion of the molten salt or different process systems. However, the surface coloring of glass has a limited ion entry content compared with the bulk coloring of glass, and the glass is light in color and lacks softness and saturation, and particularly, the glass is cheap and affects the application of the transparent high-alumina glass used for a glass cover plate. On the other hand, the glass material used for the glass cover plate has a thickness of about 0.5 to 1mm, and the ion coloring molten salt has a high melting point when being liquefied, and tends to warp the glass.
The microcrystalline glass has the basic performance of glass and the polycrystalline characteristic of ceramic, integrates the characteristics of glass and ceramic, and can be controlled by a specific formula and a heat treatment process to realize transparent and semitransparent effects. It has the brightness of glass, the texture and the beauty of ceramics like jade. Meanwhile, the glass cover plate has high mechanical strength, high hardness, good fracture toughness, good thermal stability, suitability for a high-temperature ion coloring temperature range and difficult warping, and can meet the mechanical property requirement of the glass cover plate.
Chinese patent application No. 202010527172.X "an aluminosilicate glass ionic colorant and its colored aluminosilicate glass" discloses a mixture of a silver salt and a copper salt as an ionic colorant, but it is only applicable to an ionic coloring method of aluminosilicate glass. In addition, the chinese patent with application number 202010952323.6, "an antibacterial molten salt, glass and a preparation method" discloses a ternary complex sulfate antibacterial molten salt, but copper ions thereof are implanted into the glass in an ion state, and do not cause coloring of the glass.
Disclosure of Invention
Therefore, it is necessary to provide a coloring method suitable for lithium aluminum silicate glass, which realizes light green, yellow, brown green and red colored glass ceramics, and has better color saturation and aesthetic degree.
In order to achieve the above object, in a first aspect of the present invention, the inventors provide a method for preparing a colored glass-ceramic, comprising the following steps: carrying out micro-crystallization heat treatment on the lithium-aluminum-silicon glass precursor to obtain microcrystalline glass; preheating the glass ceramics, and then putting the glass ceramics into coloring molten salt for coloring treatment, wherein the coloring temperature is controlled to be 500-650 ℃, and the coloring time is 10-120 min, so as to obtain the colored glass ceramics; the coloring molten salt is Cu-containing 2+ Sulfate of (a);
the glass base composition of the microcrystalline glass comprises the following components in percentage by mass: SiO 2 2 68％-75％、Al 2 O 3 7％-12％、P 2 O 5 1.5％-4％，Li 2 O 7％-12％、Na 2 O 0％-1％、ZrO 2 4％-6％、BaO 0-1.2％、SnO 2 0.05％-0.1％；
The microcrystallization heat treatment comprises the following three-stage step heating treatment steps:
first-step temperature rise: heating to the first step temperature of 530-560 ℃ at the normal temperature at the speed of 5-10 ℃/min, and carrying out heat preservation treatment for 150-240 min;
and (3) second step temperature rise: then heating to a second gradient temperature of 650-;
third-step temperature rise: then heating to the third gradient temperature of 760 and 810 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation treatment for 60-120min, and cooling along with the furnace to obtain the microcrystalline glass.
Description of the glass base composition of the glass ceramics:
SiO 2 : belonging to the constitution of base glassAnd the main structure of the glass ceramics, which is also the main component constituting the crystal phase. Too low a content thereof is disadvantageous for sufficient formation of the silicic acid-based crystal phase. SiO 2 2 The content should not be less than 68 wt.%. But higher SiO 2 The content of the additive can cause excessive viscosity and unsatisfactory melting process. In the present invention, SiO 2 The content of (A) is controlled between 68 wt% and 75 wt%.
Al 2 O 3 : the oxide belongs to a network intermediate oxide, can improve the mechanical property and the chemical durability of glass, can refine crystal grains and reduce the haze of the glass ceramics, and has a larger volume structure which is beneficial to the ion exchange between the glass ceramics and molten salt. Thus, Al 2 O 3 The content should not be less than 7 wt.%. But high Al content 2 O 3 The content can obviously increase the crystallization temperature and hinder the crystal growth. Thus, Al in the base glass 2 O 3 The content should not be higher than 12 wt%;
P 2 O 5 : belonging to one of the network former components, P thereof 5+ The ionic field strength is greater than that of Si 4+ Ions are easily separated from the network by combining with alkali metal ions to form crystal nuclei, so that the phase separation of the basic glass is promoted, the nucleation activation energy is reduced, and the crystallization of the glass is facilitated; at the same time, it can improve ZrO 2 Degree of fusion in glass, P 2 O 5 Too low content, difficult crystallization of the glass and unfavorable ZrO 2 Melting of (2). P is 2 O 5 The content is at least 1.5 wt%. But P is 2 O 5 Too high content can cause severe phase separation of the glass and affect the permeability of the glass ceramics, P 2 O 5 The content is at most 4 wt%.
Li 2 O and Na 2 O; belongs to a network external component, can obviously reduce the viscosity of base glass, promote the melting of the base glass and improve the low-temperature melting property and the formability of the glass, wherein Li 2 O is an essential component constituting a crystal phase, and the strong accumulation capacity thereof can significantly lower the crystallization temperature of the glass and promote the crystallization of the glass. Li 2 The O content should not be less than 7 wt.%. But too high Li 2 O in turn can cause uncontrolled crystallization of the glass, resulting in devitrification or inhomogeneity of the glass. Thus, Li in the base glass 2 The O content is not higher than 12 wt%. Excessive Na 2 The content of O causes a decrease in chemical durability of the glass and an increase in glass phase, and thus an undesirable glass phase remains in the glass ceramics, which affects performance and crystallization uniformity. Control of Na 2 The O content is at most 1 wt.%.
ZrO 2 : the method is beneficial to the refinement and distribution uniformity of the grain size, thereby improving the chemical stability of the glass. In this combination, ZrO 2 The minimum content of the components is not less than 4 wt%. But ZrO 2 Belongs to a refractory component, can quickly improve the viscosity of base glass and has overhigh ZrO content 2 The content may result in ZrO in the glass 2 An unmelted mass is present. In the present invention, ZrO 2 The content is controlled to be 4 wt% -6 wt%.
BaO: the BaO-containing glass composition is an optional component of the composition, can reduce viscosity, improve melting performance and improve the glossiness and transmittance of glass, but when the BaO content is high, the glass density is higher, and the content is controlled to be 0-1.2%.
SnO 2 : the component can promote the elimination or dissolution and absorption of bubbles in the glass liquid, and the content of the component is controlled to be 0.15 to 0.1 weight percent.
Three-step temperature-raising process description:
the first stage is crystal nucleus formation, proper treatment parameters are needed to ensure that the crystal nucleus is large and small, the temperature is too high or the time is too long, the crystal nucleus is easy to be small and large, and a compact structure is difficult to form, so that the size and the crystallinity of subsequent crystal grains are influenced; too low a temperature or too short a time affects the overall efficiency. Therefore, the first step temperature is 530-560 ℃, and the heat preservation and the heat treatment are carried out for 150-240 min; the second and third stages are crystal growth, and because the crystal growth consists of two phases of a glass phase and a crystal phase, the appearance of the glass is bright and glossy, too much glass phase can affect the saturation degree of the glass, and too much crystal phase can cause serious ceramization and lack of brightness. In order to ensure the brightness of the glass and facilitate the subsequent melting and coloring treatment of the microcrystalline glass, the heat treatment process of the microcrystalline glass needs to be accurately controlled.
If the second stage is skipped and the heat treatment is directly performed at the third stage temperature, the first phase crystal (the crystal phase is LiAlS) is generatedi 4 O 10 ) The glass is rapidly coarsened at high temperature, the internal structure is dissimilated, the external appearance is excessive ceramic of the glass, and the glass is lack of brightness.
If the third stage is not carried out, second-phase crystals (crystal phase of Li) are caused 2 Si 2 O 5 ) Not formed, which can grow crystals in the subsequent fusion tinting process, resulting in non-uniformity of the glass, or breakage of the glass. Therefore, the second gradient temperature of the invention is 650-; the third gradient temperature is 760 ℃ and 810 ℃, and the heat preservation and the heat treatment are carried out for 60-120 min.
The coloring ions in the coloring molten salt can be Cu ions and Ag ions, and the coloring ions mainly comprise the Cu ions due to the high price of the Ag. The coloring ion introduced into the molten salt can be CuSO 4 Compared with Cucl2, chloride has higher vapor pressure and is easy to volatilize irritant gas, so that the method is not suitable for industrial mass production. The molten salt of the invention is a sulfate. The copper ions are used as coloring metal ions, and can generate the transition of the implanted ion valence state under the influence of different set temperatures, time, different structures and different formulas to cause different coloring of the glass. And Cu 2+ 、Cu + And Cu 0 There will also be different color development. At the same time, the coloration is also related to the content of implanted copper ions where the transition takes place. Preferably, the microcrystalline glass has milky white appearance and an L value of 20-75.
The CIE color channels L × a and b × are optical parameters defined by the international commission on illumination (CIE) in L × a × b color space. L a b color space includes all the perceived colors in the three dimensional real space. The luminance L is represented by L ═ 0 for the darkest black, and L ═ 100 for the brightest white.
Preferably, the transmittance of the microcrystalline glass in a visible light range of 380nm-780nm is 6% -45%.
Preferably, the crystallite diameter of the microcrystalline glass is 300nm-600 nm.
Preferably, the microcrystalline glass has a crystallinity of > 86%.
Preferably, the temperature of the transition point of the glass ceramics is more than 710 ℃. The temperature of the transition point is higher than that of a pure glass material, and the high-temperature stability of the glass is greatly improved.
Preferably, the coloring molten salt is 100% CuSO 4 And (3) melting salt.
Preferably, the coloring molten salt is a mixed molten salt, and the mass percentage of the mixed molten salt is CuSO 4 45-70% of Na 2 SO 4 30-50% of K 2 SO 4 From 5 to 15% so that the melting point of the ternary composition is lower than 650 ℃.
The second aspect of the invention provides a colored glass-ceramic, which is prepared by the preparation method of the first aspect of the invention.
Preferably, the L value of the colored glass ceramics is 18-68.
Different from the prior art, the technical scheme at least comprises the following beneficial effects: the preparation method of colour glass ceramics is characterized by that firstly, it prepares the ivory-white glass ceramics whose transmissivity is 6% -45% in the range of visible light, grain size is 300nm-600nm, crystallinity is greater than 86%, and L value is between 20-75, then uses copper ion sulfate to colour molten salt to colour the ivory-white glass ceramics so as to implement the coloured glass ceramics with light green, yellow, brown green, red and various colour and colour patterns, and its L value is 18-68, so that it has good colour saturation and beautiful appearance.
Drawings
FIG. 1: the transmittance of the microcrystalline glass samples before being colored in examples 1-5 at the wavelength of 200nm-1400nm is 6.33%, 16.06%, 13.11%, 22.61% and 21.13% respectively at the wavelength of 380-780nm in visible light.
FIG. 2: scanning Electron Microscope (SEM) images of microcrystalline glass samples of example 1 before uncolored have an average grain size of < 600 nm.
FIG. 3: in the Scanning Electron Microscope (SEM) image of the microcrystalline glass sample in example 6, it can be seen from fig. 3 that the glass generates different crystalline phase structures due to the temperature difference, the left glass phase is more, the crystal grain is smaller, and the average crystal grain is 300 nm; the right side has relatively less glass phase and larger crystal grains which are about 300-500 nm.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
The glass precursors of examples 1-5 of the present invention were prepared by the following method: the mass percentage is SiO 2 73.5％、Al 2 O 3 10.2％、P 2 O 5 1.5％，Li 2 O 9.7％、Na 2 O 0.25％、ZrO 2 4.8％、SnO 2 0.05 percent of oxide, selecting corresponding introduced raw materials, weighing and uniformly mixing according to the ranges of the purity, the moisture and the proportion, putting the mixture which can be melted into a furnace, melting the mixture into molten glass at the temperature range of 1450 ℃ and 1550 ℃ according to the melting difficulty of glass composition, and preparing the basic glass plate with the thickness of 0.7mm by an overflow method, a slit downdraw method, a float method or casting and cutting.
In this example, the base glass plate was prepared by a cast-and-cut method.
Putting a basic glass plate into a crystallization furnace for three-stage step heating system treatment, and putting the glass-ceramic into coloring molten salt for ion coloring after the glass-ceramic is prepared, wherein the specific process parameters are as follows:
example 1: putting the basic glass plate into a crystallization furnace, heating to 550 ℃ at a speed of 10 ℃/min, and preserving heat for 180 min; heating to 710 deg.C at 3 deg.C/min, and maintaining for 60 min; heating to 800 deg.C at a rate of 5 deg.C/min, maintaining for 120min, cooling to below 100 deg.C, taking out, and cooling to room temperature; the transmittance (visible light range) was measured to be 6.33%, L value was 20.2, crystallinity > 90%, and grain size 500-600 nm. The Scanning Electron Microscope (SEM) image is shown in FIG. 2.
Preheating the prepared microcrystalline glass sample, and placing the preheated microcrystalline glass sample in coloring molten salt, wherein the molten salt comprises CuSO 4 60% of Na 2 SO 4 30% of K 2 SO 4 10 percent, the coloring temperature is 560 ℃, and the coloring time is 100 min; taking out the colored sample, placing the colored sample in a preheating furnace for annealing along with the furnace, and cleaning residues on the surface of the colored microcrystalline glass by hot water after the sample is cooled; the test showed a red color with a value of L of 18.83.
Example 2: putting the basic glass plate into a crystallization furnace, heating to 545 ℃ at a speed of 5 ℃/min, and keeping the temperature for 180 min; heating to 690 ℃ at a speed of 3 ℃/min, and keeping the temperature for 30 min; heating to 780 deg.C at 5 deg.C/min, maintaining for 90min, cooling to below 100 deg.C, taking out, and cooling to room temperature; the transmittance (visible range) was tested to be 16.06%, L value 41.2, crystallinity > 90%, grain size about 480 nm.
Preheating the prepared microcrystalline glass sample, and placing the preheated microcrystalline glass sample in coloring molten salt, wherein the molten salt comprises CuSO 4 57% of Na 2 SO 4 30% of K 2 SO 4 13%, coloring temperature 540 deg.C, and coloring time 60 min; taking out the colored sample, placing the colored sample in a preheating furnace for annealing along with the furnace, and cleaning residues on the surface of the colored glass ceramics by hot water after the sample is cooled; it was tested to show yellow with an L value of 27.32.
Example 3: putting the basic glass plate into a crystallization furnace, heating to 540 ℃ at a speed of 7 ℃/min, and preserving heat for 240 min; heating to 670 deg.C at 2 deg.C/min, and maintaining for 60 min; heating to 810 deg.C at 3 deg.C/min, maintaining for 60min, cooling to below 100 deg.C, taking out, and cooling to room temperature; the transmittance (visible range) was measured to be 13.11%, the L value was 35.95, the crystallinity > 90%, and the grain size was about 511 nm.
Preheating the prepared microcrystalline glass sample, and placing the preheated microcrystalline glass sample in coloring molten salt, wherein the molten salt comprises CuSO 4 65% of Na 2 SO 4 Is 30% and K 2 SO 4 5 percent, the coloring temperature is 600 ℃, and the coloring time is 120 min; taking out the colored sample, placing the colored sample in a preheating furnace for annealing along with the furnace, and cleaning residues on the surface of the colored glass ceramics by hot water after the sample is cooled; the test showed a brownish green color with a value of L of 22.12.
Example 4: putting the basic glass plate into a crystallization furnace, heating to 540 ℃ at a speed of 5 ℃/min, and preserving heat for 150 min; heating to 650 deg.C at 2 deg.C/min, and maintaining for 30 min; heating to 760 deg.C at 3 deg.C/min, maintaining for 60min, cooling to below 100 deg.C, taking out, and cooling to room temperature; the transmittance (visible light range) was 22.61%, the L value was 56.75, the crystallinity was > 86%, and the grain size was 372 nm.
The prepared microcrystalline glass samplePreheating, placing in coloring molten salt containing CuSO 4 55% of Na 2 SO 4 30% of K 2 SO 4 15 percent, the coloring temperature is 540 ℃, and the coloring time is 20 min; taking out the colored sample, placing the colored sample in a preheating furnace for annealing along with the furnace, and cleaning residues on the surface of the colored glass ceramics by hot water after the sample is cooled; the test showed a light green color with a value of L of 33.65.
Example 5: putting the basic glass plate into a crystallization furnace, heating to 540 ℃ at a speed of 5 ℃/min, and preserving heat for 150 min; heating to 650 deg.C at 2 deg.C/min, and maintaining for 50 min; heating to 760 deg.C at 3 deg.C/min, maintaining for 60min, cooling to below 100 deg.C, taking out, and cooling to room temperature; the transmittance (visible light range) was measured to be 21.13%, the value of L is 54.33, the crystallinity is > 86%, and the grain size is 377 nm.
Preheating the prepared microcrystalline glass sample, and placing the preheated microcrystalline glass sample in coloring molten salt, wherein the molten salt comprises 55% of CuSO4 and Na 2 SO 4 Is 30% and K 2 SO 4 15 percent, the coloring temperature is 540 ℃, and the coloring time is 90 min; taking out the colored sample, placing the colored sample in a preheating furnace for annealing along with the furnace, and cleaning residues on the surface of the colored glass ceramics by hot water after the sample is cooled; the test showed a green color with a value of L of 30.23.
The transmittance at 200nm-1400nm wavelength of the microcrystalline glass samples before being colored in examples 1-5 is shown in FIG. 1, and the average transmittance at the visible light wavelength of 380-780nm is 6.33%, 16.06%, 13.11%, 22.61% and 21.13%, respectively.
Example 6: placing a small refractory plate on the upper part of the basic glass plate, placing one refractory plate into a crystallization furnace, heating to 540 ℃ at a speed of 5 ℃/min, and keeping the temperature for 150 min; heating to 650 deg.C at 2 deg.C/min, and maintaining for 20 min; heating to 760 deg.C at 3 deg.C/min, maintaining for 60min, cooling to below 100 deg.C, taking out, and cooling to room temperature;
preheating the prepared microcrystalline glass sample, and placing the preheated microcrystalline glass sample in coloring molten salt, wherein the molten salt comprises CuSO 4 55% of Na 2 SO 4 Is 30% and K 2 SO 4 15 percent, the coloring temperature is 540 ℃, and the coloring time is 60 min; taking out the colored sample, and placingAnnealing in a hot furnace, and cleaning residues on the surface of the colored glass ceramics by hot water after the sample is cooled; the color of the position covered by the fire-resistant plate is tested to be green, and the color of the position uncovered by the fire-resistant plate is tested to be light green.
In example 6, as shown in fig. 3, the Scanning Electron Microscope (SEM) of the microcrystalline glass sample without coloration shows that in fig. 3, the glass generates different crystal phase structures due to the temperature difference, and the left glass phase is more, the crystal grain is smaller, and the average crystal grain is 300 nm; the right side has relatively less glass phase and larger crystal grains which are about 300-500 nm. The presence of the temperature difference causes the glass to develop a different crystalline phase structure which appears macroscopically as a difference in transmittance resulting in a difference in color development. The control of the temperature of the micro crystallization heat treatment is significant to the realization of the invention.
It can be seen from the above examples that different microcrystalline heat treatment temperatures, different microcrystalline heat treatment times, different coloring temperatures, different coloring times, and different copper ion implantation contents lead to different crystalline phase contents and crystalline phase structures, and transition of valence states of copper ions and different transmittances, which finally result in color development differences of glass.
The physical properties of examples 1-5 are defined and explained as follows:
(1) average grain size: performing determination by using an SEM (scanning electron microscope), performing surface treatment on the microcrystalline glass in HF (high-frequency) acid, performing chromium spraying coating on the surface of the microcrystalline glass, performing surface scanning under the SEM, observing the diameter of particles, and dividing the average diameter size of all the sections of the grains by the number of the grains in an SEM image;
(2) degree of crystallinity: comparing the XRD diffraction peak with a database map to determine a crystalline phase, and calculating the proportion of the diffraction intensity of the crystalline phase in the intensity of the whole map by a Rietveld method to obtain the crystallinity and the amorphous content;
(3) transmittance: testing by using a visible spectrophotometer;
(4) l a b value: and testing by using a spectrophotometer.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the present number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (7)
1. The preparation method of the colored glass ceramics is characterized by comprising the following steps:
carrying out micro-crystallization heat treatment on the lithium-aluminum-silicon glass precursor to obtain microcrystalline glass; preheating the glass ceramics, and then putting the glass ceramics into coloring molten salt for coloring treatment, wherein the coloring temperature is controlled to be 500-650 ℃, and the coloring time is 10-120 min, so as to obtain the colored glass ceramics; the coloring molten salt is Cu-containing 2+ Sulfate of (2);
the glass base composition of the microcrystalline glass comprises the following components in percentage by mass: SiO 2 2 68％-75％、Al 2 O 3 7％-12％、P 2 O 5 1.5％-4％，Li 2 O 7％-12％、Na 2 O 0％-1％、ZrO 2 4％-6％、BaO 0-1.2％、SnO 2 0.05％-0.1％；
The microcrystallization heat treatment comprises the following three-stage step heating treatment steps:
first-step temperature rise: heating to the first step temperature of 530-560 ℃ at the normal temperature at the speed of 5-10 ℃/min, and carrying out heat preservation treatment for 150-240 min;
second step temperature rise: then heating to a second gradient temperature of 650-;
third-step temperature rise: heating to a third gradient temperature of 760 and 810 ℃ at a speed of 3-5 ℃/min, carrying out heat preservation treatment for 60-120min, and cooling along with the furnace to obtain the microcrystalline glass;
the microcrystalline glass is milky white in appearance, and the L value is 20-75;
the transmittance of the microcrystalline glass is 6-45% in a visible light range of 380nm-780 nm;
the grain diameter of the microcrystalline glass is 300nm-600 nm.
2. The production method according to claim 1, wherein the microcrystalline glass has a crystallinity of > 86%.
3. The method according to claim 1, wherein the glass-ceramic has a transition point temperature of > 710 ℃.
4. The method according to claim 1, wherein the colored molten salt is 100% CuSO 4 And (3) melting the salt.
5. The method according to claim 1, characterized in that the colored molten salt is a mixed molten salt, and the mass percentage of the mixed molten salt is CuSO 4 45-70% of Na 2 SO 4 30-50% of K 2 SO 4 Is 5-15%.
6. A colored glass-ceramic, characterized in that the colored glass-ceramic is prepared by the preparation method of any one of claims 1 to 5.
7. The colored glass-ceramic according to claim 6, wherein the colored glass-ceramic has a L value of 18 to 68.
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