CN1385386A - Compound decolorized for raising photopermeability and whiteness of float glass and use method thereof - Google Patents

Compound decolorized for raising photopermeability and whiteness of float glass and use method thereof Download PDF

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Publication number
CN1385386A
CN1385386A CN 01116046 CN01116046A CN1385386A CN 1385386 A CN1385386 A CN 1385386A CN 01116046 CN01116046 CN 01116046 CN 01116046 A CN01116046 A CN 01116046A CN 1385386 A CN1385386 A CN 1385386A
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China
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glass
whiteness
decoloring agent
composite decoloring
transmittance
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CN 01116046
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CN1143834C (en
Inventor
苑同锁
侯英兰
张欣
李西平
李军
付秀君
张为民
杜振宇
孟凡广
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Yaohua Gloss Co Ltd Qinhuangdao City
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Yaohua Gloss Co Ltd Qinhuangdao City
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Priority to CNB011160462A priority Critical patent/CN1143834C/en
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Abstract

The present invention discloses a compound decolouring agent for raising whiteness and transmiltancy of float glass and plate glass and its application method. Said decolouring agent is formed from Sb2O3+CeO2, Na2O+SO3, ZnO, La2O3, Nd2O3, and SiO+CaO. After it is added into the glass material, it not only can regulate the oxidation-reduction state of glass, and can convert Fe(2+) into Fe(3+), but also can utilize colour compensation to eliminate coloration of Fe(2+) and Fe(3+) to glass so as to attain double effect of chemical and physical decolorization and attain the goal of raising "whiteness" and transmittancy of the glass. Its application method is as follows: adding 0.005-2 portions of compound decolouring agent into 100 portions of glass liquid.

Description

The composite decoloring agent and the application method thereof of a kind of raising float glass transmittance and " whiteness "
The present invention relates to the composite decoloring agent and the application method thereof of a kind of raising float glass " whiteness " and transmittance.
As everyone knows, the color of transparent float glass mainly is to be caused by the ferric oxide impurity in the starting material, and ferric oxide has iron ion Fe at a low price in glass 2+With high price iron ion Fe 3+Two states, Fe 3+The 3d track be half full state, tinting strength is very weak, is yellow-green colour, Fe 2+Ground state term of spectrum L=2 is in the D attitude, at visible region a broad absorption band is arranged, and is blue-greenish colour, Fe 2+Tinting strength be Fe 3+About 10 times, the color of glass depends primarily on the equilibrium state of the two, this shows, the color that wants to improve glass improves " whiteness " of glass and transmittance iron level, the especially Fe at first must reduction glass 2+Content, because iron oxide content is mostly between 0.07-0.15% in the present domestic transparent float glass raw material, and the content of external or joint line float glass is mostly about 0.05%, therefore domestic float glass is compared with the float glass of external or joint line and is generally presented the blue-greenish colour feature, this has just influenced the overall appearance quality of domestic float glass, improves the task of top priority that float glass " whiteness " becomes present domestic float glass industry.Higher at iron oxide content in the domestic glass raw material, general these practical situation between 0.07-0.15%, factory has adopted many methods to remedy raw-material congenital defect.First method is: with main raw material(s) sandstone, quartzite rod milling, washing, reduce the iron oxide content in the raw material, though this method can effectively improve " whiteness " of glass, cost increases a lot, invests very huge.Second method is that glass is decoloured.Glass decolouring is divided into two kinds of physical decolorization and chemical decolorizations, and CeO is generally selected in the chemical decolorization agent for use 2, As 2O 3, Sb 2O 3Etc. chemical substance, in admixtion, add a kind of oxygenant NaNO simultaneously 3, oxygenant is with the discoloring agent low-temperature oxidation, and discoloring agent high temperature is emitted oxygen, makes a part of Fe in the glass melt 2+Change into Fe 3+, reduce Fe 2+Painted to glass because this method has added oxygenant and multivalence oxide compound, easily causes the contradiction between sulphur clarification and the oxygen clarification, causes the SO in the glass 3, O 2The disorder of solubility gradients, the redox merit index of glass changes, and causes glass-board surface microvesicle to occur.Physical decolorization generally is in the color of eliminating glass through adding physics discoloring agent behind the chemical decolorization by complementary colors, selenium is generally selected in the physical decolorization agent for use, cobalt, lanthanum, neodymium etc., though physical decolorization can make the tone of glass eliminate, but the transmittance of glass is descended, and higher at iron level is that iron level is under the situation of 0.07%-0.15%, if add the physics discoloring agent, the gray scale of glass increases, the total quality of glass can not get positively improving, so under the iron level condition with higher, " whiteness " and the transmittance that improve glass become the unemployed problem that solves that urgently waits of present China glass.
The purpose of this invention is to provide a kind of composite decoloring agent, in, the glass composition constant at the basic material of glass iron level constant, cheaply under the situation, it can improve the glass transmittance, improve the color of glass.
For achieving the above object, discoloring agent of the present invention by following component by hundred parts of following weight than forming: the Sb of 30-100% 2O 3+ CeO 2, 0-8% Na 2O+SO 3, the ZnO of 0-5%, the La of 0-9% 2O 3, 0-5% Nd 2O 3, 0-43% SiO 2+ CaO.The preferred content of each component of the present invention is: the Sb of 40-97.5% 2O 3+ CeO 2, 0-6% Na 2O+SO 3, the ZnO of 1-3%, the La of 1-7% 2O 3, 0.5-3.5 Nd 2O 3, 0-43% SiO 2+ CaO.Its component of composite decoloring agent of the present invention can be by Sb 2O 3+ CeO 2Form separately, also can be by Sb 2O 3+ CeO 2With Na 2O+SO 3, ZnO, La 2O 3, Nd 2O 3, SiO 2Among+the CaO one or more combine.
The using method of above-mentioned composite decoloring agent at the starting material that do not change glass promptly under the constant situation of the major ingredient of glass, the glass metal of relative 100 weight parts adds the composite decoloring agent of 0.005-2 weight part in glass batch.
After in preparing glass charge, adding composite decoloring agent of the present invention,, utilize the oxidisability and the glass melt oxygen activity of discoloring agent itself, with the Fe in the glass because discoloring agent itself has oxidisability 2+Change into Fe 3+, the Fe that tinting strength is strong 2+Reduce, the color of glass bleaches, CeO 2In glass, produce faint yellow, with Fe 2+Blue-greenish colour complementary color each other, play the dual function of chemical decolorization and physical decolorization.La 2O 3, Nd 2O 3, in glass, produce blue, red, they with glass in yellow-green colour complementary color each other, eliminated the tone of glass, " whiteness " of glass improved, the transmittance increase.For proving discoloring agent of the present invention to improving " whiteness " and the effect of transmittance of glass, it is 500 tons floatation glass production line that the present invention selects day melt, and the glass of producing thickness and be 10mm compares, and is specially: become and molten tin bath is protected gas N before expecting 2With H 2Ratio be adjusted to 96.5: 3.5 by 96: 4, in preparing glass charge, add composite decoloring agent of the present invention, glass is decoloured, make mother glass 2 #, with the mother glass 2 that makes #Simple glass sample 1 with end adding discoloring agent of the present invention #Compare detection, the gained sample parameters contrasts as following table 1: table 1
Sample Thickness The discoloring agent consumption Transmittance ??L ??A ??b ??X ??Y ??Z ??F Specific refractory power
1 # 10mm ????0 ??84.97 ??92.19 ??-2.8 ??0.56 ??79.17 ??84.99 ??90.43 ??0.1405 ??1.51892
2 # 10mm ????0.09 ??86.56 ??93.03 ??-2.6 ??0.22 ??80.72 ??86.56 ??92.69 ??0.0938 ??1.51901
F represents colourless factor in the table, and its value is more for a short time to show that " whiteness " of glass is good more, and the color of glass levels off to colourless more, F=0.1405 before the decolouring, and transmittance is 84.97, decolouring back F=0.0938, transmittance is 86.56, as can be seen from Table 12 #The F value of sample is than 1 #The F value of sample has obvious reduction, and discoloring agent promptly of the present invention is obvious to " whiteness " effect that improves glass, and 2 #The transmittance of sample is than 1 #The transmittance of sample increases obviously, proves that not changing glass raw material be that discoloring agent of the present invention can not only effectively improve " whiteness " of glass, and can effectively improve the transmittance of glass under the constant situation of the major ingredient of glass.
Discoloring agent of the present invention by following component by hundred parts of following weight than forming: the Sb of 30-100% 2O 3+ CeO 2, 0-8% Na 2O+SO 3, the ZnO of 0-5%, the La of 0-9% 2O 3, 0-5% Nd 2O 3, 0-43% SiO 2+ CaO.The preferred content of each component of the present invention is: the Sb of 40-97.5% 2O 3+ CeO 2, 0-6% Na 2O+SO 3, the ZnO of 1-3%, the La of 1-7% 2O 3, 0.5-3.5 Nd 2O 3, 0-43% SiO 2+ CaO.Its component of composite decoloring agent of the present invention can be by Sb 2O 3+ CeO 2Form separately, also can be by Sb 2O 3+ CeO 2With Na 2O+SO 3, ZnO, La 2O 3, Nd 2O 3, SiO 2Among+the CaO one or more combine.Composite decoloring agent of the present invention is with multivalence oxide S b 2O 3And CeO 2As major ingredient, utilize the oxidisability of discoloring agent itself and the oxygen activity of glass melt, with the Fe in the glass 2+Change into Fe 3+, the Fe that tinting strength is strong 2+Reduce, reduce Fe 2+To the pigmentation of glass, CeO 2In glass, produce faint yellow, with Fe 2+Blue-greenish colour complementary color each other, play dual parts chemical decolorization and physical decolorization.The introducing of ZnO mainly is for improving the optical property of glass.La 2O 3, Nd 2O 3Can be used as the physical decolorization agent of glass, utilize in its blueness that in glass, produces, red and the glass yellow-green colour complementary color each other, eliminate the tone of glass, " whiteness " of glass improved, the transmittance increase.Na 2O+SO 3Introduce as oxygen clarification and clarifying conditioning agent of sulphur and glass fusing assistant.The using method of above-mentioned composite decoloring agent is: the starting material that do not change glass promptly under the constant situation of the major ingredient of glass in glass batch the glass metal of relative 100 weight parts add the composite decoloring agent of 0.005-2 weight part, the preferable amount of composite decoloring agent is the composite decoloring agent that the glass metal of relative 100 weight parts adds the 0.01-1.5 weight part, the most preferred quantities of composite decoloring agent is the composite decoloring agent that the glass metal of relative 100 weight parts adds the 0.02-1 weight part, the consumption of composite decoloring agent is not obvious to the raising effect that improves glass whiteness and transmittance very little, consumption easily causes the disorder between sulphur clarification and the oxygen clarification too much, make sheet glass produce defectives such as blub, and to the fusing of float glass process production line, moulding, technologies such as annealing produce considerable influence.
Discoloring agent of the present invention is not only applicable to float glass, and is applicable to sheet glass is decoloured, but each major ingredient of decolorizing effect glass when better and the weight percent content of each composition are: the SiO of 69-73% 2, 0.8-2.3% Al 2O 3, 6.3-8.9% MgO, the Fe of 0.07-0.15 of CaO, 3.5-4.2% 2O 3, 13.5-14.5% R 2O, in batching, saltcake content is 0-6%, carbon powder content is 0-6%.
Embodiment 1
(1) choosing the component of composite decoloring agent and the weight percent content of each component is: 70%
Sb 2O 3+ CeO 2, 8% Na 2O+SO 3, 5% ZnO, 9% La 2O 3, 5%
Nd 2O 3, 3% SiO 2+ CaO.
(2) with above-mentioned each component according to a conventional method mixing match form composite decoloring agent.
(3) glass metal with respect to 100 weight parts adds the above-mentioned of heavy part of 0.2-0.3 in preparing glass charge
Composite decoloring agent makes the float glass sample of 3mm, and its transmittance is 90.43%, and the end is taken off
The float glass transmittance of 3mm is 89.4% before the look, and transmittance improves 1.03%.
Embodiment 2
(1) weight percent content of choosing composite decoloring agent component and each component is: 48%
Sb 2O 3+ CeO 2, 5% Na 2O+SO 3, 3% ZnO, 2% La 2O 3, 3%
Nd 2O 3, 39% SiO 2+ CaO.(2) with above-mentioned each component according to a conventional method mixing match form composite decoloring agent.(3) glass metal with respect to 100 weight parts adds the above-mentioned of heavy part of 0.4-0.6 in preparing glass charge
Composite decoloring agent makes the float glass sample of 5mm, and its transmittance is 89.32%, and the end is taken off
The float glass transmittance of 5mm is 88.85% before the look, and transmittance improves 0.47%.
The weight percent content that embodiment 3 (1) chooses composite decoloring agent component and each component is: 95%
Sb 2O 3+ CeO 2, 2.5% Na 2O+SO 3, 1% ZnO, 1% La 2O 3, 0.5%
Nd 2O 3。(2) with above-mentioned each component according to a conventional method mixing match form composite decoloring agent.(3) in preparing glass charge with respect to the glass metal of 100 weight parts add heavy part of 0.01-0.02 on
State composite decoloring agent, make the float glass sample of 5mm, its transmittance is 89.01%, the end
The float glass transmittance of 5mm is 88.85% before the decolouring.

Claims (7)

1, the composite decoloring agent of a kind of raising float glass transmittance and " whiteness ", the weight percent content of its component and each component is:: the Sb of 30-100% 2O 3+ CeO 2, 0-8% Na 2O+SO 3, the ZnO of 0-5%, the La of 0-9% 2O 3, 0-5% Nd 2O 3, 0-43% SiO 2+ CaO.
2, the composite decoloring agent of raising glass whiteness as claimed in claim 1 and transmittance is characterized in that the weight percent content of each component is: the Sb of 40-97.5% 2O 3+ CeO 2, 0-6% Na 2O+SO 3, the ZnO of 1-3%, the La of 1-7% 2O 3, 0.5-3.5 Nd 2O 3, 0-43% SiO 2+ CaO.
3, the composite decoloring agent of raising float glass transmittance as claimed in claim 1 and whiteness, it is characterized in that: described component can be by Sb 2O 3+ CeO 2Form separately, also can be by Sb 2O 3+ CeO 2With Na 2O+SO 3, ZnO, La 2O 2, Nd 2O 2, SiO 2Among+the CaO one or more combine.
4, the composite decoloring agent of raising float glass transmittance as claimed in claim 1 and whiteness is characterized in that being applied to sheet glass.
5, as the application method of the composite decoloring agent of claim 1,2,3,4 described raising float glass transmittances and " whiteness ": the composite decoloring agent that in preparing glass charge, adds the 0.005-2 weight part with respect to the glass solution of 100 weight parts.
6, the application method of the composite decoloring agent of raising float glass transmittance as claimed in claim 5 and " whiteness " is characterized in that: the consumption of described composite decoloring agent is for adding the composite decoloring agent of 0.02-1.5 weight part with respect to the glass solution of 100 weight parts.
7, the application method that can improve the composite decoloring agent of float glass transmittance and whiteness as claimed in claim 5 is characterized in that: the consumption of described composite decoloring agent is for adding the composite decoloring agent of 0.02-1 weight part with respect to the glass solution of 100 weight parts.
CNB011160462A 2001-05-11 2001-05-11 Compound decolorized for raising photopermeability and whiteness of float glass and use method thereof Expired - Fee Related CN1143834C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102092941A (en) * 2010-12-02 2011-06-15 内蒙古科技大学 Ultra-white glass
CN102712519A (en) * 2009-10-12 2012-10-03 法国圣戈班玻璃厂 Method for producing a sheet of glass including antimony oxide
CN104529159A (en) * 2014-11-28 2015-04-22 宁波长利风玻璃制品有限公司 Super white glass ball and production process thereof
CN106966587A (en) * 2017-02-24 2017-07-21 玉林博飞商贸有限公司 A kind of solar energy super white glass
CN112592053A (en) * 2020-12-28 2021-04-02 四川中科玻璃有限公司 Novel environment-friendly glass suitable for glass bottle and can production and preparation process thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102712519A (en) * 2009-10-12 2012-10-03 法国圣戈班玻璃厂 Method for producing a sheet of glass including antimony oxide
CN102092941A (en) * 2010-12-02 2011-06-15 内蒙古科技大学 Ultra-white glass
CN102092941B (en) * 2010-12-02 2012-11-14 内蒙古科技大学 Ultra-white glass
CN104529159A (en) * 2014-11-28 2015-04-22 宁波长利风玻璃制品有限公司 Super white glass ball and production process thereof
CN106966587A (en) * 2017-02-24 2017-07-21 玉林博飞商贸有限公司 A kind of solar energy super white glass
CN112592053A (en) * 2020-12-28 2021-04-02 四川中科玻璃有限公司 Novel environment-friendly glass suitable for glass bottle and can production and preparation process thereof

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