An amber glass and a method for producing the same

Abstract

The present application relates to a kind of preparation methods of amber glass, it is characterized in that: (1) composite colorant is prepared according to the following mole percentage: 0.06-0.07% Fe2O3, 0.01-0.05% iron silicate, 0.23-0.62% Na2SO4, 0.01-0.24% NH4HSO4, 0.25-2.6% high-purity graphite powder, the rest is anhydrous ethanol;(2) after the batch is placed into oven and dried, it is filled into platinum crucible and is melted, 1450-1520 ℃ is kept for 0.5-1.5 h;(3) copper plate of glass casting is preheated, and the glass liquid that is melted and clarified is taken out from high-temperature furnace, and is cast on the copper plate that is preheated;(4) the glass that is cast is placed into annealing furnace, then with furnace cooling to room temperature, and amber glass is prepared.The present application has the following advantages: the composite colorant of the present application can strictly control Fe 2+ / Fe 3+ As 1.76-2.25, can greatly improve the uniformity of coloring, stability;The visible light transmittance of the glass of the present application is ≤35%, 10-300 nm transmittance is 0, greatly improve the performance of ultraviolet resistance;Viscosity is lower during melting process, beneficial to glass packaging vessel forming.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of special glass, and relates to amber glass and a preparation method thereof. BACKGROUND

[0002] With the rapid development of the wine, beverage, food, and medicine industries in China, the demand for various types of packaging glass bottles and cans is increasing, and the quality requirements are also increasing. Therefore, the glass bottle industry is constantly adapting to the use requirements of users, and the quality requirements for glass bottles and cans are becoming more and more stringent. The sulfur-carbon colored amber glass has a color of brown with red inside, which is bright and bright, and the color is similar to amber. Its ability to absorb ultraviolet light is higher than that of other color glasses commonly used in the light industry market, which can better meet the light storage requirements of food and medicine and prolong the preservation time. Therefore, high-end wine, cosmetics, and medicine are often packaged in amber glass bottles.

[0003] There are three common coloring methods for amber glass, namely iron-manganese coloring, iron-titanium coloring, and sulfur-carbon coloring. Iron-manganese coloring has low resistance to corrosion of stored substances, and the color adjustment is difficult to control. Iron-titanium coloring is a common coloring technology for brown pharmaceutical glass, and has high chemical stability, but the addition of TiO2 in the glass can easily cause crystallization, and the cost is high. Traditional sulfur-carbon coloring usually uses sodium-calcium glass with high alkali content as the basis for sulfur-carbon coloring. The common problems are bubbles and unstable coloring, but it can effectively cut off or shield the light sensitivity of the blue-violet band of ultraviolet or visible light, and can avoid the decomposition of video and medicine under light.

[0004] Patent No. CN101428969A discloses a kind of brown glass and its application, and the obtained brown glass has a balanced color, but from the patent technical effect, the transmittance at 313nm is still visible light, and the average visible transmittance is >40%, the light shielding effect is not good. Patent No. CN114409254A discloses a kind of high-transmittance infrared-resistant energy-saving color glass and its melting device, which provides a kind of composite colorant idea, but the introduction of reducing agent such as oxalic acid will offset the sulfur-carbon coloring effect, and does not promote the coloring effect. SUMMARY

[0005] The purpose of the present application is to solve the problems of unstable coloring, high average visible light transmittance, and the existence of ultraviolet band light and visible light blue-violet band light transmittance in the existing amber glass, and to provide an amber glass and a preparation method thereof.

[0006] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] An amber glass is characterized by being made of raw materials in the following molar percentages: 69.4-71.8% of SiO2, 0.48-1.8% of Al2O3, 0.52-2.1% of B2O3, 8.4-12.1% of Na2O, 0.5-1.5% of K2O, 8.2-11.7% of CaO, 0.25-0.8% of MgO, and 2.2-7.9% of a composite colorant; wherein the total molar percentage of Na2O+K2O is 12.1-13.2%, and the molar ratio of Na2O to K2O is 17.1-17.6; and the total molar percentage of CaO+MgO is 11.4-12.2%, and the molar ratio of CaO to MgO is 19.3-20.1.

[0008] Further, an amber glass is characterized by being made of raw materials in the following molar percentages: 69.6-71.5% of SiO2, 0.51-1.72% of Al2O3, 0.55-2.04% of B2O3, 8.6-11.9% of Na2O, 0.8-1.5% of K2O, 8.5-11.5% of CaO, 0.3-0.75% of MgO, and 2.3-7.8% of a composite colorant; wherein the total molar percentage of Na2O+K2O is 12.3-13.0%, and the molar ratio of Na2O to K2O is 17.3-17.4; and the total molar percentage of CaO+MgO is 11.5-12.0%, and the molar ratio of CaO to MgO is 19.5-20.1.

[0009] Further, the composite colorant is composed of raw materials in the following molar percentages: 0.06-0.07% of Fe2O3, 0.01-0.05% of iron aluminosilicate, 0.23-0.62% of Na2SO4, 0.01-0.24% of NH4HSO4, 0.25-2.6% of high-purity graphite powder, and the balance being anhydrous ethanol.

[0010] Further, the composite colorant is prepared by the following method: Fe2O3 and iron aluminosilicate are weighed according to the above-mentioned proportions, 20 ml of anhydrous ethanol is added, and ultrasonic mixing is performed for 0.5 h to obtain a powdery substance with uniform particles; and Na2SO4, NH4HSO4, and high-purity graphite powder are weighed, 20 ml of anhydrous ethanol is added, and ultrasonic mixing is performed for 0.5-1 h to prepare a uniformly mixed composite colorant.

[0011] A preparation method of an amber glass is characterized by comprising the following steps:

[0012] (1) The composite colorant is prepared according to the above-mentioned method, and the remaining oxides are added according to the above-mentioned proportions, 50 ml of anhydrous ethanol is added, and mixing is performed in a mixer at a speed of 50-200 r / min for 1-1.5 h;

[0013] (2) After the batch is dried in an oven, it is put into a platinum crucible for melting, the feeding temperature is 900-1000℃, nitrogen is introduced after feeding (the function is to keep the redox atmosphere in the furnace stable), the melting temperature is 1450-1520℃, and the holding time is 0.5-1.5h;

[0014] (3) The copper plate for glass casting is preheated, the preheating temperature is 480℃~520℃, the glass liquid that is melted and clarified is taken out from the high-temperature furnace and cast on the preheated copper plate;

[0015] (4) The cast glass is put into an annealing furnace, the annealing temperature system is: 480℃~520℃ for 1h, then the temperature is decreased to 400℃ at a rate of 5℃ / min, then the temperature is decreased to 280℃ at a rate of 3℃ / min, and then the furnace is cooled to room temperature, amber glass is prepared.

[0016] Further, Fe 2+ / Fe 3+ in the amber glass is 1.76-2.25.

[0017] Further, the visible light transmittance (380-780nm) of the amber glass is ≤35%.

[0018] Further, the transmittance (10-300nm) of the amber glass is 0.

[0019] Further, the colorimetric L of the amber glass is 18-24, a is 5-8, and b is 4-8.

[0020] The application controls the molar percentage of Na2O+K2O in the component at 12.1-13.2%, and the molar ratio of Na2O to K2O is 17.1-17.6; controls the molar percentage of CaO+MgO at 11.4-12.2%, the total molar percentage of CaO+MgO is 11.4-12.2%, and the molar ratio of CaO to MgO is 19.3-20.1, which can improve the glass coloring stability and reduce the transmittance, mainly because: the content of SiO2+Al2O3+B2O3 is 70.4-75.7%, which is the main body of the glass network, that is, the network former accounts for more than 70% of the glass network structure, which fundamentally determines that the glass network structure tightness can reach a relatively ideal degree); at the same time, the molar percentage of alkali metal content Na2O+K2O is controlled at 12.1-13.2%, these two factors mainly determine the glass coloring stability and transmittance; the higher the alkali metal content, the more sulfur can be retained in the glass, the longer the sulfur chain formed, the more conducive to producing brown and red transparent amber color, limiting Na2O and K2O, increasing the content of sodium ions, which can better promote the participation of alkali metal in the coloring process; the molar percentage of CaO+MgO is controlled at 11.4-12.2%, and the ratio of CaO to MgO is limited, mainly because the high and low of the crystallization temperature affects the forming process of the glass, and CaO and MgO have different effects on the crystallization temperature of the glass, limiting the ratio between the two can maximize the reduction of the crystallization temperature, and at the same time, the glass viscosity is reduced, which is beneficial to the forming of glassware and reduces the process difficulty.

[0021] The amber color of the glass in the application is caused by alkali polysulfide and iron sulfide, one central atom Fe 3+ forms a tetrahedral structure with three oxygen atoms (O 2- ) and one sulfur atom (S 2- ), which acts as a coloring group to color. In the glass melt, a certain amount of chain sulfur will be formed under certain conditions, and they will polymerize to produce polysulfide during the cooling process. At high temperature, the ends of the sulfur chain are open, and generally by absorbing alkali metal ions or alkali polysulfide, so that it reaches a saturated state, but when polysulfide is formed, the glass produces yellow to orange color, the longer the sulfur chain, the deeper and redder the color. But when the reducing property in the glass is too strong, Fe 2+ will process excess, forming Si 4+ -O-Fe 2+ structure, and the absorption of this six-coordinated Fe 2+ in the near-infrared region will make the greenish-blue tone of ferrous ferric more blue. Therefore, in order to prepare amber glass and improve the ultraviolet resistance, the reducing agent added to the glass should be appropriate, so as to strictly control the Fe 2+ / Fe 3+Proportion. In existing technologies, adding carbon powder, aluminum powder, or silicon powder alone has limited reducing performance, and excessive addition can alter glass properties, affecting glass clarification, reducing transmittance, and increasing costs. This invention employs a composite colorant, introducing Fe through Fe2O3 and aluminum ferrosilicon. 3+ Al 3+ Meanwhile, Al 3+ It has strong oxidizing properties; the introduction of NH4HSO4 gives it reducing properties, and the introduction of S... 2- It can also be used as a reducing agent, decomposing into CO and H2O upon heating. Additionally, it reacts with active metals to produce hydrogen gas, neutralizing Al. 3+ The oxidizing properties of high-purity graphite powder can reduce the carbon powder content and improve color uniformity; compared with carbon powder, high-purity graphite powder has extremely low impurity content, fine and uniform particles, and complete reaction, which can significantly improve color stability; the introduction of Na2SO4 simultaneously with S 2- As a glass clarifying agent, it ensures the glass clarification effect.

[0022] The beneficial effects of this invention are:

[0023] (1) The preparation method of the present invention has a low viscosity during the melting process, which is conducive to the forming of glass packaging vessels and has low process difficulty; the use of high temperature feeding ensures that the coloring reaction is fully carried out while greatly reducing C and S during the glass melting process. 2- This reduces the loss of coloring agents, improves coloring efficiency, and ensures coloring uniformity; the use of composite colorants allows for strict control of Fe content. 2+ / Fe 3+ The value is 1.76-2.25, which significantly improves the uniformity and stability of coloring;

[0024] (2) The amber glass prepared by the present invention has a visible light transmittance of ≤35% (380-780nm) and a transmittance of 0 in 10-300nm, which greatly improves the UV resistance and can be used for storage packaging of cosmetics, pharmaceuticals, wines and other products with high light protection requirements. Attached Figure Description

[0025] Figure 1 This is the high-temperature viscosity curve of the amber glass in Example 1 of the present invention. Detailed Implementation

[0026] To better understand the present invention, the following embodiments are provided for further explanation:

[0027] (1) Preparation of composite colorant: Weigh Fe2O3 and aluminum iron silicate according to Table 1, add 20ml of anhydrous ethanol, and ultrasonically mix for 0.5h to obtain a powder with uniform particles. Continue to weigh Na2SO4, NH4HSO4 and high-purity graphite powder, add 20ml of anhydrous ethanol, and ultrasonically mix for 0.5h to prepare a uniformly mixed composite colorant.

[0028] (2) continue to add the remaining oxide composition according to Table 1, add 50ml of anhydrous ethanol, and put into a mixer for mixing, at a speed of 120r / min for 1h;

[0029] (2) after drying the batch in an oven, pour into a platinum crucible for melting, the feeding temperature is 950℃, after feeding, introduce nitrogen, the melting temperature is 1450℃, and the holding time is 0.5h;

[0030] (3) preheat the copper plate for glass casting, the preheating temperature is 500℃, the glass liquid melted and clarified is taken out from the high-temperature furnace and cast on the preheated copper plate;

[0031] (4) put the cast glass into an annealing furnace, the annealing temperature system is: 500℃ for 1h, then reduce the temperature to 400℃ at a rate of 5℃ / min, then reduce the temperature to 280℃ at a rate of 3℃ / min, and then cool down to room temperature with the furnace, to prepare the amber glass.

[0032] The properties of the amber glasses prepared in Examples 1-8 are shown in Table 1.

[0033] Table 1: Components and properties of Examples 1-8

[0034]

[0035] It can be seen from Examples 1-8 that the glass coloration is amber, the composite colorant has better effect, and Fe 2+ / Fe 3+ is strictly controlled to be 1.76-2.25, the color is uniform, the visible light transmittance (380-780nm) of the glass is ≤35%, the transmittance at 10-300nm is 0, and the coloration uniformity and stability can be greatly improved. Figure 1 The high-temperature viscosity chart shows that the glass of the present application has lower viscosity in the melting process, which is beneficial to the forming of glass packaging vessels, and reduces the process difficulty.

Claims

1. An amber glass characterized in that It is made from the following raw materials in the following molar percentages: 69.4-71.8% SiO2, 0.48-1.8% Al2O3, 0.52-2.1% B2O3, 8.4-12.1% Na2O, 0.5-1.5% K2O, 8.2-11.7% CaO, 0.25-0.8% MgO, and 2.2-7.9% composite colorant; wherein the total molar percentage of Na2O+K2O is 12.1-13.2%, and the molar ratio of Na2O to K2O is... The molar percentage of CaO and MgO is 17.1-17.6; the total molar percentage of CaO and MgO is 11.4-12.2%, and the molar ratio of CaO to MgO is 19.3-20.1; the composite colorant is composed of the following raw materials in molar percentage: 0.06-0.07% Fe2O3, 0.01-0.05% ferric aluminosilicate, 0.23-0.62% Na2SO4, 0.01-0.24% NH4HSO4, 0.25-2.6% high-purity graphite powder, and the balance is anhydrous ethanol.

2. The amber glass of claim 1, wherein It is made from the following raw materials in the following molar percentages: 69.6-71.5% SiO2, 0.51-1.72% Al2O3, 0.55-2.04% B2O3, 8.6-11.9% Na2O, 0.8-1.5% K2O, 8.5-11.5% CaO, 0.3-0.75% MgO, and 2.3-7.8% composite colorant; wherein the total molar percentage of Na2O+K2O is 12.3-13.0%, and the molar ratio of Na2O to K2O is 17.3-17.4; the total molar percentage of CaO+MgO is 11.5-12.0%, and the molar ratio of CaO to MgO is 19.5-20.

1.

3. The amber glass of claim 1, wherein The composite colorant is prepared by the following method: Fe2O3 and aluminum iron silicate are weighed according to the above ratio, 20 ml of anhydrous ethanol is added, and ultrasonic mixing is carried out for 0.5 h to obtain a powder with uniform particles. Then, Na2SO4, NH4HSO4 and high-purity graphite powder are weighed, 20 ml of anhydrous ethanol is added, and ultrasonic mixing is carried out for 0.5-1 h to prepare a uniformly mixed composite colorant.

4. The method of claim 1, wherein the amber glass is prepared by Includes the following steps: (1) To prepare the composite colorant, continue to add the remaining oxide components according to the above ratio, add 50 ml of anhydrous ethanol, put it into a mixer for mixing, with a speed of 50-200 r / min and a time of 1-1.5 h; (2) After drying the batch material in an oven, it is placed into a platinum crucible for melting. The feeding temperature is 900-1000℃. Nitrogen gas is introduced after feeding. The melting temperature is 1450-1520℃ and the holding time is 0.5-1.5h. (3) The copper plate for glass casting is preheated to a temperature of 480℃~520℃. The molten glass that has been melted and clarified is taken out from the high-temperature furnace and cast onto the preheated copper plate. (4) Place the cast glass into an annealing furnace and anneal at a temperature of 480℃~520℃ for 1 hour. Then, cool it down to 400℃ at a rate of 5℃ / min, and then cool it down to 280℃ at a rate of 3℃ / min. Finally, cool it down to room temperature with the furnace to prepare amber glass.

5. The method of claim 4, wherein the amber glass is prepared by: Fe in the amber glass 2 + / Fe 3+ is 1.76-2.

25.

6. The method of claim 4, wherein the amber glass is prepared by: The visible light transmittance of the amber glass is ≤35%.

7. The method for preparing amber-colored glass according to claim 4, characterized in that: The amber glass has a transmittance of 0 in the 10-300 nm range.

8. The method for preparing amber-colored glass according to claim 4, characterized in that: The amber glass has a chromaticity L of 18-24, a of 5-8, and b of 4-8.

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