WO2005102948A2 - Verre colore - Google Patents

Verre colore Download PDF

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Publication number
WO2005102948A2
WO2005102948A2 PCT/IB2005/051310 IB2005051310W WO2005102948A2 WO 2005102948 A2 WO2005102948 A2 WO 2005102948A2 IB 2005051310 W IB2005051310 W IB 2005051310W WO 2005102948 A2 WO2005102948 A2 WO 2005102948A2
Authority
WO
WIPO (PCT)
Prior art keywords
glass
temperature
soda lime
coloured
cuo
Prior art date
Application number
PCT/IB2005/051310
Other languages
English (en)
Other versions
WO2005102948A3 (fr
Inventor
Theodorus H. Ketelaar
Simon Flink
Jean-Sebastien Straetmans
Original Assignee
Koninklijke Philips Electronics N.V.
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 Koninklijke Philips Electronics N.V. filed Critical Koninklijke Philips Electronics N.V.
Publication of WO2005102948A2 publication Critical patent/WO2005102948A2/fr
Publication of WO2005102948A3 publication Critical patent/WO2005102948A3/fr

Links

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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • 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

Definitions

  • the invention concerns coloured glass, the glass comprising a colloid in a soda lime glass.
  • the invention relates to an electric lamp having a coloured glass envelope.
  • the invention applies to incandescent lamps and more particularly to tail/stop lamps, for example, in automobiles.
  • the invention relates to a lamp envelope (bulb) the glass of which is red copper ruby coloured.
  • lamps and lamp units used for example, in tail/stop lamps of automobiles, that they have a specified colour point determined in accordance with standards of the International Electric Standard Conference (IEC) or Japanese Industrial Standards (US).
  • IEC International Electric Standard Conference
  • US Japanese Industrial Standards
  • the invention further aims to provide a copper ruby glass which has a decreased risk of crystallisation during its production process, being a conventional drawing technique.
  • Yet another aim of the invention is to provide a process for the manufacturing of a coloured glass, and particularly a red copper ruby bulb with a high enough temperature stability to keep its colour point during its anticipated burning time well within the limits of the ECE regulation.
  • these objects are achieved by a coloured glass as mentioned in the opening paragraph, wherein the soda lime glass has a specific resistance of 10 8 ⁇ .cm at a temperature (T ⁇ ⁇ oo) of at least 300 °C.
  • the glass of the invention comprises a colloid in a soda lime glass.
  • Glasses can be coloured by the presence of ions or by colours which result from aggregation of atoms into a colloid.
  • the invention relates to the latter form of coloured glasses.
  • the aggregation of atoms is generally obtained by a heat treatment (striking) near the annealing temperature range of the glass.
  • the atoms generally result from a reduction of a colloid forming metal oxide or a metal salt by reducing agents like carbon, Al or Si .
  • Suitable time and temperature of striking which depends on the composition of the soda lime glass, are best determined in a gradient furnace. For example, a striking temperature between 500 and 550 °C might be used.
  • Colloid-based colours such as red copper ruby used for glasses can be obtained by the addition of CuO in a percentage between 0.01 and 0.3 % by weight. Larger amounts are harmful, as they may cause muddy brown to grey colours. Lower concentrations do not produce colouring.
  • Cu 2+ , Cu + and elemental Cu° Under reducing conditions an equilibrium is established between Cu 2+ , Cu + and elemental Cu°. The presence of both Cu 2+ and Cu + produces colours ranging from blue to green, depending on the reducing agents in the soda lime glass composition. When sufficient Cu + ions are present in the glass, the concentration of Cu° in equilibrium with Cu + exceeds the solubility limits and Cu is precipitated.
  • the red colour is obtained by colloidally dispersed Cu° particles in equilibrium with Cu + when the bivalent copper has disappeared.
  • the reducing agent should therefore be able to reduce all the Cu 2+ .
  • SnO 2 is added as a metallophilic element. As soon as a nucleus of a Cu° crystal is formed, it selectively attracts the Sn 4+ ions, which form an efficient barrier against further growth of the metal crystal and thus stabilise the colloidal dispersion of the Cu° atoms and their overstriking. Without tin, the glass does not strike properly. The colour is not reproducible and the glass is likely to become turbid brown.
  • the glass of the invention comprises a soda lime glass having a specific resistance of 10 8 ⁇ .cm at a temperature of at least 300 °C.
  • Soda lime glasses fulfilling this requirement are known as sodium poor glasses.
  • the alkaline metal oxides Li O, Na 2 O and K 2 O are used as melting agents; they reduce the viscosity of the glass and determine the expansion coefficient thereof. If only one of said alkaline metal oxides is added, the temperature at which the specific resistance is 10 8 ⁇ .cm is too low to improve the colour stability of the glass.
  • Soda lime glasses with a T ⁇ i oo of at least 300 °C generally have alkali oxides within the ranges of Table 1.
  • An advantageous copper ruby glass composition comprises further constituents as given in Table 1
  • the SiO 2 content is limited to 60 - 72 %. This content, in combination with the other constituents, leads to a readily meltable glass. Al 2 O 3 improves the chemical resistance and the corrosion resistance of the glass.
  • Table 1 With the compositions given in Table 1, it is possible to make a temperature- stable red lamp with a colour point for automotive indicator lamps as defined by the ECE regulation having the following colour coordinates (X:Y): (0.657, 0.335); (0.665, 0.335); (0.732, 0.27); (0.728, 0.27).
  • An advantage of the lamp according to the invention is that the colour does not shift outside the ECE specified limits for red indicator lamps.
  • the soda lime glass has a T ⁇ ⁇ oo of at least 350 °C.
  • the soda lime glass used in Composition I in Table 2 gives an example of such a composition.
  • the coloured glass according to the invention comprises a glass wherein the colloid is formed from a mixture comprising SnO 2 and CuO.
  • This so-called copper ruby glass comprises SnO 2 and CuO in a weight ratio which is at least 1.9 + 6[CuO], wherein [CuO] denotes the copper concentration of CuO in the glass in % by weight.
  • the copper concentration [CuO] is between 0.05 and 0.2 % by weight.
  • a maximum of 0.2 % by weight of copper [CuO] a still higher stability of the colour at the burning temperature of a lamp is obtained.
  • the invention further relates to a coloured hollow glass article comprising a glass according to the invention.
  • a hollow glass article can be a bulb for an electric lamp or a glass shell for a mercury lamp.
  • the invention also relates to a red lamp comprising the coloured glass of the invention, with a colour point within the colour coordinates (X:Y): (0.657, 0.335); (0.665, 0.335); (0.732, 0.27); (0.728, 0.27).
  • the glass-making process will now be described below.
  • a batch is prepared by weighing and mixing all raw materials, including at least those mentioned in Table 1.
  • the batch is fed into a conventional continuous melting tank. Adjustments of the recipe can be made by adding separate ingredients into the feeding system for enhancing the colouring.
  • the melting conditions including temperature and gas atmosphere, are adjusted to obtain stable processing conditions for melting, refining and colour stabilization. Glass tubes are made at the end of the glass manufacturing process using the well-known Danner or Velio process.
  • the invention therefore also relates to a method for the manufacturing of a coloured hollow glass comprising the glass according to the invention by: a. forming a soda lime glass comprising colloid forming metal oxides or salts and having a specific resistance of 10 8 ⁇ .cm at a temperature of at least 300 °C into a tube; b. shaping the tube into the hollow article using a reducing flame; c. cooling the hollow article by a forced gas flow to a temperature below 800 °C; d. heating the hollow article at a temperature between 500 and 600 °C during a period between 5 minutes and 3 hours.
  • the invention will be further elucidated in the following Examples and Comparative Experiments.
  • Example I To simulate a total glass producing process (furnace and Danner profile), the following procedure was carried out: A glass composition as given in the second column of Table 2 was melted at 1470 °C, after which the temperature was decreased from the melting temperature to 1050 °C. Then the temperature was decreased from 1050 to 950 °C in about 1 hour. At 950 °C a cord was drawn and nitrogen cooling was applied immediately. Danner crystallisation did not occur. After striking for 75 minutes at 550 °C, the colour coordinates as given in Table 2 were obtained.
  • Example II The stability of the glass sample of Composition I prepared in Example I was tested by heating the sample during 24 hours at various "lamp" temperatures between 300 and 500 °C. At each temperature the colour shift per lh of the x-coordinate (dx/dt) was calculated. The results are given in column 2 of Table 3.

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

L'invention concerne un verre coloré thermostable et plus spécifiquement un verre destiné à des lampes de signalisation pour automobiles. Plus spécifiquement, l'invention concerne une composition de verre qui comprend un colloïde dans un verre sodocalcique, caractérisée en ce que ce verre sodocalcique possède une résistance spécifique de 108 O.cm à une température d'au moins 300 °C. L'invention concerne également des articles de verre creux colorés et plus spécifiquement des articles de verre de cuivre rouge rubis possédant un rapport oxyde d'étain:oxyde de cuivre spécifique afin d'empêcher la cristallisation du cuivre durant le processus de production de ces articles.
PCT/IB2005/051310 2004-04-23 2005-04-21 Verre colore WO2005102948A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04101691 2004-04-23
EP04101691.6 2004-04-23

Publications (2)

Publication Number Publication Date
WO2005102948A2 true WO2005102948A2 (fr) 2005-11-03
WO2005102948A3 WO2005102948A3 (fr) 2006-03-16

Family

ID=34977017

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2005/051310 WO2005102948A2 (fr) 2004-04-23 2005-04-21 Verre colore

Country Status (1)

Country Link
WO (1) WO2005102948A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011066967A1 (fr) * 2009-12-04 2011-06-09 Heraeus Noblelight Gmbh Lampe à décharge électrique sous haute pression pour le traitement cosmétique de la peau

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2672423A (en) * 1950-05-12 1954-03-16 Owens Illinois Glass Co Copper ruby glass
SU647271A1 (ru) * 1975-07-17 1979-02-15 Ivanova Evgeniya A Медное рубиновое стекло
SU662514A1 (ru) * 1975-06-03 1979-05-15 Ленинградский Завод Художественного Стекла Красное стекло
SU870366A1 (ru) * 1978-05-03 1981-10-07 Опытное Конструкторско-Технологическое Бюро "Кристалл" С Опытным Производством Ленинградского Технологического Института Им. Ленсовета Пурпурное стекло
SU874686A1 (ru) * 1979-02-19 1981-10-23 Ленинградский Завод Художественного Стекла Рубиновое стекло
SU1315401A1 (ru) * 1985-07-19 1987-06-07 Государственный научно-исследовательский институт стекла Рубиновое стекло
SU1379255A1 (ru) * 1986-06-19 1988-03-07 Государственный научно-исследовательский институт стекла Рубиновое стекло
DE10053450A1 (de) * 2000-10-27 2002-05-08 Schott Desag Ag Rotes Ziehglas mit hoher Farbsättigung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3904672B2 (ja) * 1997-05-14 2007-04-11 日本山村硝子株式会社 ソーダライムシリカ系銅赤ガラスの製造用バッチ組成物及び該ガラスの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2672423A (en) * 1950-05-12 1954-03-16 Owens Illinois Glass Co Copper ruby glass
SU662514A1 (ru) * 1975-06-03 1979-05-15 Ленинградский Завод Художественного Стекла Красное стекло
SU647271A1 (ru) * 1975-07-17 1979-02-15 Ivanova Evgeniya A Медное рубиновое стекло
SU870366A1 (ru) * 1978-05-03 1981-10-07 Опытное Конструкторско-Технологическое Бюро "Кристалл" С Опытным Производством Ленинградского Технологического Института Им. Ленсовета Пурпурное стекло
SU874686A1 (ru) * 1979-02-19 1981-10-23 Ленинградский Завод Художественного Стекла Рубиновое стекло
SU1315401A1 (ru) * 1985-07-19 1987-06-07 Государственный научно-исследовательский институт стекла Рубиновое стекло
SU1379255A1 (ru) * 1986-06-19 1988-03-07 Государственный научно-исследовательский институт стекла Рубиновое стекло
DE10053450A1 (de) * 2000-10-27 2002-05-08 Schott Desag Ag Rotes Ziehglas mit hoher Farbsättigung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 03, 31 March 1999 (1999-03-31) -& JP 10 316450 A (YAMAMURA GLASS CO LTD), 2 December 1998 (1998-12-02) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011066967A1 (fr) * 2009-12-04 2011-06-09 Heraeus Noblelight Gmbh Lampe à décharge électrique sous haute pression pour le traitement cosmétique de la peau

Also Published As

Publication number Publication date
WO2005102948A3 (fr) 2006-03-16

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