High-refractive-index jewelry glass with stable chemical properties and preparation method thereof

Abstract

The application discloses a kind of high refractive index chemical property stable ornament glass, it is characterized by being composed of the following mass percentage raw material components: SiO 2 11%-15%, BaCO 3 36%-45%, TiO 2 25%-35%, La 2 O 3 3%-10%, ZrO 2 7%-15%, ZnO 0%-3%, auxiliary material 0-3%, wherein the atomic mole ratio of Ti / Ba is 1.40-2.20.Its preparation method includes the following steps: (1), after raw material is allocated and prepared, it is stirred into mixer 3-4 hours to be fully uniform, with feeder 60-90 kg per time is added to continuous melting glass kiln feeding area in batches intermittently;(2), control the melting temperature of each area of continuous melting glass kiln respectively between 1320-1390 DEG C, and control the material liquid depth in the hearth of continuous melting glass kiln is 20-25cm, and melt, clarify, homogenize;(3), preheating forming mould temperature 150 DEG C-200 DEG C, and carry out casting forming;(4), the temperature of blank drops to 550 DEG C-600 DEG C's demoulding temperature, after forming blank is demoulded from mould, bury into expanded perlite and anneal, cool to normal temperature, and obtain ornament glass material.The ornament glass of the application has high refractive index and acid and alkali corrosion resistance.

Description

Technical Field

[0001] The present invention relates to the field of inorganic glass, in particular to a decorative glass with high refractive index and strong acid and alkali corrosion resistance that can be used in decorative products. Background Art

[0002] With the continuous advancement of science and technology, the jewelry market has rapidly developed, and a variety of artificial jewelry materials have emerged. Jewelry glass is one of the main materials for jewelry. Jewelry glass requires optical properties such as high refractive index and dispersion to achieve the luster required by jewelry such as diamonds and crystals. The refractive index of ordinary high-silicon glass is difficult to meet the optical performance requirements of high-refractive index jewelry, so there is a need to develop specialized high-refractive-index glass for making artificial jewelry. For example, CN109734303A, filed by Chengdu Qicai Jewelry Co., Ltd., uses auxiliary materials with a BaO content of 30-60%, a TiO2 content of 20-55%, a SiO2 content of 5-10%, and Y2O3 contents of 0-1% and 0-10% to produce high-refractive-index glass. However, this system with a BaO+TiO2 content greater than 80% has a significantly increased difficulty in obtaining stable glass because, as the TiO2 / BaO molar ratio increases, the refractive index increases, but the glass crystallization temperature range also widens, resulting in a significant increase in the difficulty of obtaining stable glass. Unfortunately, the document does not provide a process for obtaining stable glass. Furthermore, in jewelry production, decorative glass is often embedded in metal or alloy components and requires electroplating with the components, such as gold, silver, or copper. During electroplating, the decorative glass and components undergo cleaning and activation with solutions of 60-98% sulfuric acid, 30-40% hydrochloric acid, and 20-30% sodium hydroxide. This requires the decorative glass to possess excellent chemical stability and withstand the corrosion of acids and alkalis during electroplating. However, it is well known that SiO2 and alkali metal oxides in glass are not resistant to alkalis and certain acids, and the chemical stability of conventional high-refractive-index decorative glass is difficult to meet this requirement, thus hindering its application in the jewelry industry. Summary of the Invention

[0003] The purpose of the present invention is to overcome the problem that current decorative glass has poor acid and alkali abrasion resistance under the premise of ensuring high refractive index, and to provide a decorative glass that has both high refractive index and acid and alkali corrosion resistance and stable chemical properties and a preparation method thereof.

[0004] A high-refractive-index decorative glass with stable chemical properties is composed of the following raw material components in percentage by mass: SiO2 11%-15%, BaCO3 36%-45%, TiO2 25%-35%, La2O3 3%-10%, ZrO2 7%-15%, ZnO 0%-3%, and auxiliary materials 0-3%, wherein the atomic molar ratio of Ti / Ba is 1.40-2.20.

[0005] Furthermore, the high-refractive-index, chemically stable decorative glass is composed of the following raw material components in percentage by mass: SiO2 12%-14%, BaCO3 41%-43%, TiO2 27%-34%, La2O3 3%-7%, ZrO2 9%-14%, ZnO 0%-3%, and auxiliary materials 0-2.5%.

[0006] Furthermore, the high-refractive-index, chemically stable decorative glass is composed of the following raw material components in percentage by mass: SiO2 14%, BaCO3 37%, TiO2 32%, La2O3 3%, ZrO2 10%, ZnO 2.2%, and auxiliary materials 1.8%.

[0007] In the above scheme, the auxiliary material is any one of Er2O3, Nd2O3 and B2O3, or any two or three thereof.

[0008] The present invention also provides a method for producing decorative glass with high refractive index and stable chemical properties using the above components as raw materials, comprising the following steps:

[0009] Step (1), after the raw materials are prepared according to the components, they are added into a mixer and stirred for 3-4 hours until uniform, and then added into the feeding area of ​​the continuous melting glass furnace in batches of 60-90 kg each time using a feeder;

[0010] Step (2), controlling the melting temperature of each area of ​​the continuous melting glass furnace to be between 1320-1390°C, and controlling the depth of the liquid in the furnace of the continuous melting glass furnace to be 20-25 cm, and performing melting, clarification, and homogenization;

[0011] Step (3), preheating the molding mold to a temperature of 150°C-200°C for casting molding;

[0012] In step (4), the temperature of the blank is lowered to a demolding temperature of 550°C-600°C. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing and cooled to room temperature to obtain a decorative glass material.

[0013] Furthermore, the continuous melting glass furnace comprises five zones, and the temperature of each zone is controlled as follows: feeding zone 1340±20°C, material processing zone 1390±10°C, clarification zone 1380±10°C, homogenization zone 1360±10°C, and discharging zone 1350±5°C.

[0014] The present invention relates to a high-refractive-index TiO2-BaO-SiO2 glass system. SiO2, as a network-forming oxide, forms a silicon-oxygen tetrahedral grid in the glass, serving as the main component of the glass's framework and imparting excellent chemical stability. In this system, TiO2 acts as a network-forming oxide when its coordination number is 4. When its coordination number is 6 or greater, it functions similarly to a network-external oxide, significantly increasing the glass's refractive index and dispersion, improving its chemical stability. BaCO3, a network-external oxide, significantly increases the glass's density and refractive index at a high content, but reduces its chemical stability. The present invention controls the atomic molar ratio of Ti to Ba to 1.40-2.20, and adds La2O3, ZrO2, and ZnO, allowing some BaCO3 to react with some TiO2 to form BaTiO3, with a refractive index above 2.1. Crystallization is then adjusted to promote glass formation, resulting in a glass system with a high refractive index, stable chemical properties, and resistance to acid and alkali corrosion.

[0015] In the present invention, if the SiO2 content is too high, not only will the alkali corrosion resistance be deteriorated, but the high-temperature viscosity of the glass will also be increased, resulting in an excessively high melting temperature. Therefore, the present invention controls its mass percentage to be 11%-15%.

[0016] Too little TiO2 results in a low refractive index, while too much TiO2 results in difficulty in melting. Therefore, the present invention controls the mass percentage to be 25%-35%.

[0017] Because a high BaCO3 content significantly increases the density and refractive index of glass, but reduces its chemical stability, the present invention controls its mass percentage to 36%-45%. Furthermore, the atomic molar ratio of Ti / Ba is controlled to 1.40-2.20 to achieve a high refractive index while also controlling the crystallization temperature to form a stable TiO2-BaO-SiO2 glass system.

[0018] La2O3 exists as an interstitial ion in the network, with a refractive index of 2.0, making it the primary component contributing to the high refractive index of glass. An appropriate amount of La2O3 can enhance the chemical stability of glass and improve its alkali resistance. However, excessive amounts can lower the glass density, reducing the refractive index and leading to decreased alkali resistance. Therefore, the present invention limits its content to 3%-10% by weight.

[0019] ZrO2 has high refractive index and low dispersion properties, with a refractive index above 2.2. It typically acts as a network exosome in glass. The silicon-oxygen and zirconium-oxygen bonds in ZrSiO4, formed by SiO2 and ZrO2, possess strong bond energy, resulting in strong oxidation resistance and resistance to acid and alkali corrosion and chemical dissolution. Its introduction into glass can improve its chemical stability, particularly its resistance to acid and alkali corrosion. However, excessive levels can increase the glass's melting temperature and crystallization tendency. Therefore, the present invention controls its mass percentage to 7%-15%.

[0020] ZnO, as a network intermediate, can enter the glass network in the form of [ZnO4] tetrahedra or exist as an interstitial ion in the [ZnO6] state. Proper inclusion can improve the chemical stability and refractive index of the glass and reduce its high-temperature viscosity and coefficient of expansion. However, excessive BaCO3 content increases the tendency of the glass to crystallize. The present invention controls the amount of BaCO3 to ensure that the [ZnO4] state predominates, thereby enhancing the stability of the glass structure and improving glass-forming ability. Therefore, the present invention controls the mass percentage of BaCO3 to 0%-3%.

[0021] The present invention further ensures the formation of a stable glass system by controlling the glass melting furnace to 1320-1390° C. and a reasonable ratio of raw materials.

[0022] The present invention has the following beneficial effects:

[0023] (1) The refractive index of BaTiO3 formed during the melting of the present invention is above 2.1. La2O3 and ZrO2 have both high refractive index and high chemical stability, and are components that promote the formation of a stable TiO2-BaO-SiO2 glass system. At the same time, a TiO2-BaO-SiO2 high refractive index glass system is also produced during the melting, so that the refractive index of the prepared decorative glass is between 1.9 and 2.15.

[0024] (2) The raw materials such as TiO2, La2O3, ZrO2, ZnO, SiO2 in the present invention are not only chemically stable in themselves, but also the silicon-oxygen bond and zirconium-oxygen bond in ZrSiO4 formed when SiO2 and ZrO2 are melted have very strong bond energy, making its solubility in strong acid and strong alkali solutions very low, which greatly improves the chemical stability of the decorative glass. After being immersed in 80% sulfuric acid for more than 1 hour or in 40% hydrochloric acid for more than 10 minutes, the decorative glass does not become foggy or faded and remains as bright as before.

[0025] (3) The present invention uses a uniquely designed continuous melting glass kiln capable of mass production, which can effectively control the melting conditions, greatly improve production capacity, and reduce energy consumption and production costs. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and beneficial effects of the present invention more specific, the present invention is further described below with reference to examples, which however are not intended to limit the present invention.

[0027] Example 1 (Ti / Ba molar ratio 2.14)

[0028] A high-refractive-index acid- and alkali-resistant decorative glass is prepared by the following steps: raw materials are prepared according to the mass percentage of SiO2 15%, BaCO3 37%, TiO2 32%, La2O 33%, ZrO2 10%, ZnO 1.5%, and auxiliary materials 1.5%, and then added to the mixing machine and stirred for 3.5 hours. After fully stirring, 85±2 kg is added to the feeding zone of the continuous melting glass furnace by a feeding machine every 20 minutes; the melting temperature of the five zones of the furnace is controlled to be 100°C. The temperature of the furnace is controlled at 340±10℃, the material zone is 1380±5℃, the clarification zone is 1370±5℃, the homogenization zone is 1360±5℃, and the discharge zone is 1340±5℃; the depth of the liquid in the furnace pool is controlled at 22±1cm, and the speed of the stirrer in the homogenization zone is controlled at the same time; the preheating temperature of the forming mold is 200℃±20℃, and the demolding temperature is 580℃±10℃. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing and taken out after cooling to room temperature to obtain decorative glass with high refractive index and strong chemical properties.

[0029] Example 2 (Ti / Ba molar ratio 1.82)

[0030] A high-refractive-index, acid- and alkali-resistant decorative glass is prepared by the following steps: Add raw materials (by mass percentage) of SiO2 12%, BaCO3 38%, TiO2 28%, La2O 37%, ZrO2 10%, and ZnO 3%, and add auxiliary materials 2%. After preparation, add the mixture to a blender and stir for 3.5 hours. After being fully stirred, 80±2 kg of liquid is added to the feeding zone of the continuous melting glass furnace once every 20 minutes using a feeder; the melting temperatures of the five zones of the furnace are controlled to be 1340±10°C in the feeding zone, 1370±5°C in the clarification zone, 1375±5°C in the homogenization zone, and 1350±5°C in the discharge zone; the depth of the liquid in the furnace pool is controlled to be 21±1cm, and the speed of the stirrer in the homogenization zone is controlled at the same time; the preheating temperature of the forming mold is 180±20°C, and the demolding temperature is 550±10°C. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing, and then taken out after cooling to room temperature to obtain decorative glass with high refractive index and strong chemical properties.

[0031] Example 3 (Ti / Ba molar ratio 1.48)

[0032] A high-refractive-index acid- and alkali-resistant decorative glass is prepared by the following steps: raw materials are prepared according to mass percentages of SiO2 13%, BaCO3 45%, TiO2 27%, La2O 37%, ZrO 26%, and auxiliary materials 2%, and the mixture is added into a blender and stirred for 4 hours. After being thoroughly stirred, 70±2 kg of the liquid is added to the charging zone of the continuous melting glass furnace once every 20 minutes using a feeder; the melting temperatures of the five zones of the furnace are controlled to be 1340±10°C in the charging zone, 1375±5°C in the clarification zone, 1380±5°C in the homogenization zone, and 1345±5°C in the discharge zone; the depth of the liquid in the furnace pool is controlled to be 23±1cm, and the speed of the stirrer in the homogenization zone is controlled at the same time; the preheating temperature of the forming mold is 200°C±20°C, and the demolding temperature is 530°C±10°C. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing, and then taken out after cooling to room temperature to obtain decorative glass with high refractive index and strong chemical properties.

[0033] Example 4 (Ti / Ba molar ratio 1.40)

[0034] A high-refractive-index, acid- and alkali-resistant decorative glass is prepared by the following steps: Add raw materials (by mass percentage) of SiO2: 14%, BaCO3: 44%, TiO2: 25%, La2O: 36%, ZrO: 25%, ZnO: 3%, and auxiliary materials: 3%, and stir in a blender for 3.5 hours. After being thoroughly stirred, 60±2 kg of liquid is added to the feeding zone of the continuous melting glass furnace once every 20 minutes using a feeder; the melting temperatures of the five zones of the furnace are controlled to be 1340±10°C in the feeding zone, 1390±5°C in the clarification zone, 1380±5°C in the homogenization zone, and 1360±5°C in the discharge zone; the depth of the liquid in the furnace pool is controlled to be 24±2 cm, and the speed of the stirrer in the homogenization zone is also controlled; the preheating temperature of the forming mold is 150±20°C, and the demolding temperature is 550±10°C. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing, and then taken out after cooling to room temperature to obtain decorative glass with high refractive index and strong chemical properties.

[0035] Comparative Example 1 (using Y2O3 instead of La2O3+ZrO2+ZnO)

[0036] After the raw materials are prepared according to the mass percentage of SiO215%, BaCO337%, TiO232%, Y2O314.5%, and auxiliary materials 1.5%, the production method is the same as Example 1.

[0037] Comparative Example 2 (Low La2O3)

[0038] The raw materials are SiO215%, BaCO337%, TiO232%, La2O31%, ZrO212%, ZnO1.5% in percentage by mass, and auxiliary materials are 1.5%. The process method is the same as that in Example 1.

[0039] Comparative Example 3 (High SiO2 without ZnO)

[0040] The raw materials are SiO216.5%, BaCO337%, TiO232%, La2O33%, ZrO210% in percentage by mass, and auxiliary materials are 1.5%. The process method is the same as that in Example 1.

[0041] Performance testing:

[0042] 1. Refractive index test: Test according to GB / T 7962 national standard. The results are shown in Table 1.

[0043] 2. Density test: Test according to GB / T7962 national standard. The results are shown in Table 1.

[0044] 3. Corrosion resistance test:

[0045] Since the time standard for the acid corrosion resistance of electroplated jewelry is to be immersed in sulfuric acid for more than 1 hour and in hydrochloric acid for more than 10 minutes, and the jewelry glass does not become foggy or fade, the corrosion resistance test method of the present invention is as follows:

[0046] (1) Take a glass sample, cut it into a 10 mm round diamond shape, grind and polish it, clean it and dry it to form a test specimen.

[0047] (2) The samples were immersed in 80% (wt%) sulfuric acid and 40% (wt%) hydrochloric acid solutions, respectively. The maximum acid immersion time at which the decorative glass did not become foggy or faded after immersion was calculated. The results are shown in Table 1.

[0048] Table 1 Sample performance test results

[0049]

[0050] As can be seen from the results in Table 1, compared with the comparative example, Examples 1-4 of the present invention not only achieve high refractive index and high density, but also have significantly improved acid and alkali corrosion resistance, solving the problem that high refractive index imitation gemstone jewelry glass is difficult to electroplate. In particular, Examples 1-2 have a better overall effect.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. The scope of protection of the present invention is defined by the claims. Any modifications, equivalent substitutions, improvements, etc. made to the present invention by those skilled in the art within the essence and scope of protection of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high refractive index and chemically stable decorative glass, characterized in that The invention is composed of the following raw material components in mass percentage: SiO2 11%-15%, BaCO3 36%-45%, TiO2 25%-35%, La2O3 3%-10%, ZrO2 7%-15%, ZnO 0%-3%, and auxiliary materials 0-3%, wherein the atomic molar ratio of Ti / Ba is 1.40-2.

20.

2. The high refractive index and chemically stable decorative glass according to claim 1, characterized in that The invention is composed of the following raw material components in percentage by mass: SiO2 12%-14%, BaCO3 41%-43%, TiO2 27%-34%, La2O3 3%-7%, ZrO2 9%-14%, ZnO 0%-3%, and auxiliary materials 0-2.5%.

3. The high refractive index and chemically stable decorative glass according to claim 1, characterized in that It is composed of the following raw material components in the following mass percentages: SiO2 14%, BaCO3 37%, TiO2 32%, La2O3 3%, ZrO2 10%, ZnO 2.2%, and auxiliary materials 1.8%.

4. The high refractive index and chemically stable decorative glass according to any one of claims 1 to 3, characterized in that: The auxiliary material is any one of Er2O3, Nd2O3 and B2O3 or any two or three thereof.

5. A method for preparing high-refractive-index, chemically stable decorative glass using the composition of claim 1 as a raw material, comprising the following steps: Step (1), after the raw materials are prepared according to the components, they are added into a mixer and stirred for 3-4 hours until uniform, and then added into the feeding area of ​​the continuous melting glass furnace in batches of 60-90 kg each time using a feeder; Step (2), controlling the melting temperature of each area of ​​the continuous melting glass furnace to be between 1320-1390°C, and controlling the depth of the liquid in the furnace of the continuous melting glass furnace to be 20-25 cm, and performing melting, clarification, and homogenization; Step (3), preheating the molding mold to a temperature of 150°C-200°C for casting molding; In step (4), the temperature of the blank is lowered to a demolding temperature of 550°C-600°C. After the formed blank is removed from the mold, it is buried in expanded perlite for annealing and cooled to room temperature to obtain a decorative glass material.

6. The method according to claim 5, wherein The continuous melting glass furnace comprises five zones, and the temperature of each zone is controlled as follows: feeding zone 1340±20°C, material processing zone 1390±10°C, clarification zone 1380±10°C, homogenization zone 1360±10°C, and discharging zone 1350±5°C.

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