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WO1997036836A1 - Modificateur de verre de scellement utilise avec un vehicule ne contenant pas ou presque pas de composes organiques volatiles - Google Patents

Modificateur de verre de scellement utilise avec un vehicule ne contenant pas ou presque pas de composes organiques volatiles Download PDF

Info

Publication number
WO1997036836A1
WO1997036836A1 PCT/US1997/005298 US9705298W WO9736836A1 WO 1997036836 A1 WO1997036836 A1 WO 1997036836A1 US 9705298 W US9705298 W US 9705298W WO 9736836 A1 WO9736836 A1 WO 9736836A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
sealing
modifier
amount
sealing glass
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/US1997/005298
Other languages
English (en)
Inventor
Joseph Peer
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.)
Techneglas LLC
Original Assignee
Techneglas 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 Techneglas LLC filed Critical Techneglas LLC
Priority to EP97917762A priority Critical patent/EP0828693A4/fr
Priority to JP9535533A priority patent/JPH11507005A/ja
Publication of WO1997036836A1 publication Critical patent/WO1997036836A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C03C8/245—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders containing more than 50% lead oxide, by weight

Definitions

  • the present invention is concerned generally with sealing glass compositions, in
  • sealing glass paste for sealing glass
  • the invention renders a PbO-containing
  • sealing glass suitable for use in combination with a vehicle that includes much lower
  • VOC volatile organic compounds
  • glass modifier of the present invention therefore allows the sealing process to be carried
  • PbO-containing sealing glasses and particularly PbO/B 2 O 3 /ZnO sealing glasses,
  • cathode ray tube such as a color television picture tube.
  • sealing glasses have the
  • sealing glasses (sometimes referred to as “solder” glasses) are
  • crystallized glass has a melting point temperature that is higher than the fiber softening
  • the seals also must have good dielectric
  • processing steps include the separate and successive application to the face
  • a carbon or graphite background may be used to cover the face plate.
  • a carbon or graphite background may be used to form a carbon or graphite background.
  • a resinous or plastic film may be applied to the surface
  • aluminized surface is connected to a metal stud on the inner surface of the face plate.
  • a sealing glass is applied to the mating edge surfaces of the funnel.
  • the PbO constituent in the sealing glass has a natural propensity or tendency to be
  • any dielectric breakdown in the seal between the funnel and face plate will provide a source of
  • Sealing glasses typically are applied to the mating edge surfaces of the funnel in
  • the paste is made by combining the sealing glass with a vehicle that holds
  • the glass frit in a ribbon form for a period of time sufficient to enable the resultant paste to
  • the mating pieces e.g., in the case of a color television tube
  • vehicle constituents must be pyrolyzable when they are subjected to a temperature below
  • Conventional vehicles generally comprise a binder and a solvent.
  • the only binder is the binder
  • nitrocellulose usually as a 1 to
  • cellulose and hydroxypropyl cellulose may be used as binders for PbO-containing sealing
  • nitrocellulose is particularly preferred because it tends to decrease the reduction
  • Amyl acetate and butyl acetate are the preferred solvents for use in sealing glass
  • Ethylene glycol methyl ether also is a suitable binder
  • binder solvents that may be used.
  • the amount of solvent in the paste will depend upon
  • the desired paste consistency but will usually comprise about five to about fifteen weight
  • the amount of vehicle necessary for the paste is the amount that will maintain the
  • the ribbon must be wide enough to produce an
  • the weight of the ribbon being extruded for a given length may vary appreciably over time
  • dispensing apparatus must carefully monitor the ribbon and adjust the volume of the paste
  • sealing glass solids including refractory
  • fillers, nucleating agents, and any modifiers) to vehicle is usually in the range of about
  • the paste obtained by combining the vehicle with the sealing glass is
  • seals formed from pastes that employ nitrocellulose as a binder are less
  • nitrocellulose is thought to provide a source of oxygen during heating of the sealing glass
  • the devitrified seals formed by these other binders is gray or gray-black
  • glass frit did not eliminate the need for the use of at least some nitrocellulose binder.
  • containing sealing glasses include nitrocellulose, which in turn requires the use of a
  • VOC-free or low-VOC vehicle capable of being used with a VOC-free or low-VOC vehicle, and particularly an aqueous
  • low-VOC vehicle includes VOC-free formulations.
  • This invention aids in fulfilling these needs in the art by providing a sealing glass
  • modifier means any substance that
  • the modifier comprises an inorganic nitrate
  • the inorganic nitrate is Bi(NO 3 ) 3 5H 2 O and/or Zn(NO 3 ) 2
  • the modifier of the present invention may be incorporated as a component of the
  • the modified frit glass comprises a PbO-containing glass frit having a
  • sealing or firing temperature within the temperature range of about 420° C. to about 460°
  • the invention includes a sealing
  • the modifier also may be dissolved or dispersed in a sealing glass vehicle for a
  • the modified vehicle comprises a VOC-free or low-VOC vehicle
  • the invention further includes a sealing glass
  • the invention includes a method of sealing a face plate to the funnel of
  • the sealing temperature range of between about 420° C. and about 460° C. for a period of
  • this invention includes a method of sealing a face plate to the funnel of a
  • cathode ray tube using a PbO-containing sealing glass in a VOC-free or low-VOC vehicle using a PbO-containing sealing glass in a VOC-free or low-VOC vehicle
  • steps of A Combining the sealing glass with a modifier in an amount sufficient to prevent the PbO from being chemically reduced when the sealing glass is fired at a
  • the sealing temperature range of between about 420° C. and about 460° C. for a period of
  • this invention provides a method of sealing a face plate to a funnel of
  • the sealing temperature range of between about 420° C. and about 460° C. for a period of
  • PbO-containing sealing glass to be used in combination with a VOC-free or low-VOC
  • the modifier preferably comprises an inorganic nitrate that is
  • the modifier is added to the sealing glass system in an amount sufficient to
  • invention includes the use of a modifier in a sealing glass system to decrease the reduction
  • glass paste including the modified sealing glass, a vehicle inco ⁇ orating the modifier, a
  • sealing glass paste including the modified vehicle, the methods of making the modified
  • the present invention provides a sealing glass modifier that decreases the
  • sealing or firing enables the sealing glass to be used in combination with a VOC-free
  • the modifier preferentially comprises bismuth nitrate and/or zinc
  • the sealing glass is fired in the presence of reducing conditions at a temperature sufficient
  • Lead-zinc-borate solder glasses are preferred in practicing this invention. Such as
  • base glass also are referred to herein as the "base glass.”
  • the lead-zinc-borate glasses suitable for use in the present invention typically include
  • Table 1 expressed in weight percent, and wherein the total content of all oxides is 100%.
  • Li,0, CdO, and Fe 2 0 3 can be included. However, it is preferred in many instances not to
  • compositions that consist essentially only
  • the particle size of the glass frit is not particularly critical to the practice of the
  • the particle size of the glass frit will be such that about 100% of the particles
  • the base glass used in the practice of this invention have the same
  • a VOC-free vehicle that reasonably satisfies the requirements that the vehicle be
  • free vehicle is a colorless liquid comprising 97-98% water and less than 2% cellulose. It
  • sealing glass solids including refractory fillers, nucleating
  • VOC-free or low-VOC vehicle such as vehicle
  • the modifier of the present invention preferably comprises an
  • the modifier is added to the sealing glass system in
  • Bi(NO 3 ) 3 5H 2 0 and/or Zn(NO 3 ) 2 6H 2 0 are the particularly preferred modifiers.
  • the sealing glass paste or on the sealing properties of the base glass are the sealing glass paste or on the sealing properties of the base glass.
  • modifier also may be shown by dielectric tests of the resultant seal.
  • samples were prepared by inco ⁇ orating a modifier (in an amount equal to about 1 % by
  • the samples were fired at a temperature of about 420° C. to about 460° C.
  • VOC-free vehicle A9065 in a weight ratio of about 8.3: 1 and fired at a temperature of
  • porous appearance which is indicative of low seal strength and an increased likelihood of
  • the effective amount of the modifier typically will be in the range of about
  • sealing glass powder This may be accomplished, for example, using the two-step
  • sealing glass powder is blended in a twin shell or rotocone blender for about 5 to about
  • the material from Step 2 is referred to as a modifier masterblend.
  • a desired modifier masterblend A desired
  • amount of the modifier masterblend may be uniformly dispersing in the final sealing
  • a sealing glass paste of the present invention may be prepared by mixing the
  • the modified vehicle of this invention may be prepared by dissolving an
  • the amount of modifier added to the vehicle to create the modified vehicle generally includes
  • Another sealing glass paste of the present invention may be prepared by mixing
  • the weight ratio of sealing glass solids to vehicle is usually
  • the present invention includes a method of sealing a face plate to the funnel of
  • sealing amount of the sealing glass composition of this invention and B. Subjecting the applied sealing glass composition to a sealing temperature within
  • the sealing temperature range of between about 420° C. and about 460° C. for a period
  • this invention includes a method of sealing a face plate to the funnel of
  • the sealing temperature range of between about 420° C. and about 460° C. for a period
  • this invention provides a method of sealing a face plate to a funnel
  • a cathode ray tube such as a color television tube
  • sealing glass comprising the steps of:
  • the sealing temperature range of between about 420° C. and about 460° C. for a period
  • sealing glass pastes made with a VOC-free vehicle such as A9065
  • the conventional vehicle system have a stable rheology for about 0.5 to about 8 hours
  • VOC-free pastes have commercially useful, but not optimal rheology and shelf-life

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

Cette invention concerne un modificateur de verre de scellement qui permet, dans un verre de scellement contenant du PbO, de diminuer la réduction du PbO en plomb métallique lors du processus de scellage ou de cuisson. Ce modificateur permet également d'utiliser le verre de scellement en combinaison avec un véhicule ne contenant pas, ou presque pas, de composés organiques volatils. Ce modificateur comprend de préférence un nitrate non organique, lequel reste stable sur le plan thermique à des températures auxquelles la fritte de verre de scellement assure l'adhésion entre deux surfaces de verre; ce nitrate peut toutefois être réduit à un état d'oxydation inférieur lorsqu'il est soumis à des conditions de réduction. Ce modificateur est ajouté au système de verre de scellement dans une quantité suffisante pour empêcher le PbO d'être réduit chimiquement lorsque ledit verre de scellement est cuit dans des conditions de réduction et à une température suffisante pour sceller le verre. Les modificateurs particulièrement préférés consistent en du Bi(NO3)3.5H2O et/ou du Zn(NO3)2.6H2O. Ce modificateur peut être incorporé en qualité de composant du verre de scellement ou, dans un autre mode réalisation, être dissous ou dispersé dans le véhicule.
PCT/US1997/005298 1996-04-02 1997-04-01 Modificateur de verre de scellement utilise avec un vehicule ne contenant pas ou presque pas de composes organiques volatiles Ceased WO1997036836A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97917762A EP0828693A4 (fr) 1996-04-02 1997-04-01 Modificateur de verre de scellement utilise avec un vehicule ne contenant pas ou presque pas de composes organiques volatiles
JP9535533A JPH11507005A (ja) 1996-04-02 1997-04-01 揮発性有機化合物フリーまたは低揮発性有機化合物ビヒクルに使用する封止ガラス改質剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62664096A 1996-04-02 1996-04-02
US08/626,640 1996-04-02

Publications (1)

Publication Number Publication Date
WO1997036836A1 true WO1997036836A1 (fr) 1997-10-09

Family

ID=24511228

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/005298 Ceased WO1997036836A1 (fr) 1996-04-02 1997-04-01 Modificateur de verre de scellement utilise avec un vehicule ne contenant pas ou presque pas de composes organiques volatiles

Country Status (5)

Country Link
EP (1) EP0828693A4 (fr)
JP (1) JPH11507005A (fr)
KR (1) KR19990022312A (fr)
MX (1) MX9709381A (fr)
WO (1) WO1997036836A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6245699B1 (en) 1999-04-30 2001-06-12 Techneglas, Inc. High strength sealing glass
WO2004018376A1 (fr) * 2002-08-22 2004-03-04 Johnson Matthey Public Limited Company Encre ceramique
EP2053026A1 (fr) * 2007-10-26 2009-04-29 Institute of Nuclear Energy Research, Atomic Energy Council Matériau d'étanchéité pour piles à combustible d'oxyde solide
US8012895B2 (en) * 2007-09-04 2011-09-06 Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan Sealing material for solid oxide fuel cells
US9985240B2 (en) 2010-02-10 2018-05-29 Nippon Electric Glass Co., Ltd. Sealing material and sealing method using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973975A (en) * 1972-04-21 1976-08-10 Owens-Illinois, Inc. PbO-containing sealing glass with higher oxide of a cation to avoid PbO reduction
JPS59141141A (ja) * 1983-01-31 1984-08-13 Matsushita Electric Works Ltd ガラスフリツトによる封着方法
SU1578093A1 (ru) * 1987-08-26 1990-07-15 Организация П/Я А-1695 Глазурный шликер дл керамических конденсаторов

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0769670A (ja) * 1993-09-06 1995-03-14 Nippon Sheet Glass Co Ltd 封着用ガラス材料
JP3417066B2 (ja) * 1994-07-27 2003-06-16 日本板硝子株式会社 封着用材料
JPH0891870A (ja) * 1994-09-26 1996-04-09 Nippon Electric Glass Co Ltd Ｃｒｔ用フリット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973975A (en) * 1972-04-21 1976-08-10 Owens-Illinois, Inc. PbO-containing sealing glass with higher oxide of a cation to avoid PbO reduction
JPS59141141A (ja) * 1983-01-31 1984-08-13 Matsushita Electric Works Ltd ガラスフリツトによる封着方法
SU1578093A1 (ru) * 1987-08-26 1990-07-15 Организация П/Я А-1695 Глазурный шликер дл керамических конденсаторов

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0828693A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6245699B1 (en) 1999-04-30 2001-06-12 Techneglas, Inc. High strength sealing glass
WO2004018376A1 (fr) * 2002-08-22 2004-03-04 Johnson Matthey Public Limited Company Encre ceramique
US8012895B2 (en) * 2007-09-04 2011-09-06 Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan Sealing material for solid oxide fuel cells
EP2053026A1 (fr) * 2007-10-26 2009-04-29 Institute of Nuclear Energy Research, Atomic Energy Council Matériau d'étanchéité pour piles à combustible d'oxyde solide
US9985240B2 (en) 2010-02-10 2018-05-29 Nippon Electric Glass Co., Ltd. Sealing material and sealing method using the same

Also Published As

Publication number Publication date
EP0828693A1 (fr) 1998-03-18
EP0828693A4 (fr) 1998-11-18
KR19990022312A (ko) 1999-03-25
MX9709381A (es) 1998-11-29
JPH11507005A (ja) 1999-06-22

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