EP0767763A2 - Verre borosilicate - Google Patents

Verre borosilicate

Info

Publication number
EP0767763A2
EP0767763A2 EP96909020A EP96909020A EP0767763A2 EP 0767763 A2 EP0767763 A2 EP 0767763A2 EP 96909020 A EP96909020 A EP 96909020A EP 96909020 A EP96909020 A EP 96909020A EP 0767763 A2 EP0767763 A2 EP 0767763A2
Authority
EP
European Patent Office
Prior art keywords
weight
glass
mgo
cao
bao
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.)
Withdrawn
Application number
EP96909020A
Other languages
German (de)
English (en)
Inventor
Dietmar Stiebert
Hans-Georg Lich
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.)
Technische Glaswerke Ilmenau GmbH
Original Assignee
Technische Glaswerke Ilmenau GmbH
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 Technische Glaswerke Ilmenau GmbH filed Critical Technische Glaswerke Ilmenau GmbH
Publication of EP0767763A2 publication Critical patent/EP0767763A2/fr
Withdrawn legal-status Critical Current

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

  • the invention relates to a borosilicate glass with a linear thermal expansion between 20 ° C and 300 ° C of 3.9 to 4.5 x 10 ⁇ 6 K "1. It is used for the production of laboratory glass, household glass, pharmaceutical container glass, lamps ⁇ glass, flat glass and other technically and optically high-quality glass products are used according to the invention when a borosilicate glass with the aforementioned property is to be produced in known fully electrically heated melting plants according to the cold-top principle.
  • borosilicate glasses are known in the prior art. Their properties determining the utility value are high chemical resistance, low thermal expansion, high resistance to temperature changes and high mechanical strength.
  • Borosilicate glass 3.3 according to DIN ISO 3585 is usually used for laboratory, housekeeping and apparatus glass. This type of glass contains only a little alkali (below 5%), SiO 2 over 79% and B 2 0 3 to approx. 13%. It has a thermal expansion between 20 and 300 ° C of approx. 3.3 * 10 ⁇ 6 K "1. Furthermore, boron-containing melting glasses are known. They have higher alkali and / or alkaline earth contents, as well as sometimes additional oxides. The thermal expansion of these glasses is 3.6 to 5.2 * 10 -6 K "1 . Another well-known group is that of the so-called neutral pharmaceutical borosilicate glasses. In contrast to melt-down glasses, they achieve the highest chemical resistance values.
  • Neutral pharmaceutical Borosilicatglaser can still do not melt all-electric, because the necessary refining agents As 2 0 3 and / or s - ° 2 ° 3 ⁇ i e destroy conventional molybdenum rod electrodes of the heating.
  • the first approaches to a procedural problem solving are given in DE-PS 43 13 217.
  • Borosilicate glasses with a linear thermal expansion of 3.6 to 4.8 * 10 ⁇ 6 K _1 can only be melted fully electrically with strong qualitative restrictions. Due to higher flux contents (alkali, alkaline earth and boron oxide) they melt much faster than borosilicate glasses with a thermal expansion of 3.3 * 10 -6 K _1 . However, since approximately the same melting temperatures are required for complete glass formation, homogenization and refining despite higher flux contents, the well-insulating, cold batch mixture required for the fully electrical cold-top melting process cannot be produced in a stable manner, and the heat balance is disturbed. At worst, the process no longer allows the desired temperatures to be reached, so that blistered glass or unmelted particles leave the furnace.
  • the methods known in the prior art do not provide any information on fixing or controlling the redox potential of the borosilicate glasses.
  • the invention is based on the object of specifying a soft borosilicate glass with a thermal expansion of 3.9 to 4.5 * 10 ⁇ 6 K "1 with a high chemical resistance, which, under the ecologically and energetically advantageous conditions of the known fully electric cold-top process can be produced.
  • the object is achieved in that a processing temperature at 10 4 dPa s of 1200 to 1270 ° C, a viscosity at 1550 ° C of 10 2 ' 6 to 10 2 ' 8 dPa s, a spec. electrical resistance at 1550 ° C from 20 to 33 .... cm or an electrical conductivity at 1550 ° C from 3.0 to 5.0 S / m, under cold-top conditions at about 1600 ° C melts at 0.3 to 0.5 mm / min and has the following basic composition:
  • the new glass belongs to the group of chemically resistant borosilicate glasses, which are characterized by the following properties:
  • the glass Because of its use as pharmaceutical and / or domestic glass, the glass is produced without toxic heavy metal oxides. It contains components to increase the brilliance and can be colored. So that it can be melted fully electrically in known furnaces, no PbO, SnO, CuO, NiO, CdO, FeO, Cr 2 0 3 , ZnO, As 2 0 3 and / or Sb 2 0 3 may be contained. For ecological reasons, no fluorides are used as refining agents.
  • the composition of the borosilicate glass which can be melted completely electrically under cold-top conditions takes into account not only chemical-physical glass properties but also process-related requirements.
  • the fully electric cold-top method can be used with borosilicate glass with a thermal expansion of up to 4.5 * 10 ⁇ 6 K_1 and enables good glass quality if high-temperature material values such as viscosity and conductivity are close to them due to the process of a borosilicate glass 3.3. So that stable cold-top conditions prevail, the mixture is also melted at approximately the same speed as in borosilicate glass 3.3. The following of these values were demonstrated in melting tests:
  • Trial melting showed that the high processing temperature and the 1550 ° C. viscosity with a content of SiO 2 plus ZrO 2 of over 77% and a content of A1 2 0 3 of 3.5 to 5.0 % can be achieved. Over 81% Si0 2 plus Zr0 2 , however, the processing temperature and the viscosity at 1550 ° C. rise to uncontrollably high values and relics of these meltable components must also be expected. At 77% Si0 2 plus Zr0 2 , the linear thermal expansion rises above 4.5 * 10 -6 K ⁇ with the Al 2 0 3 content according to the invention.
  • the B 2 0 3 content influences the chemical resistance and is limited at the bottom by an excessively high processing temperature above 1300 ° C. and an excessively high 1550 ° C. viscosity.
  • a range of 10.5 to 12.5% B 2 0 3 was determined in order to achieve the required chemical resistance.
  • the linear thermal expansion is strongly influenced by the content of alkali and alkaline earth. It was found that under Taking into account the limits of the alkaline earths for conductivity and carbonate addition, below, at least 5.4%, but at most 7.0% alkali plus alkaline earth may be used, so that the linear thermal expansion between 20 ° C and 300 ° C in the range of 3.9 to 4.5 * 10 ⁇ 6 K -1 is to be kept. Furthermore, it was found that the desired chemical resistance can be achieved by using the mixed alkali and additionally the mixer alkaline effect if, in addition to 5.0 to 5.8% Na 2 0, 0.3 to 1.5% K 2 0 or 0.6 to 0.9% alkaline earth or a combination of K 2 0 plus alkaline earth are added. Since BaO shows the most favorable effect from the alkaline earths, as well as from the advantages explained below, it is preferred. Since Li 2 0 would increase the tendency to devitrify, its use is dispensed with.
  • Zr0 2 is known to improve the chemical resistance, in particular to alkalis, the mechanical strength and in particular the grinding hardness of the glass, which has been shown to increase its use value, but also the effort required for mechanical processing. So that the glass can also be processed economically, the Zr0 2 content should be less than 2.4%. Surprisingly, when this glass was produced on an industrial scale, up to this value there was no risk of devitrification if A1 2 0 3 was 3.7 to 4.9%. To limit the processing temperature, the Al 2 O 3 content is preferably 4.1 to 4.5% and the ZrO 2 content is preferably between 0.8 and 1.0%.
  • MgO increases the tendency to devitrification and is therefore excluded as a raw material component.
  • BaO increases the refractive index and promotes the brilliance of the glass, as is desirable when used as a household glass. Because of this property and its favorable influence on the acid class, only BaO is used as an alkaline earth component. This means that only impurities in CaO and MgO are permitted which, despite all precautions, can be brought into the glass up to 0.1%.
  • the glass preferred according to the invention is alkaline earth-free to completely avoid the susceptibility to reboil except for the tolerated impurities.
  • cerium-IV-oxide does not destroy the molybdenum rod electrodes installed on the side or from below, since released oxygen no longer comes into contact with them. It was also found that the corrosive influence known from As 2 0 3 or Sb 2 0 3 does not occur with the amount of cerium oxide used according to the invention, despite the high melting temperature present in sulfate-free borosilicate glass. At the same time, the desired redox state can be set or controlled.
  • the borosilicate gel according to the invention dispenses with alkaline earth (apart from unavoidable impurities) and thus completely excludes the use of carbonates. This reduces the susceptibility to reboil.
  • the alkalis are only introduced as borates, aluminum and / or silicates.
  • This preferred glass according to the invention is characterized by the following composition: 76.6 to 77.7% by weight?
  • the borosilicate glass according to the invention with its chemical composition and its physical properties, can be produced using the ecologically, energetically and economically highly efficient, fully electric cold-top melting process.
  • the glass according to the invention is used with the linear thermal expansion between 20 ° C. and 300 ° C.
  • Glasses No. 5 to 19 shown in the table are examples of continuously working, fully electrically heated cold-top melting furnaces. Glass 9 to 11 was melted with 20 to 30% cullet.
  • Glasses 1 to 4 are used for comparison and can be melted fully electrically using the cold-top method.
  • Glass 1 is a borosilicate glass 3.3 according to DIN ISO 3585.
  • Glass 20 is used for comparison and cannot be produced with the fully electrical cold-top method without bubbles (alkali plus alkaline earth too high, specific electrical resistance too low, basicity module too high).
  • Ep sink point or processing temperature at
  • No. 14 additionally 0.40% CeO.
  • No. 20 additionally 0.33% CeO

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

La présente invention se rapporte à un verre borosilicaté subissant à une température comprise entre 20 °C et 300 °C une dilatation thermique linéaire de 3,9 à 4,5*10-6 K-1 pour donner un verre de laboratoire, un verre domestique, un verre pour récipient pharmaceutique, un verre de lampe, un verre plat et d'autres verres spéciaux à usage technique, et qui peut être fondu et conditionné par voie entièrement électrique dans des conditions dites 'à voûte froide'. Pour fixer la composition de verre, il faut, outre l'obtention des propriétés de verre désirées, prendre en compte la spécificité du processus de fusion entièrement électrique, d'où une limitation de la plage de variations de plusieurs oxydes de verre, l'exclusion de certaines matières premières et le choix d'agents d'affinage appropriés, etc. La composition du verre est la suivante: SiO¿2? + ZrO2 77,0 à 81,0 % en poids; B2O3 + Na2O + K2O + CaO + MgO + BaO 16,0 à 18,5 % en poids; dont Na2O + K2O + CaO + MgO + BaO 5,4 à 7,0 % en poids; dont CaO + MgO + BaO à 0,9 % en poids; Al2O3 3,7 à 4,9 % en poids; Cl?-¿ 0,05 à 0,4 % en poids; CeO 0,0 à 1,0 % en poids; avec les relations suivantes: rapport CaO + MgO + BaO / ZrO¿2? 0,0 à 1,5; rapport Na2O + K2O + CaO + MgO + BaO / B2O3 + SiO2 + Al2O3 + ZrO2 0,060 à 0,075. Seul NaC1 ou Kc1 est utilisé comme agent d'affinage. Une modification entre ce verre et le verre borosilicaté 3,3 est réversible et peut se répéter aussi souvent que l'on veut et aussi souvent que possible dans un court laps de temps.
EP96909020A 1995-04-28 1996-04-06 Verre borosilicate Withdrawn EP0767763A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19515608 1995-04-28
DE1995115608 DE19515608C1 (de) 1995-04-28 1995-04-28 Borosilicatglas und seine Verwendung
PCT/DE1996/000610 WO1996033954A2 (fr) 1995-04-28 1996-04-06 Verre borosilicate

Publications (1)

Publication Number Publication Date
EP0767763A2 true EP0767763A2 (fr) 1997-04-16

Family

ID=7760566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96909020A Withdrawn EP0767763A2 (fr) 1995-04-28 1996-04-06 Verre borosilicate

Country Status (5)

Country Link
EP (1) EP0767763A2 (fr)
CA (1) CA2193999A1 (fr)
DE (1) DE19515608C1 (fr)
MX (1) MX9700022A (fr)
WO (1) WO1996033954A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19913227C1 (de) * 1999-03-23 2000-07-27 Schott Glas Verwendung eines Glases für temperaturwechselbeständige Getränkebehälter
DE10150884A1 (de) * 2001-10-16 2003-05-08 Schott Glas Thermisch vorspannbares Alkaliborosilikatglas, seine Herstellung und seine Verwendung
JP2014088293A (ja) * 2012-10-31 2014-05-15 Nippon Electric Glass Co Ltd 医薬用ガラス及び医薬用ガラス管
DE102014119594B9 (de) 2014-12-23 2020-06-18 Schott Ag Borosilikatglas mit niedriger Sprödigkeit und hoher intrinsischer Festigkeit, seine Herstellung und seine Verwendung
WO2017014066A1 (fr) * 2015-07-17 2017-01-26 日本電気硝子株式会社 Verre de borosilicate pour récipient médical.
KR102056359B1 (ko) * 2016-05-03 2019-12-16 주식회사 엘지화학 붕규산 유리, 이것을 포함하는 도광판 및 그 제조 방법
DE102017102485A1 (de) * 2017-02-08 2018-08-09 Schott Ag Gläser mit verbesserter hydrolytischer und Laugenbeständigkeit
EP4444665A1 (fr) * 2021-12-06 2024-10-16 Corning Incorporated Compositions de verre borosilicaté chimiquement durables pour le stockage de compositions pharmaceutiques et articles formés à partir de celles-ci
CN114349336B (zh) * 2022-01-13 2022-09-27 浙江大学 一种低膨胀硼硅酸盐透明琉璃及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3722130A1 (de) * 1987-07-02 1989-01-12 Schott Glaswerke Borosilikatglas
DD301821A7 (de) * 1990-03-23 1994-04-07 Jenaer Glaswerk Gmbh Zirkonhaltiges borosilikatglas
DE4012288C1 (fr) * 1990-04-17 1991-07-18 Schott Glaswerke, 6500 Mainz, De
DE4230607C1 (de) * 1992-09-12 1994-01-05 Schott Glaswerke Chemisch und thermisch hochbelastbares, mit Wolfram verschmelzbares Borosilikatglas und dessen Verwendung
DE4313217C1 (de) * 1993-04-22 1994-09-01 Jenaer Schmelztechnik Jodeit G Verfahren und Vorrichtung zur vollelektrischen Schmelze von Neutralglas
DE4325656C2 (de) * 1993-07-30 1996-08-29 Schott Glaswerke Verwendung eines Glaskörpers zur Erzeugung eines als Brandschutzsicherheitsglas geeigneten vorgespannten Glaskörpers auf einer herkömmlichen Luftvorspannanlage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9633954A3 *

Also Published As

Publication number Publication date
DE19515608C1 (de) 1996-08-08
WO1996033954A2 (fr) 1996-10-31
WO1996033954A3 (fr) 1996-12-12
MX9700022A (es) 1997-12-31
CA2193999A1 (fr) 1996-10-31

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