CN102092942B - Energy-saving environmental protection glass with high transmittance - Google Patents

Energy-saving environmental protection glass with high transmittance Download PDF

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CN102092942B
CN102092942B CN2010105846386A CN201010584638A CN102092942B CN 102092942 B CN102092942 B CN 102092942B CN 2010105846386 A CN2010105846386 A CN 2010105846386A CN 201010584638 A CN201010584638 A CN 201010584638A CN 102092942 B CN102092942 B CN 102092942B
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glass
transmittance
simple substance
visible light
sncl
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CN102092942A (en
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李梅
柳召刚
张晓伟
王觅堂
胡艳宏
张永强
邵明迪
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Inner Mongolia University of Science and Technology
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Abstract

The invention relates to energy-saving environmental protection glass with high transmittance. The preparation method of the glass is as follows: Fe2O3, SnCl2, Ce2(CO3)3, Nd2(CO3)3 and elementary substance Se are added in common float glass, wherein the thickness of the molten glass is 4mm, the visible light transmittance is more than 88%, the ultraviolet transmittance is less than 4% and the infrared transmittance is less than 15%. The glass can absorb ultraviolet and infrared strongly and has higher visible light transmittance; SnCl2 is used as a reducing agent, and rare earth elements are added in the glass; by adopting the physical decoloring method, the transmittance of the glass can be increased, and the ultraviolet transmittance and infrared transmittance of the glass can also be increased; and the glass in the invention can be widely used in the protection fields such as automobile glass, building glass, spectacle glass, experimental apparatus and the like.

Description

The energy-saving environment-friendly glass of high permeability
Technical field:
The present invention relates to a kind of high permeability energy-saving environment-friendly glass, be widely used in windshield, building glass, spectacle glass and laboratory apparatus, belong to the glass preparation field.
Background technology:
In recent years along with China's rapid economic development; The also fast development of automobile and construction industry; Yet the obnoxious flavour of heavy industry discharging makes depletion of the ozone layer serious day by day, and ultraviolet radiation intensity increases, and the luxurious decoration in automobile and the buildings is on the rise by the destruction of uviolizing.In summer, automobile and buildings etc. receives that sunshine is near infrared to be influenced, and temperature is higher, has increased air conditioner load greatly, has consumed a large amount of energy.Some special laboratory apparatuss need be in low ultraviolet ray and infrared ray radiation, and the environment of high visible is work down, therefore studies a kind of prevent effectively ultraviolet ray and ultrared seeing through, and the glass that increases visible light transmissive becomes a big research direction of glass art.
Several kinds of antiultraviolets and ultrared glass have been developed in the glass art; For example, Nippon Sheet Glass Co Ltd is in Chinese patents: CN 1336904A, a kind of infrared and ultraviolet radiation absorbing glass with green tone; More concretely; It has high-transmission rate and bluish-green tone, and this glass contains the following composition that calculates with weight %: sodium calcium-silicon-dioxide alkali glass and some coloring ingredients; Coloring components comprises with Fe 2O 3Meter 0.40% is to the total ferric oxide (T-Fe that is lower than 0.58% 2O 3), 0.05% to the CeO below 0.5% 2, 0 to 0.5% TiO 2Reach 0.0001% to 0.002%CoO, wherein 20% to the T-Fe that is lower than 30% 2O 3Be with Fe 2O 3The FeO of meter.
Nippon Sheet Glass Co Ltd is in Chinese patents: CN 1167093A, disclosing a kind of is the ultraviolet ray and the infrared absorbing glass of green that is used for the window of automobile or buildings.This glass comprises in weight %: 65-80% SiO 2, 0-5%Al 2O 3, 0-10%MgO, 5-15%CaO, 10-18%Na 2O, 0-5%K 2O, 5-15%MgO+CaO, 10-20%Na 2O+K 2O, 0-5%B 2O 3The dyeing component contains 0.40-0.70 with Fe 2O 3Count total red stone (T-Fe 2O 3), 1.4-1.7%CeO 2And 0-0.5%TiO 2, 27-40% weight wherein with Fe 2O 3The T-Fe of meter 2O 3Be FeO.
The patent of Shanghai Yaohua Pilkington Glass Co., Ltd's application: CN 1451621A; A kind of strong absorption ultraviolet and infrared green glass are provided; It is in common sodium calcium silicon sheet glass composition, to add tinting material, and the proportioning of tinting material is: total iron content (Fe in the tinting material 2O 3) between 0.5～0.9%, the ferrous (Fe in wherein total iron 2+) content is 18～28%, TiO 2Content be 0.2～0.7%, CeO 2Content be 0.05～0.15%.The color of this glass is a deep green, and its advantage is, ultraviolet ray transmissivity is no more than 17%, and the infrared rays transmitance is no more than 28%, and visible light transmissivity is more than 70%.
U.S. PPG company is in Chinese patents: CN 1165788A, a kind of green glass is provided, and its adopts iron, cerium, chromium and the optional titanium of the soda lime glass base composition of standard as infrared rays and ultraviolet radiation absorbing material and tinting material.This green glass contains the total iron of 0.50-1.0% weight, about 0.35-0.65% weight Fe 2O 3, about 0.8-1.5% weight CeO 2, and about 20-150PPMCr 2O 3Said composition has light transmission (LTA) at least about 65%, be no more than total solar ultraviolet perviousness (TSUV) of 38%, be no more than total solar infrared perviousness (TSIR) of about 35%.Glass of the present invention has the green of predominant wavelength in the 500-550 nanometer range, and its purity of color is no more than about 5%.
PPG company is in ZL 97104961.0 patents of China's application; Related to a kind of " infrared and ultravillet radiation absorbing green glass composition ", its adopts the Sodelimesilica Glass base composition of standard and as iron, cerium, chromium and optional titanium infrared and uv-absorbing substance and tinting material.This glass has the light transmission (LAT) at least about 65%, is no more than total solar ultraviolet perviousness (TSUV) of about 38%.
More than a large amount of red stone, cerium oxide and the titanium oxide of the most utilization adding of invention waits and reaches painted and absorption ultraviolet and infrared effect; Find in the experiment; Cerium oxide and titanium oxide have the certain absorption effect to ultraviolet ray; But near infrared ray is not had sorption basically, and that infrared rays is played sorption is Fe 2+, but the iron major part is with Fe in glass 3+Exist, expect Fe 2+Just must add the high temperature reduction agent, however the Fe of iron in glass 2+And Fe 3+The capital makes glass coloring, and the transmitance of glass is descended.
Summary of the invention:
The object of the present invention is to provide a kind of higher visible light transmissivity ability that has, can absorb ultraviolet ray and ultrared high permeability energy-saving environment-friendly glass consumingly.
Technical solution:
The present invention as the basis, adds Fe with the composition of common sodium calcium silicon float glass again in the batching 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each set of dispense is than percentage meter by weight:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.1～0.2%
Tin protochloride SnCl 2: 0.2～0.4%
Cerous carbonate Ce 2(CO 3) 3: 0.05～0.08%
Neodymium carbonate Nd 2(CO 3) 3: 0.03～0.05%
Simple substance selenium Se:0.02～0.04%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 89%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 25%, in the near infrared transmitance of 780～2500nm wavelength less than 60%.
Another embodiment of the present invention: the energy-saving environment-friendly glass of high permeability adds Fe in common sodium calcium silicon float glass 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each set of dispense is than percentage meter by weight:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.2～0.4%
Tin protochloride SnCl 2: 0.4～0.7%
Cerous carbonate Ce 2(CO 3) 3: 0.08～0.1%
Neodymium carbonate Nd 2(CO 3) 3: 0.05～0.07%
Simple substance selenium Se:0.04～0.06%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 12%, in the near infrared transmitance of 780～2500nm wavelength less than 45%.
The third embodiment of the present invention: the energy-saving environment-friendly glass of high permeability is in common sodium calcium silicon float glass, to add Fe 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each set of dispense is than percentage meter by weight:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.4～0.6%
Tin protochloride SnCl 2: 0.6～0.8%
Cerous carbonate Ce 2(CO 3) 3: 0.1～0.12%
Neodymium carbonate Nd 2(CO 3) 3: 0.07～0.1%
Simple substance selenium Se:0.06～0.09%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 8%, in the near infrared transmitance of 780～2500nm wavelength less than 18%.
The 4th kind of embodiment of the present invention: the energy-saving environment-friendly glass of high permeability adds Fe in common sodium calcium silicon float glass 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each set of dispense is than percentage meter by weight:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.6～0.8%
Tin protochloride SnCl 2: 0.8～1%
Cerous carbonate Ce 2(CO 3) 3: 0.12～0.15%
Neodymium carbonate Nd 2(CO 3) 3: 0.1～0.14%
Simple substance selenium Se:0.09～0.12%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 4%, in the near infrared transmitance of 780～2500nm wavelength less than 15%.
Explanation reason that the composition of the energy-saving environment-friendly glass of high permeability is limited below, below all percentage number averages be weight percentage.
SiO 2Be the staple that constitutes the glass skeleton, can reduce the thermal expansivity of glass, improve thermostability, chemicalstability, softening temperature, thermotolerance, hardness, physical strength and the viscosity etc. of glass.Content is low excessively, and the various performances of glass can descend, too high levels, and raw material is difficult to fusing.
Na 2O is the outer oxide body of glass network, can reduce the viscosity of glass, makes glass be easy to fusion; Be the good solubility promoter of glass, but it can increase the thermal expansivity of glass simultaneously, reduce thermostability, chemicalstability and the physical strength of glass; So can not introduce too much; Generally be no more than 18%, introduce very fewly, the fusing effect of glass is just poor.
CaO is the outer oxide body of glass network, and the main effect in glass is a stablizer, promptly increases the chemicalstability and the physical strength of glass, but content increases the crystallization tendency of glass, and be prone to make the glass embrittlement when higher, generally is no more than 12.5%.
Red stone is a kind of impurity that contains in the sandstone, and its existence form has FeO and Fe 2O 3Two kinds, FeO can make glass be dark green, Fe 2O 3Can make glass be yellow-green colour, the tinting strength of low price iron is approximately 10 times of high price iron tinting strength.No matter be the transparency that high price iron or low price iron all can reduce glass,, influence the quality of glass so the iron-holder increase can reduce transparency and glossiness in the glass.Fe 2+And Fe 3+Ultraviolet ray all there is the intense absorption effect, but Fe 2+Infrared rays had intense absorption effect, Fe 3+Infrared rays there is not sorption basically.
Tin protochloride is colourless or white oblique system crystallization.Specific density 2.710.37.7 ℃ of fusing points.Under fusing point, be decomposed into hydrochloric acid and subsalt.In air, be oxidized to insoluble oxychloride gradually.Or a kind of reductive agent can be with most Fe in the glass 2O 3Be reduced to FeO fully, but cost is higher.
Ce 2(CO 3) 3At high temperature can be decomposed into CeO 2, CeO in glass 2Can play the absorption action of ultraviolet ray, select Ce (CO among the present invention for use 3) 2And directly do not select CeO for use 2, be because Ce 2(CO 3) 3Pyrolytic decomposition discharges CO 2Gas can quicken the effusion of bubble in the glass, has substituted the part saltcake, has reduced environmental pollution.
CeO 2At high temperature can also continue to decompose, chemical formula is following:
Figure BSA00000383603900051
Figure BSA00000383603900052
CeO 2In pyroreaction, make oxygenant, promptly can reducing iron oxides weaken the tinting strength of iron, can play clarification again and absorb ultraviolet function.But CeO 2Content can not be too high, and the too high high price iron level that makes easily increases, and makes glass show faint yellow.
Nd 2(CO 3) 3At high temperature can decomposite Nd 2O 3, discharge CO simultaneously 2Gas has quickened the clarifying process of glass metal, Nd 2O 3Can glass into lavender, can neutralize strong absorption 568～590nm sodium yellow part, Nd simultaneously with the pale bluish green of iron 2O 3Ultraviolet ray there is the certain absorption effect.
Simple substance selenium can be present in the glass under neutrallty condition, produces lilac red, with CeO 2Mix and use, it can change selenoliteization into colourless selenate in the glass smelting process, and under reducing atmosphere, colourless selenate is decomposed to form purple simple substance selenium, makes glass purple, just in time with Fe 2+Dark green complementation.
The energy-saving environment-friendly glass of high permeability of the present invention has higher visible light transmissivity; Can absorb ultraviolet ray and infrared rays consumingly; And can directly on the basis of common float glass batch materials, carry out the composition design; And can realize suitability for industrialized production, the lower and economic environmental protection of cost is the optimal selection of protective glass such as automobile, building, spectacle glass and laboratory apparatus.
Embodiment
The present invention will be described in more detail through following instance, but the present invention is not subject to following examples.
All use the base furnish of common float glass in following examples, each component content such as table 1:
Table 1 embodiment base furnish component list/% (by weight percentage)
Figure BSA00000383603900053
Figure BSA00000383603900061
Basic ingredient through sandstone, rhombspar, Wingdale, soda ash and saltcake introducing glass adds the Fe that requires 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, see table 1.With the admixtion thorough mixing, total mass is 100g altogether, puts into corundum crucible.Put on the platform of glass melter, be cast to the glass metal of fusing on the steel plate that scribbles zirconium powder after 5 hours after, put in 550 ℃ the holding furnace and anneal.The thickness of sample of making is about 6mm, and thickness is 4mm after the corase grind polishing.
The thick glass of 4mm that every polishing is good is measured visible light transmissivity, ultraviolet ray transmissivity and near infrared ray transmitance with BTF-1 visible light transmissivity tester, TV-1901I twin-beam ultra-violet and visible spectrophotometer and Fourier's near infrared ray transmission measurement appearance, sees table 2.
The test result of table 2 embodiment glass
Figure BSA00000383603900062
Can find out that through last table thickness of the present invention is that the glass of 4mm has 380～780nm wavelength greater than 89% visible light transmissivity; At the ultraviolet ray transmissivity of 280～380nm wavelength less than 25%, preferably at the ultraviolet ray transmissivity of 280～380nm wavelength less than 4%; In the near infrared transmitance of 780～2500nm wavelength less than 60%, preferably can be less than 15%, effect is very desirable.
Industrial applicibility:
As above describe in detail; The glass that the present invention produces has high visible light transmissivity and intensive ultraviolet, infra-red absorption rate; And do not change the production technique of float glass; Directly add the additive that requires and can realize large-scale commercial prodn, can be applied in widely automobile and building window with and field such as spectacle glass.

Claims (2)

1. the high permeability energy-saving environment-friendly glass is characterized in that: add Fe at common sodium calcium silicon float glass 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each set of dispense is than percentage meter by weight:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.4～0.6%
Tin protochloride SnCl 2: 0.6～0.8%
Cerous carbonate Ce 2(CO 3) 3: 0.1～0.12%
Neodymium carbonate Nd 2(CO 3) 3: 0.07～0.1%
Simple substance selenium Se:0.06～0.09%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 8%; In the near infrared transmitance of 780～2500nm wavelength less than 18%.
2. the high permeability energy-saving environment-friendly glass is characterized in that: add Fe at common sodium calcium silicon float glass 2O 3, SnCl 2, Ce 2(CO 3) 3, Nd 2(CO 3) 3, simple substance Se, each composition accounts for glass weight per-cent and is:
Silicon oxide sio 2: 64～85%
Sodium oxide Na 2O:6～14%
Quicklime CaO:4～12%
Natural manganese dioxide MgO:2～7%
Aluminium oxide Al 2O 3: 0～3%
Red stone Fe 2O 3: 0.6～0.8%
Tin protochloride SnCl 2: 0.8～1%
Cerous carbonate Ce 2(CO 3) 3: 0.12～0.15%
Neodymium carbonate Nd 2(CO 3) 3: 0.1～0.14%
Simple substance selenium Se:0.09～0.12%
This kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 4%; In the near infrared transmitance of 780～2500nm wavelength less than 15%.
CN2010105846386A 2010-12-02 2010-12-02 Energy-saving environmental protection glass with high transmittance Expired - Fee Related CN102092942B (en)

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Publication number Priority date Publication date Assignee Title
CN112830676B (en) * 2021-02-09 2022-11-08 上海大学 Preparation method of energy-saving glass
CN113072301B (en) * 2021-05-12 2022-09-09 斯卡特(北京)新材料技术有限公司 High-light-transmittance high-heat-insulation energy-saving float glass and production process thereof

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Publication number Priority date Publication date Assignee Title
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US20050170944A1 (en) * 2004-01-29 2005-08-04 Mehran Arbab High performance blue glass
WO2005082799A3 (en) * 2004-02-25 2006-05-26 Guardian Industries Clear glass composition
CN101717192A (en) * 2009-12-11 2010-06-02 内蒙古科技大学 Anti-glare purple glass for adsorbing ultraviolet rays strongly
CN101857360A (en) * 2010-05-13 2010-10-13 内蒙古科技大学 Glass capable of strongly absorbing ultraviolet rays and infrared rays

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Publication number Priority date Publication date Assignee Title
US3652303A (en) * 1970-01-26 1972-03-28 Ppg Industries Inc Heat absorbing blue soda-lime-silica glass
CN1275964A (en) * 1997-10-20 2000-12-06 Ppg工业俄亥俄公司 Infrared and ultraviolet radiation absorbing blue glass composition
US20050170944A1 (en) * 2004-01-29 2005-08-04 Mehran Arbab High performance blue glass
WO2005082799A3 (en) * 2004-02-25 2006-05-26 Guardian Industries Clear glass composition
CN101717192A (en) * 2009-12-11 2010-06-02 内蒙古科技大学 Anti-glare purple glass for adsorbing ultraviolet rays strongly
CN101857360A (en) * 2010-05-13 2010-10-13 内蒙古科技大学 Glass capable of strongly absorbing ultraviolet rays and infrared rays

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