US20040014582A1 - Barium lanthanum silicate glass-ceramics - Google Patents

Barium lanthanum silicate glass-ceramics Download PDF

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Publication number
US20040014582A1
US20040014582A1 US10/362,168 US36216803A US2004014582A1 US 20040014582 A1 US20040014582 A1 US 20040014582A1 US 36216803 A US36216803 A US 36216803A US 2004014582 A1 US2004014582 A1 US 2004014582A1
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United States
Prior art keywords
glass
materials
ceramic
ceramic materials
sio
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Abandoned
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US10/362,168
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English (en)
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Michael Budd
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Norsk Hydro ASA
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Individual
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Assigned to NORSK HYDRO ASA reassignment NORSK HYDRO ASA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BUDD, MICHAEL
Publication of US20040014582A1 publication Critical patent/US20040014582A1/en
Priority to US11/008,151 priority Critical patent/US7189668B2/en
Abandoned legal-status Critical Current

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    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • 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

Definitions

  • the present invention relates to glass-ceramic materials in the BaO—La 2 O 3 —SiO 2 system possessing a coefficient of thermal expansion in excess of 10 ⁇ 10 ⁇ 6 ° C. ⁇ 1 (20-1000° C.) and dilatometric softening points in excess of 1000° C. These materials may be advantageously employed at high temperatures in direct combination with other materials of high expansion or may be used to join or hermetically seal components made of other materials having similarly high expansion.
  • hermetic, electrical feed-through seals which are able to operate at elevated temperature, e.g. for current leads in electrically driven oxygen generation devices where stabilised zirconia is used as the electrolyte, or in high temperature sensors.
  • a noble metal conductor such as platinum or a platinum alloy.
  • the seal and surrounding materials will be required to have expansion coefficients in excess of 10 ⁇ 10 ⁇ 6 ° C. ⁇ 1 (20-1000° C.) and have sufficient refractoriness to be able to operate for extended times at the desired temperature.
  • High expansion glass-ceramics are well known, particularly in the areas of glass-ceramic to metal feed-through seals and in oxidation resistant coatings on nickel based alloys.
  • the sealing materials which are normally selected are based on alkali containing systems such as the Li 2 O—ZnO—SiO 2 system described by McMillan & Partridge (U.S. Pat. No. 3,170,805).
  • alkali containing systems such as the Li 2 O—ZnO—SiO 2 system described by McMillan & Partridge (U.S. Pat. No. 3,170,805).
  • the high alkali metal oxide content reduces the refractoriness of the glass-ceramic, so the maximum operating temperature of the feed-through seal is severely restricted.
  • Andrus & MacDowell disclose a range of glass-ceramic coatings based on either the BaO—SiO 2 or SrO—SiO 2 systems for protecting metal alloy substrates. These coating materials contain additives to enhance the flow characteristics during the coating process. These additives are selected from one or more of the following oxides Al 2 O 3 , ZrO 2 , Y 2 O 3 , MnO, CoO, NiO, FeO and MgO.
  • Glass-ceramic coatings for oxidation protection of titanium aluminide substrates are disclosed.
  • the main object of the present invention was to arrive at glass-ceramic materials which have a combination of high thermal expansion coefficient and high temperature stability.
  • Another object of the present invention was to arrive at glass-ceramic materials which can be employed at high temperatures in direct combination with other materials of high expansion or may be used to join or hermetically seal components made of other materials having similarly high expansion.
  • the inventor has found that by processing certain glass raw materials according to a selected route, glass-ceramic materials having the above-mentioned properties can be obtained.
  • the materials according to the present invention are glass-ceramics from the BaO—La 2 O 3 —SiO 2 system which the inventor has found have the desired combination of high thermal expansion coefficient and high temperature stability.
  • the present invention will thus in its widest scope comprise glass-ceramic materials possessing high softening temperature ( ⁇ 1000° C. or above) and a thermal expansion coefficient in excess of 10 ⁇ 10 ⁇ 6 ° C. ⁇ 1 (measured over the range 20-1000° C.), where said materials are prepared by controlled thermal treatment of precursor glass powders to a temperature in excess of 900° C., wherein said glass powders contain, on a weight percent basis, 10-55% BaO, 3-50% La 2 O 3 and 25-48% SiO 2 . Furthermore, the present invention will comprise a use of the glass-ceramic materials.
  • the glass-ceramic materials are prepared via a powder route, i.e. by the sintering and subsequent crystallisation of precursor glass powders of appropriate composition.
  • a powder route i.e. by the sintering and subsequent crystallisation of precursor glass powders of appropriate composition.
  • there is a significant variation in the rate of crystallisation such that the more slowly crystallising glasses may be considered for use as sealing or bonding materials, whereas those which crystallise most rapidly retain a significant degree of rigidity during the thermal treatment and could not be considered for such a purpose.
  • the glass-ceramic produced will not soften or deform at temperatures below 1000° C. after heat-treatment. It will additionally have a coefficient of thermal expansion in excess of 10 ⁇ 10 ⁇ 6 ° C. ⁇ 1 measured over the temperature range 20-1000° C.
  • Lanthanum oxide which is found to be a beneficial and essential ingredient in the glass-ceramic materials according to the present invention, is not referred to in any of the afore-mentioned patent publications for high expansion, refractory glass-ceramics which are intended to provide an oxidation resistant coating on either metal alloy or titanium aluminide substrates.
  • silicate based, inorganic coatings which have been disclosed in patents where lanthanum oxide is a necessary ingredient. For example in U.S. Pat. Nos.
  • lanthanum oxide in refractory, alumino-silicate based glass-ceramics is referred to by MacDowell & Frasier in DE 1496090.
  • it is considered to be one of the many oxides which can be used for reducing the tendency of the glass melt to devitrify during cooling.
  • the glass-ceramics referred to by MacDowell & Frasier in DE 1496090 were extremely refractory and could be used at temperatures as high as 1400° C., they were of relatively low expansion because the predominant crystal phase developed during heat- treatment was mullite. As such, these materials could not be employed in the same application areas as the glass-ceramics of the present invention since a high thermal expansion is an essential requirement.
  • the lanthanum oxide which is an essential component of the materials of the present invention, serves a dual function. At small levels of addition, e.g. 3-10 wt %, it retards the crystallisation process and therefore improves the sintering (and flow) characteristics of the precursor glass powders during thermal processing. However, unlike other crystallisation inhibitors which are more commonly used in alkaline-earth silicate based glass-ceramics, such as Al 2 O 3 , Y 2 O 3 and ZrO 2 , it does not lead to a significant decrease in the thermal expansion coefficient of the material after heat-treatment due to the development of crystalline phases of low thermal expansion.
  • lanthanum silicate La 2 Si 2 O 7 forms as one of the main crystalline phases in the glass-ceramic.
  • This lanthanum silicate is extremely refractory, with a melting point in the region of 1750° C. As such it contributes to the overall performance of these glass-ceramics in terms of excellent high temperature stability.
  • the glass-ceramics according to the present invention are substantially free ( ⁇ 1 wt %) from alkali metal oxides and boron oxide such that the refractoriness of the glass-ceramic materials is not compromised.
  • the glass-ceramics may contain only limited amounts ( ⁇ 5 wt %) of aluminium oxide as this latter ingredient is known to lower the coefficient of thermal expansion of the glass-ceramic significantly.
  • the first stage in the production of the materials according to the present invention is the melting of the precursor glasses.
  • suitable raw materials such as metal oxides and carbonates are thoroughly mixed in the appropriate proportions to form the glass batch, and this is melted at a temperature of between 1400° C. and ⁇ 1700° C.
  • the material is cooled to form a solid glass which can be processed further.
  • the solid glass is then mechanically broken down to form a powder of suitable particle size distribution.
  • the glass powder is then shaped, preferably but not necessarily with the help of added processing aids, using well established ceramic powder processing means such as slip casting, isostatic pressing, etc.
  • the material is to be used directly as a sealing or bonding material, it is applied to the surface(s) to be joined, or alternatively placed directly in the joint gap.
  • the powder compact is then subjected to a heat-treatment in one or more stages, such that in the course of the entire thermal treatment, it is exposed to a temperature of at least 900° C., or preferably higher, whereby it is converted to a substantially crystalline material with a combination of high thermal expansion coefficient and excellent refractoriness.
  • the heating rate used during the course of the thermal treatment should be compatible with the size and complexity of the components, or assemblies of components being heat-treated. For example, if large or thick-walled green-bodies are being heat-treated, or if large components are being sealed or bonded together, particularly components which are made of high expansion ceramic materials, then the maximum heating rate used during thermal processing should be controlled to avoid any likelihood of fracture due to excessive temperature gradients.
  • FIG. 1 shows the close match in expansion between glass-ceramic support, glass-ceramic sealant and lanthanum nickelate ceramic.
  • FIG. 2 shows a back-scattered electron image of a polished section of a crack-free joint made between glass-ceramic support (bottom) and lanthanum nickelate (top) using glass-ceramic sealant.
  • the support material is glass-ceramic No. 2 and the sealant is glass-ceramic No. 13 (as defined in Table 1).
  • one material with good flow characteristics was used to seal a 10 mm diameter, 2 mm thick disc of lanthanum nickelate, La 2 NiO 4 (CTE 20-1000° C. ⁇ 14 ⁇ 10 ⁇ 6 ° C. ⁇ 1 ) on to a 5 mm thick support of another glass-ceramic material.
  • Lanthanum nickelate was used, as this mixed ionic/electronic conducting ceramic is of interest as an oxygen-selective membrane material in high temperature, electro-chemical reactors.
  • the glass-ceramics which were chosen as the seal and support materials (Nos. 13 and 2, respectively, Table 1) were selected on the basis of their excellent expansion match with lanthanum nickelate (FIG. 1).
  • the glass-ceramic support was produced by pressing a 13 mm diameter disc of glass powder No. 2 containing 1 wt % polyacrylic binder (Acryloid B-72, Rohm & Haas, Philadelphia) to 30 MPa in a uniaxial die. The pressed body was then heated slowly in air to 450° C. in order to remove the organic binder, and subsequently heated at 6° C./minute to a temperature of 1250° C. to effect sintering/crystallisation. After holding at 1250° C. for 2 hours, the sample was cooled at 6° C./minute to 700° C. and then furnace cooled to room temperature. One of the flat surfaces of the disc was ground in preparation for bonding to the lanthanum nickelate.
  • a free-flowing paste was made up by mixing glass powder No. 13 with an organic liquid carrier (pentyl acetate) containing 2 wt% polyacrylic binder (Acryloid B-72).
  • An organic liquid carrier penentyl acetate
  • polyacrylic binder Acryloid B-72
  • a thin layer of this glass powder paste was applied to the surfaces of the glass-ceramic support and the lanthanum nickelate disc which were to be bonded, and allowed to dry.
  • the two halves of the joint were then assembled and transferred to a heat-treatment furnace.
  • a small load of approximately 200 g was placed on the assembled joint in order to facilitate the development of a sound bond during thermal treatment.
  • the assembly was then heated at 2° C./minute to 450° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Dental Preparations (AREA)
  • Surface Treatment Of Glass (AREA)
US10/362,168 2000-08-23 2001-07-27 Barium lanthanum silicate glass-ceramics Abandoned US20040014582A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/008,151 US7189668B2 (en) 2000-08-23 2004-12-10 Barium lanthanum silicate glass-ceramics

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO20004233A NO314897B1 (no) 2000-08-23 2000-08-23 Barium-lantan-silikat baserte glasskeramer og deres anvendelse
NO20004233 2000-08-23
PCT/NO2001/000323 WO2002016278A1 (en) 2000-08-23 2001-07-27 Barium lanthanum silicate glass-ceramics

Related Child Applications (1)

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US11/008,151 Division US7189668B2 (en) 2000-08-23 2004-12-10 Barium lanthanum silicate glass-ceramics

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US20040014582A1 true US20040014582A1 (en) 2004-01-22

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US10/362,168 Abandoned US20040014582A1 (en) 2000-08-23 2001-07-27 Barium lanthanum silicate glass-ceramics
US11/008,151 Expired - Fee Related US7189668B2 (en) 2000-08-23 2004-12-10 Barium lanthanum silicate glass-ceramics

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Country Status (11)

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US (2) US20040014582A1 (de)
EP (1) EP1322566B1 (de)
JP (1) JP2004506589A (de)
AT (1) ATE318248T1 (de)
AU (1) AU2001280281A1 (de)
DE (1) DE60117390T2 (de)
DK (1) DK1322566T3 (de)
ES (1) ES2258540T3 (de)
NO (1) NO314897B1 (de)
PT (1) PT1322566E (de)
WO (1) WO2002016278A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100693938B1 (ko) 2005-09-20 2007-03-12 요업기술원 고체산화물 연료전지용 고온 밀봉재
CN106630636A (zh) * 2016-09-18 2017-05-10 中南大学 一种主晶相为二硅酸镧的微晶玻璃及制备方法和应用
US11205569B2 (en) * 2018-07-20 2021-12-21 Schott Ag Glass-metal feedthrough
CN116514566A (zh) * 2023-03-23 2023-08-01 江西博鑫环保科技股份有限公司 一种全陶瓷膜元件组合专用高温无机胶及组合工艺方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7281412B2 (en) 2005-09-08 2007-10-16 Olenick John A In-situ seal integrity monitoring
US7897530B2 (en) * 2008-01-14 2011-03-01 Atomic Energy Council-Institute Of Nuclear Energy Research Glass-ceramic sealant for planar solid oxide fuel cells
US8481357B2 (en) * 2008-03-08 2013-07-09 Crystal Solar Incorporated Thin film solar cell with ceramic handling layer
US8664963B2 (en) * 2009-07-24 2014-03-04 Alliance For Sustainable Energy, Llc Test device for measuring permeability of a barrier material
JP5999297B2 (ja) * 2011-09-08 2016-09-28 日本電気硝子株式会社 結晶性ガラス組成物およびそれを用いた接着材料
EP2979319B1 (de) 2013-03-29 2018-09-26 Saint-Gobain Ceramics & Plastics, Inc. Auf sanbornit basierende glaskeramische dichtung für hochtemperaturanwendungen
JP6238408B2 (ja) * 2014-01-20 2017-11-29 株式会社ネモト・ルミマテリアル 波長変換部材

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467534A (en) * 1964-10-12 1969-09-16 Corning Glass Works Barium silicate glass-ceramic body and method of making it
US4566987A (en) * 1982-06-16 1986-01-28 Schott-Glaswerke Scintillation glass
US4965229A (en) * 1988-02-05 1990-10-23 Matsushita Electric Industrial Co., Ltd. Glass ceramic for coating metal substrate
US6475938B1 (en) * 1997-04-14 2002-11-05 Norsk Hydro Asa Method of forming a glass ceramic material
US6623845B1 (en) * 1998-03-17 2003-09-23 Matsushita Electric Industrial Co., Ltd. Glass-ceramic composition, and electronic component and multilayer LC composite component using the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5939783A (ja) * 1982-08-26 1984-03-05 日本特殊陶業株式会社 結晶化グレ−ズ基板
JP3225851B2 (ja) 1996-09-26 2001-11-05 松下電器産業株式会社 複合積層セラミック部品
JPH1160266A (ja) * 1997-08-07 1999-03-02 Matsushita Electric Ind Co Ltd ガラス及びガラスセラミック材料
KR100558990B1 (ko) 1999-06-16 2006-03-10 마츠시타 덴끼 산교 가부시키가이샤 유리 세라믹 조성물 및 그것을 이용한 전자 부품 및 적층ｌｃ 복합 부품

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467534A (en) * 1964-10-12 1969-09-16 Corning Glass Works Barium silicate glass-ceramic body and method of making it
US4566987A (en) * 1982-06-16 1986-01-28 Schott-Glaswerke Scintillation glass
US4965229A (en) * 1988-02-05 1990-10-23 Matsushita Electric Industrial Co., Ltd. Glass ceramic for coating metal substrate
US6475938B1 (en) * 1997-04-14 2002-11-05 Norsk Hydro Asa Method of forming a glass ceramic material
US6623845B1 (en) * 1998-03-17 2003-09-23 Matsushita Electric Industrial Co., Ltd. Glass-ceramic composition, and electronic component and multilayer LC composite component using the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100693938B1 (ko) 2005-09-20 2007-03-12 요업기술원 고체산화물 연료전지용 고온 밀봉재
CN106630636A (zh) * 2016-09-18 2017-05-10 中南大学 一种主晶相为二硅酸镧的微晶玻璃及制备方法和应用
US11205569B2 (en) * 2018-07-20 2021-12-21 Schott Ag Glass-metal feedthrough
US11217440B2 (en) * 2018-07-20 2022-01-04 Schott Ag Glass-metal feedthrough
US20220059337A1 (en) * 2018-07-20 2022-02-24 Schott Ag Glass-metal feedthrough
US11728156B2 (en) * 2018-07-20 2023-08-15 Schott Ag Glass-metal feedthrough
CN116514566A (zh) * 2023-03-23 2023-08-01 江西博鑫环保科技股份有限公司 一种全陶瓷膜元件组合专用高温无机胶及组合工艺方法

Also Published As

Publication number Publication date
ES2258540T3 (es) 2006-09-01
NO20004233D0 (no) 2000-08-23
US20050130823A1 (en) 2005-06-16
NO314897B1 (no) 2003-06-10
DK1322566T3 (da) 2006-07-03
ATE318248T1 (de) 2006-03-15
WO2002016278A1 (en) 2002-02-28
DE60117390T2 (de) 2006-10-12
DE60117390D1 (de) 2006-04-27
JP2004506589A (ja) 2004-03-04
PT1322566E (pt) 2006-07-31
EP1322566A1 (de) 2003-07-02
US7189668B2 (en) 2007-03-13
NO20004233L (no) 2002-02-25
AU2001280281A1 (en) 2002-03-04
EP1322566B1 (de) 2006-02-22

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BUDD, MICHAEL;REEL/FRAME:014117/0360

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