Highly transparent blue light-proof solid arsenic micro-ceramic glass and preparation method thereof

Abstract

The present invention relates to a highly transparent, blue-light-proof solid arsenic glass-ceramic and a preparation method thereof. Crystals are uniformly distributed in the highly transparent, blue-light-proof solid arsenic glass-ceramic, and the crystals include pseudo sapphire, cordierite, rutile, and spinel. The highly transparent, blue-light-proof solid arsenic glass-ceramic has a crystallinity of 82.4% or higher, an equivalent spherical diameter of the crystals of 10 to 20 nm, D5 ≥ 10 nm, and D97 ≤ 20 nm. The preparation method comprises the following steps: preparing raw materials, thoroughly mixing them, and then heating and melting them without volatile reaction to obtain a glass liquid, pouring the glass liquid into a mold and performing an annealing treatment to obtain a base glass, and then performing a microcrystallization heat treatment on the base glass to obtain the highly transparent, blue-light-proof solid arsenic glass-ceramic. The method of the present invention can effectively treat non-ferrous metal solid waste, achieve recycling, reduce the impact of arsenic pollution on the environment, and the obtained solid arsenic glass-ceramic has both high visible light transmittance and high blue light blocking performance.

Description

Technical Field

[0001] The present invention belongs to the field of glass solidification hazardous waste technology and microcrystalline glass preparation, and relates to a highly transparent blue light-proof solid arsenic microcrystalline glass and a preparation method thereof. Background Art

[0002] Arsenic slag is one of the major pollutants produced by the nonferrous metals industry. Previously, arsenic slag treatment primarily involved landfill or simple solidification, which poses significant risks to the environment and humans. With increasing awareness of environmental pollution, chemical recovery has become the primary method for arsenic slag treatment in recent years. However, the majority of recovered arsenic is stored as arsenates and elemental arsenic, resulting in very limited utilization. Furthermore, arsenic is highly oxidizing and mobile, making the selection of an appropriate solidification method crucial.

[0003] Currently, research on arsenic solidification mainly includes cement solidification methods and a small number of glass solidification methods. The cement solidification method has low cost, but has no resource application potential and can only be landfilled. Glass solidification methods, such as patent CN112919801B, disclose a method for preparing arsenic-containing borosilicate glass by treating arsenic solid waste. The prepared arsenic-containing borosilicate glass can be used for decorative glass, but the glass has a large expansion coefficient and has high requirements for the environment, especially the operating temperature.

[0004] Glass-ceramics are multiphase solid materials derived from base glass through a rational microcrystallization heat treatment process. Due to their excellent mechanical, thermal, dielectric, corrosion resistance, and low expansion properties, they have become a hot topic in inorganic materials research and are widely used in aerospace, automotive, electronic devices, and optical instruments. The ability to produce solid arsenic glass-ceramics could potentially address the challenges of existing arsenic-containing borosilicate glass.

[0005] Ultraviolet and blue-violet light are harmful to the human eye. On the one hand, they affect the surface structures of the eye, causing lesions in the cornea or conjunctiva, leading to photokeratitis and photoconjunctivitis. On the other hand, they affect the deep structures of the eye, causing opaque patches in the lens due to prolonged light exposure. Excessive patches can lead to cataracts. Studies have shown that blocking ultraviolet light while also increasing the shielding of blue light is the most effective way to protect the retina from light-induced damage. Currently, the anti-blue light technology for glass materials such as imaging equipment and lenses mainly takes the form of glass surface coating or reducing the overall visible light transmittance. For example, patent CN216832677U discloses an anti-blue light tempered glass protective film. This patent achieves the purpose of double blue light absorption and increases the blue light absorption effect by fixedly connecting a PET film with a blue light absorbing layer. Patent CN115180828A discloses a low-energy anti-blue light glass and its preparation method. This patent adds cerium dioxide, zinc chromate, calcium chromate, iron oxide and chromium nitride during the preparation process to reduce the transmission of sunlight thermal radiation and ultraviolet rays. However, the visible light transmittance of the above two patented products is only about 50%.

[0006] It would be of great significance if solid arsenic microcrystalline glass with both high visible light transmittance and high blue light blocking performance could be produced. Summary of the Invention

[0007] The purpose of the present invention is to solve the problems existing in the prior art and provide a highly transparent blue light-proof solid arsenic microcrystalline glass and a preparation method thereof. The present invention proposes a preparation technology of solid arsenic microcrystalline glass for the first time, and further optimizes the heat treatment process, improves the performance of solid arsenic microcrystalline glass, and expands the resource application prospects of solid arsenic microcrystalline glass.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A highly transparent, blue-light-blocking, solid arsenic glass-ceramic, in which crystals are evenly distributed, including pseudo sapphire (4MgO5Al2O3 2SiO2), cordierite (2MgO 2Al2O3 5SiO2), rutile (TiO2), and spinel (MgO Al2O3);

[0010] The crystallinity of the highly transparent blue light-proof solid arsenic microcrystalline glass is above 82.4%, the equivalent spherical diameter of the crystal is 10~20nm, preferably 15.35~18.35nm, D5≥10nm (the particle size corresponding to the cumulative particle size distribution number of a sample reaches 5%), and D97 (the particle size corresponding to the cumulative particle size distribution number of a sample reaches 97%) ≤20nm.

[0011] The solid arsenic glass-ceramics of the present invention can have both high visible light transmittance and high blue light blocking performance for the following reasons:

[0012] The solid arsenic glass-ceramics of the present invention has a crystallinity of 82.4% or more, a large number of crystals, and can block most light. The equivalent spherical diameter of the crystals of the solid arsenic glass-ceramics of the present invention is 10-20 nm, D5 ≥ 10 nm, and D97 ≤ 20 nm. The crystals are evenly distributed with little agglomeration. When visible light with relatively long wavelengths, such as red and green light, encounters crystal obstruction, the light has strong penetration and diffraction capabilities because the wavelength is much larger than the equivalent spherical diameter of the crystal. When blue-violet light with relatively short wavelengths encounters crystal obstruction, it produces more refraction and scattering.

[0013] Crystals such as pseudo sapphire, cordierite, rutile, and spinel have relatively high refractive indices, all exceeding 1.7. This results in a higher deflection angle for blue-violet light in the wavelength range below 500nm, further causing the blue-violet light to travel a longer path within the glass and encounter more crystal obstructions. Consequently, the probability of blue-violet light being scattered and absorbed is also greater. The uniform distribution of pseudo sapphire, cordierite, rutile, and spinel crystals in the solid arsenic glass-ceramics of the present invention effectively reduces blue-violet light transmittance while ensuring good visible light transmittance.

[0014] As the preferred technical solution:

[0015] The highly transparent blue light-proof solid arsenic micro-ceramic glass-ceramic has an average light transmittance of 74-85% in the wavelength range of 500-700 nm and an average light transmittance of 19-43% in the wavelength range of 380-500 nm, effectively blocking the transmission of blue-violet light. The highly transparent blue light-proof solid arsenic micro-ceramic glass-ceramic has a nanoindentation hardness of ≥9.8 GPa, an elastic modulus of 104.3-109.6 GPa, and an expansion coefficient of 4.4×10 -6 ~4.2×10 -6 / K, the uniformity and high crystallinity of nano-scale crystals improve the mechanical properties of microcrystalline glass and reduce the expansion coefficient.

[0016] As described above, the total amount of pseudo sapphire, cordierite, rutile and spinel in the highly transparent blue light proof solid arsenic microcrystalline glass is more than 95wt% of the total amount of crystals.

[0017] The highly transparent blue light-proof solid arsenic micro-ceramic glass-ceramic as described above is a magnesium-aluminum-silicon system, and arsenic participates in the construction of the glass network as a glass network former (the present invention uses the inVia Reflex model Raman spectrometer produced by Renishaw of the United Kingdom to test the base glass using a 532nm laser to test the sample, and it is found that as the content of arsenic oxide increases, the 830cm in the Raman spectrum increases. -1The characteristic peaks nearby reflect the stretching vibration of the As-O bond, indicating that arsenic, as a former, forms [AsO4] tetrahedrons and enters the glass network).

[0018] The highly transparent blue light-proof solid arsenic glass-ceramic of the present invention can effectively prevent the precipitation of arsenic ions for the following reasons:

[0019] Microcrystalline glass is a material in which glassy state and crystals coexist. The glassy state is similar to the sea, and the crystals are similar to densely packed islands distributed in the sea. In the present invention, since arsenic participates in the construction of the glass network as a glass network former, arsenic is distributed in the sea, and the sea area around the arsenic is full of densely packed islands, which will inevitably increase the exchange path between the active metal cations of depolymerization and arsenic, greatly increasing the difficulty of arsenic being exchanged and migrated out; in the glassy state, there are many network formers, but silicon-oxygen bonds and aluminum-oxygen bonds are two types of bonds with relatively high bond energy and a high degree of polymerization, so silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons are the most chemically stable network structures in the glassy state. The high-transparency, blue-light-proof, solid arsenic microcrystalline glass of the present invention is a magnesium-aluminum-silicon system, and arsenic participates in the construction of the glass network as a glass network former. Therefore, the glassy state contains arsenic-oxygen tetrahedrons, silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons at the same time. Arsenic-oxygen tetrahedrons are distributed in silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons, and are protected by the two and are not easily corroded by active metal cations of depolymerization and exchanged out.

[0020] The arsenic solidification principle of the prior art is different from that of the present invention. For example, patent 202110199075.7 realizes arsenic solidification by adding calcium arsenate to borosilicate glass. The arsenic solidification principle is: high-content silicon dioxide introduces elements such as boron and sodium, and through the structural reorganization of glass network intermediates and modifiers, while increasing the arsenic concentration in the glass, the glass network structure is also very stable. Arsenic is difficult to migrate out of the silicon-oxygen tetrahedral structure of the glass, thereby making the arsenic precipitation amount of arsenic-containing borosilicate glass low.

[0021] The highly transparent blue light-proof solid arsenic micro-ceramic glass-ceramic as described above has a curing rate of arsenic trioxide of 91.1-95.0 wt % as measured by XRF (XRF) spectrophotometer. The precipitation amount is tested according to GB 19778-2005 standard. The arsenic precipitation amount of the highly transparent blue light-proof solid arsenic micro-ceramic glass-ceramic is ≤0.52 μg / dm 2 The arsenic precipitation amount of glass without microcrystallization treatment made from the same raw materials is ≤20.41μg / dm 2 .

[0022] As described above, a highly transparent blue light-proof solid arsenic microcrystalline glass comprises 47.3~51.5wt% silicon dioxide, 25.5~27.1wt% aluminum oxide, 8.5~10.6wt% magnesium oxide, 7.8~8.3wt% titanium dioxide, 1.5~1.6wt% boron trioxide, 0.87~0.92wt% zirconium dioxide and less than 8.4wt% arsenic trioxide.

[0023] The present invention also provides a method for preparing the highly transparent blue light-proof solid arsenic micro-ceramic glass as described above, comprising preparing raw materials, fully mixing them, heating and melting them without volatilization to obtain a glass liquid, pouring the glass liquid into a mold and performing an annealing treatment to obtain a base glass, and then performing a microcrystallization heat treatment on the base glass to obtain the highly transparent blue light-proof solid arsenic micro-ceramic glass;

[0024] The melting temperature of non-volatile heating melting is 1450~1550℃, and the holding time is 2~3h;

[0025] The specific steps of performing microcrystallization heat treatment on base glass are as follows:

[0026] (i) heating the base glass to a nucleation temperature and then maintaining the temperature for 45 to 60 hours. The nucleation temperature is Tg-T1 to Tg+T2, where T1 is 5°C and T2 is 20°C. Tg is the glass transition temperature of the base glass (measured by differential scanning calorimetry (DSC)).

[0027] (ii) after heating to the crystallization temperature, the temperature is maintained for 30 to 90 minutes, and the absolute difference between the crystallization temperature and the crystallization peak temperature of the base glass (obtained by DSC test) does not exceed 50°C;

[0028] (iii) Cooling with the furnace.

[0029] In the present invention, arsenic trioxide (added in the form of magnesium arsenate during batching and converted to arsenic trioxide during processing) plays a clarifying role in the glass melt. By regulating the melting temperature and holding time of the non-volatile heating and melting process, the various components of the glass are fully clarified and homogenized, thereby ensuring that crystals and titanium dioxide are uniformly distributed in the highly transparent, blue light-blocking solid arsenic micro-ceramic glass.

[0030] The present invention achieves a higher nucleation success rate by regulating the nucleation temperature and a larger number of crystals by regulating the nucleation time. The present invention also achieves an equivalent spherical diameter of 10 to 20 nm, D5 ≥ 10 nm, and D97 ≤ 20 nm by regulating the crystallization temperature and time. The number and size of the crystals together result in a crystallinity of 82.4% or higher in the highly transparent, blue light-blocking, solid arsenic micro-ceramic glass.

[0031] The highly transparent blue light-proof solid arsenic microcrystalline glass of the present invention is a magnesium-aluminum-silicon system and adopts a microcrystalline process, so crystals such as pseudo sapphire, cordierite, rutile and spinel are formed.

[0032] As the preferred technical solution:

[0033] In the method described above, the non-volatile heating and melting adopts a sealed crucible electric melting furnace or a cold top process electric melting furnace, and the top temperature of the cold top process electric melting furnace is not higher than 200°C.

[0034] According to the above method, the specific steps of pouring the glass liquid into the mold and annealing it to obtain the base glass are as follows:

[0035] (a) Place the mold on a heating table (about 400°C) for reheating;

[0036] (b) quickly pouring the molten glass into the mold to form a glass block;

[0037] (c) Place the glass block in the mold in an annealing furnace at 550-650°C and anneal for 2-3 hours to obtain the base glass.

[0038] In the above method, in step (i), the heating rate is 8-12 K / min; in step (ii), the heating rate is 3-6 K / min.

[0039] Beneficial effects:

[0040] (1) The high-transparency blue-light-proof solid arsenic glass-ceramics of the present invention has excellent arsenic solidification efficiency, and its arsenic precipitation amount is ≤0.86μg / dm 2 , which is lower than the arsenic precipitation amount of glass without microcrystallization treatment (≤20.41μg / dm 2 ), which is much lower than the arsenic precipitation amount of GB 19778-2005 glass packaging standard (≤70μg / dm 2 ).

[0041] (2) The solid arsenic glass-ceramics of the present invention has excellent mechanical properties, high visible light transmittance, low thermal expansion coefficient and good blue light protection function, and has industrial application potential in optical glass, electronic glass, cover glass, aerospace materials, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is an SEM image of the highly transparent blue light-proof solid arsenic glass-ceramics prepared in Example 1;

[0043] Figure 2 1 is the DSC graph of the base glass prepared in Examples 1 to 4;

[0044] Figure 3 : XRD patterns of the highly transparent blue light-proof solid arsenic glass-ceramics prepared in Examples 1 to 4;

[0045] Figure 4 Schematic diagram of the visible light transmittance of the highly transparent blue light-proof solid arsenic glass-ceramics prepared in Examples 1, 3, and 4;

[0046] Figure 5 These are Raman spectra of the base glass prepared in Examples 1 and 4 and the base glass prepared in Comparative Example 1. DETAILED DESCRIPTION

[0047] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0048] The following are the test methods for various properties in the examples:

[0049] Curing rate: The glass components of the prepared highly transparent blue light-proof solid arsenic micro-ceramic glass were tested using a fluorescence spectrometer (XRF). The curing rate was calculated using the following formula: Curing rate = arsenic trioxide measured value / arsenic trioxide added amount.

[0050] Light transmittance: The samples were processed into thin slices with a thickness of 2 mm. After polishing both surfaces, the visible light transmittance in the wavelength range of 380-700 nm was measured using a Hitachi U-3310 UV-visible spectrophotometer.

[0051] Nanoindentation hardness and modulus: The hardness and modulus of solid arsenic glass-ceramics were tested by nanoindentation. The sample was ground and polished, and then tested using a G200X nanoindenter produced by KLA, USA. A load gradually increasing to 50mN (strain rate of 0.2S) was applied to the sample surface using a Bergvich indenter. -1 ), and nanoindentation hardness and modulus were obtained.

[0052] Expansion coefficient: The sample was processed into a long strip with a size of 20×3×3 mm and polished on both ends of the long side. It was tested using a TMA402F3 thermomechanical analyzer produced by Mettler, Switzerland. The expansion coefficient α was calculated using the temperature change ΔT, initial length L0 and final length L using the formula: α=(L-L0) / (L0×ΔT).

[0053] Crystallinity: The micromorphology of the solid arsenic glass-ceramics was observed using a scanning electron microscope (SEM). The samples were immersed in hydrofluoric acid for 15 seconds, cleaned and dried, and then observed using a Hitachi SU8010. ImageJ image processing software was used to analyze the crystal type and calculate the crystallinity.

[0054] Arsenic leaching amount: According to GB 19778-2005 glass packaging standard, samples were processed into a size of 50×50×50 mm and immersed in a 4 wt% acetic acid aqueous solution at 22±2°C for 24 h. The arsenic leaching amount was measured using a Fisher iCAP Q inductively Coupled Plasma Atomic Emission Mass Spectrometer (ICP-Ms) produced by Thermo Fisher Scientific.

[0055] Example 1

[0056] A highly transparent blue light-proof solid arsenic microcrystalline glass, which is composed, by weight percentage, of 49.5wt% silicon dioxide, 26.8wt% aluminum oxide, 10.1wt% magnesium oxide, 8.2wt% titanium dioxide, 1.6wt% boron trioxide, 0.91wt% zirconium dioxide and the balance arsenic trioxide.

[0057] The method for preparing the highly transparent blue light-proof solid arsenic micro-ceramic glass as described above comprises the following steps:

[0058] (1) Prepare raw materials;

[0059] Prepare silicon dioxide, aluminum oxide, magnesium carbonate, titanium dioxide, boric acid, zirconium dioxide, and magnesium arsenate;

[0060] (2) using a sealed crucible electric melting furnace, placing the raw materials prepared in step (1) into a mixer, ball milling and fully mixing, and then heating and melting without volatilization to obtain glass liquid; wherein, the melting temperature is 1550°C and the holding time is 3 hours;

[0061] (3) Pour the glass liquid into the mold and anneal it to obtain the base glass. The specific steps are as follows:

[0062] (3.1) Place the mold on a heating table and heat it at 400°C;

[0063] (3.2) Quickly pour the molten glass into the mold to form a glass block;

[0064] (3.3) Place the glass block in the mold in an annealing furnace at 650℃ and anneal for 3 hours to obtain the base glass. Use DSC to perform thermal analysis on the obtained base glass. Figure 2 As shown, the test shows that the glass transition temperature of the base glass is 753℃ and the crystallization peak temperature is 950℃; the inVia Reflex model Raman spectrometer produced by Renishaw Company of the United Kingdom was used to test the obtained base glass using a 532nm laser. The Raman spectrum obtained is shown in Figure 5 As shown;

[0065] (4) Performing microcrystallization heat treatment on the base glass. The specific steps are as follows:

[0066] (4.1) Heating the base glass obtained in step (3.3) to 753°C at a heating rate of 8 K / min and holding the temperature for 60 h;

[0067] (4.2) Heating to 935°C at a rate of 5 K / min and holding for 30 min;

[0068] (4.3) Cool down to room temperature in the furnace to obtain highly transparent blue light-proof solid arsenic microcrystalline glass.

[0069] The final highly transparent blue light proof solid arsenic micro-ceramic glass (such as Figure 1 The crystallinity of the crystal is 82.43%, the equivalent spherical diameter of the crystal is 15.62nm, D5 is 12nm, and D97 is 19nm. Figure 3 As shown in the figure, compared with the standard X-ray diffraction pattern, it can be seen that the crystal is composed of pseudo sapphire, cordierite, rutile and spinel, of which the total amount of pseudo sapphire, cordierite, rutile and spinel is 96wt% of the total amount of the crystal; the solidification rate of arsenic trioxide in the high-transparency anti-blue light solid arsenic micro-ceramic glass is 93.5wt%, and the arsenic precipitation amount is 0.43μg / dm 2 ;like Figure 4 As shown in the figure, the average light transmittance of the highly transparent blue light blocking solid arsenic micro-ceramic glass in the wavelength range of 500-700 nm is 84.74%, and the average light transmittance in the wavelength range of 380-500 nm is 40.82%. The nanoindentation hardness of the highly transparent blue light blocking solid arsenic micro-ceramic glass is 10.6 GPa, the elastic modulus is 104.34 GPa, and the expansion coefficient is 4.39×10 -6 / K.

[0070] Comparative Example 1

[0071] A method for preparing microcrystalline glass is basically the same as that in Example 1, except that: magnesium arsenate is not prepared in step (1); and the base glass obtained in step (3.3) is tested using an inVia Reflex Raman spectrometer produced by Renishaw, UK, using a 532 nm laser. The Raman spectrum obtained is as shown in FIG. Figure 5 shown.

[0072] The final microcrystalline glass produced had stripes inside, its crystallinity was 53.2%, the crystal distribution was uneven, local crystals showed agglomeration, the size of the largest grain was 815nm, and the average light transmittance of the microcrystalline glass in the wavelength range of 500~700nm was 69.75%.

[0073] By comparing Comparative Example 1 with Example 1, it can be seen that since magnesium arsenate is not added in Comparative Example 1, the base glass is not effectively clarified and homogenized during the melting process, and the oxides, especially the nucleating agents such as Zr and Ti, are unevenly distributed in the glass body. During the nucleation process, it is easy to produce localized accumulation of crystal nuclei or a small number of crystal nuclei in local areas, resulting in large deviations in crystal size and uncontrollable preparation.

[0074] Comparative Example 2

[0075] A solid arsenic glass-ceramic, same as in Example 1.

[0076] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the melting temperature of the non-volatile heating and melting in step (2) is 1400°C.

[0077] The base glass of the solid arsenic glass-ceramics finally obtained has obvious internal stripes, and the glass-ceramics prepared after microcrystallization treatment is easy to break.

[0078] By comparing Comparative Example 2 with Example 1, it can be seen that since the temperature during the non-volatile heating and melting in Comparative Example 2 is too low, the microcrystalline glass prepared after microcrystallization treatment is prone to breakage. This is because during the crystallization process, microcracks will be generated at the original stripes, and the microcracks will expand along the grain boundaries until the entire piece of microcrystalline glass breaks.

[0079] Comparative Example 3

[0080] A solid arsenic glass-ceramic, same as in Example 1.

[0081] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the melting temperature of the non-volatile heating and melting in step (2) is 1600°C.

[0082] The resulting solid arsenic glass-ceramics had a crystallinity of 75.6%, a D5 of 14 nm, and a D97 of 19 nm. The crystals were composed of pseudo sapphire, cordierite, rutile, and spinel, with the total amount of pseudo sapphire, cordierite, rutile, and spinel accounting for 74.3 wt% of the total crystal volume. The solidification rate of arsenic trioxide in the solid arsenic glass-ceramics was 73%, and the amount of arsenic precipitation was 0.45 μg / dm 2 The average light transmittance of the solid arsenic glass-ceramics in the wavelength range of 500-700 nm is 85.33%, and the average light transmittance in the wavelength range of 380-500 nm is 56.05%. The nanoindentation hardness of the solid arsenic glass-ceramics is 9.81 GPa, the elastic modulus is 96.25 GPa, and the expansion coefficient is 5.3×10 -6 / K.

[0083] By comparing Comparative Example 3 with Example 1, it can be seen that since the temperature during the non-volatile heating and melting in Comparative Example 3 is too high, the solid arsenic efficiency is low, the crystallinity is reduced, the blue-violet light transmittance is increased, the mechanical properties are reduced, and the expansion coefficient is increased. This is because the higher the temperature, the stronger the volatility of the arsenide in the glass liquid, and the components in the corundum crucible are added to the glass liquid due to high-temperature corrosion, causing the glass composition to change, so that the proportion of crystals such as pseudo sapphire, cordierite, rutile and spinel in the total number of crystals is not high.

[0084] Comparative Example 4

[0085] A solid arsenic glass-ceramic, same as in Example 1.

[0086] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the holding time during the non-volatile heating and melting in step (2) is 1.8 h.

[0087] The base glass finally obtained has obvious internal stripes, and the microcrystalline glass prepared after microcrystallization treatment is easy to break.

[0088] By comparing Comparative Example 4 with Example 1, it can be seen that since the holding time during the non-volatile heating and melting in Comparative Example 4 is too short, the microcrystalline glass prepared after microcrystallization treatment is prone to breakage. This is because during the crystallization process, microcracks will be generated at the original stripes, and the microcracks will expand along the grain boundaries until the entire piece of microcrystalline glass breaks.

[0089] Comparative Example 5

[0090] A solid arsenic glass-ceramic, same as in Example 1.

[0091] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the holding time during the non-volatile heating and melting in step (2) is 3.5 hours.

[0092] The resulting solid arsenic glass-ceramics had a crystallinity of 81%, an equivalent spherical diameter of 18.33 nm, a D5 of 14 nm, and a D97 of 20 nm. The crystals were composed of pseudo sapphire, cordierite, rutile, and spinel, with the total amount of pseudo sapphire, cordierite, rutile, and spinel accounting for 86 wt% of the total crystal volume. The solidification rate of arsenic trioxide in the solid arsenic glass-ceramics was 77%, and the amount of arsenic precipitation was 0.51 μg / dm 2 The average light transmittance of solid arsenic glass-ceramics in the wavelength range of 500-700 nm is 83.36%, and the average light transmittance in the wavelength range of 380-500 nm is 53.49%. The nanoindentation hardness of solid arsenic glass-ceramics is 9.97 GPa, the elastic modulus is 102.07 GPa, and the expansion coefficient is 4.9×10 -6 / K.

[0093] By comparing Comparative Example 5 with Example 1, it can be seen that since the holding time during the non-volatile heating and melting in Comparative Example 5 is too long, the solid arsenic efficiency is low, the crystallinity is reduced, the blue-violet light transmittance is increased, the mechanical properties are reduced, and the expansion coefficient is increased. This is because the volatilization time of arsenide in the glass liquid is increased under high temperature for a long time, and the components in the corundum crucible are added to the glass liquid due to long-term high-temperature erosion, causing the glass composition to change, so that the proportion of crystals such as pseudo sapphire, cordierite, rutile and spinel in the total number of crystals is not high.

[0094] Comparative Example 6

[0095] A solid arsenic glass-ceramic, same as in Example 1.

[0096] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the holding time during nucleation in step (4.1) is 40 hours.

[0097] The resulting solid arsenic glass-ceramics had a crystallinity of 75.5%, a D5 of 16 nm, and a D97 of 23 nm. The crystals were composed of pseudo sapphire, cordierite, rutile, and spinel, with the total amount of pseudo sapphire, cordierite, rutile, and spinel accounting for 92 wt% of the total crystal volume. The solidification rate of arsenic trioxide in the solid arsenic glass-ceramics was 92 wt%, and the amount of arsenic precipitation was 0.50 μg / dm 2 The average light transmittance of solid arsenic glass-ceramics in the wavelength range of 500-700 nm is 77%, and the average light transmittance in the wavelength range of 380-500 nm is 37%. The nanoindentation hardness of solid arsenic glass-ceramics is 10.71 GPa, the elastic modulus is 105.54 GPa, and the expansion coefficient is 4.6×10 -6 / K.

[0098] By comparing Comparative Example 6 with Example 1, it can be seen that since the holding time during nucleation during the microcrystallization heat treatment in Comparative Example 6 is too short, the crystallinity is slightly smaller, the range of the crystal equivalent spherical diameter is larger, and the expansion coefficient is larger. This is because the nucleation time is insufficient and the number of crystal nuclei formed is small.

[0099] Comparative Example 7

[0100] A solid arsenic glass-ceramic, same as in Example 1.

[0101] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the nucleation temperature in step (4.1) is 780°C.

[0102] The final solid arsenic microcrystalline glass is translucent milky white, and its average light transmittance in the wavelength range of 500~700nm is 8.73%.

[0103] By comparing Comparative Example 7 with Example 1, it can be seen that since the difference between the nucleation temperature and the glass transition temperature of the base glass in Comparative Example 7 is too large, the microcrystalline glass will become devitrified. This is because the high nucleation temperature causes crystal growth during the nucleation process. The long-term crystal growth causes the crystal size to exceed the wavelength of visible light, blocking the transmission of visible light.

[0104] Comparative Example 8

[0105] A solid arsenic glass-ceramic, same as in Example 1.

[0106] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the holding time in step (4.2) is 10 minutes.

[0107] The resulting solid arsenic glass-ceramics had a crystallinity of 69.8%, an equivalent spherical diameter of 10 nm (D5), and 17 nm (D97). The crystals were composed of pseudo-sapphire, cordierite, rutile, and spinel, with the total amount of pseudo-sapphire, cordierite, rutile, and spinel accounting for 93 wt% of the total crystal volume. The solidification rate of arsenic trioxide in the solidified arsenic glass-ceramics was 92 wt%, and the amount of arsenic precipitated was 0.57 μg / dm 2 The average light transmittance of solid arsenic glass-ceramics in the wavelength range of 500-700 nm is 85%, and the average light transmittance in the wavelength range of 380-500 nm is 47%. The nanoindentation hardness of solid arsenic glass-ceramics is 9.68 GPa, the elastic modulus is 99.19 GPa, and the expansion coefficient is 4.7×10 -6 / K.

[0108] Comparing Comparative Example 8 with Example 1, it can be seen that since the holding time during crystallization in Comparative Example 8 is too short, the crystallinity is relatively small, the elastic modulus is relatively small, and the expansion coefficient becomes larger. This is because the crystal growth time is insufficient and the crystal size is relatively small.

[0109] Comparative Example 9

[0110] A solid arsenic glass-ceramic, same as in Example 1.

[0111] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the holding time in step (4.2) is 120 minutes.

[0112] The final solid arsenic microcrystalline glass is translucent milky white, and its average light transmittance in the 500~700nm wavelength range is 4.99%.

[0113] Comparing Comparative Example 9 with Example 1, it can be seen that since the holding time during crystallization in Comparative Example 9 is too long, the crystals grow too large and squeeze each other to form larger agglomerated crystals, which blocks the transmission of visible light.

[0114] Comparative Example 10

[0115] A solid arsenic glass-ceramic, same as in Example 1.

[0116] The method for preparing the solid arsenic glass-ceramics as described above is basically the same as that in Example 1, except that the crystallization temperature in step (4.2) is 1000°C.

[0117] The final solid arsenic microcrystalline glass is translucent milky white, and its average light transmittance in the 500~700nm wavelength range is 9.85%.

[0118] Comparing Comparative Example 10 with Example 1, it can be seen that since the difference between the crystallization temperature in Comparative Example 10 and the glass transition temperature of the base glass is too large, the crystals will grow too large and squeeze each other to form larger agglomerate crystals, blocking the transmission of visible light.

[0119] Example 2

[0120] A highly transparent blue light-proof solid arsenic microcrystalline glass, which is composed, by weight percentage, of 50.1wt% silicon dioxide, 27.1wt% aluminum oxide, 10.6wt% magnesium oxide, 8.3wt% titanium dioxide, 1.6wt% boron trioxide, 0.92wt% zirconium dioxide and the balance arsenic trioxide.

[0121] The method for preparing the highly transparent blue light-proof solid arsenic micro-ceramic glass as described above comprises the following steps:

[0122] (1) Prepare raw materials;

[0123] Prepare silicon dioxide, aluminum oxide, magnesium carbonate, titanium dioxide, boric acid, zirconium dioxide, and magnesium arsenate;

[0124] (2) using a sealed crucible electric melting furnace, placing the raw materials prepared in step (1) into a mixer, ball milling and fully mixing, and then heating and melting without volatilization to obtain glass liquid; wherein, the melting temperature is 1550°C and the holding time is 3 hours;

[0125] (3) Pour the glass liquid into the mold and anneal it to obtain the base glass. The specific steps are as follows:

[0126] (3.1) Place the mold on a heating table and heat it at 400°C;

[0127] (3.2) Quickly pour the molten glass into the mold to form a glass block;

[0128] (3.3) Place the glass block in the mold in an annealing furnace at 650℃ and anneal for 3 hours to obtain the base glass. Use DSC to perform thermal analysis on the obtained base glass. Figure 2As shown, the test shows that the glass transition temperature of the base glass is 758℃ and the crystallization peak temperature is 958℃;

[0129] (4) Performing microcrystallization heat treatment on the base glass. The specific steps are as follows:

[0130] (4.1) Heating the base glass obtained in step (3.3) to 758°C at a heating rate of 10 K / min and holding the temperature for 48 h;

[0131] (4.2) Heating to 940°C at a rate of 6 K / min and holding for 30 min;

[0132] (4.3) Cool down to room temperature in the furnace to obtain highly transparent blue light-proof solid arsenic microcrystalline glass.

[0133] The crystallinity of the high-transparency blue-light-proof solid arsenic micro-ceramic glass-ceramic finally obtained is 87.39%, the equivalent spherical diameter of the crystal is 15.35nm, D5 is 10nm, and D97 is 18nm. Figure 3 As shown in the figure, compared with the standard X-ray diffraction pattern, it can be seen that the crystal is composed of pseudo sapphire, cordierite, rutile and spinel, of which the total amount of pseudo sapphire, cordierite, rutile and spinel is 95wt% of the total amount of the crystal; the solidification rate of arsenic trioxide in the high-transparency anti-blue light solid arsenic micro-ceramic glass is 95.0wt%, and the arsenic precipitation amount is 0.18μg / dm 2 The average light transmittance of the highly transparent blue light-proof solid arsenic micro-ceramic glass in the wavelength range of 500-700nm is 84.9%, and the average light transmittance in the wavelength range of 380-500nm is 37.88%. The nanoindentation hardness of the highly transparent blue light-proof solid arsenic micro-ceramic glass is 9.8GPa, the elastic modulus is 104.92GPa, and the expansion coefficient is 4.30×10 -6 / K.

[0134] Example 3

[0135] A highly transparent blue light-proof solid arsenic microcrystalline glass, which is composed, by weight percentage, of 48.4wt% silicon dioxide, 26.1wt% aluminum oxide, 9.3wt% magnesium oxide, 8wt% titanium dioxide, 1.5wt% boron trioxide, 0.89wt% zirconium dioxide and the balance arsenic trioxide.

[0136] The method for preparing the highly transparent blue light-proof solid arsenic micro-ceramic glass as described above comprises the following steps:

[0137] (1) Prepare raw materials;

[0138] Prepare silicon dioxide, aluminum oxide, magnesium carbonate, titanium dioxide, boric acid, zirconium dioxide, and magnesium arsenate;

[0139] (2) Using a sealed crucible electric melting furnace, the raw materials prepared in step (1) are placed in a mixer, ball-milled and fully mixed, and then heated and melted without volatilization to obtain glass liquid; wherein the melting temperature is 1500°C and the holding time is 2.5 hours;

[0140] (3) Pour the glass liquid into the mold and anneal it to obtain the base glass. The specific steps are as follows:

[0141] (3.1) Place the mold on a heating table and heat it at 400°C;

[0142] (3.2) Quickly pour the molten glass into the mold to form a glass block;

[0143] (3.3) Place the glass block in the mold in an annealing furnace at 650℃ and anneal for 3 hours to obtain the base glass. Use DSC to perform thermal analysis on the obtained base glass. Figure 2 As shown, the test shows that the glass transition temperature of the base glass is 750℃ and the crystallization peak temperature is 944℃;

[0144] (4) Performing microcrystallization heat treatment on the base glass. The specific steps are as follows:

[0145] (4.1) Heating the base glass obtained in step (3.3) to 753°C at a heating rate of 12 K / min and holding the temperature for 45 h;

[0146] (4.2) Heating to 930°C at a rate of 3 K / min and holding for 60 min;

[0147] (4.3) Cool down to room temperature in the furnace to obtain highly transparent blue light-proof solid arsenic microcrystalline glass.

[0148] The crystallinity of the high-transparency blue-light-proof solid arsenic micro-ceramic glass finally obtained is 90.55%, the equivalent spherical diameter of the crystal is 17.97nm, D5 is 14nm, and D97 is 19nm. Figure 3 As shown in the figure, compared with the standard X-ray diffraction pattern, it can be seen that the crystal is composed of pseudo sapphire, cordierite, rutile and spinel, of which the total amount of pseudo sapphire, cordierite, rutile and spinel is 98wt% of the total amount of the crystal; the solidification rate of arsenic trioxide in the high-transparency anti-blue light solid arsenic micro-ceramic glass is 92.1wt%, and the arsenic precipitation amount is 0.52μg / dm 2 ;like Figure 4 As shown in the figure, the average light transmittance of the highly transparent blue light blocking solid arsenic micro-ceramic glass in the wavelength range of 500-700 nm is 80.78%, and the average light transmittance in the wavelength range of 380-500 nm is 42.73%. The nanoindentation hardness of the highly transparent blue light blocking solid arsenic micro-ceramic glass is 10.31 GPa, the elastic modulus is 106.22 GPa, and the expansion coefficient is 4.26×10 -6 / K.

[0149] Example 4

[0150] A highly transparent blue light-proof solid arsenic microcrystalline glass, which is composed, by weight percentage, of 47.3wt% silicon dioxide, 25.5wt% aluminum oxide, 8.5wt% magnesium oxide, 7.8wt% titanium dioxide, 1.5wt% boron trioxide, 0.87wt% zirconium dioxide and the balance arsenic trioxide.

[0151] The method for preparing the highly transparent blue light-proof solid arsenic micro-ceramic glass as described above comprises the following steps:

[0152] (1) Prepare raw materials;

[0153] Prepare silicon dioxide, aluminum oxide, magnesium carbonate, titanium dioxide, boric acid, zirconium dioxide, and magnesium arsenate;

[0154] (2) Using a cold top process electric melting furnace, the raw materials prepared in step (1) are placed in a mixer for ball milling and fully mixed, and then heated and melted without volatile reaction to obtain glass liquid; wherein the melting temperature is 1450°C, the holding time is 2 hours, and the top temperature of the cold top process electric melting furnace is not higher than 200°C;

[0155] (3) Pour the glass liquid into the mold and anneal it to obtain the base glass. The specific steps are as follows:

[0156] (3.1) Place the mold on a heating table and heat it at 400°C;

[0157] (3.2) Quickly pour the molten glass into the mold to form a glass block;

[0158] (3.3) Place the glass block in the mold in an annealing furnace at 550℃ and anneal for 2 hours to obtain the base glass; perform thermal analysis on the obtained base glass using DSC, as shown in the following figure: Figure 2 As shown, the test shows that the glass transition temperature of the base glass is 741℃ and the crystallization peak temperature is 941℃. The inVia Reflex Raman spectrometer produced by Renishaw of the United Kingdom was used to test the obtained base glass using a 532nm laser. The Raman spectrum obtained is shown in the figure below. Figure 5 As shown;

[0159] (4) Performing microcrystallization heat treatment on the base glass. The specific steps are as follows:

[0160] (4.1) Heating the base glass obtained in step (3.3) to 745°C at a heating rate of 10 K / min and holding the temperature for 48 h;

[0161] (4.2) Heating to 930°C at a rate of 6 K / min and holding for 90 min;

[0162] (4.3) Cool down to room temperature in the furnace to obtain highly transparent blue light-proof solid arsenic microcrystalline glass.

[0163] The crystallinity of the high-transparency blue-light-proof solid arsenic micro-ceramic glass-ceramic finally obtained is 90.63%, the equivalent spherical diameter of the crystal is 18.35nm, D5 is 13nm, and D97 is 20nm. Figure 3 As shown in the figure, compared with the standard X-ray diffraction pattern, it can be seen that the crystal is composed of pseudo sapphire, cordierite, rutile and spinel, of which the total amount of pseudo sapphire, cordierite, rutile and spinel is 97wt% of the total amount of the crystal; the solidification rate of arsenic trioxide in the high-transparency anti-blue light solid arsenic micro-ceramic glass is 91.1wt%, and the arsenic precipitation amount is 0.5μg / dm 2 ;like Figure 4 As shown in the figure, the average light transmittance of the highly transparent blue light blocking solid arsenic micro-ceramic glass in the wavelength range of 500-700 nm is 74.62%, and the average light transmittance in the wavelength range of 380-500 nm is 19.17%. The nanoindentation hardness of the highly transparent blue light blocking solid arsenic micro-ceramic glass is 10.28 GPa, the elastic modulus is 109.62 GPa, and the expansion coefficient is 4.25×10 -6 / K.

Claims

1. A highly transparent blue light-proof solid arsenic micro-ceramic glass, characterized in that: Evenly distributed among them are crystals, including pseudo-sapphire, cordierite, rutile and spinel; The crystallinity of the highly transparent blue light-proof solid arsenic micro-ceramic glass is above 82.4%, and the equivalent spherical diameter of the crystal is 10-20nm. D5≥10nm, D97≤20nm; The highly transparent blue light-proof solid arsenic micro-ceramic glass comprises 47.3-51.5 wt% silicon dioxide, 25.5-27.1 wt% aluminum oxide, 8.5-10.6 wt% magnesium oxide, 7.8-8.3 wt% titanium dioxide, 1.5-1.6 wt% boron trioxide, 0.87-0.92 wt% zirconium dioxide and less than 8.4 wt% arsenic trioxide. The preparation method of the high-transparency blue light-proof solid arsenic micro-ceramic glass comprises: preparing raw materials, fully mixing them, heating and melting them without volatilization to obtain glass liquid, pouring the glass liquid into a mold, annealing the mold to obtain base glass, and then performing microcrystallization heat treatment on the base glass to obtain the high-transparency blue light-proof solid arsenic micro-ceramic glass; The melting temperature of non-volatile heating melting is 1450-1550℃, and the holding time is 2-3h; The specific steps of performing microcrystallization heat treatment on base glass are as follows: (i) heating the base glass to a nucleation temperature and then maintaining the temperature for 45 to 60 hours, wherein the nucleation temperature is Tg-T1 to Tg+T2, where T1 is 5°C, T2 is 20°C, and Tg is the glass transition temperature of the base glass; (ii) after heating to the crystallization temperature, holding the temperature for 30 to 90 minutes, the absolute difference between the crystallization temperature and the crystallization peak temperature of the base glass does not exceed 50°C; (iii) Cooling with the furnace.

2. The highly transparent blue light-proof solid arsenic glass-ceramic according to claim 1, characterized in that: The high-transparency blue light-proof solid arsenic micro-ceramic glass has an average light transmittance of 74-85% in the wavelength range of 500-700nm, and an average light transmittance of 19-43% in the wavelength range of 380-500nm. The nanoindentation hardness of the high-transparency blue light-proof solid arsenic micro-ceramic glass is ≥9.8GPa, the elastic modulus is 104.3-109.6GPa, and the expansion coefficient is 4.4×10 -6 ~4.2×10 -6 / K.

3. The highly transparent blue light-proof solid arsenic micro-ceramic glass according to claim 1, characterized in that: The total amount of pseudo sapphire, cordierite, rutile and spinel in the highly transparent blue light-proof solid arsenic micro-ceramic glass is more than 95wt% of the total amount of the crystal.

4. The highly transparent blue light-proof solid arsenic glass-ceramic according to any one of claims 1 to 3, characterized in that: Highly transparent, blue-light-proof solid arsenic microcrystalline glass is a magnesium-aluminum-silicon system, and arsenic participates in the construction of the glass network as a glass network former.

5. The highly transparent blue light-proof solid arsenic micro-ceramic glass according to claim 4, characterized in that: The curing rate of arsenic trioxide in the high-transparency blue light-proof solid arsenic micro-ceramic glass was measured by fluorescence spectrometer to be 91.1-95.0wt%. The precipitation amount was tested according to GB19778-2005 standard. The arsenic precipitation amount of the high-transparency blue light-proof solid arsenic micro-ceramic glass was ≤0.52μg / dm 2 .

6. The method for preparing a highly transparent blue light-proof solid arsenic glass-ceramic according to claim 1, characterized in that: The raw materials are prepared and fully mixed, and then heated and melted without volatilization to obtain glass liquid, and then the glass liquid is poured into a mold for annealing to obtain base glass, and then the base glass is subjected to microcrystallization heat treatment to obtain highly transparent blue light-proof solid arsenic micro-ceramic glass; The melting temperature of non-volatile heating melting is 1450-1550℃, and the holding time is 2-3h; The specific steps of performing microcrystallization heat treatment on base glass are as follows: (i) heating the base glass to a nucleation temperature and then maintaining the temperature for 45 to 60 hours, wherein the nucleation temperature is Tg-T1 to Tg+T2, where T1 is 5°C, T2 is 20°C, and Tg is the glass transition temperature of the base glass; (ii) after heating to the crystallization temperature, holding the temperature for 30 to 90 minutes, the absolute difference between the crystallization temperature and the crystallization peak temperature of the base glass does not exceed 50°C; (iii) Cooling with the furnace.

7. The method according to claim 6, characterized in that Volatile-free heating and melting uses a sealed crucible electric melting furnace or a cold top process electric melting furnace.

8. The method according to claim 6, characterized in that The specific steps of pouring the glass liquid into the mold and annealing it to obtain the base glass are as follows: (a) Place the mold on a heating table for reheating; (b) pouring the molten glass into a mold to form a glass block; (c) The glass block in the mold is placed in an annealing furnace at 550-650° C. and annealed for 2-3 hours to obtain the base glass.

9. The method according to claim 6, characterized in that In step (i), the heating rate is 8 to 12 K / min; in step (ii), the heating rate is 3 to 6 K / min.

Images