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WO2012036899A2 - Propriétés solaires-optiques améliorées pour verres à transmission visible élevée - Google Patents

Propriétés solaires-optiques améliorées pour verres à transmission visible élevée Download PDF

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Publication number
WO2012036899A2
WO2012036899A2 PCT/US2011/049860 US2011049860W WO2012036899A2 WO 2012036899 A2 WO2012036899 A2 WO 2012036899A2 US 2011049860 W US2011049860 W US 2011049860W WO 2012036899 A2 WO2012036899 A2 WO 2012036899A2
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WO
WIPO (PCT)
Prior art keywords
glass
solar
transmission
group
batch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2011/049860
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English (en)
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WO2012036899A3 (fr
WO2012036899A8 (fr
Inventor
Darryla J Costin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HIGH PERFORMANCE GLASS INNOVATIONS LLC
Original Assignee
HIGH PERFORMANCE GLASS INNOVATIONS LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HIGH PERFORMANCE GLASS INNOVATIONS LLC filed Critical HIGH PERFORMANCE GLASS INNOVATIONS LLC
Publication of WO2012036899A2 publication Critical patent/WO2012036899A2/fr
Publication of WO2012036899A3 publication Critical patent/WO2012036899A3/fr
Publication of WO2012036899A8 publication Critical patent/WO2012036899A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

Definitions

  • the first method is to deposit physical or chemical vapor deposition coating stacks on the glass that allow the transmission of visible light but reflect the solar radiation. The remaining solar energy is then transmitted through the glass, where a small part of the energy is absorbed and a smaller part of the energy is re-radiated back out of the glass.
  • Such coatings unfortunately substantially increase the price of the base glass, often tripling or quadrupling the cost. Further, such coatings generally require some form of protection because they are not by themselves durable.
  • the second method to reduce solar transmission in glass is through chemical modifications to the base glass chemistry to achieve higher near infrared absorption.
  • the limitation in using traditional solar absorbing glasses in reducing solar transmission is that dopants that typically exhibit absorption bands in the near infrared portion of the spectrum also exhibit absorption in the visible portion of the spectrum. The extent of this issue is reduced for the development of privacy glass and some commercial building glass products where the visible transmission requirements are as low as 25%.
  • Compounds, which exhibit absorption bands in the ultraviolet and/or near Infrared parts of the electromagnetic spectrum but also exhibit absorption bands in the visible spectrum, can be used to reduce the solar transmission of such low visible transmission glasses.
  • Such compounds for example, include Fe 2 0 3 , NiO, V 2 0 5 , CoO, Mn0 2 , Cr 2 0 3 , etc.
  • Such compounds include Fe 2 0 3 , NiO, V 2 0 5 , CoO, Mn0 2 , Cr 2 0 3 , etc.
  • the ideal dopant would, of course, exhibit quite different properties than the ideal dopants to achieve minimum solar transmission at low visible transmission.
  • the ideal dopants to achieve low solar transmission at high visible transmission would exhibit high absorption in the UV, low absorption in the visible, high absorption in the near infrared and low to medium absorption in the middle to high Infrared (to enhance melt ability). Of course, there is no such "perfect filter”. Nevertheless, there are select dopants that exhibit strong absorption bands in the near infrared.
  • Ferrous iron, FeO derived from the reduction of Fe 2 0 3 has been the dopant of choice to develop high visible transmission glasses. However, other dopants in combination with Fe 2 0 3 can be employed in specific combinations to reduce the solar transmission of high visible transmission glasses.
  • dopants include primary dopants which reduce near infrared absorption, secondary dopants which indirectly and favorably provide high visible with low solar transmission, reducing agents to generate proper valence states for infrared absorption, and importantly specific combinations of the host glass to impart favorable ratios of visible to solar transmission.
  • Samarium has absorption bands at 374, 402, 470, 1 130, 1250 and 1770 nm, which seems to be quite unique in that it absorbs in the UV and IR but not much in the visible.
  • Samarium oxide is used in optical glass to absorb infrared light and would be a new ideal near infrared absorber in the development of reduced solar transmission glass with relatively high visible transmission.
  • Praseodymium Oxide Pr 2 0 3
  • Praseodymium has absorption bands at 440, 469, 481 , 588 nm with two sharp absorption bands at about 1550, and 1770 nm, and thus imparts a green color to the glass.
  • Praseodymium may produce enhanced melt ability because it exhibits relatively weak absorption in the middle IR where photon conduction becomes important and where heat is to be transferred during the melting process.
  • CuO and specifically Cu +2 absorbs strongly in the near IR. Copper absorption occurs at 450 and 780 nm and thus imparts a blue color. Cu is only weakly absorbing in the mid region of the IR where heat is to be transferred during melting. Cu might increase IR reflection much like Ag. Cu may be decolorized by Fluorine. Cu may result in significant color shifts with Ti0 2 . Cu may absorb in the UV with SnO additions.
  • a first embodiment of the invention is then to incorporate one or more of the above primary dopants in standard soda-lime-silicate glass batch compositions, either singularly or in combination with Fe 2 0 3 with appropriate reducing conditions or compounds (to reduce some portion of Fe 2 0 3 to FeO), as the primary means to enhance near infrared absorption and subsequently reduce solar transmission while maintaining a high visible transmission
  • SnO additions to the glass have been reported in a few patents to reduce the ferric iron, but only in small quantities. SnO does increase the index of refraction of soda-lime-silicate glasses which may prove helpful in improving the photon conduction, the primary means for glass melting as described below. SnO may be contributing to improved solar-optical properties in ways other then reported in the literature as a reducing agent, and thus is an important secondary dopant.
  • Selected metal oxides can have their wavelength of maximum absorption shifted by addition of high field strength cations such as MnO, Zr0 2 and Ti0 2 .
  • the latter can accomplish this by altering the cation-ligand bond lengths and/or the redox state of the dopants by virtue of changes in glass basicity.
  • the current thinking regarding reducing agents does not include these compounds. However, by virtue of the changes in glass basicity, these compounds are important secondary dopants.
  • Photon Conduction becomes the dominant mode of heat transfer at glass melting temperatures.
  • the conduction of heat in glass occurs by the direct absorption of electromagnetic radiation.
  • the photon conductivity K is related to the index of refraction, n, the temperature, T, and the absorbance or optical density, A, as follows:
  • ⁇ (16 ⁇ * ⁇ 2 * ⁇ 3 )/ (3A)
  • ⁇ is the Stefan-Boltzmann constant, 5.688 x 10 "8 W/m 2 K 4 . Therefore, anything done to increase absorption decreases melt- ability and anything done to increase the index of refraction increases melt ability.
  • BaO which when substituted for MgO and CaO in the batch, increases index of refraction with an associated change in glass basicity.
  • glass basicity affects transition metal redox equilibria. BaO may enable improved visible transmissions and may also increase reflectivity.
  • Bi 2 0 3 is known to increase the index of refraction in glass at 5 wt.% levels.
  • Nd 2 0 3 Neodymium Oxide
  • Nd 2 0 3 has sharp absorption in the yellow part of the spectrum, thereby imparting blue color to the glass. Neodymium absorption occurs at 513, 529, 573, 584, 730, 775, and 885 nm.
  • Nd 2 0 3 does not interact with the transitional metal cations and is a good colorant due to the narrowness of the absorption peak in the UV to eliminate the yellow color without significantly affecting solar transmission.
  • Calcium Fluoride CaF 2
  • Fluorine has a specific influence on the absorption of infrared and is an additive effect with the reduction of MgO and the addition of BaO. The effect is a slight displacement of the maximum of the FeO absorption band in the IR and a straightening of the slope of the band in the visible.
  • the third embodiment is then to utilize some or all of the secondary dopants cited above along with some or all of the primary dopants in combination with Fe 2 0 3 with appropriate reducing conditions or reducing agents in the development of low solar transmission high visible transmission glass.
  • Optimum combinations of the glass batch primary and secondary dopants, reducing agents and host glass compounds can then be determined from statistically designed experiments, regression models and optimization programs, which is a fourth embodiment of this invention.
  • the reason why such techniques are required is that it would be impossible to conduct all the necessary experiments to quantify the effects with conventional experimental techniques. For example, consider an experimental study with 15 glass batch compounds, 1 1 of which have 3 different concentration levels, 1 of which has 4 levels and 1 of which has 2 levels. In this case with interactions and quadratic terms added, the number of admissible experiments is 12,754,584. Thus, it would take several lifetimes of experimentation to identify the optimum combinations of glass batch compounds to achieve the minimum solar transmission at different levels of visible transmission.
  • regression models correlate the solar-optical properties to the batch ingredients and their interaction. For example, equations relating the absorption at individual wavelengths to the batch ingredients and their interaction can be developed. The absorption or optical density can be computed from a logarithmic transformation of the transmission data. Regression coefficients can then be derived which can be fed into optimization models. Optimum batch chemistries for minimizing the solar transmission at fixed levels of visible transmission can then be predicted with reasonable accuracy.
  • the fifth embodiment of this invention is to use such optimized glass batch compounds to achieve, for the first time, solar transmission less than 35% at a minimum visible transmission of 70% for automotive glass (based on ISO 9050 standards).
  • the sixth embodiment of this invention is to use such optimized glass batch compounds to achieve solar transmission, for the first time, less than 50% at a minimum visible transmission of 80% for residential glass (based on ISO 9050 standards).
  • the seventh embodiment is to utilize some of the primary and secondary dopants with Fe 2 0 3 and appropriate reducing conditions or reducing agents to increase the refractive index and/or reduce the absorption in the middle infrared spectrum to improve the melt-ability of glass in conventional large-scale glass furnaces.
  • Specific ranges of glass and/or batch composition are part of this invention and are disclosed below as standard soda-lime-silicate glass batch composition with additions of the primary and secondary dopants and Fe 2 0 3 and reducing agents.
  • the iron is shown as Fe 2 0 3 , that is the iron supplied in the batch ingredients.
  • the ferrous version of this iron then is FeO and is derived from the reduction of Fe 2 0 3 by reducing agents and/or adjustments to the fuel/air mixture and/or adjustments to the glass melt temperature.
  • the glass or batch composition ranges shown below (in weight or mole percent) are then an eighth embodiment of this invention:
  • a ninth embodiment of this invention is to utilize two or more near infrared absorbing elements or compounds, each of which has maximum absorption peaks at different wavelengths in the near infrared electromagnetic spectrum. In this way the solar transmission can be reduced vs. from that obtained from the conventional use of only one near infrared absorber compound, FeO.
  • a tenth embodiment of this invention is to utilize two or more near infrared absorbing elements or compounds, each of which has maximum absorption peaks at different wavelengths in the near infrared electromagnetic spectrum, and where one of the compounds is FeO.

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  • 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

L'invention concerne une nouvelle approche technique permettant d'obtenir des performances solaires sensiblement meilleures pour un verre à transmission visible élevée à partir de modifications chimiques. L'invention consiste à identifier de nouveaux composés (concentrations et combinaisons) outre le fer, qui possèdent des propriétés de transmission solaire réduite pour un verre à transmission visible élevée. De nombreux composés de verre peuvent interagir de façons qui ne sont toujours pas bien comprises mais qui donnent néanmoins des résultats positifs en ce qui concerne la transmission solaire améliorée pour un verre à transmission visible élevée. Des techniques expérimentales développées statistiquement suivies par une modélisation de régression et par une optimisation permettent uniquement de découvrir ces composés et ces interactions, ainsi que leurs concentrations optimales.
PCT/US2011/049860 2010-09-14 2011-08-31 Propriétés solaires-optiques améliorées pour verres à transmission visible élevée Ceased WO2012036899A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38253610P 2010-09-14 2010-09-14
US61/382,536 2010-09-14

Publications (3)

Publication Number Publication Date
WO2012036899A2 true WO2012036899A2 (fr) 2012-03-22
WO2012036899A3 WO2012036899A3 (fr) 2012-05-03
WO2012036899A8 WO2012036899A8 (fr) 2012-10-11

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Family Applications (1)

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PCT/US2011/049860 Ceased WO2012036899A2 (fr) 2010-09-14 2011-08-31 Propriétés solaires-optiques améliorées pour verres à transmission visible élevée

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014089302A1 (fr) * 2012-12-06 2014-06-12 High Performance Glass Innovations, Ltd. Vitrages à transmission de lumière visible élevée et à faible transmission solaire
CN104743586A (zh) * 2013-12-27 2015-07-01 中国科学院过程工程研究所 一种拜耳法赤泥中铝碱浸取与氧化铝分解母液蒸发排盐的联合生产方法
CN105948490A (zh) * 2016-05-10 2016-09-21 刘康宁 一种教学用试剂瓶玻璃及其制备方法
US10703669B2 (en) 2017-04-28 2020-07-07 Schott Ag Filter gas

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ20012687A3 (cs) * 1999-02-15 2002-03-13 Schott Glas Sklo s vysokým obsahem kysličníku zirkoničitého a jeho pouľití
WO2002022515A1 (fr) * 2000-09-15 2002-03-21 Costin Darryl J Verres et procedes de production de verres a transmission solaire reduites
US7538054B2 (en) * 2005-08-09 2009-05-26 Guardian Industries Corp. Grey glass composition including erbium, neodymium and/or praseodymium

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014089302A1 (fr) * 2012-12-06 2014-06-12 High Performance Glass Innovations, Ltd. Vitrages à transmission de lumière visible élevée et à faible transmission solaire
CN104743586A (zh) * 2013-12-27 2015-07-01 中国科学院过程工程研究所 一种拜耳法赤泥中铝碱浸取与氧化铝分解母液蒸发排盐的联合生产方法
CN104743586B (zh) * 2013-12-27 2017-11-14 中国科学院过程工程研究所 一种拜耳法赤泥中铝碱浸取与氧化铝分解母液蒸发排盐的联合生产方法
CN105948490A (zh) * 2016-05-10 2016-09-21 刘康宁 一种教学用试剂瓶玻璃及其制备方法
US10703669B2 (en) 2017-04-28 2020-07-07 Schott Ag Filter gas

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Publication number Publication date
WO2012036899A3 (fr) 2012-05-03
WO2012036899A8 (fr) 2012-10-11

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