CN115959830A - SiO (silicon dioxide) 2 Crystallized glass of-CaO system and method for producing same - Google Patents
SiO (silicon dioxide) 2 Crystallized glass of-CaO system and method for producing same Download PDFInfo
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- CN115959830A CN115959830A CN202111170585.8A CN202111170585A CN115959830A CN 115959830 A CN115959830 A CN 115959830A CN 202111170585 A CN202111170585 A CN 202111170585A CN 115959830 A CN115959830 A CN 115959830A
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- 239000011521 glass Substances 0.000 title claims abstract description 204
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 5
- 239000000377 silicon dioxide Substances 0.000 title claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 20
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 43
- 239000002699 waste material Substances 0.000 claims description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 27
- 239000011575 calcium Substances 0.000 claims description 27
- 229910052791 calcium Inorganic materials 0.000 claims description 27
- 239000003086 colorant Substances 0.000 claims description 20
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 description 42
- 239000008188 pellet Substances 0.000 description 27
- 239000010456 wollastonite Substances 0.000 description 24
- 229910052882 wollastonite Inorganic materials 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910008556 Li2O—Al2O3—SiO2 Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000008395 clarifying agent Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Abstract
The invention provides SiO 2 -CaO-based crystallized glass, process for producing the same, siO 2 The composition of the-CaO-based crystallized glass includes SiO 2 50.0～70.0wt％、CaO 9～22.0wt％、Al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O 1.0～6.0wt％、K 2 O 0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O 0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F 0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
Description
Technical Field
The invention relates to the technical field of crystallized glass, in particular to SiO 2 CaO-based crystallized glass which is used for exterior materials of buildings, interior materials, surface plates of furniture, surface plates of office tables, and the like, and a method for producing the same.
Background
Crystallized glass having various appearances is required for various applications (for example, exterior materials, interior materials, surface plates for furniture, and office desk plates for buildings). In order to form crystallized glass for these applications, various glass materials have been proposed. For example, in patent document 1, β -wollastonite (β -wollastonite, β -CaO. SiO. Is used 2 ) Crystallized glass is formed for the precipitation of main crystals. In patent document 2, β -wollastonite and diopside (CaO. MgO.2SiO) are used 2 ) Crystallized glass is formed for the precipitation of main crystals. In patent document 3, β -wollastonite is precipitated as a main crystal to form crystallized glass. In patent document 4, β -wollastonite and diopside are precipitated as main crystals to form crystallized glass.
Since any of the above-mentioned crystallized glasses does not contain a core-forming agent, crystals are deposited almost perpendicularly from the surface to the inside of the crystallized glass, and a crystallized glass of a so-called surface crystal type is formed. When a crystallized glass of this type is produced, a plate-like glass is produced by a method such as roll pressing, and then the plate-like glass is crystallized by heat treatment, a pattern does not appear on the surface, and thus a natural marble pattern cannot be obtained.
Therefore, when the crystallized glass article is produced, an assembly method may be used, in which a plurality of crystallized glass particles are stacked in a refractory mold and then crystallized by heat treatment. When the aggregation method is used, a plurality of crystalline glass particles can be fused to form crystallized glass. Since the crystal in the crystallized glass is limited by the shape of the crystallized glass grains, the crystal can be patterned by the existence and the direction of the crystal. Thus, a natural marble pattern can be obtained.
In addition, as the human beings continuously exploit the resources on the earth, the resources on the earth gradually decrease and face exhaustion. At the same time, as a result of the high degree of industrialization, a large amount of industrial waste is produced. If industrial waste is discarded at will, the earth is polluted, and the living environment of human beings is further deteriorated.
[ patent document 1] Japanese patent publication No. 53-39884;
[ patent document 2] Japanese patent application laid-open No. Hei 6-24768;
[ patent document 3] Japanese patent application laid-open No. 2011-136893;
[ patent document 4] Japanese patent laid-open No. 2012-197188.
Disclosure of Invention
In order to solve the above problems, the present invention provides a SiO 2 CaO-based crystallized glass and a method for producing the same. In the production of such crystallized glass, calcium-containing waste is used as a main raw material to form SiO precipitated as a main crystal of β -wollastonite 2 CaO-based crystallized glass. The crystallized glass has excellent optical, thermal, mechanical and chemical properties.
The invention provides SiO 2 CaO-based crystallized glass in which SiO is 2 The CaO-based crystallized glass comprises the following components: siO 2 2 50.0-70.0 wt% (weight percentage), caO 9-22.0 wt%, al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O 1.0～6.0wt％、K 2 O0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O 0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
In one embodiment, siO 2 The CaO-based crystallized glass further contains a colorant to form SiO of various colors 2 CaO-based crystallized glass. The colorant may comprise Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 And SnO 2 One or more of them.
The invention also provides a SiO 2 A method for producing a CaO-based crystallized glass, comprising the steps of: preparing a glass raw material from calcium-containing waste; (b) Melting and granulating the glass raw material to obtainTo a plurality of SiO 2 -CaO-system crystalline glass grains; and (c) subjecting the plurality of SiO 2 Forming and crystallizing the-CaO-based crystalline glass particles to obtain SiO 2 CaO-based crystallized glass. In one embodiment, the calcium-containing waste comprises the following components: siO 2 2 0.1～1.0wt％、CaO 18.0～30.0wt％、Al 2 O 3 0.1～0.5wt％、ZnO 20.0～30.0wt％、Na 2 O 0～2.0wt％、K 2 O 0～1.0wt％、B 2 O 3 0～1.0wt％、MgO 0～0.5wt％、Li 2 O 0.1～3.0wt％、P 2 O 5 1.0～5.0wt％、As 2 O 3 30.0～40.0wt％、Cl 0.1～1.0wt％、SO 3 0.1～1.0wt％、F 1.0～10.0wt％、Fe 2 O 3 0.01-0.2 wt% and V 2 O 5 0.1 to 1.0wt percent. In one embodiment, the method is used to fabricate the SiO 2 CaO-based crystallized glass.
In one embodiment, the glass raw material comprises the following components: siO 2 2 50.0～70.0wt％、CaO9～22.0wt％、Al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O1.0～6.0wt％、K 2 O 0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F 0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0 to 2.0wt%. In one embodiment, the glass frit composition further comprises a colorant. The colorant may comprise Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 And SnO 2 One or more of them.
Drawings
FIG. 1 is SiO 2- A process for producing a CaO-based crystallized glass.
Reference numerals: 100, a method;
102,104,106,108, 110.
Detailed Description
FIG. 1 shows SiO according to the invention 2 Method 100 for producing CaO-based crystallized glass. First, in step 102, a glass raw material is prepared using calcium-containing waste as a main raw material, and is uniformly stirred. The glass raw material comprises the following components: siO 2 2 50.0-70.0 wt% (weight percentage), caO 9-22.0 wt%, al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O1.0～6.0wt％、K 2 O 0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F 0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
In one embodiment, the composition of the acquisition component includes SiO 2 0.1～1.0wt％、CaO 18.0～30.0wt％、Al 2 O 3 0.1～0.5wt％、ZnO 20.0～30.0wt％、Na 2 O 0～2.0wt％、K 2 O 0～1.0wt％、B 2 O 3 0～1.0wt％、MgO 0～0.5wt％、Li 2 O 0.1～3.0wt％、P 2 O 5 1.0～5.0wt％、As 2 O 3 30.0～40.0wt％、Cl 0.1～1.0wt％、SO 3 0.1～1.0wt％、F 1.0～10.0wt％、Fe 2 O 3 0.01 to 0.2wt% and V 2 O 5 0.1-1.0 wt% of calcium-containing waste, and uniformly stirring the calcium-containing waste. Then, other raw material components are added to the uniformly stirred calcium-containing waste to prepare a glass raw material having the above-mentioned composition, and the glass raw material is uniformly stirred. In one embodiment, the glass batch composition may further include a colorant, such as Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 、SnO 2 Or a combination thereof.
At step 104, the glass raw materials are melted. The melting temperature is about 1500-1600 ℃ and the melting time is about 5-20 hours.
In step 106, the molten glass is granulated. In one embodiment, the molten glass is water-milled, dried and sieved to obtain crystalline (crystallized) glass particles having a particle size of about 3 to 7 mm.
In step 108, a plurality of crystallized glass particles are laid in a mold, and then heat-treated to crystallize and mold the glass, thereby forming crystallized glass having high mechanical strength and good acid and alkali resistance. In one embodiment, the heat treatment is performed by first heating to a temperature of about 800-900 ℃ at a heating rate of about 2-20 ℃ per minute for 0.5-4 hours; then heating to 1050-1200 deg.C at 1-10 deg.C/min for 0.5-4 hr.
Thereafter, in step 110, cooling is slowly performed to obtain SiO 2 CaO-based crystallized glass. The crystallized glass comprises the following components: siO 2 2 50.0～70.0wt％、CaO 9～22.0wt％、Al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O 1.0～6.0wt％、K 2 O0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O 0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
SiO of the invention 2 The CaO-based crystallized glass contains a plurality of components, and the functions and contents of the main components are as follows.
SiO 2 Is a component in which needle-like crystals of β -wollastonite (β -wollastonite) are precipitated from the surface of the crystalline glass toward the inside, and the content is preferably 50.0 to 70.0wt%, more preferably 55.0 to 65.0wt%. SiO 2 2 When the content of (B) is less than 50.0wt%, the glass is easily devitrified during molding and molding is difficult. On the other hand, siO 2 When the content of (2) is more than 70.0wt%, the glass melting temperature becomes high, which is disadvantageous in handling, and the fluidity at the time of heat treatment is deteriorated because the viscosity of the glass is increased.
CaO is a component of β -wollastonite, and when the content exceeds 22.0wt%, devitrification is liable to occur and molding tends to become difficult; when the amount of precipitated crystals of β -wollastonite is too large, the surface smoothness desired cannot be easily obtained. On the other hand, when the CaO content is less than 9.0wt%, the amount of precipitated β -wollastonite crystals tends to be too small, and the mechanical strength tends to be deteriorated. Therefore, the preferable content of CaO is 9.0 to 22.0wt%.
Al 2 O 3 Is a component for inhibiting devitrification. Al (aluminum) 2 O 3 When the content of (2) is more than 12.0wt%, the meltability of the glass raw material is deteriorated, and other crystals tend to be precipitated to deteriorate the fluidity at the time of heat treatment. On the other hand, al 2 O 3 When the content of (b) is less than 3.0wt%, the glass tends to be devitrified and the chemical durability tends to be lowered. Thus, al 2 O 3 The content of (B) is preferably 3.0 to 12.0 wt%.
ZnO is a component added to promote the fluidity of the glass during heat treatment. If the content of ZnO is less than 3.0wt%, no effect is obtained; on the other hand, when the content of ZnO is more than 10.0wt%, the precipitation of the β -wollastonite crystal tends to be difficult. Therefore, the content of ZnO is preferably 3.0 to 10.0 wt%.
BaO is also a component added to promote the fluidity of the glass during heat treatment, like ZnO. If the content of BaO is less than 3.0wt%, no effect is obtained; when the content of BaO is more than 10.0wt%, the amount of precipitated crystals of β -wollastonite tends to be small. Therefore, the content of BaO is preferably 3.0 to 10.0 wt%.
Na 2 O is a component added to lower the viscosity of the crystalline glass. Na (Na) 2 When the content of O is less than 1.0wt%, the viscosity of the glass increases and the meltability and the fluidity tend to deteriorate; na (Na) 2 If the content of O is more than 6.0wt%, chemical durability will be improvedThe expansion coefficient tends to become high, which is undesirable. Thus, na 2 The content of O is preferably 1.0 to 6.0 wt%.
K 2 O is a component added to lower the viscosity of the crystalline glass. K is 2 When the content of O is less than 0.5wt%, the viscosity of the glass increases and the meltability or fluidity tends to deteriorate; k is 2 When the content of O is more than 5.0wt%, the chemical durability tends to be poor and the expansion coefficient tends to be high, which is undesirable. Thus, K 2 The content of O is preferably 0.5 to 5.0wt%.
Is added with B 2 O 3 The component (A) reduces the viscosity of the crystallized glass under the condition that the thermal expansion coefficient of the crystallized glass is not changed. B is 2 O 3 When the content of (2) is less than 0.3% by weight, the fluidity of the glass tends to be poor, and surface smoothness tends not to be obtained; b 2 O 3 When the content of (2) is more than 2.0% by weight, other crystals tend to be precipitated, and the crystallized glass is difficult to obtain desired characteristics. Thus, B 2 O 3 The content of (B) is preferably 0.3 to 2.0wt%.
MgO is a component added to promote the fluidity of the glass during heat treatment. However, if the content of MgO is more than 1.0wt%, the thermal expansion coefficient increases, and the thermal characteristics of the crystallized glass deteriorate. Therefore, the MgO content is preferably 0 to 1.0wt%.
Li 2 The content of O is 0.01 to 2.0wt percent. The method for producing crystallized glass of the present invention uses calcium-containing waste containing Li as a main raw material of glass 2 O 0.1～3.0wt％。Li 2 O is constituent Li 2 O-Al 2 O 3 -SiO 2 Composition of the crystals. Small amount of Li 2 O-Al 2 O 3 -SiO 2 The crystal can lower the expansion coefficient of the crystallized glass, but if Li 2 O-Al 2 O 3 -SiO 2 When the content of the crystal is large, various physical and chemical properties of the crystallized glass are changed. Thus, li 2 The content of O is preferably 0.01 to 2.0wt%.
P 2 O 5 For the crystal nucleus forming agent ZrO 2 Has obvious improvement effect on the refractory property. P 2 O 5 The content of (B) is 0.1-2.0 wt%. P 2 O 5 If the content of (b) is less than 0.1wt%, the improvement effect is not significant; p 2 O 5 When the content of (B) is more than 2.0wt%, a uniform glass is liable to be obtained by phase separation.
As 2 O 3 Usually as a clarifying agent. But due to As 2 O 3 It has an adverse effect on the environment, and therefore, the amount of the catalyst used is usually controlled to 0.5 to 2.0wt%. The method for manufacturing crystallized glass of the present invention uses calcium-containing waste As a main raw material of glass, since the calcium-containing waste itself contains 30.0 to 40.0wt% of As 2 O 3 So As is 2 O 3 The content of (B) is set to 0.5 to 2.0wt%.
Cl also serves As a clarifying agent, and the clarifying effect of Cl is free from As 2 O 3 Good results are obtained. But due to As 2 O 3 Has adverse effect on environment, so that part of Cl is used to replace As 2 O 3 To reduce As 2 O 3 The amount of (2) used. The invention makes full use of the Cl component in the calcium-containing waste and controls the Cl content to be 0.01-0.5 wt%.
SO 3 Also As a clarifying agent, the clarifying effect is free of As 2 O 3 Good results are obtained. But due to As 2 O 3 Has adverse effect on environment, SO part of SO is used 3 To replace As 2 O 3 To reduce As 2 O 3 The amount of (2) used. The invention makes full use of SO in calcium-containing waste 3 Component (A) SO 3 The content is controlled between 0.01 and 0.5 weight percent.
F is a component added to reduce the viscosity of the crystalline glass, thereby improving the melting property and the fluidity of the crystalline glass. On the other hand, F is aggressive to the furnace wall, so the F content cannot be too high. The invention makes full use of the F component in the calcium-containing waste and controls the content of F to be 0.1-5.0 wt%.
Fe 2 O 3 Is a colorant, and the content of the colorant is 0.01 to 5.0 weight percent. Fe 2 O 3 If the content of (B) is less than 0.01wt%, the ratio isThe effect of the colorant is poor. Fe 2 O 3 If the content of (B) is more than 5.0wt%, the crystallized glass tends to be brittle, which is undesirable.
V 2 O 5 Is a colorant. V 2 O 5 If the content of (B) is less than 0.01wt%, the effect as a colorant is not good; v 2 O 5 If the content of (B) is more than 2.0wt%, the cost is too high. Thus, V 2 O 5 The content of (c) cannot be too high. The invention makes full use of V in calcium-containing wastes 2 O 5 Component (A) is prepared from 2 O 5 The content of (A) is controlled to be 0.01-2.0 wt%.
TiO may be added 2 As a nucleating agent, the content thereof is 0 to 4.0wt%. Some colors of crystallized glass do not add TiO for increasing stereoscopic impression 2 TiO is added to some colored crystallized glass to increase the crystal 2 . However, tiO 2 When the content of (2) is more than 4.0wt%, the crystalline glass is liable to devitrify and the crystalline glass is liable to be colored with impurities.
ZrO may be added 2 As a nucleating agent, the content thereof is 0 to 2.0wt%. Colored crystallized glass without adding ZrO for increasing color depth 2 ZrO added to some colored crystallized glass for increasing crystals 2 . However, zrO 2 When the content of (b) is more than 2.0wt%, the glass is difficult to melt, and the crystalline glass is easily devitrified.
The effects of the present invention are explained below based on exemplary embodiments and comparative examples.
Example 1
First, calcium-containing waste is used as a main raw material, and the weight composition is prepared into SiO 2 56.1wt％、CaO 12.6wt％、Al 2 O 3 6.3wt％、ZnO 6.7wt％、BaO 6.0wt％、Na 2 O 3.6wt％、K 2 O2.3wt％、B 2 O 3 0.8wt％、MgO 0.2wt％、Li 2 O 0.4wt％、P 2 O 5 0.3wt％、As 2 O 3 0.5wt％、Cl 0.3wt％、SO 3 0.3wt％、F 0.8wt％、Fe 2 O 3 2.2wt％、V 2 O 5 0.2wt％、TiO 2 0.2wt％、ZrO 2 0.2wt% of glass raw material, and after uniformly mixing them, the mixture was held at 1500 ℃ for 16 hours to melt the raw material. Next, the molten glass is subjected to water-crushing, drying and classification to obtain crystallized glass particles having a particle diameter of 3 to 7 mm. These crystallized glass particles are heat treated to precipitate needle-like crystals of beta-wollastonite and become yellow-green crystallized glass having a coefficient of thermal expansion of 60x10 at 30 to 380 ℃ -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. Then, the temperature was raised to 1100 ℃ at a rate of 120 ℃ per hour and held for 2 hours. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 2
Using calcium-containing waste as main raw material, and making it into SiO 2 55.1wt％、CaO16.6wt％、Al 2 O 3 5.8wt％、ZnO 5.7wt％、BaO 5.0wt％、Na 2 O 3.3wt％、K 2 O 2.3wt％、B 2 O 3 0.8wt％、MgO 0.2wt％、Li 2 O 2.0wt％、P 2 O 5 0.5wt％、As 2 O 3 1.0wt％、Cl0.3wt％、SO 3 0.3wt％、F 1.0wt％、Fe 2 O 3 0.01wt％、V 2 O 5 0.01wt％、TiO 2 0.04wt％、ZrO 2 0.04wt% of glass raw material, and after mixing them uniformly, the mixture was kept at 1550 ℃ for 16 hours to melt the raw material. Then, the glass particles are crushed with water, dried and classified to obtain crystalline glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat treated to precipitate needle-like crystals of beta-wollastonite and become white crystallized glass having a coefficient of thermal expansion of 65x10 at 30 to 380 ℃ -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm. The temperature was raised to 750 ℃ at a rate of 5 ℃ per minute and held for 30 minutes, then to 850 ℃ at a rate of 5 ℃ per minute and held for 60 minutes, and then to 1100 ℃ at a rate of 3 ℃ per minute and held for 2 hours. Through such a crystallization process, the glass pellets are crystallized while being softened and bonded, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 3
Using calcium-containing waste as main raw material, and making it into SiO 2 57.2wt％、CaO16.6wt％、Al 2 O 3 5.8wt％、ZnO 3.0wt％、BaO 5.0wt％、Na 2 O 3.3wt％、K 2 O 0.5wt％、B 2 O 3 0.78wt％、MgO 1.0wt％、Li 2 O 2.0wt％、P 2 O 5 0.5wt％、As 2 O 3 1.0wt％、Cl0.3wt％、SO 3 0.3wt％、F 1.0wt％、Fe 2 O 3 0.01wt％、V 2 O 5 0.01wt％、TiO 2 1.0wt％、CeO 2 0.7wt% of glass raw material, and after uniformly mixing them, the mixture was held at 1500 ℃ for 16 hours to melt the raw material. Then, the glass particles are crushed with water, dried and classified to obtain crystalline glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat-treated to precipitate needle-like crystals of β -wollastonite to give yellow crystallized glass and to precipitate a β -spodumene solid solution. The yellow crystallized glass has a thermal expansion coefficient of 40x10 at 30-380 deg.C -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm. The temperature was raised to 750 ℃ at a rate of 5 ℃ per minute and held for 30 minutes, then to 850 ℃ at a rate of 5 ℃ per minute and held for 60 minutes, and then to 1100 ℃ at a rate of 3 ℃ per minute and held for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 4
Using calcium-containing waste as main raw material, and making it into SiO 2 60.8wt％、CaO11.0wt％、Al 2 O 3 5.5wt％、ZnO 5.8wt％、BaO 4.2wt％、Na 2 O 3.9wt％、K 2 O 1.2wt％、B 2 O 3 0.4wt％、MgO 0.8wt％、Li 2 O 0.05wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 4.2wt％、V 2 O 5 0.01wt％、TiO 2 0.4wt%, coO 0.3wt%, and NiO0.02wt%, and after mixing them uniformly, the mixture was held at 1500 ℃ for 16 hours to melt the raw materials. Then, the mixture was crushed with water, dried and classified to obtain crystallized glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat treated to precipitate needle-like crystals of beta-wollastonite and become black crystallized glass having a coefficient of thermal expansion of 70x10 at 30 to 380 ℃ -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. The temperature was raised to 850 ℃ at a rate of 5 ℃ per minute and held for 60 minutes, and then to 1100 ℃ at a rate of 3 ℃ per minute and held for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 5
Using calcium-containing waste as main raw material, and making it into SiO 2 58.8wt％、CaO11.2wt％、Al 2 O 3 5.5wt％、ZnO 5.8wt％、BaO 4.2wt％、Na 2 O 3.9wt％、K 2 O 1.2wt％、B 2 O 3 0.4wt％、MgO 0.78wt％、Li 2 O 2.0wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 0.3wt％、V 2 O 5 0.3wt％、TiO 2 1.0wt％、ZrO 2 2.0wt％、CoO 0.6wt％、SnO 2 0.6wt% of glass raw material, and after uniformly mixing them, the mixture was held at 1500 ℃ for 16 hours to melt the raw material. Then, the glass particles are crushed with water, dried and classified to obtain crystalline glass particles having a particle size of 3 to 7 mm. These crystalline glass particles are heat-treated to precipitate needle-like crystals of β -wollastonite to form blue-colored crystallized glass, and to precipitate a β -spodumene solid solution. The blue crystallized glass has a thermal expansion coefficient of 45x10 between 30 and 380 DEG C -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm. The temperature was raised to 750 ℃ at a rate of 5 ℃ per minute and held for 30 minutes, then to 850 ℃ at a rate of 5 ℃ per minute and held for 60 minutes, and then to 1100 ℃ at a rate of 3 ℃ per minute and held for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 6
Using calcium-containing waste as main raw material, and making it into SiO 2 58.8wt％、CaO11.2wt％、Al 2 O 3 6.0wt％、ZnO 6.0wt％、BaO 4.9wt％、Na 2 O 3.9wt％、K 2 O 1.2wt％、B 2 O 3 0.4wt％、MgO 0.77wt％、Li 2 O 2.0wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 0.01wt％、V 2 O 5 0.3wt％、TiO 2 1.0wt％、ZrO 2 1.5wt％、CoO 0.1wt％、SnO 2 0.2wt% and 0.3wt% of CuO, and the glass raw materials were uniformly mixed and then kept at 1500 ℃ for 16 hours to melt the raw materials. Then, the glass particles are crushed with water, dried and classified to obtain crystalline glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat-treated to precipitate needle-like crystals of beta-wollastonite to give red crystallized glass and precipitateBeta-spodumene solid solution. The red crystallized glass has a thermal expansion coefficient of 50x10 at 30-380 deg.C -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. The temperature was raised to 750 ℃ at a rate of 5 ℃ per minute and held for 30 minutes, then to 850 ℃ at a rate of 5 ℃ per minute and held for 60 minutes, and then to 1100 ℃ at a rate of 3 ℃ per minute and held for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Example 7
Using calcium-containing waste as main raw material, and making it into SiO 2 59.8wt％、CaO14.5wt％、Al 2 O 3 5.5wt％、ZnO 3.8wt％、BaO 3.2wt％、Na 2 O 3.9wt％、K 2 O 2.2wt％、B 2 O 3 0.4wt％、MgO 0.8wt％、Li 2 O 0.02wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 2.0wt％、V 2 O 5 0.01wt％、TiO 2 2.4wt%, coO0.01wt%, and NiO 0.04wt%, and after mixing them uniformly, the mixture was held at 1500 ℃ for 16 hours to melt the raw materials. Then, the glass particles are crushed with water, dried and classified to obtain crystalline glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat-treated to precipitate needle-like crystals of beta-wollastonite and become gray crystallized glass having a coefficient of thermal expansion of 70x10 at 30 to 380 ℃ -7 /℃。
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. The temperature was raised to 850 ℃ at a rate of 5 ℃ per minute for 60 minutes and then to 1100 ℃ at a rate of 3 ℃ per minute for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Comparative example 1
In the comparative examples, calcium-containing waste was also used as the main raw material, but the composition of the glass raw material after the preparation did not fall within the scope of the present invention. First, the composition was prepared to be SiO 2 66.3wt％、CaO 8.0wt％、Al 2 O 3 5.5wt％、ZnO 3.8wt％、BaO 3.2wt％、Na 2 O 3.9wt％、K 2 O 2.2wt％、B 2 O 3 0.4wt％、MgO 0.8wt％、Li 2 O 0.02wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl 0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 2.0wt％、V 2 O 5 0.01wt％、TiO 2 2.4wt%, coO0.01wt%, and NiO 0.04wt%, and after mixing them uniformly, the mixture was held at 1500 ℃ for 16 hours to melt the raw materials. Then, the mixture was crushed with water, dried and classified to obtain crystallized glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat-treated to precipitate needle-like crystals of beta-wollastonite and become gray crystallized glass having a coefficient of thermal expansion of 90x10 at 30 to 380 ℃ -7 V. C. However, these crystallized glass particles fail to precipitate sufficient needle-like crystals of β -wollastonite upon heat treatment, resulting in a glass article formed later being uneven in color and being easily broken.
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. The temperature was raised to 850 ℃ at a rate of 5 ℃ per minute for 60 minutes and then to 1100 ℃ at a rate of 3 ℃ per minute for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
Comparative example 2
First, the composition was prepared to be SiO 2 50.8wt％、CaO 23.0wt％、Al 2 O 3 4.0wt％、ZnO 3.8wt％、BaO 3.0wt％、Na 2 O 2.9wt％、K 2 O 1.2wt％、B 2 O 3 0.4wt％、MgO0.8wt％、Li 2 O 0.05wt％、P 2 O 5 0.8wt％、As 2 O 3 0.5wt％、Cl 0.01wt％、SO 3 0.01wt％、F 0.1wt％、Fe 2 O 3 4.2wt％、V 2 O 5 0.01wt％、TiO 2 4.1wt%, coO 0.3wt%, and NiO0.02wt%, and mixing them uniformly, and then holding at 1500 ℃ for 16 hours to melt the raw materials. Then, the mixture was crushed with water, dried and classified to obtain crystallized glass particles having a particle size of 3 to 7 mm. These crystallized glass particles are heat treated to precipitate needle-like crystals of beta-wollastonite and become black crystallized glass having a coefficient of thermal expansion of 70x10 at 30 to 380 ℃ -7 V. C. However, these crystallized glass particles precipitate too many needle-like crystals of β -wollastonite upon heat treatment, resulting in a glass article formed later being uneven in color and having a too low black ratio.
Then, the above-mentioned crystalline glass pellets of 3 to 7mm are laid in a refractory mold coated with a release agent, and the laid glass pellets are leveled to a thickness of about 20mm after leveling. The temperature was raised to 850 ℃ at a rate of 5 ℃ per minute for 60 minutes and then to 1100 ℃ at a rate of 3 ℃ per minute for 1 hour. Through such a crystallization process, the glass pellets are softened and bonded while precipitating crystals, thereby forming a crystallized glass article having a thickness of about 18 mm.
In general, in the production of the SiO of the invention 2 When the CaO-based crystallized glass is produced, wastes containing calcium are used as a main raw material, and therefore, the wastes can be reused, environmental friendliness is improved, and a great help is provided for environmental protection. The invention can easily control the component content in the chemical composition of the raw material formula and stabilize the component composition of the product. Formed SiO 2 The CaO-based crystallized glass is excellent in optical, thermal, mechanical and chemical properties, and can be formed into various colors as required. Therefore, the invention has good efficacy and practicability.
Claims (10)
1. SiO (silicon dioxide) 2 -CaO-based crystallized glass, wherein the SiO is 2 The CaO-based crystallized glass comprises the following components: siO 2 2 50.0-70.0 wt% (weight percentage), caO 9-22.0 wt%, al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O 1.0～6.0wt％、K 2 O 0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O 0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
2. SiO as claimed in claim 1 2 -CaO-based crystallized glass, wherein the SiO is 2 The compositional composition of the CaO-based crystallized glass further includes a coloring agent to form the SiO in various colors 2 CaO-based crystallized glass.
3. SiO as claimed in claim 2 2 -CaO-based crystallized glass, wherein the coloring agent comprises Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 And SnO 2 One or more than two of them.
4. SiO (silicon dioxide) 2 A method for producing a CaO-based crystallized glass, which comprises producing the SiO of claim 1 2 -CaO-based crystallized glass, the manufacturing method comprising the steps of:
(a) Preparing a glass raw material by using calcium-containing waste, wherein the calcium-containing waste comprises the following components: siO 2 2 0.1～1.0wt％、CaO 18.0～30.0wt％、Al 2 O 3 0.1～0.5wt％、ZnO20.0～30.0wt％、Na 2 O 0～2.0wt％、K 2 O 0～1.0wt％、B 2 O 3 0～1.0wt％、MgO0～0.5wt％、Li 2 O 0.1～3.0wt％、P 2 O 5 1.0～5.0wt％、As 2 O 3 30.0～40.0wt％、Cl0.1～1.0wt％、SO 3 0.1～1.0wt％、F 1.0～10.0wt％、Fe 2 O 3 0.01-0.2 wt% and V 2 O 5 0.1～1.0wt％；
(b) Melting and granulating the glass raw material to obtain a plurality of SiO 2 CaO-based crystalline glass particles; and
(c) The plurality of SiO 2 -CaO-based crystalline glass particles are formed and crystallized to obtain the SiO 2 CaO-based crystallized glass.
5. SiO as claimed in claim 4 2 A method for producing a crystallized glass of CaO-based glass, comprising the steps of: siO 2 2 50.0～70.0wt％、CaO 9～22.0wt％、Al 2 O 3 3.0～12.0wt％、ZnO 3.0～10.0wt％、BaO 3.0～10.0wt％、Na 2 O 1.0～6.0wt％、K 2 O 0.5～5.0wt％、B 2 O 3 0.3～2.0wt％、MgO 0～1.0wt％、Li 2 O 0.01～2.0wt％、P 2 O 5 0.1～2.0wt％、As 2 O 3 0.5～2.0wt％、Cl 0.01～0.5wt％、SO 3 0.01～0.5wt％、F0.1～5.0wt％、Fe 2 O 3 0.01～5.0wt％、V 2 O 5 0.01～2.0wt％、TiO 2 0 to 4.0wt% and ZrO 2 0～2.0wt％。
6. SiO as claimed in claim 5 2 A method for producing a CaO-based crystallized glass, wherein the glass raw material further contains a colorant to form SiO in each color 2 -CaO-based crystallized glass.
7. SiO as claimed in claim 6 2 -CaOA method for producing a crystallized glass, wherein the coloring agent comprises Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 And SnO 2 One or more than two of them.
8. SiO (silicon dioxide) 2 A method for producing a CaO-based crystallized glass, comprising the steps of:
(a) Preparing a glass raw material by using calcium-containing waste, wherein the calcium-containing waste comprises the following components: siO 2 2 0.1～1.0wt％、CaO 18.0～30.0wt％、Al 2 O 3 0.1～0.5wt％、ZnO20.0～30.0wt％、Na 2 O 0～2.0wt％、K 2 O 0～1.0wt％、B 2 O 3 0～1.0wt％、MgO0～0.5wt％、Li 2 O 0.1～3.0wt％、P 2 O 5 1.0～5.0wt％、As 2 O 3 30.0～40.0wt％、Cl0.1～1.0wt％、SO 3 0.1～1.0wt％、F 1.0～10.0wt％、Fe 2 O 3 0.01-0.2 wt% and V 2 O 5 0.1～1.0wt％；
(b) Melting and granulating the glass raw material to obtain a plurality of SiO 2 -CaO-system crystalline glass grains; and
(c) The plurality of SiO 2 -CaO-based crystalline glass particles are formed and crystallized to obtain the SiO 2 CaO-based crystallized glass.
9. SiO as claimed in claim 8 2 A method for producing a crystallized glass of the CaO-based system, wherein the glass raw material contains a colorant in a component composition to form the SiO with each color 2 CaO-based crystallized glass.
10. SiO as claimed in claim 9 2 A method for producing a CaO-based crystallized glass, wherein the coloring agent comprises Fe 2 O 3 、CoO、NiO、CuO、MnO、Cr 2 O 3 、CeO 2 And SnO 2 One or more than two of them.
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| JP2012020922A (en) * | 2010-06-17 | 2012-02-02 | Nippon Electric Glass Co Ltd | Natural marble-like crystallized glass, natural marble-like crystallized glass article and production method therefor |
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| CN102781864A (en) * | 2010-02-24 | 2012-11-14 | 日本电气硝子株式会社 | Process for production of LAS-system crystalline glass |
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