WO2001028945A1 - Vitroceramique transparente de forsterite - Google Patents

Vitroceramique transparente de forsterite Download PDF

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Publication number
WO2001028945A1
WO2001028945A1 PCT/US2000/028637 US0028637W WO0128945A1 WO 2001028945 A1 WO2001028945 A1 WO 2001028945A1 US 0028637 W US0028637 W US 0028637W WO 0128945 A1 WO0128945 A1 WO 0128945A1
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WO
WIPO (PCT)
Prior art keywords
glass
ceramic
forsterite
weight percent
ceramics
Prior art date
Application number
PCT/US2000/028637
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English (en)
Inventor
George Beall
Original Assignee
Corning Incorporated
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 Corning Incorporated filed Critical Corning Incorporated
Priority to AU12076/01A priority Critical patent/AU1207601A/en
Publication of WO2001028945A1 publication Critical patent/WO2001028945A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/0229—Optical fibres with cladding with or without a coating characterised by nanostructures, i.e. structures of size less than 100 nm, e.g. quantum dots
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03C10/0036—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 SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—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 SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/646—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/685—Aluminates; Silicates

Definitions

  • MEDIA filed as a United States Provisional Application Serial Number 60/160,053, on October 18, 1999, in the names of George H. Beall et al., and assigned to the same assignee as this application, is directed to transition- metal doped, glass ceramic materials that exhibit properties that make them suitable as gain media for use in optical amplifiers and/or laser pumps.
  • Pinckney, William Vockroth and Ji Wang and assigned to the same assignee as this application is directed to glass-ceramic materials containing nanocrystals and being doped with a transition metal, and to a method of producing such glass-ceramics in the form of optical fibers.
  • the present invention relates to transparent glass ceramics, in particular, to substantially transparent glass-ceramics based on a predominant crystal phase of forsterite.
  • Glass-ceramics are polycrystalline materials formed by a controlled crystallization of a precursor glass.
  • the method for producing such glass- ceramics customarily involves three fundamental steps: first, a glass-forming batch is melted; second, the melt is simultaneously cooled to a temperature at least below the transformation range thereof and a glass body of a desired geometry shaped therefrom; and third, the glass body is heated to a temperature above the transformation range of the glass in a controlled manner to generate crystals in situ.
  • the glass body is exposed to a two-stage treatment.
  • the glass will be heated initially to a temperature within, or somewhat above, the transformation range for a period of time sufficient to cause the development of nuclei in the glass.
  • the temperature will be raised to levels approaching, or even exceeding, the softening point of the glass to cause the growth of crystals on the previously-formed nuclei.
  • the resultant crystals are commonly more uniformly fine-grained and the articles are typically more highly crystalline.
  • Internal nucleation allows glass-ceramics to possess such favorable qualities as a very narrow, particle size distribution and highly uniform dispersion throughout the glass host.
  • Transparent glass-ceramics are well known to the art; the classic study thereof being authored by G. H. Beall and D.A. Duke in "Transparent Glass-ceramics-
  • Glass-ceramic bodies will display transparency to the human eye when the crystals present therein are considerably smaller than the wavelength of visible light. More specifically, transparency generally results from crystals less than 50 nm, and preferably as low as 10 nm, in size. Transparency in glass-ceramics can also be produced with crystals larger than 50 nm if the crystal birefringence and the index of refraction mismatch between the crystal phase and the glassy phase are both low.
  • Transparent glass-ceramics which contain a relatively small volume percentage of crystals, can be of great use in cases where the parent glass provides an easy-to-melt or an-easy-to-form vehicle for a crystal.
  • the crystal in itself, may be difficult or expensive to synthesize, but may provide highly desirable features, such as optical activity.
  • the crystals in the glass-ceramic are generally oriented randomly throughout the bulk of the glass, unlike a single crystal which has a specific orientation. Random orientation, and consequent anisotropy, are advantageous for many applications, one example being that of optical amplifiers, where polarization-independent gain is imperative.
  • Transparent glass-ceramics, doped with transition elements can combine the optical efficiency of crystals with the forming flexibility of glass. For example, both bulk (planar) and fiber forms can be fabricated from these glass-ceramics.
  • transparent, glass-ceramic materials which contain small tetrahedral and interstitial sites, and hence are suitable as potentially valuable hosts for small, optically active, transition elements.
  • Such elements include, but are not limited to, Cr 4+ , Cr 3+ , Co 2+ , Cu 2+ , Mn 2+ , Ni 2+ , Fe 3+ , Fe 2+ , and Cu + , which impart luminescence and fluorescence thereto.
  • the doped glass-ceramic materials are suitable for application in the optical field industry.
  • chromium-doped, forsterite, single crystals could be used as a laser material in the 1210 nm to 1260 nm range. Further work determined that the active ion was Cr 4+ , a rare valence state of chromium, and that strong luminescence and tunable laser action could be expected in the broad spatial region from 1.1 ⁇ to 1.4 ⁇ , and perhaps deeper into the infrared.
  • United States Patent 5,717,517 is directed at a method for amplifying a signal pulse of a laser light by providing an amplifying medium which contains an elongated core having crystalline particles dispersed within a non-gaseous medium.
  • Cr 4+ doped forsterite single crystals are provided as an example of a suitable crystalline particle.
  • the primary object of the present invention is to provide glass-ceramic materials which are substantially, and desirably totally, transparent, and which contain a predominant crystal phase of forsterite.
  • Another object of the present invention is to provide such forsterite glass-ceramics which are capable of being doped with ingredients which confer luminescence and/or fluorescence thereto.
  • An important advantage of the present glass-ceramic family is that it provides a material containing forsterite crystals which selectively incorporate transition metal ions including, but not limited to Cr 4+ , Cr 3+ , Co 2+ , Cu 2+ , Mn 2+ , Ni 2+ , Fe 3+ , Fe 2+ , and Cu + .
  • the material is glass-based, thus providing the important flexibility of allowing for fabrication of both bulk (such as planar substrates) and fiber (such as optical fiber) forms.
  • a transparent glass-ceramic containing a predominant crystal phase of forsterite and having a composition consisting essentially of, in weight percent on an oxide basis, SiO 2 30-60; AI 2 O 3 10-25; MgO 13-30; K 2 O 8-25; TiO 2 0-10; and GeO 2 0-25.
  • composition range for best transparency, is based on a composition consisting essentially, in weight percent on an oxide basis, of
  • the present inventive, forsterite glass- ceramics are doped with up to 1 wt. % chromium oxide, and preferably with 0.003 to 0.3 wt. % chromium oxide.
  • a method of making the inventive glass-ceramic materials comprising the steps of: a.) melting a batch for a glass having a composition consisting essentially, in weight percent on an oxide basis, of SiO 2 30-60; AI 2 O 3 10-25; MgO 13-30; K 2 O 8-25; TiO 2 0-10; and GeO 2 0-25. b.) cooling the glass to a temperature at least below the transformation range of the glass; c.) exposing the glass to a temperature between about 600-1000°C for a period of time sufficient to cause the generation of a glass-ceramic which is substantially transparent and which contains a predominant crystal phase of forsterite; and, d.) cooling the glass-ceramic to room temperature.
  • FIG. 1 shows the fluorescence spectra for the glass-ceramic of Example 3 doped with 0.05 wt. % Cr 2 O 3 .
  • the present invention is based on the discovery of a family of compositions that can produce glasses of excellent stability which can be cerammed to produce substantially transparent glass-ceramics containing forsterite as the predominant crystal phase.
  • the present inventive forsterite glass-ceramics are suitable for employment in the telecommunications industry when doped with transition metal ions, such as Cr 4+ .
  • transition metal ions such as Cr 4+ .
  • Forsterite (Mg 2 SiO 4 ) an orthosilicate of the olivine family with only 33 mole % silica, does not form a glass, even on rapid quenching.
  • the challenge then, was to create a stable glass from which forsterite, and not the more siliceous Mg-rich crystals like enstatite (MgSiO 3 ), could form.
  • the best approach seemed to be to attempt to produce a stable glass with a tendency towards amorphous phase separation on cooling or subsequent reheating.
  • the dispersed phase could be made rich in MgO and the continuous phase rich in glass-formers like silica and alumina.
  • the present inventive, substantially transparent glass-ceramic is based on a composition consisting essentially, in weight percent on an oxide basis, of SiO 2 30-60
  • alkali other than K 2 O can be used. Partial molar replacement of K 2 O up to about 50%, by Li 2 O, Na 2 O, Rb 2 O, and Cs 2 O is possible.
  • the most preferred composition range, for best transparency, is based on a composition consisting essentially, in weight percent on an oxide basis, of
  • substantially transparent forsterite glass-ceramics up to 1 wt. % chromium oxide is added to the parent glass, with the preferred range being about 0.003 to 0.3 wt. % chromium oxide.
  • the following Table sets forth a number of glass compositions, expressed in terms of parts by weight on the oxide basis, illustrating the parameters of the present invention. The Table also presents the ceramming schedule in °C and hours, as well as the crystal phases observed in each resulting glass-ceramic. Inasmuch as the sum of the individual components in each recited glass approximates 100, for all practical purposes the tabulated values may be deemed to reflect weight percent.
  • the batch ingredients for preparing glasses falling within the inventive composition ranges may comprise any materials, either the oxides or other compounds, which, upon being melted together, will be converted into the desired oxide in the proper proportions.
  • the exemplary glasses were produced in the following manner.
  • the batch materials were compounded, mixed together to assist in securing a homogeneous melt, and then placed into platinum crucibles.
  • the crucibles were introduced into a furnace operating at temperatures of 1400-1600°C, and the batches were melted for 4-16 hours.
  • the melt was poured as free "patties" and transferred to an annealer operating at about 550-600°C.
  • the glass patties were subjected to a ceramming cycle by placing them into a furnace and heat treating according to the following schedule: a first exposure to a temperature within the range of about 600-800°C for a period of time sufficient to generate the development of nuclei therein, usually about between 2-16 hours. Second, the nucleated glass patties were then exposed to a temperature within the range of about 900-1000°C for a period of time sufficient to effect the growth of crystals on the nuclei. The period of time will generally be about between 1-4 hours.
  • inventive compositions are self-nucleating due to liquid-liquid phase separation and therefore require no added nucleating agents. More specifically, nucleation is promoted by amorphous phase separation. However, even though nucleating agents are not required, in most cases the addition of nucleating agents, such as TiO 2 (up to 5 wt. %), results in a finer crystal size and improved transparency.
  • the crystalline phases of the resulting glass-ceramic materials were identified using X-ray powder diffraction.
  • the microstructure of the inventive glass-ceramics contains forsterite microcrystals of 10-50 nm in size (in preferred compositions) in a stable alkali aluminosilicate glass.
  • the total crystallinity ranges from about 10% to 50% by volume depending on the individual composition.
  • the forsterite microcrystals which make-up the crystalline phase are internally grown in the base glass during the ceramming cycle.
  • the forsterite crystal structure in the present inventive, glass-ceramic material provides both tetrahedral and octahedral cation sites of appropriate size to house transition metal cations.
  • the forsterite microcrystals can concentrate certain transition metals into specific crystalline sites, for example Cr 4+ into tetrahedrally-coordinated sites, and Cr 3+ , Ni + , Co 2+ , Cu 2+ , and Mn 2+ into octahedrally-coordinated sites.
  • optical activity is obtained in the inventive glass-ceramics.
  • crystals with tetrahedrally- coordinated Cr 4+ ions provide unique optical characteristics. Therefore, in one possible application, the present inventive, transparent, forsterite glass- ceramics doped with transition metal ions, are suitable for employment in the optics and laser industries in such specific applications as optical amplifiers and pump lasers.
  • Example 3 was doped with 0.05 wt. % Cr 2 O 3 , and fluorescence measurements were taken.
  • the chromium emission spectra for the present forsterite glass-ceramics vary with the state of oxidation. Generally, a Cr 3+ peak just below 1 ⁇ m is observed as a shoulder on a Cr 4+ peak centered near 1.2 ⁇ m. The latter is enhanced by increasing the state of oxidation of the parent glass.
  • substantially transparent, forsterite glass-ceramic materials include femtosecond and tunable lasers, wide-band optical fiber amplifiers, and regenerative amplifiers in the near infrared.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une vitrocéramique sensiblement et préférablement transparente dans sa totalité, qui comprend une phase cristal prédominante de fostérite. La vitrocéramique est formée de verres précurseurs ayant les compositions suivantes en pourcentage poids sur une base d'oxyde : SiO2 30-60, Al2O3 10-25, MgO 13-30, K2O 8-20, TiO2 0-10 et GeO2 0-25. La vitrocéramique peut être dopée jusqu'à 1 % en pds d'oxyde de chrome afin de lui conférer une activité optique.
PCT/US2000/028637 1999-10-18 2000-10-13 Vitroceramique transparente de forsterite WO2001028945A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU12076/01A AU1207601A (en) 1999-10-18 2000-10-13 Transparent forsterite glass-ceramics

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US16009399P 1999-10-18 1999-10-18
US60/160,093 1999-10-18
US17386399P 1999-12-30 1999-12-30
US60/173,863 1999-12-30

Publications (1)

Publication Number Publication Date
WO2001028945A1 true WO2001028945A1 (fr) 2001-04-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003022767A1 (fr) * 2001-09-13 2003-03-20 Alstom Traitement de vitrocérame transparent
US6660669B2 (en) 1999-10-18 2003-12-09 Corning Incorporated Forsterite glass-ceramics of high crystallinity and chrome content
EP1391015A1 (fr) * 2001-05-03 2004-02-25 Corning Incorporated Source a large bande dotee d'ions metalliques de transition
JP2004284829A (ja) * 2003-03-19 2004-10-14 National Institute For Materials Science 透光性ケイ酸マグネシウム焼結体及びその製造方法
US6813903B2 (en) 1999-10-18 2004-11-09 Corning Incorporated Method of making forsterite glass-ceramics

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717517A (en) * 1995-01-13 1998-02-10 The Research Foundation Of City College Of New York Method for amplifying laser signals and an amplifier for use in said method
US5958807A (en) * 1995-01-27 1999-09-28 Sarnoff Corporation Low dielectric loss glass ceramic compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717517A (en) * 1995-01-13 1998-02-10 The Research Foundation Of City College Of New York Method for amplifying laser signals and an amplifier for use in said method
US5958807A (en) * 1995-01-27 1999-09-28 Sarnoff Corporation Low dielectric loss glass ceramic compositions
US6017642A (en) * 1995-01-27 2000-01-25 Sarnoff Corporation Low dielectric loss glasses

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660669B2 (en) 1999-10-18 2003-12-09 Corning Incorporated Forsterite glass-ceramics of high crystallinity and chrome content
US6813903B2 (en) 1999-10-18 2004-11-09 Corning Incorporated Method of making forsterite glass-ceramics
EP1391015A1 (fr) * 2001-05-03 2004-02-25 Corning Incorporated Source a large bande dotee d'ions metalliques de transition
EP1391015A4 (fr) * 2001-05-03 2009-04-15 Corning Inc Source a large bande dotee d'ions metalliques de transition
WO2003022767A1 (fr) * 2001-09-13 2003-03-20 Alstom Traitement de vitrocérame transparent
JP2004284829A (ja) * 2003-03-19 2004-10-14 National Institute For Materials Science 透光性ケイ酸マグネシウム焼結体及びその製造方法

Also Published As

Publication number Publication date
AU1207601A (en) 2001-04-30

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