A jade-colored high-borosilicate glass profile and preparation method thereof

Abstract

The invention relates to a jade-colored high-borosilicate glass profile and a preparation method thereof, and belongs to the technical field of glass manufacturing. The profile comprises the following raw materials in parts by weight: 60-70 parts of silicon dioxide, 10-20 parts of boron oxide, 2-6 parts of aluminum oxide, 5-10 parts of alkali metal oxides, 2-4 parts of calcium oxide, 3-5 parts of clarifiers and 1-3 parts of modified colorants. In the technical scheme of the invention, hollow glass microspheres are functionalized with amino groups to adsorb metal ions in water to obtain the modified colorant, aminosilane can adsorb metal ions in water, and improves the adsorption performance of metal ions in aqueous solution, the prepared modified colorant has stable color under high temperature and high pressure conditions, is not easy to volatilize, and has high color fastness, the added clarifier is composed of a mixture of sodium chloride, rare earth oxides and barium sulfate, improves the clarity of the glass, effectively reduces the volatilization of boron, generally improves the mechanical strength and optical uniformity of the high-borosilicate glass, and improves the quality of the glass.

Description

Technical Field

[0001] The invention belongs to the technical field of glass manufacturing, and in particular relates to a jade-colored high-borosilicate glass profile and a preparation method thereof. Background Art

[0002] High borosilicate glass is a kind of glass with enhanced fire resistance. It has good fire resistance and high physical strength. Compared with ordinary glass, it has no toxic side effects, and has good mechanical properties, thermal stability, water resistance, alkali resistance, acid resistance and other properties. It is widely used in chemical industry, aerospace, military, family, medicine and other fields. The content of silicon dioxide and boron oxide in high borosilicate glass is high, reaching 65-85% and 15-25% respectively, and the alkali metal content is low, about 6-11%. It also contains 2-6% aluminum oxide to ensure that the glass has good physical and chemical properties. With the improvement of glass melting technology and the progress of glass forming and processing technology, colored high borosilicate glass has also attracted more and more attention, and higher requirements have been put forward for the performance of high borosilicate glass.

[0003] At present, due to the particularity of high borosilicate glass components, its preparation is still very difficult, mainly manifested in high melting point, high viscosity, and serious boron volatilization, which makes it difficult to clarify, and bubbles and streaks are difficult to eliminate, seriously affecting the optical uniformity and mechanical strength of the glass. In addition, colored high borosilicate glass is usually made by high-temperature fusion of colorants and high borosilicate glass production raw materials, but the colorant will produce a volatilization effect at high temperature, changing the internal properties of the high borosilicate glass, resulting in the production of glass products with insufficient color, easy bubbling, easy to have water marks, and easy to crack when directly heat treated. Summary of the invention

[0004] The object of the present invention is to provide a jade-green high borosilicate glass profile and a preparation method thereof. A modified colorant is prepared by functionalizing hollow glass microspheres with amino groups to adsorb metal ions in water. Aminosilane is grafted onto the surface of the hollow glass microspheres. The surface of the hollow glass microspheres is coated with aminosilane and can be used as an adsorbent. The amino groups and epoxy groups on the aminosilane can adsorb metal ions in water, thereby improving the adsorption performance of metal ions in aqueous solution. The adsorbent adsorbed with metal ions is collected to obtain a modified colorant. The dried adsorbent contains metal ions, which are trivalent chromium ions and divalent iron ions, both of which are green. The modified colorant is added to the raw materials for preparing high borosilicate glass. The prepared high borosilicate glass presents a jade color, and the color is stable under high temperature and high pressure and is not easy to volatilize; silicon dioxide, boron oxide, aluminum oxide, alkali metal oxide, calcium oxide, a clarifier and a modified colorant are mixed, ball milled, melted at high temperature, clarified and homogenized, annealed, and cooled to finally obtain a jade-colored high borosilicate glass profile; the added clarifier has a good clarification effect, can promote the removal of bubbles in the glass melt, improve the clarity of the glass, and effectively reduce the volatilization of boron; the added alkali metal oxide can improve the thermal properties and chemical stability of the glass; the finally prepared jade-colored high borosilicate glass profile has good chemical stability and mechanical properties, while reducing the production cost and improving the quality of the high borosilicate glass.

[0005] Technical problem to be solved by the present invention: At present, due to the particularity of high borosilicate glass components, its preparation is still very difficult, mainly manifested in high melting point, high viscosity, and serious boron volatilization, which makes it difficult to clarify, and bubbles and streaks are difficult to eliminate, seriously affecting the optical uniformity and mechanical strength of the glass. The colored high borosilicate glass is usually obtained by high-temperature fusion of colorants and the raw materials for the production of high borosilicate glass. However, the colorant will produce a volatilization effect at high temperature, changing the internal properties of the high borosilicate glass, resulting in the glass products produced having insufficient color, easy bubbling, easy to have water marks, and easy to crack when directly heat treated.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A jade-colored high borosilicate glass profile, characterized in that it comprises the following raw materials in parts by weight: 60-70 parts of silicon dioxide, 10-20 parts of boron oxide, 2-6 parts of aluminum oxide, 5-10 parts of alkali metal oxide, 2-4 parts of calcium oxide, 3-5 parts of clarifier and 1-3 parts of modified colorant;

[0008] The modified colorant is prepared by functionalizing hollow glass microspheres with amino groups and then adsorbing metal ions in water.

[0009] Furthermore, the preparation method of the modified colorant comprises the following steps:

[0010] A1: Add alkali-treated hollow glass microspheres into anhydrous toluene and mix them evenly, then add aminosilane when the temperature of the mixture is raised to 110-120°C, stir and reflux for 8-10 hours, wash with a toluene / methanol mixed solution, filter, and dry at 85-95°C to obtain a silane-modified adsorbent;

[0011] A2: Take an aqueous solution containing metal ions, and adjust the pH value of the aqueous solution to 4-5, then add a silane-modified adsorbent, and adsorb for 1-2 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant.

[0012] During the above reaction process, the surface of the alkali-treated hollow glass microspheres has hydroxyl groups, and the aminosilane has silanol groups after hydrolysis. The silanol groups after hydrolysis of the aminosilane can combine with the hydroxyl groups on the alkali-treated hollow glass microspheres, and the aminosilane is grafted to the surface of the alkali-treated hollow glass microspheres to obtain a silane-modified adsorbent; the amino groups and epoxy groups on the aminosilane can adsorb metal ions in the aqueous solution, and the silane-modified adsorbent adsorbed with metal ions is collected to finally obtain a modified colorant.

[0013] Furthermore, in step A1, the mass ratio of the alkali-treated hollow glass microspheres to anhydrous toluene is 4.5-5.5:80-120.

[0014] Furthermore, in step A1, the alkali-treated hollow glass microsphere preparation method comprises the following steps:

[0015] The hollow glass microspheres were mixed with a 0.67M sodium hydroxide solution, and then stirred at 80°C and 300 rpm for 3.5 hours, washed with ultrapure water, filtered, and dried at 70°C to obtain alkali-treated hollow glass microspheres.

[0016] Furthermore, in step A1, the aminosilane is prepared by compounding 3-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:1.

[0017] Furthermore, in step A2, the mass ratio of the aqueous solution containing metal ions to the silane-modified adsorbent is 40-60:0.4-0.6.

[0018] Furthermore, in step A2, in the aqueous solution containing metal ions, the metal ions are a mixture of trivalent chromium ions and divalent iron ions.

[0019] Furthermore, the concentrations of the trivalent chromium ions and the divalent iron ions are both 0.1-0.2 g / L.

[0020] Furthermore, the trivalent chromium ions are obtained by dissolving chromium trioxide in water, and the divalent iron ions are obtained by dissolving ferrous sulfate in water.

[0021] Furthermore, the alkali metal oxide is at least one of lithium oxide, sodium oxide and potassium oxide.

[0022] Furthermore, the clarifier is composed of sodium chloride, rare earth oxide and barium sulfate mixed in a mass ratio of 1:1:0.2-0.3.

[0023] Furthermore, the rare earth oxide is cerium oxide or lanthanum oxide.

[0024] Furthermore, the method for preparing the jade-colored high borosilicate glass profile comprises the following steps:

[0025] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, alkali metal oxide, calcium oxide, a clarifier and a modified colorant, and ball mill them for 1-3 hours to obtain a uniformly mixed powder A;

[0026] S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting for 1-2 hours to obtain molten glass liquid B;

[0027] S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into a forming mold, and the clarification and homogenization temperature is 1550-1650° C.;

[0028] S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing time is 3-5 hours, and then it is cooled at a cooling rate of 2-4°C / min. After 1-2 hours, it is cooled to room temperature at a cooling rate of 5-8°C / min, and finally a jade-green high-borosilicate glass profile is obtained.

[0029] Furthermore, in step S1, the silicon dioxide is dried before being added, the drying temperature is 50-70° C., and the drying time is 2-3 hours.

[0030] Furthermore, in step S2, the melting temperature is 1650-1750°C.

[0031] Furthermore, in step S4, the annealing temperature is 650-750°C.

[0032] Beneficial effects of the present invention:

[0033] (1) In the technical scheme of the present invention, the modified colorant is prepared by adsorbing metal ions in water through the amino-functionalized hollow glass microspheres. The hollow glass microspheres are first treated with alkali to increase the hydroxyl groups on their surface and provide more reaction sites. Then, aminosilane is grafted onto the surface of the hollow glass microspheres. The surface of the hollow glass microspheres is coated with aminosilane and can be used as an adsorbent. The amino groups and epoxy groups on the aminosilane can adsorb metal ions in water, thereby improving the adsorption performance of metal ions in aqueous solution. Before the adsorption of metal ions, the pH value of the aqueous solution containing metal ions is first adjusted to 4-5 to ensure that the metal ions are mainly present in a free state during the adsorption process, which is beneficial to the subsequent adsorption and can effectively avoid the formation of precipitation, so that the adsorbent has an adsorption effect on metal ions. The best method is to collect the adsorbent that has absorbed the metal ions, and after drying, obtain the modified colorant. The dried adsorbent contains metal ions, and the metal ions are trivalent chromium ions and divalent iron ions. Both the trivalent chromium ions and the divalent iron ions are green. The modified colorant is added to the raw materials for preparing high borosilicate glass, so that the prepared high borosilicate glass can present a green jade color, and the ratio of the colorant to other raw materials is proportional to the opacity of the product. The larger the amount of colorant added, the higher the opacity of the product, and the darker the green jade color. Otherwise, the product is clear and the green jade color is lighter, making the green jade color more realistic. At the same time, the prepared modified colorant is stable in color under high temperature and high pressure conditions, never fades, is not easy to volatilize, and has high color fastness. The hollow glass microspheres used also further improve the heat resistance and mechanical properties of the high borosilicate glass profiles.

[0034] (2) In the technical solution of the present invention, silicon dioxide, boron oxide, aluminum oxide, alkali metal oxide, calcium oxide, a clarifier and a modified colorant are mixed, ball-milled, melted at high temperature, clarified and homogenized, annealed and cooled to finally obtain a jade-colored high-borosilicate glass profile; drying treatment is performed before adding silicon dioxide, which can reduce the moisture content in silicon dioxide, reduce impurities, and improve the quality and stability of the glass; the added clarifier is composed of a mixture of sodium chloride, rare earth oxides and barium sulfate, among which sodium chloride has a good clarification effect. It vaporizes and volatilizes at high temperature, which can promote the removal of bubbles in the glass melt and improve the clarity of the glass, and the cost is low. Cerium oxide and lanthanum oxide, as rare earth oxides, also have a good clarification effect and can eliminate tiny bubbles and gray bubbles in the glass, thereby improving the clarity of the glass. Improve the transparency and appearance quality of glass. Barium sulfate can not only improve the clarity of glass, but also improve the heat resistance of glass. Adding a clarifier can effectively reduce the volatilization of boron and improve the quality of glass. Adding calcium oxide can further enhance the clarification and homogenization of glass, reduce the viscosity of glass during melting, inhibit the volatilization of boron, and improve the stability of boron. Adding alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide can improve the thermal properties and chemical stability of glass. Adding aluminum oxide can improve the chemical stability and mechanical strength of glass and improve the thermal stability of glass. The finally prepared jade-colored high borosilicate glass profile has good chemical stability and mechanical properties, while reducing the content of silica system, reducing production costs, and improving the quality of high borosilicate glass. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] The specific parameters of the raw materials used in the present invention are as follows:

[0037] Hollow glass microspheres are micron-sized (10-250μm) low-density (<1 g / cm 3 ) material, mainly composed of amorphous silicon dioxide, and the hollow glass microspheres used are iM16K purchased from Minnesota, USA.

[0038] The aminosilane used in the following examples and comparative examples is prepared by compounding 3-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:1; in the aqueous solution containing metal ions, the metal ions are composed of a mixture of trivalent chromium ions and divalent iron ions; the concentrations of trivalent chromium ions and divalent iron ions are both 0.15 g / L; trivalent chromium ions are obtained by dissolving chromium trioxide in water, and divalent iron ions are obtained by dissolving ferrous sulfate in water; in step S1, the silicon dioxide is dried before being added, the drying temperature is 60°C, and the drying time is 2.5 h.

[0039] The method for preparing alkali-treated hollow glass microspheres comprises the following steps:

[0040] Hollow glass microspheres were mixed with a 0.67 M sodium hydroxide solution at a mass ratio of 10:300, and then stirred at 80°C at a speed of 300 rpm for 3.5 h, washed three times with ultrapure water (the mass of ultrapure water each time was 20 wt% of the mass of the sodium hydroxide solution), filtered, and dried at 70°C to obtain alkali-treated hollow glass microspheres.

[0041] Example 1

[0042] The preparation method of the modified colorant comprises the following steps:

[0043] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 4.5:80 and mix well. Then, when the temperature of the mixture is raised to 110°C, add aminosilane (the mass of aminosilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 8h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 85°C for 24h to obtain a silane-modified adsorbent;

[0044] A2: taking an aqueous solution containing metal ions at a mass ratio of 40:0.4, adjusting the pH value of the aqueous solution to 4, then adding a silane-modified adsorbent, and adsorbing for 1 hour under shaking. After the adsorption is completed, collecting the used adsorbent and drying it to obtain a modified colorant;

[0045] A jade-colored high-borosilicate glass profile comprises the following raw materials in parts by weight: 60 parts of silicon dioxide, 10 parts of boron oxide, 2 parts of aluminum oxide, 5 parts of lithium oxide, 2 parts of calcium oxide, 3 parts of a clarifier and 1 part of a modified colorant;

[0046] The preparation method of the jade-colored high borosilicate glass profile comprises the following steps:

[0047] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, lithium oxide, calcium oxide, a clarifier and a modified colorant, and ball mill them for 1 hour to obtain a uniformly mixed powder A, wherein the clarifier is composed of sodium chloride, cerium oxide and barium sulfate mixed in a mass ratio of 1:1:0.2;

[0048] S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting at a temperature of 1650° C. for a melting time of 1 h to obtain molten glass liquid B;

[0049] S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into the forming mold, and the clarification and homogenization temperature is 1550° C.;

[0050] S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing temperature is 650°C and the annealing time is 3 hours. It is then cooled at a cooling rate of 2°C / min. After 1 hour, it is cooled to room temperature at a cooling rate of 5°C / min. Finally, a jade-green high-borosilicate glass profile is obtained.

[0051] Example 2

[0052] The preparation method of the modified colorant comprises the following steps:

[0053] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 5:100 and mix well. Then, when the temperature of the mixture is raised to 115°C, add aminosilane (the mass of aminosilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 9h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 90°C for 24h to obtain a silane-modified adsorbent;

[0054] A2: Take an aqueous solution containing metal ions at a mass ratio of 50:0.5, adjust the pH value of the aqueous solution to 4.5, then add a silane-modified adsorbent, and adsorb for 1.5 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant;

[0055] A jade-colored high borosilicate glass profile comprises the following raw materials in parts by weight: 65 parts of silicon dioxide, 15 parts of boron oxide, 4 parts of aluminum oxide, 8 parts of sodium oxide, 3 parts of calcium oxide, 4 parts of a clarifier and 2 parts of a modified colorant;

[0056] The preparation method of the jade-colored high borosilicate glass profile comprises the following steps:

[0057] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, sodium oxide, calcium oxide, a clarifier and a modified colorant, and ball mill for 2 hours to obtain a uniformly mixed powder A, wherein the clarifier is composed of sodium chloride, lanthanum oxide and barium sulfate mixed in a mass ratio of 1:1:0.25;

[0058] S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting at a temperature of 1700°C for a melting time of 1.5 hours to obtain molten glass liquid B;

[0059] S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into a forming mold, and the clarification and homogenization temperature is 1600° C.;

[0060] S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing temperature is 700°C and the annealing time is 4 hours. It is then cooled at a cooling rate of 3°C / min. After 1.5 hours, it is cooled to room temperature at a cooling rate of 6°C / min. Finally, a jade-green high-borosilicate glass profile is obtained.

[0061] Example 3

[0062] The preparation method of the modified colorant comprises the following steps:

[0063] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 5.5:120 and mix well. Then, when the temperature of the mixture is raised to 120°C, add aminosilane (the mass of aminosilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 10h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 95°C for 24h to obtain a silane-modified adsorbent;

[0064] A2: taking an aqueous solution containing metal ions at a mass ratio of 60:0.6, adjusting the pH value of the aqueous solution to 5, then adding a silane-modified adsorbent, and adsorbing for 2 hours under shaking. After the adsorption is completed, collecting the used adsorbent and drying it to obtain a modified colorant;

[0065] A jade-colored high-borosilicate glass profile comprises the following raw materials in parts by weight: 70 parts of silicon dioxide, 20 parts of boron oxide, 6 parts of aluminum oxide, 10 parts of potassium oxide, 4 parts of calcium oxide, 5 parts of a clarifier and 3 parts of a modified colorant;

[0066] The preparation method of the jade-colored high borosilicate glass profile comprises the following steps:

[0067] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, potassium oxide, calcium oxide, a clarifier and a modified colorant, and perform ball milling for 3 hours to obtain a uniformly mixed powder A, wherein the clarifier is composed of sodium chloride, cerium oxide and barium sulfate mixed in a mass ratio of 1:1:0.3;

[0068] S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting at a temperature of 1750°C for a melting time of 2 hours to obtain molten glass liquid B;

[0069] S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into a forming mold, and the clarification and homogenization temperature is 1650° C.;

[0070] S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing temperature is 750°C and the annealing time is 5 hours. It is then cooled at a cooling rate of 4°C / min. After 2 hours, it is cooled to room temperature at a cooling rate of 8°C / min. Finally, a jade-green high-borosilicate glass profile is obtained.

[0071] Comparative Example 1

[0072] The difference between this comparative example and Example 3 is that when preparing the modified colorant, the aminosilane in step A1 is replaced by 3-aminopropyltriethoxysilane, and the remaining steps and raw materials are the same as those in Example 3;

[0073] The preparation method of the modified colorant comprises the following steps:

[0074] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 5.5:120 and mix well. Then, when the temperature of the mixture is raised to 120°C, add 3-aminopropyltriethoxysilane (the mass of 3-aminopropyltriethoxysilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 10h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 95°C for 24h to obtain a silane-modified adsorbent;

[0075] A2: Take an aqueous solution containing metal ions according to a mass ratio of 60:0.6, and adjust the pH value of the aqueous solution to 5, then add a silane-modified adsorbent, and adsorb for 2 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant.

[0076] Comparative Example 2

[0077] The difference between this comparative example and Example 3 is that when preparing the modified colorant, the mass of the aqueous solution containing metal ions in step A2 is replaced by an aqueous solution containing trivalent chromium ions, and the remaining steps and raw materials are the same as those in Example 3;

[0078] The preparation method of the modified colorant comprises the following steps:

[0079] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 5.5:120 and mix well. Then, when the temperature of the mixture is raised to 120°C, add aminosilane (the mass of aminosilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 10h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 95°C for 24h to obtain a silane-modified adsorbent;

[0080] A2: Take an aqueous solution containing trivalent chromium ions at a mass ratio of 60:0.6, adjust the pH value of the aqueous solution to 5, then add a silane-modified adsorbent, and adsorb for 2 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant.

[0081] Comparative Example 3

[0082] The difference between this comparative example and Example 3 is that when preparing the modified colorant, the mass of the aqueous solution containing metal ions in step A2 is replaced by an aqueous solution containing trivalent chromium ions, divalent iron ions and divalent copper ions, and the remaining steps and raw materials are the same as those in Example 3;

[0083] The preparation method of the modified colorant comprises the following steps:

[0084] A1: Add alkali-treated hollow glass microspheres to anhydrous toluene at a mass ratio of 5.5:120 and mix well. Then, when the temperature of the mixture is raised to 120°C, add aminosilane (the mass of aminosilane is 60wt% of the mass of the alkali-treated hollow glass microspheres), stir and reflux for 10h, wash with a toluene / methanol mixed solution (the mass of the toluene / methanol mixed solution is 50wt% of the mass of anhydrous toluene), filter, and dry at 95°C for 24h to obtain a silane-modified adsorbent;

[0085] A2: Take an aqueous solution containing trivalent chromium ions, divalent iron ions and divalent copper ions in a mass ratio of 60:0.6, and adjust the pH value of the aqueous solution to 5, then add a silane-modified adsorbent, and adsorb for 2 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant, in which the concentration of divalent copper ions is 0.15g / L.

[0086] Comparative Example 4

[0087] The difference between this comparative example and Example 3 is that when preparing the jade-colored high borosilicate glass profile, the mass of the clarifier added in step S1 is replaced by a clarifier composed of sodium chloride and cerium oxide mixed in a mass ratio of 1:1.3, and the remaining steps and raw materials are the same as Example 3;

[0088] A jade-colored high-borosilicate glass profile comprises the following raw materials in parts by weight: 70 parts of silicon dioxide, 20 parts of boron oxide, 6 parts of aluminum oxide, 10 parts of potassium oxide, 4 parts of calcium oxide, 5 parts of a clarifier and 3 parts of a modified colorant;

[0089] The preparation method of the jade-colored high borosilicate glass profile comprises the following steps:

[0090] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, potassium oxide, calcium oxide, a clarifier and a modified colorant, and perform ball milling for 3 hours to obtain a uniformly mixed powder A, wherein the clarifier is composed of sodium chloride and cerium oxide mixed in a mass ratio of 1:1.3.

[0091] Comparative Example 5

[0092] The difference between this comparative example and Example 3 is that when preparing the jade-colored high borosilicate glass profile, the modified colorant in step S1 is replaced by chromium oxide, the preparation step of the modified colorant is deleted, and the remaining steps and raw materials are synchronized with Example 3;

[0093] A jade-colored high borosilicate glass profile comprises the following raw materials in parts by weight: 70 parts of silicon dioxide, 20 parts of boron oxide, 6 parts of aluminum oxide, 10 parts of potassium oxide, 4 parts of calcium oxide, 5 parts of a clarifier and 3 parts of chromium oxide;

[0094] The preparation method of the jade-colored high borosilicate glass profile comprises the following steps:

[0095] S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, potassium oxide, calcium oxide, a clarifier and chromium oxide, and ball mill for 3 hours to obtain a uniformly mixed powder A, wherein the clarifier is composed of sodium chloride, cerium oxide and barium sulfate mixed in a mass ratio of 1:1:0.3;

[0096] S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting at a temperature of 1750°C for a melting time of 2 hours to obtain molten glass liquid B;

[0097] S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into a forming mold, and the clarification and homogenization temperature is 1650° C.;

[0098] S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing temperature is 750°C and the annealing time is 5 hours. It is then cooled at a cooling rate of 4°C / min. After 2 hours, it is cooled to room temperature at a cooling rate of 8°C / min. Finally, a jade-green high-borosilicate glass profile is obtained.

[0099] The emerald high borosilicate glass profiles prepared in Examples 1-3 and Comparative Examples 1-5 are now tested for bending strength, boron volatilization rate, bubble degree, striation degree and optical uniformity. The bending strength test method is as follows: the emerald high borosilicate glass profiles prepared in Examples 1-3 and Comparative Examples 1-5 are made into a number of glass samples with a length of 120 mm, a width of 20 mm and a thickness of 5 mm. A bending test is performed on a testing machine according to the bending strength test method for glass materials published in "JC / T 676-1997". The bending strength of the high borosilicate glass sample is obtained by calculating the maximum complete stress at the cross section under load. The bending strength of the glass sample is obtained by averaging the values ​​of the repeated bending tests. The boron content is determined according to "GBZ / T 160.27-2004" to determine the boron volatilization rate. The bubble degree is tested according to the standard "GB / T 7962.8-2010". The bending strength of the glass sample is obtained by averaging the values ​​of ... The stripe degree test was carried out according to the GB / T 7962.7-2010 standard; the optical uniformity test was carried out according to the GB / T 7962.3-2010 standard; the test results are shown in Tables 1 and 2 below:

[0100] Table 1 Performance parameters of flexural strength and boron volatility of jade-colored high borosilicate glass profiles prepared in Examples 1-3 and Comparative Examples 1-5

[0101]

[0102] Table 2 Performance parameters of bubble degree, striae degree and optical uniformity of jade-colored high borosilicate glass profiles prepared in Examples 1-3 and Comparative Examples 1-5

[0103]

[0104] It can be seen from the data in Table 1 and Table 2 above that, by comparing Comparative Example 1 with Example 3, it can be seen that the modified colorant is prepared by grafting hollow glass microspheres with 3-aminopropyl triethoxysilane to adsorb metal ions in water, and its test results are worse than those of Example 3, indicating that 3-aminopropyl triethoxysilane and γ-glycidyloxypropyl trimethoxysilane are compounded in a mass ratio of 1:1 to prepare aminosilane, and the adsorption performance of metal ions in water is increased by grafting hollow glass microspheres with aminosilane, more metal ions can be adsorbed, and the content of metal ions in the modified colorant can be increased, which can not only increase the jade green effect of high borosilicate glass, but also effectively reduce the volatilization of boron, and improve the mechanical strength and quality of glass;

[0105] By comparing Comparative Examples 2-3 with Example 3, it can be seen that in step S2, a silane-modified adsorbent is used to adsorb an aqueous solution containing trivalent chromium ions or an aqueous solution containing trivalent chromium ions, divalent iron ions and divalent copper ions, and finally a modified colorant is prepared. The test result is poorer than that of Example 3, indicating that the modified colorant prepared by adsorbing an aqueous solution containing trivalent chromium ions and divalent iron ions by a silane-modified adsorbent can not only enhance the mechanical strength of high borosilicate glass and reduce the volatilization amount of boron, but also make the green jade color of high borosilicate glass more significant, further improving the quality of the glass;

[0106] From the comparison between Comparative Example 4 and Example 3, it can be seen that the clarifier added in step S1 is replaced with a clarifier composed of a mixture of sodium chloride and cerium oxide to prepare a green jade-colored high borosilicate glass profile, and its test result is worse than that of Example 3, indicating that the addition of a clarifier composed of a mixture of sodium chloride, cerium oxide and barium sulfate in a mass ratio of 1:1:0.3, the mixture of sodium chloride, cerium oxide and barium sulfate can play a synergistic clarification role, wherein barium sulfate can also improve the heat resistance of the glass. The clarifier not only improves the clarity of the glass during the melting process of the glass, but also further improves the mechanical strength of the high borosilicate glass profile, effectively reduces the volatilization of boron, reduces the bubbles and streaks generated, and ultimately improves the quality of the glass;

[0107] By comparing Comparative Example 5 with Example 3, it can be seen that the test result of the jade-colored high borosilicate glass profile prepared by replacing the modified colorant in step S1 with chromium oxide is worse than that of Example 3, indicating that the jade-colored high borosilicate glass profile prepared by mixing the modified colorant with other glass raw materials not only improves the mechanical strength of the high borosilicate glass profile, effectively reduces the volatilization of boron, reduces the generation of bubbles and stripes, and increases its optical uniformity, but also makes the prepared high borosilicate glass profile have a significant jade color, and the coloring is more stable and not easy to volatilize.

[0108] It can be seen from Table 1 and Table 2 above that the jade-colored high borosilicate glass profiles prepared in Examples 1-3 are compared with the jade-colored high borosilicate glass profiles prepared in Comparative Examples 1-5. The modified colorant is obtained by functionalizing the hollow glass microspheres with amino groups to adsorb metal ions in water, and then mixing silicon dioxide, boron oxide, aluminum oxide, alkali metal oxides, calcium oxide, a clarifier and the modified colorant. After ball milling, high-temperature melting, clarification and homogenization, annealing and cooling, the jade-colored high borosilicate glass profiles are obtained, which meet the test performance requirements, while the jade-colored high borosilicate glass profiles prepared in Comparative Examples 1-5 do not meet the performance requirements. This shows that the jade-colored high borosilicate glass profiles prepared by the present invention can not only effectively reduce the volatilization of boron, reduce the generation of bubbles and stripes, and improve the mechanical strength and optical uniformity of the glass, but also make the high borosilicate glass profile have a more significant jade color, the coloring is more stable and lasting, and the quality of the glass is improved.

[0109] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

Claims

1. A jade-colored high borosilicate glass profile, characterized in that: The invention comprises the following raw materials in parts by weight: 60-70 parts of silicon dioxide, 10-20 parts of boron oxide, 2-6 parts of aluminum oxide, 5-10 parts of alkali metal oxide, 2-4 parts of calcium oxide, 3-5 parts of clarifier and 1-3 parts of modified colorant; The modified colorant is prepared by functionalizing hollow glass microspheres with amino groups and then adsorbing metal ions in water; The preparation method of the modified colorant comprises the following steps: A1: Add alkali-treated hollow glass microspheres into anhydrous toluene and mix them evenly, then add aminosilane when the temperature of the mixture is raised to 110-120°C, stir and reflux for 8-10 hours, wash with a toluene / methanol mixed solution, filter, and dry at 85-95°C to obtain a silane-modified adsorbent; A2: Take an aqueous solution containing metal ions, adjust the pH value of the aqueous solution to 4-5, then add a silane-modified adsorbent, and adsorb for 1-2 hours under shaking. After the adsorption is completed, collect the used adsorbent and dry it to obtain a modified colorant; The clarifier is composed of sodium chloride, rare earth oxide and barium sulfate mixed in a mass ratio of 1:1:0.2-0.

3.

2. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: In step A1, the mass ratio of the alkali-treated hollow glass microspheres to anhydrous toluene is 4.5-5.5:80-120.

3. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: In step A1, the aminosilane is prepared by compounding 3-aminopropyltriethoxysilane and γ-glycidyloxypropyltrimethoxysilane in a mass ratio of 1:

1.

4. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: In step A2, the mass ratio of the aqueous solution containing metal ions to the silane-modified adsorbent is 40-60:0.4-0.

6.

5. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: In step A2, in the aqueous solution containing metal ions, the metal ions are a mixture of trivalent chromium ions and divalent iron ions.

6. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: The alkali metal oxide is at least one of lithium oxide, sodium oxide and potassium oxide.

7. The jade-colored high borosilicate glass profile according to claim 1, characterized in that: The rare earth oxide is cerium oxide or lanthanum oxide.

8. A method for preparing the jade-colored high borosilicate glass profile according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: Weigh the raw materials by mass, mix silicon dioxide, boron oxide, aluminum oxide, alkali metal oxide, calcium oxide, a clarifier and a modified colorant, and ball mill them for 1-3 hours to obtain a uniformly mixed powder A; S2: feeding the powder A in step S1 into a melting furnace for high-temperature melting for 1-2 hours to obtain molten glass liquid B; S3: the molten glass liquid B in step S2 is clarified and homogenized and then flows into a forming mold, and the clarification and homogenization temperature is 1550-1650° C.; S4: After being clarified and homogenized, the molten glass liquid B flows into the molding mold and then enters the annealing furnace. The annealing time is 3-5 hours, and then it is cooled at a cooling rate of 2-4°C / min. After 1-2 hours, it is cooled to room temperature at a cooling rate of 5-8°C / min, and finally a jade-green high-borosilicate glass profile is obtained.

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