CN1060456C - Fast-microcrystallized devitrified agrellite glass and its production process - Google Patents

Abstract

A kind of rapid microcrystallization fluorine-alkali calcium silicate glass-ceramic and its production method, belong to the field of glass-ceramic, it is characterized in that it realizes rapid overall microcrystallization under heat treatment temperature, and the glass composition is (wt%)

SiO ₂ 51~61, CaO18~23, F4.5~6,

_Na2O5 ～10, _K2O0.8 ～3.5, _R2O ( _Na2O + _K2O )6～14

_{B2O3 1.7} ～3.8, BaO1.6～2.6, _{P2O5 0.9} ～2.5,

ZnO1.8～5.6, TiO ₂ 0.6～6.4, Al ₂ O ₃ 0～0.3

Additional colorant is added;

In one-step heat treatment temperature of 750-850°C and constant temperature for 2-10 minutes, glass-ceramics of various colors are prepared. The material of the invention has good performance, low cost and bright color.

Description

Fluorine-alkali calcium-silica glass-ceramics of rapid microcrystallization and production method thereof

The invention relates to a rapidly microcrystallized opaque or translucent fluorine-alkali calcium silicate glass-ceramics, which belongs to the field of glass-ceramics.

Compared with conventional glass, glass-ceramic has higher mechanical strength, surface hardness, impact resistance and particularly excellent durability and corrosion resistance. It can be applied in the fields of building materials, chemical industry, electronics, medicine and daily life. Among them, the largest amount is used in construction materials. As a building decoration material, glass-ceramics not only has better mechanical properties than other materials, but also has a hard and fine texture, bright color and high gloss. It can replace natural granite and be used as an advanced decoration material for indoor and outdoor walls, floors and countertops of various buildings. , It is also expected to become a new type of curtain wall glass.

In the early 1960s, the former Soviet Union used blast furnace slag as raw material to produce architectural glass-ceramics by calendering. In the 1980s, Japan used melting and sintering to produce high-grade decorative glass-ceramic plates that are as white as jade and durable. In the 1990s, the country also imitated the above process to produce architectural glass-ceramics. However, the existing glass-ceramic production process has the problems of small scale, high energy consumption and high cost, which cannot meet the market demand.

Glass-ceramics is realized by controlling the heat treatment temperature and heat treatment time to produce a certain amount of microcrystals in the glass matrix. Usually, after the high-temperature melting glass body is shaped and cooled, it can be obtained by reheating to the nucleation or crystal growth temperature for a long period of heat preservation treatment. In order to shorten the heat treatment time, two-step heat treatment is often used. That is, after a certain period of time at the microcrystal nucleation temperature, the temperature is raised to the crystal growth temperature for constant temperature treatment; however, the heat treatment time required for the second-step heat treatment is at least 0.5 to 2 hours. Such a long heat treatment time is the main reason why glass-ceramic production can only be manufactured by discontinuous process at present, which limits the production efficiency and scale of glass-ceramics.

As we all know, artificial glass-ceramics with fluorine-alkali calcium silicate as the main crystal phase has been developed in 1983 U. S． Pat． Disclosed in No 4386162. The disclosed fluorine-alkali calcium silicate glass-ceramics with high mechanical strength and toughness has the following composition by weight percentage: SiO ₂ 45-75, CaO 8-30, F 3.5-12, Na ₂ O 3-15, K ₂ O 0-20, Na ₂ O+K ₂ O 5-25, B ₂ O ₃ 0-6, Al ₂ O ₃ 0-7, ZrO ₂ 0-12.

The glass-ceramic glass with fluorine-alkali calcium silicate as the main crystal phase uses zirconia as the crystal nucleating agent; the four microcrystalline phases formed within the disclosed glass composition range are: Ca ₅ Na ₄ K ₂ [Si ₁₂ O ₃₀ ]F ₄ , Ca ₅ Na ₃ K ₃ [Si ₁₂ O ₃₀ ]F ₄ , NaCa ₂ Si ₄ O ₁₀ F and K _0.3 CaNa _0.9 Al _0.2 Si _3.8 O ₉ F. As disclosed in this patent, the melted base glass must be reheated to 900-1000°C for 0.25 hours, or kept at 750°C for 12 hours to achieve microcrystallization; The temperature is 550-700°C, and the temperature is kept for 0.5-6 hours, and then the crystal growth temperature is 800-950°C for 0.5-8 hours. The 29 examples disclosed in the patent require heat treatment in the range of 500-900°C for 1-2 hours. Although compared with other system glass-ceramics, this type of glass-ceramic has a faster crystallization rate. However, the continuous heat treatment time of 1 to 2 hours is still not suitable for the requirements of continuous scale production process, and can only be limited to small-scale production such as casting, sintering and calendering.

From the architectural point of view, glass-ceramic plates used for architectural decoration are bulk products. However, the production process of architectural glass-ceramic plates is still limited to high-cost small-scale production, and cannot be mass-produced by float process like flat glass. . The float process proposed by Pilkington and PPG glass manufacturing companies in the world today is an advanced technology for manufacturing high-quality flat glass. Very high forming speed is one of the main characteristics of the float process. In the float glass production line, the melted glass melt flows into the tin bath, and when the glass is pulled out of the tin bath, it has formed a solid glass plate; It takes a few minutes to ten minutes to cool down to the annealing temperature (about 600°C). Such a fast cooling rate makes it difficult to achieve microcrystallization in most system glass-ceramics disclosed so far. Certain glass-ceramics that crystallize at higher melting temperatures (>1100°C) will obviously cause harm to the entire melting process; in addition, glass melts that begin to crystallize at higher than 900°C will be affected by a sharp increase in melt viscosity. The increase will cause the molten glass to condense at the bottom of the furnace, or bring difficulties to the subsequent forming process. Only below the forming temperature range (the temperature at which the melt viscosity is 10 ⁶ to 10 ³ poise), the glass-ceramic that can be rapidly microcrystallized after a few minutes of heat treatment is suitable for continuous float process production.

Therefore, the existing glass-ceramic used in construction and its production process have the following disadvantages: 1. The crystallization temperature of matrix glass is too high, which is not conducive to melting and forming in mass production; 2. The microcrystallization heat treatment time is too long to meet the requirements of continuous high-speed production.

In order to overcome the above-mentioned deficiencies in the prior art, produce base glass with a lower crystallization temperature, opaque and translucent glass-ceramics that can be quickly or instantaneously crystallized through short-time heat treatment at a temperature lower than the forming temperature, this paper is proposed. Invented technical solutions.

The basic concept of the present invention is: 1) using titanium oxide as a nucleating agent that can promote phase separation and has a lower nucleation temperature; 2) forming fluorine and various oxides in the matrix glass composition: B ₂ O ₃ , P The joint effect of ₂ O ₅ , CaO, BaO, ZnO and TiO ₂ enables the matrix glass to accelerate phase separation, realize instantaneous nucleation and have a stable and rapid crystallization phase during high-temperature cooling; 3) Strictly control the content of potassium oxide, Form the fluorine-alkali calcium silica crystal form with rapid microcrystallization characteristics; 4) Avoid introducing alumina that is harmful to the rapid crystallization phase, and reduce its content to a minimum. Finally, the technical solution of the present invention is realized by rapidly cooling to a heat treatment system close to the transition temperature.

The rapid microcrystallization fluorine-alkali calcium silicate glass-ceramic and its production method designed by the present invention, the ingredients of the glass-ceramics include SiO ₂ , CaO, F, Na ₂ O, K ₂ O, B ₂ O ₃ , Al ₂ O ₃ , characterized in that the ingredients also include BaO, P ₂ O ₅ , ZnO, TiO ₂ ; the weight percentages of each ingredient in the ingredients are: SiO ₂ 51-61, CaO 18-23 , F 4.5~6, Na ₂ O 5~10, K ₂ O 0.8~3.5, R ₂ O(Na ₂ O+K ₂ O)6~14, B ₂ O ₃ 1.7~ 3.8, BaO 1.6~2.6, P ₂ O ₅ 0.9~2.5, ZnO 1.8~5.6, TiO ₂ 0.6~6.4, Al ₂ O ₃ 0~ 0.3;

A variety of colorants are additionally added to the ingredients, and the weight percentage is as follows. Under oxidation conditions, different purple glass-ceramics are prepared by adding 0.8-2.0% MnO, and made by adding 1.0-2.5% CuO. To get different lake blue glass-ceramics, add 0.2-1.2% Cr ₂ O ₃ to make different green glass-ceramics, add 0.08-0.5% CoO to make different blue glass-ceramics, add 0.5-1.5% Fe ₂ O ₃ to make different gray glass-ceramics; under reducing conditions, add 0.5-1.0% CdS and 0.5-1.0% Se, and add 2% ZnO at the same time , making different red glass-ceramics; adding 1.5-2.5% CeO, while increasing the content of TiO ₂ between 1-6.5%, making different orange-yellow glass-ceramics.

The production method of the rapid microcrystallization fluorine-alkali calcium silicate glass-ceramics designed by the present invention, the production method of the glass-ceramics includes: batching, melting, forming, microcrystallization heat treatment and annealing process, characterized in that the batching composition And the weight percentage wt% is: SiO ₂ 51~61, CaO 18~23, F 4.5~6, Na ₂ O 5~10, K ₂ O 0.8~3.5, R ₂ O(Na ₂ O +K ₂ O)6~14, B ₂ O ₃ 1.7~3.8, BaO 1.6~2.6, P ₂ O ₅ 0.9~2.5, ZnO 1.8~5.6 , TiO ₂ 0.6~6.4, Al ₂ O ₃ 0~0.3; a variety of colorants can be added to the ingredients to produce glass-ceramics of various bright colors. Under oxidation conditions, adding 0 ．8-2.0% MnO to make different purple glass-ceramics, add 1.0-2.5% CuO to make different lake-blue glass-ceramics, add 0.2-1.2% Cr ₂ O ₃ Prepare different green glass-ceramics, add 0.08-0.5% CoO to make different blue glass-ceramics, add 0.5-1.5% Fe ₂ O ₃ to make different gray glass-ceramics , it should be noted that the above-mentioned colorants can be introduced alone, or multiple colorants can be introduced at the same time, and a series of colors from purple, blue to green can be obtained by changing the type and ratio of the colorants. The displayed color is fresher than that under reducing conditions, therefore, a small amount of oxidizing agent, such as sodium nitrate, etc. should be added to the ingredients; under reducing conditions, 0.5-1.0% CdS and 0.5-1. 0% Se, while adding 2% ZnO, to produce light red to bright red glass-ceramic, if adding 1.5-2.5% CeO, while increasing the _TiO2 content between 1-6.5% , different orange-yellow glass-ceramics can be obtained. It should be noted that there should be no nitrate-based oxidants in the ingredients under reducing conditions, otherwise it will cause the decomposition of cadmium sulfide; if no coloring agent is added, the prepared glass-ceramic the glass is white;

The forming and microcrystallization heat treatment process of glass ceramics are:

a. The glass melt melted at 1350 ℃ ~ 1450 ℃ is rapidly cooled to a temperature below the transformation temperature during the forming process, about 300 ℃, and then rapidly heated to 20 ~ 50 ℃ above the microcrystallization temperature at 300 ℃ / h, and the temperature is constant. Slowly cool down to room temperature after 5-10 minutes;

b. Cool the glass melt to the forming temperature, that is, cooling to 850-1100°C for forming, then rapidly cooling to 550°C at 50-150°C/min, and then rapidly heating to 70-70°C above the microcrystallization temperature at 50-150°C/min 150°C, keep the temperature constant for 2 to 5 minutes, then slowly cool to room temperature.

The present invention's rapid microcrystallized fluorine-alkali-calcium-silica glass-ceramics and its production method are further characterized in that the ingredients for preparing the glass-ceramics are cheap natural mineral raw materials and chemical raw materials, such as quartz sand, limestone, fluorite and soda ash, etc. Some industrial waste residues can also be used to replace some natural mineral raw materials, such as the waste residue of quartz vein gold mine after gold extraction; therefore, the cost of ingredients is relatively low, which is equivalent to the cost of conventional soda lime silicate glass ingredients.

The glass-ceramics of the present invention are melted according to conventional glass technology. Melt the composition ingredients determined by the present invention, and the melting temperature is 1350-1450°C; the prepared glass melt is cooled, formed and microcrystallized by the above-mentioned two methods of a and b respectively; then annealing treatment is carried out to eliminate internal stress, the glass-ceramic provided by the present invention can be prepared.

The glass melt is cooled to 550°C or below the transition temperature, and the reheating leads to rapid phase separation in the glass matrix; the rapid phase separation of the glass as a whole promotes the instantaneous generation of a large number of crystal nuclei. Rapid phase separation leading to instantaneous generation of crystal nuclei is one of the main characteristics of the material of the present invention. Therefore, the cooled glass body does not need to be heat-preserved at the nucleation temperature, and has been heated up to the crystal growth temperature, and the overall microcrystallization can be achieved by one-step heat treatment. This is the difference between the fluorine-containing alkali-calcium-silica glass-ceramics of the present invention and other types of fluorine-alkali-calcium-silica glass-ceramics. The rapid phase separation and instantaneous nucleation process significantly shorten the microcrystallization time; at the crystal growth temperature, the glass substrate only needs a short heat treatment to achieve microcrystallization. After the basic glass of the present invention is formed and cooled by different methods, the temperature is raised to the crystal growth temperature (700-880° C.), and the temperature is kept constant for 2-10 minutes, and enough microcrystals are formed in the glass matrix. Even though one-step heat treatment is adopted, there is no stay at the nucleation temperature during the heating process, and uniform and fine-grained microcrystals are still produced in the matrix glass. If it is kept at the crystal growth temperature (750°C) for 15 minutes, a highly crystallized material can be obtained. This is the same as U. S． Pat． The fluorine-alkali calcium silicate glass-ceramics disclosed in No 4386162 needs to be kept at 750°C for 12 hours to realize a significant difference in high crystallization materials, which is also another main feature of the material of the present invention. Apparently, microcrystallization proceeds more rapidly with increasing temperature. With one-step heat treatment, the nucleation is completed instantaneously during the heating process, and then in the temperature range higher than the microcrystallization temperature and lower than the lower limit of the forming temperature, the microcrystallization is completed by heat preservation for 2 to 10 minutes, which is suitable for rapid prototyping by float process Manufactured glass-ceramic material.

The material of the present invention uses titanium oxide as a nucleating agent, and this is because titanium oxide in glass-ceramics has the effect of improving the luster and color of the material in addition to promoting phase separation and nucleation; Compared with the nucleating agent, titanium oxide has a lower microcrystallization temperature as the nucleating agent material.

The main crystal phase in the glass-ceramic material of the present invention is fluorine-alkali wollastonite. There are many crystal forms of this kind of crystal, and the ratio of different alkaline earth metal and alkali metal ions in the crystal has a significant impact on the crystal form change. According to chemical composition analysis, differential thermal analysis and X-ray diffraction structure analysis, it is confirmed that the crystal form of the fluorine-alkali calcium silica crystal phase in the glass-ceramics of the present invention is Ca ₅ Na _5.5 K _0.5 [Si ₁₂ O ₃₀ ] F ₄ and Ca ₅ Na ₅ K[Si ₁₂ O ₃₀ ]F ₄ . The properties of the two crystal forms are very close and can form a solid solution. Fluorine-alkali wollastonite belongs to poly-chain silicate crystals. Potassium ions and some sodium ions in a single unit cell are in a flat cylindrical network surrounded by silicon-oxygen tetrahedrons, and the two sides of the flat cylindrical network are composed of Ca(O, F) ₆ and Na(O, F) ₆ The octahedron constitutes a wavy sidewall, similar to a multilayer structure. The voids in the silicon-oxygen tetrahedral flat cylinder network are approximately prismatic, for U. S． Pat． The Ca ₅ Na ₄ K ₂ [Si ₁₂ O ₃₀ ] F ₄ crystalline fluorine-alkali wollastonite disclosed in No 4386162 is occupied by a sodium ion in the middle of the gap, and two potassium ions occupy the corners of the gap; For Ca ₅ Na ₅ K[Si ₁₂ O ₃₀ ]F ₄ crystalline fluorine-alkali wollastonite, one larger potassium ion occupies the middle of the prismatic void, and two smaller sodium ions occupy the corners of the void. Obviously, the latter is easier to form than the former in terms of crystal structure. It shows that the proportion of alkali metal ions in the crystal structure is an important factor for the rapid microcrystallization of fluorine-alkali wollastonite, and it is also one of the main contents of the secret disclosure of the glass-ceramics of the present invention.

In the chemical composition of the basic glass, potassium oxide is an essential component for the formation of rapid microcrystalline fluorine-alkali calcium silica crystal phase; although it is in a small amount in the total composition, accounting for 0.8-3.5wt% of the total, more than this No matter how other conditions change, the rapid microcrystalline fluorine-alkali calcium silica crystal phase cannot be formed, and only other types of crystals can be formed. The joint effect of F, B ₂ O ₃ , P ₂ O ₅ , CaO, BaO, ZnO and TiO ₂ in the basic glass composition is:1. Form rapid phase separation; 2. Promote the instantaneous generation and rapid growth of crystal nuclei; 3. Improves the stability of the rapidly crystalline phase. Without the joint action of fluorine and these oxides, only one or two kinds of the above oxides are added, the basic glass cannot form rapid phase separation, crystal nuclei will not be formed instantaneously, and the rapid crystallization phase of fluorine-alkali-calcium-silica cannot exist stably. In addition, it is necessary to limit the content of alumina in the glass composition to no more than 0.5 wt%. Excess alumina will seriously inhibit and destroy the formation of rapid crystallization phase. The above chemical composition restrictions are the same as U. S． Pat． The optimal composition disclosed in No 4386162 is substantially different from the chemical composition in the examples, which is another main content of the secret disclosure of the glass-ceramics of the present invention.

The rapid crystalline phase formed in the material of the present invention has a habit similar to that of other types of fluorine-alkali calcium silica crystals; uniform and fine crystal grains are precipitated in the glass-ceramic after one-step heat treatment, and the grain size is in the range of 0.5 to 2.5 μm . By adjusting the heat treatment conditions, the crystals in the glass-ceramics can grow up to form a microstructure that is staggered and laminated like cabbage leaves. This cross-laminated structure increases the toughness of the material. In many cases, the content of microcrystals in the glass-ceramics of the present invention is above 50 Vol%; the content of microcrystals can reach 90 Vol% after adjusting the composition and heat treatment conditions. Glass-ceramics prepared under various conditions contain residual glass phases in different volume percentages, and the residual glass phases can improve the surface state of glass-ceramics. Glass-ceramic panels used for architectural decoration will thus significantly improve the surface gloss and color.

The advantages of the glass-ceramic material of the present invention are: 1. The heat treatment time only needs a few minutes to ten minutes; 2. Reduce process, reduce cost and energy consumption; 3. It can be applied to float process for large-scale production; 4. Has good strength and toughness; 5. Bright color and decorative effect.

The accompanying table of the present invention is described as follows:

Table 1 shows the chemical composition (wt%) and color of 17 examples of glass ceramics of the present invention. The horizontal direction of the table is the sorting of glass example numbers, and the vertical direction is the oxide content and color in the formula of each example;

Table 2 is the forming and microcrystallization heat treatment process conditions of 17 examples of glass-ceramics of the present invention. The horizontal direction of the table is the order of the glass case numbers, and the vertical direction is the processing conditions of each case. A in the table represents the first forming and heat treatment method: that is, during the forming process of the glass melt, it is rapidly cooled to a temperature below the transition temperature (about 300°C), and then rapidly heated to a temperature 20~ above the microcrystallization temperature at 300°C/h. 50°C, keep the temperature constant for 5-10 minutes and then slowly cool to room temperature. b in the table represents the second forming and heat treatment method: cooling the melt to the forming temperature (850-1100°C) for forming, then quenching to 550°C at 50-150°C/min, and then rapid cooling at 50-150°C/min Raise the temperature to 70-150°C above the microcrystallization temperature, keep the temperature constant for 2-5 minutes, and then cool slowly to room temperature.

Table 3 is the physical properties of the glass-ceramics of the present invention.

Concrete implementation method (embodiment) of the present invention is as follows:

Implementation method 1:

The mineral raw materials used in glass batch materials include quartz sand, limestone and fluorite, etc., and the waste slag of quartz vein gold mine after gold extraction can also be used to replace quartz sand; the chemical raw materials used include soda ash, borax, zinc white and titanium dioxide. In principle, any raw materials can be used for the preparation of the batches within the scope of the chemical composition given in the present invention.

Prepare glass batch materials according to the chemical composition of Example No. 1 in Table 1; mix the batch materials evenly by ball milling, put the mixed batch materials into a 1 liter quartz crucible, put the crucible in an electric furnace, and keep the temperature at 1450°C 1 hour; according to the above-mentioned forming and microcrystallization heat treatment method a, cast the melted glass melt into a steel mold preheated to 300°C to make a glass sample of 100×100×10mm; the formed glass sample is quickly Put it into a muffle furnace with a furnace temperature of 500°C, raise the temperature at 300°C/h to 750°C, microcrystallize for 10 minutes, then slowly cool at 2°C/min to 580°C, and then gradually cool at 5°C/min to room temperature.

No coloring agent is added in the batching of example 1, so the crystallized glass that makes is white. Example numbers 3, 4, 7, 8, and 9 in Table 1 are all implemented according to the process steps of implementation method 1. The difference is that different colorants are added to the ingredients, and the glass-ceramic shows light yellow, light red, and light blue respectively. , dark green and light gray. In the batching of Example No. 9, gold ore waste slag was used to replace quartz sand as raw material, and 0.5% iron oxide was brought into the glass-ceramic by gold ore waste slag to make the glass-ceramic appear light gray. In order to make the melt be in a reducing state, the oxidant such as sodium nitrate can not be introduced in the batching of example numbers 3 and 4.

Implementation method 2:

Prepare glass batch material with the chemical composition of Example No. 1 in Table 1 according to the steps given in Implementation Method 1; the batch material is mixed evenly by multiple sieving methods, and the mixed ingredients are prepared in a crucible kiln for glass ceramics. Put the batch material into a clay crucible with a capacity of 200Kg, and melt it in a crucible kiln; the maximum melting temperature is 1450°C, and the total melting time is 16 hours; according to the above-mentioned forming and microcrystallization heat treatment method a, melt The prepared glass melt is cast in a steel mold preheated to 300°C to make a glass plate of 300×300×10mm; the formed glass plate is quickly put into a muffle furnace with a furnace temperature of 500°C, /h to 750°C, microcrystallization treatment for 10 minutes, then slowly cooled to 580°C at 2°C/min, and then gradually cooled to room temperature at 5°C/min.

In addition to Example 1, Example No. 2, 5, 6, and 7 in Table 1 are also implemented according to the process steps of Implementation Method 2, and different coloring agents are added to the ingredients, and the glass-ceramic shows lake blue, light green, and dark blue respectively. and light blue.

Implementation method 3:

The steps given in Embodiment Method 1 were used to prepare glass-ceramics with the batching of Example No. 14 in Table 1. Put the mixed ingredients into a 1 liter quartz crucible, put the crucible into an electric furnace, and keep the temperature at 1450°C for 1 hour; into the graphite mold in the discontinuous float forming tin bath; the discontinuous float forming tin bath is filled with pure nitrogen gas to prevent the oxidation of metal tin liquid and graphite; the graphite mold is a 300×250mm square in the middle Hole graphite plate (20mm thick); the glass melt is poured into the square hole and floats on the metal tin surface together with the graphite. The surroundings of the glass melt are limited by the graphite mold, and only the bottom is in contact with the tin surface. When the glass melt is poured into the mold, a very flat thin plate is naturally formed; the thickness of the thin plate is controlled between 6 and 15 mm by the amount of glass melt poured into the mold. Since the temperature gradient distribution along the moving direction of the graphite in the tin bath has been pre-set, by moving the graphite mold, it can be formed at 900°C, quenched at 100°C/min to 550°C, and then heated to 850°C at 100°C/min, with a constant temperature of 2 After a few minutes, gradually cool to room temperature. Example Nos. 10-17 were all carried out according to the implementation method 3; different coloring agents were introduced into the ingredients, and the glass-ceramic showed orange, bright red, light purple, purple, blue, green, gray and light lake blue respectively. No oxidant can be present in the batching of Example Nos. 10 and 11 to ensure that the glass melt is in a reduced state. In the batching of Example No. 16, gold mine waste slag was used instead of quartz sand as a raw material, and 1.5% iron oxide was contained in the batching to make the glass-ceramics appear gray.

Table 1. Chemical composition (wt%) and color example of glass ceramics

glass case number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 SiO ₂ CaOFNa ₂ OK ₂ OB ₂ O ₃ ZNOBaOP ₂ O ₅ TiO ₂ Al ₂ O ₃ MNOCuOCr ₂ O ₃ CoOFe ₂ O ₃ CeOCdSSe Color 56.621.75.35.60.82.12.42.51.90.90.2 White 55.621.35.25.61.42.12.42.62.51.20.22.5 lake blue 54.820.65.16.02.12.04.62.31.51.10.01.5 light yellow 53.720.14.95.63.51.95.62.31.41.10.00.50.5 light red 53.520.95.49.72.01.92.42.11.20.90.30.2 light green 54.222.95.27.41.92.12.11.91.41.10.20.5 dark blue 55.320.55.78.81.91.81.82.01.30.80.30.08 light blue 58.520.65.95.21.91.72.21.91.20.90.21.2 dark green 60.518.05.45.91.91.72.41.81.20.90.30.5 light gray 51.619.34.75.51.81.95.32.21.36.40.02.5 Orange 54.520.45.05.81.92.05.62.31.41.10.01.01.0 bright red 55.719.95.19.21.91.82.32.01.10.80.20.8 light purple 56.720.25.97.01.62.03.11.71.00.70.32.0 Purple 57.619.34.96.91.53.42.91.90.90.70.20.3 blue 59.218.24.57.01.43.82.71.60.90.60.30.6 green 58.618.24.67.01.53.63.21.60.90.70.31.5 gray 54.422.25.57.81.72.62.21.81.00.80.31.0 shallow lake

Table 2. Examples of glass-ceramic forming and heat treatment processes

Glass case number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17   Microcrystallization temperature (°C) 720 720 720 730 700 714 720 700 700 780 730 700 705 730 730 730 714  Heat treatment temperature (°C) 750 750 750 750 750 750 750 750 750 850 850 850 850 850 850 850 850  Heat treatment time (min) 10 10 10 10 5 8 8 5 5 5 3 2 2 2 3 5 2   Forming process a a a a a a a a a b b b b b b b b

table 3. Physical properties of glass-ceramics of the present invention

Density (g/cm ³ ) Bending strength (MPa) Compressive strength (MPa) Impact strength (kg·cm/cm ² ) Mohs hardness Water absorption (%) 2.62 55～65 400～450 2.1～2.3 6 0.0

Claims (3)

1. the quick fluorine alkali wollastonite devitrified glass of micritization, its food ingredient includes SiO ₂, CaO, F, Na ₂O, K ₂O, B ₂O ₃And Al ₂O ₃, it is characterized in that:

A. also include in the food ingredient: BaO, P ₂O ₅, ZnO and TiO ₂,

B. the weight percent wt% of each composition was respectively during batching was formed,

SiO ₂ 51～61， CaO 18～23， F 4．5～6，

Na ₂O 5～10， K ₂O 0．8～3．5，R ₂O(Na ₂O+K ₂O)6～14，

B ₂O ₃ 1．7～3．8，BaO 1．6～2．6，P ₂O ₅ 0．9～2．5，

ZnO 1．8～5．6，TiO ₂ 0．6～6．4，Al ₂O ₃ 0～0．3；

C. can additionally add multiple tinting material in batching, its weight percent wt% is,

Under the oxidizing condition, add 0.8～2.0%MnO and make different purple devitrified glasses, add 1.0～2.5%CuO and make different turquoise devitrified glasses, add 0.2～1.2%Cr ₂O ₃Make different green glass-ceramics, add 0.08～0.5%CoO and make different blue glass ceramics, add 0.5～1.5%Fe ₂O ₃Make different grey devitrified glasses;

Under the reductive condition, add 0.5～1.0%CdS and 0.5～1.0%Se, increase 2%ZnO simultaneously, make different red devitrified glasses; Add 1.5～2.5%CeO, increase TiO simultaneously ₂Content between 1～6.5%, make different orange-yellow devitrified glasses.

2. the fluorine alkali wollastonite devitrified glass production method of quick micritization according to claim 1, the production method of its devitrified glass comprises: prepare burden, found, shaping, micritization thermal treatment and annealing process, it is characterized in that:

A. batching composition and weight percent wt% thereof are,

SiO ₂ 51～61， CaO 18～23， F 4．5～6，

Na ₂O 5～10， K ₂O 0．8～3．5，R ₂O(Na ₂O+K ₂O)6～14，

B ₂O ₃ 1．7～3．8，BaO 1．6～2．6，P ₂O ₅ 0．9～2．5，

ZnO 1．8～5．6，TiO ₂ 0．6～6．4，Al ₂O ₃ 0～0．3；

In batching, can additionally be added with multiple tinting material, obtain the devitrified glass of different colours, under the oxidizing condition, add 0.8～2.0%MnO and make different purple devitrified glasses, add 1.0～2.5%CuO and make different turquoise devitrified glasses, add 0.2～1.2%Cr ₂O ₃Make different green glass-ceramics, add 0.08～0.5%CoO and make different blue glass ceramics, add 0.5～1.5%Fe ₂O ₃Make different grey devitrified glasses; Under reductive condition, add 0.5～1.0%CdS and 0.5～1.0%Se, increase 2%ZnO simultaneously, make different red devitrified glasses, add 1.5～2.5%CeO, increase TiO simultaneously ₂Content between 1～6.5%, make different orange-yellow devitrified glasses; If the devitrified glass that does not add tinting material then make is white in color;

B. the shaping of devitrified glass and micritization thermal treatment process are:

With 1350 ℃～1450 ℃ glass melts of founding, in forming process, be cooled fast to the temperature below the transition temperature, about 300 ℃, be rapidly heated more than the micritization temperature 20～50 ℃ with 300 ℃/h again, constant temperature slow cool to room temperature after 5～10 minutes; Perhaps glass melt is cooled to forming temperature, promptly be cooled to 850～1100 ℃ of shapings, be quenched to 550 ℃ with 50～150 ℃/min again, then, be rapidly heated more than the micritization temperature 70～150 ℃ with 50～150 ℃/min, constant temperature slow cool to room temperature after 2～5 minutes.

3. the fluorine alkali wollastonite devitrified glass production method of quick micritization according to claim 2, it is characterized in that: the batching of preparation devitrified glass adopts natural mineral raw and industrial chemicals, also can adopt some industrial residue to substitute the part natural mineral raw.