Chrome iron wollastonite glass-ceramics and preparation method thereof

Abstract

The present invention discloses a chromite wollastonite glass-ceramics and a preparation method thereof, belonging to the technical field of glass-ceramics. The present invention uses furnace slag, cullet and batch as raw materials, and prepares glass-ceramics by a one-step melting heat treatment process. The prepared chromite wollastonite [Ca(FeCr2O4)SiO3] glass-ceramics has excellent properties, and its performance indicators are superior to those of similar glasses. It has high mechanical strength, high hardness, good wear resistance, good chemical corrosion resistance, small thermal expansion coefficient and pays attention to environmental protection. It can adapt to harsh use environments and has good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of glass-ceramics, and in particular to chromium-iron wollastonite glass-ceramics and a preparation method thereof. Background Art

[0002] Glass-ceramics, also known as glass-ceramics, is a material made by controlling the precipitation of microcrystals from the base glass of certain specific glass systems, and its microcrystalline phase is evenly distributed in the glass phase. Glass-ceramics are composed of fine crystals and residual glass phases, contain a large amount of glass phases, and can be highly crystallized. Glass-ceramics contain at least one glass phase and one microcrystalline phase. The size of the uniformly distributed microcrystals in glass-ceramics is generally between tens of nanometers and tens of micrometers. During the growth of crystals in the base glass, the stress in all directions is the same, making the strength of glass-ceramics about one order of magnitude higher than that of ordinary glass, and the expansion coefficient of glass-ceramics is adjustable, which can be designed and adjusted according to application needs within the range of positive expansion, negative expansion, and zero expansion. At the same time, the base glass structure is dense and pore-free. The crystallized glass-ceramics has excellent thermodynamic properties, mechanical properties, chemical stability and good processing characteristics, and has a high operating temperature and is hard and wear-resistant.

[0003] The melt of wollastonite glass-ceramics is mainly surface crystallization, generating a large number of crystal aggregates, showing crystals of different sizes, forming a three-dimensional visual effect through the glass phase, and having mechanical properties and wear and corrosion resistance that exceed ordinary glass. For example, Chinese invention patent CN106430984A discloses a method for preparing wollastonite glass-ceramics using wollastonite, wherein wollastonite, SiO 2 、Na 2 O.B 2 O 3 、ZnO、Al 2 O 3 , MgO, K 2 O and rare earth oxides are mixed evenly, and then anhydrous ethanol is used to prepare a slurry, the slurry is mixed evenly by ball milling, dried, and then melted to obtain glass powder; the glass powder is mixed with wollastonite powder and pressed into shape, sintered at 950-1100°C for 1-4h, and then crystallized at 650-1180°C for 2-6h to obtain wollastonite glass-ceramics.

[0004] In the process of glass production in kilns, a large amount of kiln slag is generated, which is a harmful substance in the kiln. At the same time, NG products are inevitably produced in the process of producing finished glass products (NG products are glass products with defects such as streaks and stones during quality inspection). If kiln slag and broken glass are directly treated as production waste, it will cause waste. Therefore, it is urgent to recycle kiln slag and broken glass to prepare chromium iron wollastonite microcrystalline glass with superior performance. Summary of the invention

[0005] The technical problem to be solved by the present invention is: to overcome the shortcomings of the prior art and provide a chromium-iron-wollastonite glass-ceramics and a preparation method thereof, wherein the prepared chromium-iron-wollastonite glass-ceramics has high mechanical strength, good chemical corrosion resistance and unique optical properties.

[0006] The technical solution of the present invention is:

[0007] In one aspect, the present invention provides a chromium-iron-wollastonite glass-ceramic, comprising the following components in percentage by mass: 10-15% of kiln slag, 35-45% of cullet, and 40-55% of batch material; wherein the kiln slag comprises the following components in percentage by mass: SiO 2 28-32%, Al 2 O 3 16-18%, CaO 35-42%, MgO 6-8%, K 2 O 2-4%, Na 2 O 2-4%, TiO 2 1.5-3.5%, Fe 2 O 3 0.05-2%, P 2 O 5 0.03-0.05%; Cullet includes the following components by mass percentage: SiO 2 58-65%, Al 2 O 3 15-18%, CaO 2.5-5%, MgO 2-5%, K 2 O 2-4%, Na 2 O 10-13%, Nd 2 O 3 1-3%, Fe 2 O 3 0.03-0.08%, Na 2 SO 4 0.02-0.06%; the batch material includes the following components in mass percentage: SiO 2 40-46%, Al 2 O 3 13-16%, CaO 22-28%, MgO 1.8-3%, Na 2 O 4-5.5%, K 2 O 3-4%, NaOH 2-4%, Fe 2 O 3 0.5-0.8%, Cr 2 O 3 2-4%, B 2 O3 2.5-4%, Nd 2 O 3 1-3%.

[0008] The kiln slag of the present invention is produced by the kiln during the production process and is a harmful substance in the kiln. The kiln slag of the present invention is obtained by taking the kiln slag out of the kiln, drying it in a drying chamber, grinding it with a grinder, and passing it through a 180-mesh sieve.

[0009] The indispensable raw material for manufacturing float glass is cullet, and its particle size must meet the specified standards. If the particle size of cullet is too large, it cannot be evenly distributed during use, which will affect uniform melting; if the particle size of cullet is too small or cullet powder is used directly, it will affect the clarification of the glass; in addition, cullet with too small particle size is easy to produce debris, and dust will appear during transportation, causing pollution to the environment and causing harm to the health of on-site construction workers.

[0010] The cullet of the present invention is the NG product in the production of finished glass products (NG product is a glass product with defects such as streaks and stones during quality inspection). The cullet is taken out from the cullet warehouse and crushed into cullet with a particle size of 20-40 mm to obtain the cullet raw material of the present invention.

[0011] Preferably, the following components are included in percentage by mass: 13% of kiln slag, 38% of cullet and 49% of batch material.

[0012] Preferably, the kiln slag comprises the following components in percentage by mass: SiO 2 30.25%, Al 2 O 3 17.10%, CaO38.42%, MgO 6.99%, K 2 O 2.45%, Na 2 O 2.54%, TiO 2 2.18%, Fe 2 O 3 0.11%, P 2 O 5 0.04%.

[0013] Preferably, the cullet comprises the following components in percentage by mass: SiO 2 61.20%、Al 2 O 3 16.50%, CaO3.56%, MgO 2.95%, K 2 O 2.45%, Na 2 O 11.45%, Nd 2 O 3 1.84%, Fe 2O 3 0.05%、Na 2 SO 4 0.04%.

[0014] Preferably, the batch material includes the following components in percentage by mass: SiO 2 42%, Al 2 O 3 13.5%, CaO 24%, MgO 2.1%, Na 2 O 5%, K 2 O 3.5%, NaOH 2.5%, Fe 2 O 3 0.75%、Cr 2 O 3 2%, B 2 O 3 3.5%, Nd 2 O 3 1.15%.

[0015] SiO in the main components of kiln slag 2 、Al 2 O 3 As a glass network former, along with SiO 2 、Al 2 O 3 As the content of CaO and MgO increases, the integrity of the glass network increases, and the melting temperature of the base glass increases. CaO and MgO are components in the kiln slag, which can change the network structure of the glass. As the content of CaO and MgO increases, the integrity of the glass network decreases, and the diffusion and migration of ions in the network becomes easier, which enhances the crystallization ability of the base glass. At the same time, a small amount of NaO in the kiln slag 2 O and K 2 O can act as a solvent and play a role in network modification. TiO in kiln slag 2 In addition to being an alkali-resistant high-temperature solvent, the component can also reduce the alkali resistance of glass. The chemical reaction is: Ti+4OH - +(n-2)H 2 O→TiO 2 ·nH 2 O,TiO 2 ·nH 2 O is deposited on the glass surface, which can further prevent the glass from being corroded by alkali solution. In addition, P in kiln slag 2 O 5 It is easy to oxidize, which can accelerate the melting of cullet and batch materials. 2 O 5 The addition of 2 O 3The following reaction occurs: 2Si-O-B+POP→2P-O-B+Si-O-Si, which increases the degree of polymerization of the glass network structure and improves the hardness of the glass.

[0016] The addition of cullet is a secondary use of glass fragments, which can save energy loss and protect the ecological environment. From the perspective of the production process of microcrystalline glass, adding an appropriate amount of cullet in the kiln can speed up the melting process, reduce the amount of fuel required for the melting process, save fuel, and increase the economic benefits of the enterprise. On the other hand, cullet can replace sodium sulfate and soda ash, thereby protecting the pool wall from erosion. The temperature required for the melting of cullet is lower than that of the batch material. The melted cullet can quickly surround the batch material, and the broken particles of the batch material are controlled in time, which reduces the erosion damage of the broken particles to the inner wall of the kiln and effectively extends the service life of the kiln. The chemical composition of the kiln slag and cullet is basically consistent with the raw materials required by the present invention.

[0017] In the batch material of the present invention, SiO 2 In glass, [SiO 4 ] tetrahedral structure as a glass former, SiO 2 The content of SiO has a crucial influence on both the degree of polymerization of the glass network and the type of short-range ordered structure. 2 It is used to increase the melting temperature, viscosity, chemical stability, thermal stability and mechanical strength of glass, and at the same time it can reduce the thermal expansion coefficient and density of glass; appropriately increase SiO 2 The content is beneficial to slow down the tendency of high temperature crystallization.

[0018] Al 2 O 3 It is an intermediate oxide of glass and mainly forms [A1O 4 ]tetrahedral coordination structure, for Al-rich 2 O 3 The composition will produce some [A1O 6 ] coordination structure, this part [A1O 6 ] cannot enter the glass network structure, so it will increase the viscosity of the glass and increase the crystallization activation energy, which is beneficial to the precipitation and control of microcrystals in the glass; and Al 2 O 3 The stability and mechanical properties of the glass can be improved. 2 and Al 2 O 3 It is the former of the glass network and the key to obtaining basic glass.

[0019] CaO is an invariant oxide outside the glass structure network. It is mainly used as a stabilizer, that is, it increases the chemical stability and mechanical properties of glass. The CaO content in kiln slag accounts for a large proportion. During the heating process after the kiln slag is evenly mixed with cullet and batch materials and put into the kiln, the slag and cullet will melt before the batch materials and react with the CO2 not discharged in the kiln. 2 Reaction to generate CaCO 3 , which can accelerate the clarification of the entire glass liquid. CaO helps to improve the crystallization tendency of glass and can also effectively improve the density and hardness of glass. This is because as CaO replaces SiO 2 The amount of CaSiO increases and the precipitation 3 The amount of crystals gradually increases, that is, CaO+SiO 2 →CaSiO 3 The CaO in the kiln slag will decompose first and replace part of the SiO in the batch. 2 , so that the precipitated CaSiO 3 The amount of [Ca(FeCr 2 O 4 )SiO 3 ]The formation of the crystal phase further improves the wear resistance of the microcrystalline glass of the present invention.

[0020] MgO is an oxide outside the glass structure network and can depolymerize large tetrahedrons, thereby reducing the viscosity of the glass. The present invention uses part of MgO to replace part of CaO, which can slow down the hardening speed during the glass forming process, reduce the tendency of glass crystallization, and improve the compressive strength of the glass. In microcrystalline glass, the influence of MgO on the overall glass is similar to that of CaO and SiO. 2 is closely related to its content.

[0021] Na 2 O is an oxide outside the network, and the sodium ions reside in the holes of the glass structure network. 2 O can provide free oxygen to increase the O / Si ratio in the glass structure and cause bond breaking, thereby reducing the viscosity of the glass and making it easier to melt. It is a good solvent for glass. 2 O can reduce the thermal expansion coefficient of glass and improve the thermal stability, chemical stability and mechanical properties of glass. 2 The higher the O content, the lower the melting point of the mixture. + It leads to low degree of polymerization and rapid phase separation, thus promoting nucleation, accelerating the diffusion rate of ions, and facilitating crystal growth.

[0022] K 2 The role of O in glass and Na 2 O is similar, in addition K 2O can reduce the crystallization tendency of glass, increase the driving force of crystallization, promote crystallization, thereby reducing the crystallization temperature, reducing the temperature difference between nucleation and crystallization, increasing the transparency and gloss of glass, and realizing the one-step melting heat treatment to obtain the microcrystalline glass of the present invention. Because the content of alkaline oxides in the kiln slag is insufficient, alkaline oxide Na is added to the cullet and batch materials. 2 O.K 2 O, TiO in kiln slag 2 React with alkaline oxides to make part of TiO 2 Composition [TiO 4 ]tetrahedron, [TiO 4 ]tetrahedron will react with [SiO 4 ]The tetrahedron undergoes substitution to form a -Si-O-Ti- mixed skeleton, which can effectively increase the chemical stability of the glass.

[0023] Cr 2 O 3 It is beneficial to the phase separation and crystallization of glass, forming micro-ceramic glass with excellent performance. 3+ It is a high-field transition metal ion. In the separated glass, it is enriched in the microphase with greater coordination ability, that is, in the low-viscosity calcium-rich phase. As the degree of phase separation increases, Ca 2+ With Cr 3+ Enriched together, Cr 3+ While attracting non-bridging oxygen, it will give a significant ordering effect to the surrounding cations, making it easy for the chromium-rich phase to precipitate in the form of a certain compound, becoming a non-uniform nucleation center and inducing crystallization. 2 O 3 Can change the viscosity and activation energy of kiln slag glass system, Cr 3+ The ions combine with non-bridging oxygen to form Cr-O bonds, which increases the wear resistance of the glass. Cr, as a glass network structure former, increases the complexity of the glass structure, and the crystallization mechanism changes from surface crystallization to overall crystallization. In addition, Cr 2 O 3 With CaSiO 3 The following reaction will also occur: Cr 2 O 3 +CaSiO 3 →Ca(Cr 2 O3)SiO 3 , so Cr 2 O 3 It can accelerate the formation of chromium iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] crystal nuclei, resulting in the production of a large amount of wollastonite crystal phase in the glass.

[0024] B 2 O 3 It helps to melt the glass powder, lower the melting temperature of the glass, improve the crystallization ability of the glass, reduce the expansion coefficient of the glass, and improve the mechanical strength and wear resistance of the base glass. In order to increase the strength of the glass, prevent the base glass from softening before reaching the crystallization temperature, and lower the crystallization temperature of the crystal phase, B is introduced 2 O 3 Improve the crystallization performance of glass-ceramics. 2 O 3 It can also improve the flexural strength and surface gloss of glass-ceramics.

[0025] NaOH is used as a binder in the batch material of the present invention. As the amount of NaOH added increases, the critical pressure value of the densification of the glass batch material decreases. The main component of the glass raw material is SiO 2 , NaOH is an alkaline oxide, and the two react chemically under 0.2-0.31MPa and hydrothermal synthesis conditions: SiO 2 +NaOH→Na 2 SiO 3 +H 2 O, thereby acting as a binder.

[0026] Fe 2 O 3 It is introduced into the glass as a network external body, does not participate in the formation of the glass network, exists in the gaps of the glass structure, and can effectively improve the chemical stability of the glass. Both the furnace slag and the cullet contain very small amounts of Fe 2 O 3 Therefore, Fe was selected as the nucleating agent in the batch. 2 O 3 This can reduce the types of raw materials and reduce economic costs; in addition, the Fe in kiln slag and cullet 2 O 3 The component content is not enough to meet the needs of the overall microcrystalline glass, so an appropriate amount of Fe is added to the batch. 2 O 3 , which can reduce the contents of Al-O-Al, Al-O-Si and Si-O-Si in the system of the present invention, and increase the contents of Fe-O-Si and Fe-O-Al, so that [SiO 4 ] and [AlO 4 ] content is decreasing, [FeO 4 ] content increases, which strengthens the network structure of the glass system and improves its chemical stability. 2 O 3 and Fe 2 O 3In the present invention, it is used as a composite crystal nucleating agent because the furnace slag and cullet contain Fe 2 O 3 So choose Cr 2 O 3 and Fe 2 O 3 It is a crystal nucleating agent. The addition of crystal nucleating agent can significantly reduce the viscosity of glass liquid and improve its fluidity, thereby reducing the lowest temperature at which glass liquid can flow freely, that is, the melting temperature. 2 O 3 Can reduce the viscosity of glass, while Cr 2 O 3 Belongs to the transition metal oxides, can also provide O 2- , so that the complex silicon oxygen complex ion group disintegrates and the viscosity flow activation energy of the glass liquid is reduced. Therefore, a small amount of Cr 2 O 3 It can also reduce the viscosity of molten glass. 2 O 3 The addition of increases the number of oxygen atoms in the glass. At this time, the network external ion Fe 3+ The effect on density increase is greater than the effect of density decrease caused by network breakage, expansion and volume increase, and the thermal expansion coefficient is reduced. 2 O 3 The addition of can increase the acid and alkali resistance of glass, and the following reactions occur when it is corroded:

[0027] Negative electrode: 2Fe 3+ +4 e- =2Fe 2+

[0028] Positive electrode: 2H 2 O+O 2 +4 e- =4OH -

[0029] Fe 2 O 3 Adding it to the glass system can prevent water molecules from entering the glass network structure, slow down the dissolution rate of glass in water, and improve the acid and alkali resistance and wear resistance of the glass.

[0030] Fe 2 O 3 It has a strong depolymerization effect on the glass network, making the structure loose. 2 O 3 Separation first occurs in the glass phase, forming smaller amorphous phase particles, which are evenly distributed in the glass phase. When Si-rich phase is formed, CaSiO is precipitated. 3 , CaSiO 3Phase separation reduces the crystallization activation energy and crystallization temperature. When the iron content is high, the crystal is distorted and the following reaction occurs: Ca(Cr 2 O 3 )SiO 3 +Fe 2 O 3 →[Ca(FeCr 2 O 4 )SiO 3 ]+FeO, thereby increasing the energy of crystal formation and increasing the activation energy.

[0031] Nd 2 O 3 With Na in broken glass 2 SO 4 The components play a coordinating role, Nd 2 O 3 At the same time, it can also improve the strength of glass and increase the activation energy of crystallization. 2 SO 4 Components and SiO in batches 2 , CaO reacts as follows: Na 2 SO 4 +CaCO 3 +2SiO 2 →CaSiO 3 +Na 2 SiO 3 +CO 2 +SO 3 ; Generated SO 3 Continue to decompose, the following reaction occurs: 2SO 3 →2SO 2 +O 2 The generated oxygen may oxidize the reducing medium to generate oxides, and the reaction is as follows: 2 +C→CO 2 These reactions release a large amount of gas, and bubbles rise continuously, giving the molten glass a rapid stirring, forming a phenomenon similar to boiling, promoting the homogenization of the glass and promoting the large number of bubbles of different sizes contained in it to gather together, thereby accelerating the homogenization and clarification process of the glass. 3+ The radius is too large to enter the silicon-oxygen structure of the glass, but is outside the network structure. However, its ionic charge is high, the field is strong, and it has a strong accumulation effect, making the glass structure tight. When the glass is heat treated, it can hinder the orderly rearrangement of the structure and increase crystallization.

[0032] In a second aspect, the present invention also provides a method for preparing the above-mentioned chromium iron wollastonite glass-ceramics, wherein the components of the chromium iron wollastonite glass-ceramics are mixed uniformly and poured into a glass melting furnace, melted at high temperature into a uniform glass liquid, and a protective gas (N) is continuously flowed into the melting furnace. 2 and H 2 ) in a tin bath, the glass liquid floats on the surface of the tin liquid with a relatively high density. Under the action of gravity and surface tension, the glass liquid spreads and flattens on the tin liquid surface to form a glass liquid with smooth upper and lower surfaces. After cooling, it is led to the transition roller table. The rollers of the roller table rotate to pull the glass ribbon out of the tin bath, and then enter the annealing kiln for annealing. After annealing, it is rapidly cooled. The mother glass obtained by cutting is then heat-treated in a one-step method to simultaneously nucleate and crystallize it, and finally annealed to obtain chromium-iron wollastonite glass-ceramics.

[0033] Preferably, the melting temperature of each component of the chromium-iron-wollastonite glass-ceramics in the glass melting furnace is 1000-1300°C.

[0034] Preferably, the annealing temperature after entering the annealing furnace from the tin bath is 500-600°C; the annealing temperature in the one-step heat treatment is 400-500°C.

[0035] Preferably, the one-step heat treatment refers to heating the matrix glass to 950-1050° C. at a heating rate of 3-5° C. / min for nucleation and crystallization.

[0036] The nucleation crystallization temperature is selected to be 950-1050℃, mainly due to Cr 2 O 3 The melting temperature is 1000℃. When the crystallization temperature is lower than this, it will affect Cr 2 O 3 The present invention adopts a one-step heat treatment process, the main purpose of which is to obtain more predetermined chromium iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]Crystal structure and properties, the microcrystalline glass prepared by nucleation and crystallization of the molten glass matrix has the advantages of uniform composition, few micropores, small size change, etc., and the float forming process of ordinary glass can also be used to prepare products of complex shapes, which is convenient for mechanized production.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. The present invention rationally designs the components of glass-ceramics to make it present chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3] crystal phase, NaOH is the binder in the batch material of the present invention, which can effectively bind the kiln slag, broken glass and batch material together; using Cr 2 O 3 and Fe 2 O 3 As a composite nucleating agent, chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] Provide nucleation sites for the growth of crystals; the addition of nucleating agents can significantly reduce the viscosity of the glass liquid and improve its fluidity, thereby lowering the lowest temperature at which the glass liquid can flow freely, namely the melting temperature, and increasing the solubility in the glass, thereby promoting the precipitation of the microcrystalline glass phase, and ultimately preparing environmentally friendly wear-resistant chromium-iron wollastonite microcrystalline glass with high mechanical strength, good chemical corrosion resistance, unique optical properties and other excellent properties.

[0039] 2. The present invention adopts a one-step heat treatment process, selecting Cr 2 O 3 and Fe 2 O 3 When used as a nucleating agent, the chromium iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The driving force of the main crystal phase nucleus can greatly promote the nucleation and crystallization of the glass, reduce the nucleation and crystallization temperature, and complete the two processes of grain precipitation and growth at the same time. It is more economical, energy-saving and flexible than the two-step heat treatment process. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is the XRD spectrum of the glass-ceramics prepared in Example 1 of the present invention.

[0041] Figure 2 This is the XRD spectrum of the glass-ceramics prepared in Example 2 of the present invention.

[0042] Figure 3 This is the XRD spectrum of the glass-ceramics prepared in Example 3 of the present invention.

[0043] Figure 4 This is the XRD spectrum of the glass-ceramics prepared in Example 4 of the present invention.

[0044] Figure 5 This is the XRD spectrum of the glass-ceramics prepared in Example 5 of the present invention.

[0045] Figure 6 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 1 of the present invention.

[0046] Figure 7 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 2 of the present invention.

[0047] Figure 8 This is the XRD spectrum of the glass-ceramics prepared in Comparative Example 3 of the present invention.

[0048] Fig. 9 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 4 of the present invention.

[0049] Fig.10 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 5 of the present invention.

[0050] Fig.11 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 6 of the present invention.

[0051] Fig.12 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 7 of the present invention.

[0052] Fig.13 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 8 of the present invention.

[0053] Fig.14 It is the XRD spectrum of the microcrystalline glass prepared in Comparative Example 9 of the present invention. DETAILED DESCRIPTION

[0054] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0055] Examples 1-5 and Comparative Examples 1-9

[0056] The 3.3 mm thick environmentally friendly wear-resistant ferrochrome wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]The formula of the microcrystalline glass material is shown in Table 1; the formula of the microcrystalline glass material of Comparative Examples 1-9 is the same as that of Example 1.

[0057] Table 1 Glass-ceramic material of Examples 1-5

[0058] Components Example 1 Example 2 Example 3 Example 4 Example 5 Kiln slag % 13 11 12 14 15 Broken glass% 38 35 40 45 42 Mixing material% 49 54 48 41 43 total% 100％ 100％ 100％ 100％ 100％

[0059] Among them, the material formula of the kiln slag in Examples 1-5 and Comparative Examples 1-6 and Comparative Example 8 is shown in Table 2, the material formula of the kiln slag in Comparative Example 7 is shown in Table 3, and the material formula of the kiln slag in Comparative Example 9 is shown in Table 4; the material formula of the cullet in Examples 1-5 and Comparative Examples 1-7 and 9 is shown in Table 5, and the material formula of the cullet in Comparative Example 8 is shown in Table 6.

[0060] Table 2 Kiln slag material formula of Examples 1-5 and Comparative Examples 1-6 and Comparative Example 8

[0061] <![CDATA[SiO 2 ]]> <![CDATA[Al 2 THE 3 ]]> CaO MgO <![CDATA[K 2 The]]> <![CDATA[Na 2 The]]> <![CDATA[TiO 2 ]]> <![CDATA[Fe 2 THE 3 ]]> <![CDATA[P 2 THE 5 ]]> 30.25％ 17.10％ 38.34％ 6.99％ 2.45％ 2.54％ 2.18％ 0.11％ 0.04％

[0062] Table 3 Kiln slag material of comparative example 7

[0063] <![CDATA[SiO 2 ]]> <![CDATA[Al 2 THE 3 ]]> CaO MgO <![CDATA[K 2 The]]> <![CDATA[Na 2 The]]> FeO MnO <![CDATA[CaF 2 ]]> 46.8％ 14.3％ 25.2％ 5.8％ 1.9％ 2.9％ 0.25％ 1.85％ 1％

[0064] Table 4 Kiln slag material of comparative example 9

[0065] <![CDATA[SiO 2 ]]> <![CDATA[Al 2 THE 3 ]]> CaO MgO <![CDATA[K 2 The]]> <![CDATA[Na 2 The]]> <![CDATA[TiO 2 ]]> <![CDATA[Fe 2 THE 3 ]]> <![CDATA[P 2 THE 5 ]]> 30.29％ 17.10％ 38.34％ 6.99％ 2.45％ 2.54％ 2.18％ 0.11％ 0

[0066] Table 5 Broken glass material of Examples 1-5 and Comparative Examples 1-7 and 9

[0067] <![CDATA[SiO 2 ]]> <![CDATA[Al 2 THE 3 ]]> CaO MgO <![CDATA[K 2 The]]> <![CDATA[Na 2 The]]> <![CDATA[Nd 2 THE 3 ]]> <![CDATA[Fe 2 THE 3 ]]> <![CDATA[Na 2 SO 4 ]]> 61.20％ 16.50％ 3.52％ 2.95％ 2.45％ 11.45％ 1.84％ 0.05％ 0.04％

[0068] Table 6 Broken glass material of comparative example 8

[0069] <![CDATA[SiO 2 ]]> <![CDATA[Al 2 THE 3 ]]> CaO MgO <![CDATA[K 2 The]]> <![CDATA[Na 2 The]]> ZrO2 <![CDATA[Fe 2 THE 3 ]]> C powder 61.5 15.2 4.42 2.62 2.35 12.45 1.28 0.08 0.1

[0070] The 3.3 mm thick environmentally friendly wear-resistant ferrochrome wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]The formula of the batch materials in the microcrystalline glass is shown in Tables 7-8; the formula of the batch materials in Comparative Examples 6-9 is the same as that in Example 1.

[0071] Table 7 Material formula of the batch materials of Examples 1-5

[0072] Components Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[SiO 2 %]]> 42 41 41.5 45 40 <![CDATA[Al 2 THE 3 %]]> 13.5 13.5 14 15 13 CaO% 24 25 23.55 23 23 MgO% 2.1 1.9 2.5 1.8 2 <![CDATA[Na 2 O%]]> 5 4.5 4.4 4 4.5 <![CDATA[K 2 O%]]> 3.5 3 4 3 3 NaOH% 2.5 3 3 2 3 <![CDATA[Fe 2 THE 3 %]]> 0.75 0.65 0.55 0.6 0.5 <![CDATA[Cr 2 THE 3 %]]> 2 2.45 2.5 2 4 <![CDATA[B 2 THE 3 %]]> 3.5 3 2.5 2.5 4 <![CDATA[Nd 2 THE 3 %]]> 1.15 2 1.5 1.1 3 total% 100％ 100％ 100％ 100％ 100％

[0073] Table 8 Material formula of the batch materials of comparative examples 1-5

[0074] Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 <![CDATA[SiO 2 %]]> 44.75 42.75 44.5 45.5 45.5 <![CDATA[Al 2 THE 3 %]]> 13.5 13.5 13.5 13.5 13.5 CaO% 24 24 24 24 24 MgO% 2.1 2.1 2.1 2.1 2.1 <![CDATA[Na 2 O%]]> 5 5 5 5 5 <![CDATA[K 2 O%]]> 3.5 3.5 3.5 3.5 0 NaOH% 2.5 2.5 0 2.5 2.5 <![CDATA[Fe 2 THE 3 %]]> 0 0 0.75 0.75 0.75 <![CDATA[Cr 2 THE 3 %]]> 0 2 2 2 2 <![CDATA[B 2 THE 3 %]]> 3.5 3.5 3.5 0 3.5 <![CDATA[Nd 2 THE 3 %]]> 1.15 1.15 1.15 1.15 1.15 total% 100％ 100％ 100％ 100％ 100％

[0075] The preparation methods of the chromium iron wollastonite glass-ceramics of Examples 1-5 and Comparative Examples 1-5 and Comparative Examples 7-8 are as follows: the components of the chromium iron wollastonite glass-ceramics are uniformly mixed and poured into a glass melting furnace, melted at a high temperature of 1200° C. into a uniform glass liquid, and a protective gas (N 2 and H 2) in a tin bath, the glass liquid floats on the surface of the tin liquid with a relatively high density. Under the action of gravity and surface tension, the glass liquid spreads and flattens on the tin liquid surface to form a glass liquid with smooth upper and lower surfaces. After cooling, it is led to the transition roller table. The rollers of the roller table rotate, pulling the glass ribbon out of the tin bath and entering the annealing kiln for annealing at 550°C. After annealing, it is rapidly cooled and then cut to obtain the mother glass. Subsequently, the mother glass is heated to 1000°C at a heating rate of 4°C / min for nucleation and crystallization at the same time, and finally annealed at 450°C in the annealing kiln to obtain chromium-iron wollastonite microcrystalline glass.

[0076] Comparative Example 6 adopts a two-step heat treatment process, specifically: the mother glass prepared by the float glass process adopts a two-step heat treatment system, the temperature is increased at a heating rate of 4°C / min, the temperature is increased to 650°C for nucleation, and the nucleation time is 180 minutes; the temperature is increased at a heating rate of 5°C / min, the temperature is increased to 900°C for crystallization, and the crystallization time is 60 minutes. After annealing at 450°C, a finished microcrystalline glass is obtained.

[0077] The water absorption and density of the glass-ceramics prepared in Examples 1-5 and Comparative Examples 1-9 were tested with reference to the national standard GB / T9966.3-2001 "Natural facing stone test methods: bulk density, true density, true porosity, water absorption test methods". The test steps are: put the sample in an oven at 105°C and dry it to constant weight, place it in a drying oven and cool it to room temperature, and weigh its mass m 0 ; Then put the sample into distilled water at room temperature and soak it for 48 hours. Take it out and gently wipe the surface moisture of each sample with a wrung wet towel, then weigh it immediately and record the mass m 1 ; Place the sample in a basket and put it into distilled water, and weigh its mass m in water 2 . Calculate the water absorption and density of the sample. The calculation formula is: Water absorption Ev = (m 1 -m 0 ) / m 0 ×100%, density ρ=ρ w m 0 / (m 2 -m 0 ), where ρ w : Density of distilled water at room temperature, g.cm 3 .

[0078] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3]The method for measuring the viscosity of microcrystalline glass is: use the RTW-10-02 high-temperature rotary viscometer to measure the "temperature-viscosity" curve of the water-quenched microcrystalline glass sample. Specifically: dry 200g of microcrystalline glass sample, place it in a molybdenum crucible in the viscometer heating furnace and heat it to 1500℃. After keeping it warm for 2 hours, use a molybdenum rod probe to detect the liquid level, then replace the molybdenum rod probe with a viscosity probe, raise the furnace body to the liquid level, and then raise it 30mm to ensure that the viscosity probe is completely immersed in the liquid. When the angular variable of the viscometer is basically constant, start measuring the constant temperature viscosity of the sample at 1500℃; after adjusting the process parameters, let the furnace temperature begin to drop, and continue to measure the cooling viscosity. When the angular variable of the viscometer reaches 80%, stop measuring and measure the data.

[0079] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 The acid and alkali resistance of microcrystalline glass is tested in accordance with the building materials industry standard JC / T 872-2000 "Test Method for Acid and Alkali Resistance of Microcrystalline Glass for Architectural Decoration". The test steps are as follows: First, place the microcrystalline glass sample in an oven at 110°C and dry it to constant weight, then place it in a drying oven and cool it to room temperature, and weigh its mass m 0 ; Then immerse the sample in 30wt.%HCl and 10wt.%NaOH solution for 48h and then take it out; After repeatedly rinsing the surface of the sample, put it in an oven to dry to constant weight, and then weigh its mass m 1 . Calculate the 48h mass loss rate of the sample K = (m 0 -m 1 ) / m 0 ×100%.

[0080] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 The glossiness of glass-ceramics is tested in accordance with the industry standard JC / T 872-2000 “Determination of glossiness of glass-ceramics for architectural decoration”, and a 60° incident angle probe is used for measurement.

[0081] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3The method for determining the Vickers hardness of microcrystalline glass is as follows: cut the microcrystalline glass into 14mm×1.5mm thin slices as test specimens, and test them with a micro / Vickers hardness tester TUKON2100. After maintaining a load of 100g for 20s, remove the load and an indentation will be left on the surface of the specimen; measure the length of the diagonal of the indentation and calculate the surface area of ​​the indentation, find the load stress per unit area, and substitute it into the following formula to obtain the Vickers hardness value. Measure each specimen 5 times and take the average value.

[0082] Hv=P / S=1.8544P / d 2

[0083] Where, Hv: Vickers hardness value (N / mm 2 ); P: load (N); S: indentation surface area (mm) 2 ; d: average length of the indentation diagonal (mm).

[0084] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]The compressive strength test method of glass-ceramics is as follows: Use the WEP-600 hydraulic universal testing machine to test the compressive strength of glass-ceramics samples. The test is mainly based on GB / T9966.1-2001. Put the φ50mm×50m cylindrical sample into the fixture of the universal testing machine and measure the pressure value. The calculation formula for the compressive strength of the sample is: P=F / S, where P: compressive strength (MPa); F: sample destructive force load (N); S: sample force surface area (mm 2 ).

[0085] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3]The wear resistance test method of microcrystalline glass is as follows: the wear resistance of microcrystalline glass samples is tested using a JM45-4I Doray wear tester. Its working principle is: the microcrystalline glass sample is ground for a specified time, number of revolutions and a certain pressure is applied to the sample on the wear tester, and its mass before and after grinding is weighed, and the mass wear per unit area is calculated; the flow rate of the abrasive is constant. The samples are clamped on four fixtures respectively, and the wear surface of the glass is close to the grinding disc. During work, the sample rotates at a speed of 45rpm under the action of the fixture, and the column also rotates at a speed of 45rpm at the same time; in this way, the sample is equivalent to rotating and revolving at the same time. The abrasive flows onto the grinding disc through the funnel at a speed of 20g±5g / min, and under the action of its own centrifugal force, it gradually moves from the inside to the outside, and finally falls into the abrasive basin for recovery. In this test, 130 mesh English sand and 100 mesh silicon carbide are mixed in a mass ratio of 2:1 as abrasives, and the wear time is set to 30min.

[0086] The 3.3 mm thick chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]The performance test results of microcrystalline glass are shown in Tables 9-10.

[0087] Table 9 Chrome ferrostalite [Ca(FeCr 2 O 4 )SiO 3 ]Performance test results of glass-ceramics

[0088] Test items Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[Density / Kg / m 3 > 2.612 2.625 2.629 2.613 2.627 Water absorption / % 0 0.1 0.05 0.05 0.15 Viscosity / ℃ 1012 1010 1008 1015 1016 <![CDATA[Coefficient of thermal expansion / ×10 -7 / °C]]> 45 51 55 48 53 Acid resistance / % 0.06 0.10 0.12 0.09 0.08 Alkali resistance / % 0.01 0.02 0.01 0.01 0.02 Glossiness / ° 95 94 92 91 92 <![CDATA[Vickers hardness / N / mm 2 > 6.79 6.66 6.74 6.64 6.71 Compressive strength / MPa 526 498 486 488 477 <![CDATA[Wear amount / g / m 2 > 85 90 89 82 94

[0089] Table 10 Chromium ferrostalcite [Ca(FeCr 2 O 4 )SiO 3 ]Performance test results of glass-ceramics

[0090]

[0091]

[0092] From the data comparison of Tables 9-10, it can be seen that compared with Example 1, the density of the microcrystalline glass prepared in Comparative Example 1 is increased and the wear resistance is reduced. This is mainly due to the fact that Fe 2 O 3 and Cr 2 O 3 The addition of increases the number of oxygen atoms in the glass. At this time, the network external ion Fe 3+ The effect on density increase is greater than the effect of density decrease caused by network breakage, expansion and volume increase. 2O 3 Can change the viscosity and activation energy of kiln slag glass system, Cr 3+ The ions combine with non-bridging oxygen to form Cr-O bonds, which increases the wear resistance of the glass.

[0093] It can also be seen that compared with Example 1, the acid and alkali resistance of the microcrystalline glass prepared in Comparative Example 2 is reduced, which is mainly due to the Fe 2 O 3 The addition of can increase the acid and alkali resistance of glass. When glass is corroded, the reaction is as follows:

[0094] Negative electrode: 2Fe 3+ +4 e- =2Fe 2+

[0095] Positive electrode: 2H 2 O+O 2 +4 e- =4OH -

[0096] Fe 2 O 3 Adding it to the glass system can prevent water molecules from entering the glass network structure, slow down the dissolution rate of glass in water, and improve the acid and alkali resistance and wear resistance of the glass.

[0097] In addition, compared with Example 1, various properties of the glass prepared in Comparative Example 3 are reduced. This is mainly because NaOH, as a binder in the batch of microcrystalline glass materials, can play a bonding role. Without its addition, the raw materials will be clarified and homogenized unevenly in the kiln, and the gloss of the produced glass will be poor.

[0098] Compared with Example 1, the expansion coefficient of the glass prepared in Comparative Example 4 is increased and the glossiness is reduced. This is mainly due to the fact that B 2 O 3 It helps to melt the glass powder, lower the melting temperature of the glass, improve the crystallization ability of the glass, reduce the expansion coefficient of the glass, and improve the mechanical strength and chemical stability of the base glass; at the same time, B 2 O 3 It can also improve the surface gloss of glass-ceramics.

[0099] Compared with Example 1, the mechanical strength of the glass prepared in Comparative Example 5 is reduced, mainly due to K 2 O can reduce the thermal expansion coefficient of glass and thus increase the mechanical strength of glass. 2+ The addition of enhances the gloss of the glass.

[0100] Compared with Example 1, the density and viscosity of the glass prepared in Comparative Example 6 increase. This is mainly because the two-step heat treatment process separates nucleation and crystallization, resulting in the contact between the grains becoming gradually tighter as the grains grow, which in turn leads to an increase in the density of the glass. The increase in density will lead to a decrease in the acid and alkali resistance of the microcrystalline glass and affect the chemical stability of the glass; the increase in viscosity will reduce the rising speed of bubbles during the clarification process of the float process, affect the clarification of the glass liquid, and further affect the overall appearance quality of the glass.

[0101] Compared with Example 1, the alkali resistance of the glass prepared in Comparative Example 7 is reduced, mainly due to the TiO 2 The components can undergo the following chemical reactions: Ti+4OH - +(n-2)H 2 O→TiO 2 ·nH 2 O,TiO 2 ·nH 2 O is deposited on the glass surface, which can further prevent the glass from being corroded by alkali solution. Compared with Example 1, the glossiness of the glass prepared in Comparative Example 8 is reduced, mainly due to the Na 2 SO 4 The glass clarification effect is better than C powder, and the Na in the cullet 2 SO 4 The reaction discharges a large amount of gas, which accelerates the homogenization and clarification process of the glass liquid and enhances the gloss of the finished glass product.

[0102] Compared with Example 1, the hardness of the glass prepared in Comparative Example 9 is reduced, mainly due to the P in the kiln slag. 2 O 5 It is easy to oxidize, which can accelerate the melting of cullet and batch materials. 2 O 5 The addition of 2 O 3 The following reaction occurs: 2Si-O-B+POP→2P-O-B+Si-O-Si, which increases the degree of polymerization of the glass network structure and improves the hardness of the glass.

[0103] The chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3] Qualitative or semi-quantitative analysis of the physical phase of microcrystalline glass. By analyzing the position, relative intensity and number of diffraction peaks in the diffraction spectrum, the substances contained in the sample can be determined. The test method is as follows: grind the microcrystalline glass sample into a powder of less than 200 mesh, and use the D / MAX-II rotating target X-ray diffraction analyzer of Rigaku Electric Co., Ltd. to analyze the physical phase of microcrystalline glass; experimental conditions: target material is Cu target; Kα line radiation; tube voltage is 35kV; tube current is 30mA; scanning speed is 3° / min; scanning angle is 5-90°; temperature is room temperature. Data processing: Scan the sample with an X-ray diffractometer, and obtain its X-ray diffraction spectrum on the recorder.

[0104] The 3.3 mm thick chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] XRD detection spectrum of glass-ceramics is as follows Figure 1-14 shown.

[0105] The XRD detection spectrum shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The crystal phase spectrum of the glass-ceramics has a high reproducibility, and the intensity of the main absorption band is increased compared with the comparative example, which shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]The crystallization degree of the crystalline phase continues to increase. 2 O 3 It helps the overall crystallization of glass and easily accelerates the precipitation of crystals; Fe 2 O 3 The energy of crystal formation is increased, and the activation energy is increased. In the microcrystalline glass structure prepared by the present invention, there is an ultra-strong crystal phase peak, which makes the glass have high mechanical properties, good chemical corrosion resistance, wear resistance and good gloss.

[0106] In addition, compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 1 does not contain chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] crystal phase peak. This is mainly due to the presence of Cr 2 O 3 and Fe 2 O 3 As a composite nucleating agent, the following reaction will occur: Cr 2 O 3 +CaSiO3 →Ca(Cr 2 O 3 )SiO 3 , Ca(Cr 2 O 3 )SiO 3 +Fe 2 O 3 →[Ca(FeCr 2 O 4 )SiO 3 ]+FeO, so no Cr is added 2 O 3 and Fe 2 O 3 The glass-ceramics prepared in Comparative Example 1 contain no chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]Formation of crystal phase.

[0107] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 2 contains a very small amount of chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] crystal phase peak. This is mainly due to the Fe 2 O 3 and Fe in the batch 2 O 3 The following reaction occurs when Ca(Cr 2 O 3 )SiO 3 +Fe 2 O 3 →[Ca(FeCr 2 O 4 )SiO 3 ]+FeO, causing it to separate first in the glass phase, forming smaller amorphous phase particles, which are evenly distributed in the glass phase, thus forming a small amount of [Ca(FeCr 2 O 4 )SiO 3 ] Crystal phase.

[0108] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 3 shows that the crystal phase is disordered, and chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The crystal phase peak does not exist. This is mainly because NaOH is used as a binder in the glass-ceramic batch. If NaOH is not added, it is easy to cause uneven mixing of the glass raw materials, thus generating mixed-phase glass-ceramics.

[0109] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 4 shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The crystal phase peak intensity is low and the number is small. This is mainly due to the fact that B 2 O 3 It can improve the crystallization ability of glass, reduce the crystallization temperature of the crystallization phase, and improve the crystallization performance of microcrystalline glass.

[0110] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 5 shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The number of crystal phase peaks is small and the distribution is not concentrated enough. This is mainly due to the fact that K 2 O can reduce the crystallization tendency of glass, increase the driving force of crystallization, promote crystallization, thereby reducing the crystallization temperature and narrowing the temperature difference between nucleation and crystallization.

[0111] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 6 shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The number of crystal phase peaks remains unchanged, but the intensity of the crystal phase peaks decreases. This is mainly because Comparative Example 6 adopts a two-step heat treatment system, which performs nucleation and crystallization at different temperatures and a certain heating rate, which takes a long time. The crystal nucleus formation time is also longer than that of the one-step heat treatment system, which will affect the precipitation and growth of grains.

[0112] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 7 shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The number of crystal phase peaks is small, which is mainly due to the Fe 2 O 3 The addition of is beneficial to glass phase separation, nucleation and crystal growth.

[0113] Compared with the XRD spectrum of the glass-ceramics prepared in Example 1, the XRD spectrum of the glass-ceramics prepared in Comparative Example 8 has a disordered crystal phase and no chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] crystal phase peak. This is mainly due to the Nd 3+The radius is too large to enter the silicon-oxygen structure of the glass, but is outside the network structure. However, its ionic charge is high, the field is strong, and it has a strong accumulation effect, making the glass structure tight. When the glass is heat treated, it can hinder the orderly rearrangement of the structure and increase crystallization.

[0114] Compared with the XRD pattern of the glass-ceramics prepared in Example 1, the XRD pattern of the glass-ceramics prepared in Comparative Example 9 shows that the chromium-iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ] The crystal phase precipitation time is prolonged. This is mainly due to the P in the kiln slag. 2 O 5 It is easy to oxidize, which can accelerate the melting of cullet and batch materials and accelerate the chromium iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]Precipitation of crystal phase.

[0115] Through the above experiments, it can be seen that the design of the material formula and process in glass production has an important influence on the comprehensive properties of glass forming ability, crystallization mechanism, crystal phase composition, etc. The present invention uses kiln slag, cullet and batch materials as raw materials, adopts a melting one-step heat treatment process to prepare microcrystalline glass, and the prepared chromium iron wollastonite [Ca(FeCr 2 O 4 )SiO 3 ]Microcrystalline glass has excellent properties, and its performance indicators are better than similar glasses. It has high mechanical strength, high hardness, good wear resistance, good chemical corrosion resistance, small thermal expansion coefficient, and pays attention to environmental protection. It can adapt to harsh operating environments and has good application prospects.

Claims

1. Chrome iron wollastonite glass-ceramics, It is characterized in that It includes the following components in percentage by mass: 10-15% kiln slag, 35-45% cullet and 40-55% batch material; The kiln slag includes the following components by mass percentage: SiO 2 28-32%, Al 2 O 3 16-18%, CaO 35-42%, MgO 6-8%, K 2 O 2-4%, Na 2 O 2-4%, TiO 2 1.5-3.5%, Fe 2 O 3 0.05-2%, P 2 O 5 0.03-0.05%; Cullet glass contains the following components in mass percentage: SiO 2 58-65%, Al 2 O 3 15-18%, CaO 2.5-5%, MgO 2-5%, K 2 O 2-4%, Na 2 O 10-13%, Nd 2 O 3 1-3%, Fe 2 O 3 0.03-0.08%, Na 2 SO 4 0.02-0.06%; The batch material includes the following components in mass percentage: SiO 2 40-46%, Al 2 O 3 13-16%, CaO 22-28%, MgO 1.8-3%, Na 2 O 4-5.5%, K 2 O 3-4%, NaOH 2-4%, Fe 2 O 3 0.5-0.8%, Cr 2 O 3 2-4%, B 2 O 3 2.5-4%, Nd 2 O 3 1-3%; Preparation method of chrome-iron wollastonite glass-ceramics: After uniformly mixing the components of the chrome-iron wollastonite glass-ceramics, pour the mixture into a glass melting furnace, melt the mixture at high temperature into a uniform glass liquid and flow it into a tin bath filled with a protective gas, and then enter the annealing furnace for annealing. After annealing, the mother glass obtained by cutting is subjected to a one-step heat treatment to simultaneously perform nucleation and crystallization, and finally subjected to annealing treatment to obtain the chrome-iron wollastonite glass-ceramics.

2. The chromium iron wollastonite glass-ceramics according to claim 1, It is characterized in that The invention comprises the following components in percentage by mass: 13% of kiln slag, 38% of cullet and 49% of batch material.

3. The chromium-iron-wollastonite glass-ceramics according to claim 1, It is characterized in that The kiln slag includes the following components by mass percentage: SiO 2 30.25%, Al 2 O 3 17.10%, CaO 38.34%, MgO 6.99%, K 2 O 2.45%, Na 2 O 2.54%, TiO 2 2.18%, Fe 2 O 3 0.11%, P 2 O 5 0.04%.

4. The chromium-iron-wollastonite glass-ceramics according to claim 1, It is characterized in that Cullet glass contains the following components in mass percentage: SiO 2 61.20%, Al 2 O 3 16.50%, CaO 3.52%, MgO 2.95%, K 2 O 2.45%, Na 2 O 11.45%, Nd 2 O 3 1.84%, Fe 2 O 3 0.05%, Na 2 SO 4 0.04%.

5. The chromium-iron-wollastonite glass-ceramics according to claim 1, It is characterized in that The batch material includes the following components in mass percentage: SiO 2 42%, Al 2 O 3 13.5%, CaO 24%, MgO 2.1%, Na 2 O 5%, K 2 O 3.5%, NaOH 2.5%, Fe 2 O 3 0.75%, Cr 2 O 3 2%, B 2 O 3 3.5%, Nd 2 O 3 1.15%.

6. The chromium iron wollastonite glass-ceramics according to claim 1, It is characterized in that The melting temperature of each component of chromium-iron-wollastonite glass-ceramics in the glass melting furnace is 1000-1300°C.

7. The chromium iron wollastonite glass-ceramics according to claim 1, It is characterized in that The annealing temperature after entering the annealing kiln from the tin bath is 500-600℃; the annealing temperature in the one-step heat treatment is 400-500℃.

8. The chromium iron wollastonite glass-ceramics according to claim 1, It is characterized in that One-step heat treatment refers to heating the matrix glass to 950-1050°C at a heating rate of 3-5°C / min for nucleation and crystallization.

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