CN114804618B - Glass composite clarifying agent and preparation method and application thereof - Google Patents
Glass composite clarifying agent and preparation method and application thereof Download PDFInfo
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- CN114804618B CN114804618B CN202210431877.0A CN202210431877A CN114804618B CN 114804618 B CN114804618 B CN 114804618B CN 202210431877 A CN202210431877 A CN 202210431877A CN 114804618 B CN114804618 B CN 114804618B
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- 239000011521 glass Substances 0.000 title claims abstract description 134
- 239000008395 clarifying agent Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 44
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 32
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- 239000011780 sodium chloride Substances 0.000 claims abstract description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 13
- 239000006025 fining agent Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 238000005352 clarification Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- LPDSDOANOZHWLH-UHFFFAOYSA-N sodium cerium(3+) oxygen(2-) Chemical compound [O-2].[Ce+3].[O-2].[Na+] LPDSDOANOZHWLH-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to the technical field of glass production, and particularly discloses a glass composite clarifying agent, a preparation method and application thereof; a glass composite clarifying agent comprises a component A and a component B; the component A is tin oxide; the component B is any one of cerium oxide, sodium sulfate and sodium chloride; the weight ratio of the component A to the component B is (1-4): (1-6). The glass composite clarifying agent can clarify glass liquid in stages, can better eliminate bubbles of the glass liquid, and Cl in the glass liquid in the clarification process 2 、SO 2 And O 2 The solubility gradient of the equal gas is not disturbed, the clarification effect is good, and the glass flaws caused by the compound clarifier can be reduced or even avoided to a great extent.
Description
Technical Field
The application relates to the technical field of glass production, in particular to a glass composite clarifying agent, a preparation method and application thereof.
Background
Bubbles are one of the most common defects in the glass production process, and they affect the appearance, transparency, mechanical strength, optical uniformity, etc. of glass products, directly related to the quality of glass, so the effect of defoaming bubbles is a primary goal of each glass manufacturer. The fining process of glass is an extremely important step in glass production and largely determines the yield and quality of the glass. In the silicate glass forming stage, a large amount of gas is generated due to decomposition of salts, volatilization of partial components, action of a fining agent, reaction of molten glass and refractory materials, and the like. Some of these gases escape into the atmosphere while another part dissolves in the glass liquid, and there are also few gases that exist in the glass in the form of bubbles or react with the components in the glass liquid to form new compounds. Thus, there are three forms of gas in the glass liquid: bubbles, dissolved gas, and chemically bound gas. The glass liquid and the gas in the bubbles are different in types and amounts due to the difference of glass composition, raw material selection, partial pressure of gas in the furnace and the like, wherein the most common gas is CO 2 、O 2 、N 2 、H 2 O and SO 2 。
The traditional effective method for eliminating bubbles is to raise the melting temperature and the clarifying temperature, but the energy consumption is high, and the service life of the kiln is also reduced. Thus, in the glass production process, a fining agent is added to the glass formulation. The clarifying agent can be divided into: oxide clarifiers, sulfate clarifiers, halide clarifiers, and complex clarifiers. Oxide clarifying agent, sulfate type clarifying agent and halide clarifying agent belong to a single clarifying agent, the action temperature section of the single clarifying agent is shorter, the glass clarifying process is longer, bubbles can not grow up and escape due to insufficient gas quantity in the later period of clarifying, and a plurality of small bubbles remain in glass liquid, so that the use of the clarifying agent is limited. The compound clarifier mainly utilizes at least two clarification advantages of oxygen clarification, sulfur clarification and halogen clarification in the clarifier, and fully exerts synergistic effect and superposition effect.
However, the inventor found that the existing composite clarifying agent in the market is generally realized by adding an oxidant, sulfur clarifying and halogen clarifying, which is easy to cause contradiction among the three clarifying agents, and lead to Cl in glass 2 、SO 2 And O 2 Turbulence of the solubility gradient of the gas causes micro-bubbles in the glass, causing flaws in the glass.
Disclosure of Invention
In order to solve the defects of the existing glass, the application provides a glass composite clarifying agent, a preparation method and application.
In a first aspect, the application provides a glass composite clarifying agent, which adopts the following technical scheme:
a glass composite clarifying agent comprises a component A and a component B;
the component A is tin oxide;
the component B is selected from any one of cerium oxide, sodium sulfate and sodium chloride;
the weight ratio of the component A to the component B is (1-4): (1-6).
The tin oxide has an action temperature of about 1400 ℃, the sodium sulfate has an action temperature of about 1200 ℃, the cerium oxide has an action temperature of about 1350 ℃, the sodium chloride has an action temperature of about 1420 ℃, any one of the cerium oxide, the sodium sulfate and the sodium chloride is mixed with the tin oxide according to a specific proportion, the obtained glass composite clarifying agent can carry out staged clarification on glass liquid, can better eliminate bubbles of the glass liquid, and Cl in the glass liquid during clarification 2 、SO 2 And O 2 The solubility gradient of the equal gas is not disturbed, the clarification effect is good, and the glass flaws caused by the compound clarifier can be reduced or even avoided to a great extent.
Preferably, the component B is sodium sulfate, and the weight ratio of the tin oxide to the sodium sulfate is 1: (1.32-1.65), further preferably 1:1.4,1:1.45,1:1.5,1:1.52,1:1.57, most preferably 1:1.5.
By adopting the technical scheme, the weight ratio of the tin oxide to the sodium sulfate is 1: (1.32-1.65) and adding the compound clarifying agent into glass, wherein the number of bubbles in glass liquid is greatly increased, the size of the bubbles is rapidly increased, the overflow of the bubbles is facilitated, and the clarifying effect of the glass is best. And the average escape rate of bubbles in the glass liquid is 0.084-0.089cm/min, and the average absorption rate of bubbles in the glass liquid is 60% -60.9%. In the tin oxide and sodium sulfate composite clarifying agent, excessive or too little sodium sulfate can influence the escape rate and average absorptivity of bubbles in the glass liquid.
Preferably, the component B is cerium oxide, and the weight ratio of the tin oxide to the cerium oxide is 1: (0.77-0.95), further preferably 1:0.8,1:0.85,1:0.875,1:0.83, most preferably 1:0.875.
By adopting the technical scheme, the weight ratio of the tin oxide to the cerium oxide is 1: (0.77-0.95) is used as a compound clarifying agent, and when the compound clarifying agent is added into the glass, the clarifying effect of the glass is good. And the average escape rate of bubbles in the glass liquid is high, and can reach 0.09-0.11cm/min, and the average absorption rate of the bubbles is 61.7-62.5%. In the tin oxide and cerium oxide composite clarifying agent, too much or too little cerium oxide can influence the escape rate and average absorptivity of bubbles in the glass liquid.
Preferably, the component B is sodium chloride, and the weight ratio of the tin oxide to the sodium chloride is 1: (0.21-0.43), further preferably 1:0.25,1:0.28,1:0.3,1:0.33,1:0.35, most preferably 1:0.3.
By adopting the technical scheme, when the weight ratio of the tin oxide to the sodium chloride is 1: (0.21-0.43) when the glass is mixed with the composite clarifying agent, the clarifying effect of the glass is good when the composite clarifying agent is added into the glass. And when the glass is clarified, melted and clarified, the average escape rate of bubbles in the glass liquid is 0.079-0.085cm/min, and the average absorption rate of the bubbles is 62.2% -62.8%.
In a second aspect, the application provides a preparation method of a glass composite clarifying agent, which adopts the following technical scheme:
the preparation method of the glass composite clarifying agent comprises the following steps:
and (3) uniformly mixing the component A and the component B, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent.
Preferably, the water content of the glass composite clarifying agent is 1% -3% after drying.
By adopting the technical scheme, the preparation method of the glass composite clarifying agent is simple, easy to implement and convenient for mass production.
The water content of the glass composite clarifying agent is controlled to be 1-3%, and when the glass composite clarifying agent is applied to glass, moisture is not introduced into glass liquid, the viscosity of the glass liquid is not affected, so that bubbles in the glass liquid can escape.
In a third aspect, the application provides an application of a glass composite clarifying agent, which adopts the following technical scheme:
the use of a glass composite fining agent as described above or a glass composite fining agent produced by the above-described production method in glass production, wherein the glass composite fining agent is present in an amount of 0.7% to 1.1% by weight based on the total weight of the glass raw materials.
Further preferably, the glass raw materials have the following composition:
SiO 2 60％-64％、Al 2 O 3 15％-20％、Na 2 O 14％-16％、MgO 3％-4％、K 2 0 1％-3％、CaO 0.1％-0.3％、Fe 2 O 3 0.005% -0.01% and TiO 2 0.005％-0.01％。
Further preferably, the glass raw materials and the glass composite clarifying agent are uniformly mixed according to the formula proportion to obtain a mixture, the mixture is melted for 1-2 hours at 1400-1500 ℃, and then clarified for 0.5-1 hour at 1550-1600 ℃ to obtain glass liquid, and the glass product is obtained by molding, annealing and cooling.
The glass composite clarifying agent disclosed by the application has the advantages of good clarifying effect, no virulent or pollutant, safety and environmental friendliness, and in addition, the glass composite clarifying agent can realize a good clarifying effect with a small dosage during use, has good clarifying efficiency and can save cost.
In summary, the application has the following beneficial effects:
1. the glass composite clarifying agent can clarify glass liquid in stages, can better eliminate bubbles of the glass liquid, and Cl in the glass liquid in the clarification process 2 、SO 2 And O 2 The solubility gradient of the isopipe gas is not disturbed, the clarification effect is good, and glass flaws caused by the composite clarifier can be reduced or even avoided to a great extent;
2. when the applied composite clarifying agent is applied to glass, moisture is not introduced into glass liquid, viscosity of the glass liquid is not affected, quality of formed glass is not affected, and a good clarifying effect can be achieved by few composite clarifying agents.
3. The composite clarifying agent disclosed by the application does not contain extremely toxic substances or environmental pollutants, is safe to use and is beneficial to environmental protection.
Detailed Description
The present application will be described in further detail with reference to examples. The specific description is: the following examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted; the raw materials used in the following examples were all commercially available from ordinary sources except for the specific descriptions.
Example one (tin oxide and sodium sulfate composite clarifying agent)
Example 1-1
Uniformly mixing tin oxide and sodium sulfate according to a weight ratio of 1:1, grinding into powder with a particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent with a water content of 2%.
Examples 1-2 to 1-5 differ from example 1-1 only in the weight ratio of tin oxide to sodium sulfate, and the remainder are the same as example 1-1. The weight ratio of tin oxide to sodium sulfate in examples 1-2 to 1-5 is shown in Table 1 below.
TABLE 1
| Example 1 | Weight ratio of tin oxide to sodium sulfate |
| Example 1-1 | 1:1 |
| Examples 1 to 2 | 1:1.32 |
| Examples 1 to 3 | 1:1.5 |
| Examples 1 to 4 | 1:1.65 |
| Examples 1 to 5 | 1:2 |
Example two (tin oxide and cerium oxide composite clarifying agent)
Example 2-1
Uniformly mixing tin oxide and cerium oxide according to the weight ratio of 1:0.5, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent with the water content of 2%.
Examples 2-2 to 2-5 differ from example 2-1 only in the weight ratio of tin oxide to cerium oxide, and the remainder are the same as example 2-1. The weight ratio of tin oxide to sodium cerium oxide in examples 2-2 to 2-5 is shown in Table 2 below.
TABLE 2
| Example two | Weight ratio of tin oxide to cerium oxide |
| Example 2-1 | 1:0.5 |
| Example 2-2 | 1:0.77 |
| Examples 2 to 3 | 1:0.875 |
| Examples 2 to 4 | 1:0.95 |
| Examples 2 to 5 | 1:2 |
Example III (tin oxide and sodium chloride composite clarifying agent)
Example 3-1
Uniformly mixing tin oxide and sodium chloride according to the weight ratio of 1:0.1, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent with the water content of 2%.
Examples 3-2 to 3-5 differ from example 3-1 only in the weight ratio of tin oxide to sodium chloride, and the remainder are the same as example 3-1. The weight ratio of tin oxide to sodium chloride in examples 3-2 to 3-5 is shown in Table 3 below.
TABLE 3 Table 3
| Example III | Weight ratio of tin oxide to sodium chloride |
| Example 3-1 | 1:0.1 |
| Example 3-2 | 1:0.21 |
| Examples 3 to 3 | 1:0.3 |
| Examples 3 to 4 | 1:0.43 |
| Examples 3 to 5 | 1:1 |
Comparative example
Comparative examples 1 to 4
Comparative examples 1-4 selected a single ingredient as a clarifying agent, specifically as follows:
comparative example 1
Grinding tin oxide into powder with particle size of 0.2-0.4mm, drying to water content of 2%, and making into glass clarifier.
Comparative example 2
Grinding cerium oxide into powder with particle size of 0.2-0.4mm, drying to water content of 2%, and making into glass clarifier.
Comparative example 3
Grinding sodium sulfate into powder with particle size of 0.2-0.4mm, drying to water content of 2%, and making into glass clarifier.
Comparative example 4
Grinding sodium chloride into powder with particle size of 0.2-0.4mm, drying to water content of 2%, and making into glass clarifier.
Comparative example 5
Uniformly mixing tin oxide, sodium sulfate, cerium oxide and sodium chloride according to the weight ratio of 1:1.5:0.875:0.3, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent with the water content of 2%.
Comparative example 6
Uniformly mixing sodium sulfate and sodium chloride according to the weight ratio of 1.5:0.3, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent with the water content of 2%.
Application example
Uniformly mixing glass raw materials, wherein the glass raw materials are as follows: siO (SiO) 2 61.78％、Al 2 O 3 17％、Na 2 O 14％、MgO 4％、K 2 0 3％、CaO 0.2％、Fe 2 O 3 0.01% and TiO 2 0.01％；
Uniformly mixing the uniformly mixed glass raw materials with a glass composite clarifying agent (prepared in the embodiment 1-1), wherein the weight of the glass composite clarifying agent accounts for 0.85% of the weight of the glass raw materials, so as to obtain a mixture;
melting the mixture at 1500 ℃ for 1.5h, then clarifying at 1550 ℃ for 0.5h to obtain glass liquid, and forming, annealing and cooling to obtain a glass product.
Performance test
The glass panels were prepared by using 15 glass multiple fining agents of examples one, two and three and 6 fining agents or multiple fining agents of comparative examples 1 to 6 in the method of application example, and during the preparation, the fining conditions of the respective glasses were detected and observed, and specific detection data are shown in the following table 4.
The overall fining effect of the 21 glass sheets was ranked, and the ranking results are shown in table 4 below, with the earlier ranking indicating the better final fining effect.
TABLE 4 Table 4
In combination with application examples 1 to 5 (tin oxide and sodium sulfate composite clarifier), 6 to 10 (tin oxide and cerium oxide composite clarifier) and 11 to 15 (tin oxide and sodium chloride composite clarifier), it can be seen in combination with Table 4 that:
the number of bubbles remaining in the glass is relatively minimal when the glass is treated with a tin oxide and sodium sulfate composite fining agent, and the fining effect is best, probably due to the fact that: when tin oxide and sodium sulfate are matched with each other to act, the number of bubbles in the molten glass is greatly increased, and the size of the bubbles is rapidly increased, so that the bubbles can rapidly overflow, and a good clarification effect is achieved;
the average escape rate of bubbles in glass liquid is fastest when glass is treated by tin oxide and cerium oxide composite clarifying agent, and can reach 0.09-0.11cm/min, and possible reasons are that: when tin oxide and cerium oxide act, the composite clarifying agent only releases oxygen, so that when melting and clarifying, bubbles and gas in glass are mainly oxygen, and when the partial pressure of the gas rises sharply, the bubbles are facilitated to overflow at a higher speed;
the glass is treated by the tin oxide and sodium chloride composite clarifying agent, the average escape rate of bubbles in the glass liquid is 0.079-0.083cm/min, the average absorption rate of bubbles is the fastest and is 62.2% -62.8%, and the possible reasons are that: when tin oxide and sodium chloride act, the composite clarifying agent releases oxygen, chlorine and sodium chloride steam, so that the partial pressure of each gas is reduced compared with the single oxygen partial pressure during melting and clarifying, and the escape rate of bubbles can be influenced, but the glass liquid can absorb a plurality of gases at the same time, so that the average absorption rate of the bubbles is relatively better.
As can be seen from the combination of application examples 3, 8 and 13 and application examples 16 to 19 in combination with Table 4, the formulation and preparation method according to the present application produced a composite clarifying agent having a better clarifying effect than a single clarifying agent.
It can be seen from the combination of application examples 3, 8 and 13 and application examples 16 to 19, 20 to 21 in combination with Table 4 that not all of the multiple clarifiers have a synergistic effect, that some of the multiple clarifiers do not have a synergistic effect, but rather do not have a synergistic effect, and that the clarification effect is impaired, and that if not matched well, the clarification effect of the multiple clarifiers may be worse than that of the single clarifiers.
In application example 21, no data of the average escape rate and the average absorption rate of bubbles were measured, and since flash occurred during clarification, a large error was generated to avoid inaccuracy of the obtained data, and no record was made.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
1. A glass composite clarifying agent, which is characterized in that: comprises a component A and a component B;
the component A is tin oxide;
the component B is selected from any one of cerium oxide, sodium sulfate and sodium chloride;
the component B is sodium sulfate, and the weight ratio of the tin oxide to the sodium sulfate is 1: (1.32-1.65);
or the component B is cerium oxide, and the weight ratio of the tin oxide to the cerium oxide is 1: (0.77-0.95);
or the component B is sodium chloride, and the weight ratio of the tin oxide to the sodium chloride is 1: (0.21-0.43).
2. The method for preparing a glass composite clarifying agent according to claim 1, wherein: the method comprises the following steps:
and (3) uniformly mixing the component A and the component B, grinding into powder with the particle size of 0.2-0.4mm, and drying to obtain the glass composite clarifying agent.
3. The method for preparing a glass composite clarifying agent according to claim 2, wherein: after drying, the water content of the glass composite clarifying agent is 1-3%.
4. Use of the glass composite fining agent according to claim 1 or produced by the production method according to any one of claims 2 to 3 in glass production, characterized in that: the weight of the glass composite clarifying agent accounts for 0.7-1.1% of the total weight of the glass raw materials.
5. The use of a glass composite fining agent according to claim 4, wherein: the glass raw materials comprise the following components:
SiO 2 60%-64%、Al 2 O 3 15%-20%、Na 2 O 14%-16%、MgO 3%-4%、K 2 0 1%-3%、CaO 0.1%-0.3%、Fe 2 O 3 0.005% -0.01% and TiO 2 0.005%-0.01%。
6. The use of a glass composite fining agent according to claim 5, wherein: uniformly mixing glass raw materials and a glass composite clarifying agent according to a formula ratio to obtain a mixture, melting the mixture at 1400-1500 ℃ for 1-2h, clarifying at 1550-1600 ℃ for 0.5-1h to obtain glass liquid, and forming, annealing and cooling to obtain a glass product.
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