CN1379742A - Transparent glass-ceramics based on alpha-and beta-willemite - Google Patents

Transparent glass-ceramics based on alpha-and beta-willemite Download PDF

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CN1379742A
CN1379742A CN 00814337 CN00814337A CN1379742A CN 1379742 A CN1379742 A CN 1379742A CN 00814337 CN00814337 CN 00814337 CN 00814337 A CN00814337 A CN 00814337A CN 1379742 A CN1379742 A CN 1379742A
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glass
ceramic
willemite
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transparent
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CN1184157C (en
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L·平克尼
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Corning Inc
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Corning Inc
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    • 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
    • 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

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

Abstract

A glass-ceramic which is substantially and desirably totally transparent, and which contains a willemite predominant crystal phase within the ternary Mg2SiO4-Zn2SiO4-Li4SiO4 system. The glass-ceramic is formed from precursor glasses having the following compositions, in weight percent on an oxide basis, of 25-60 SiO2, 4-20 Al2O3, 20-55 ZnO, 0-12 MgO, 0-18 K2O, 0-12 Na2O, 0-30 GeO2, with the condition that SIGMA K2O+ Na2O >/= 5. The glass-ceramic may be doped with up to 1 wt. % Cr2O3 to impart optical activity thereto.

Description

Based on α-and the transparent glass ceramics of β-willemite
Consult related application
Being filed in Augusts 18 in 1999 Japan and the United States state provisional application sequence numbers is 60/160,053, the application that is entitled as " TRANSITION-METAL GLASS-CERAMIC GAINMEDIA (transition metal glass-ceramic gain media) " that transfers the same beneficiary of the application such as George H.Beall relates to the glass ceramic material that is mixed with transition metal, and the performance that this material showed is applicable in optical amplifier and/or the laser pump as gain media them.
Being filed in Augusts 18 in 1999 Japan and the United States state provisional application sequence numbers is 60/159,967, the application that transfers being entitled as of the same beneficiary of the application " TRANSPARENT (LITHIUM; ZINC; MAGNESIUM) ORTHOSILICATE GLASS-CERAMICS (transparent orthosilicic acid (lithium, zinc, magnesium) glass-ceramic) " such as George H.Beall relates to the glass ceramic material that is mixed with transition metal, and the performance that this material showed is applicable in optical amplifier and/or the laser pump as gain media them.
Being filed in Augusts 18 in 1999 Japan and the United States state provisional application sequence numbers is 60/160,052, the application that is entitled as " GLASS-CERAMIC FIBER AND METHOD (glass ceramic fibre and manufacture method thereof) " that transfers the same beneficiary of the application such as GeorgeH.Beall, Linda R.Pinckney, William Vockroth and Ji Wang relates to the glass ceramic material that contains fine brilliant (nanocrystals) and be mixed with transition metal, and relates to the manufacture method of this glass-ceramic of optical fiber form.
Being filed in Augusts 18 in 1999 Japan and the United States state provisional application sequence numbers is 60/160,093, the application that is entitled as " TRANSPARENT AND TRANSLUCENT FORSTERITE GLASS-CERAMICS (transparent and translucent forsterite glass-ceramic) " of George H.Beall, with being filed in December in 1999 U.S. on the 30th provisional application sequence number is the same title application of 60/174,012 George H.Beall.
Being filed in Augusts 18 in 1999 Japan and the United States state provisional application sequence numbers is 60/160,138, being entitled as of LindaR.Pinckney " GLASS-CERAMICS BASED ON ALPHA-AND BETA-WILLEMITE (and based on α-and the glass-ceramic of β willemite) " application, with being filed in November 29 in 1999 Japan and the United States state provisional application sequence numbers is the same title application of 60/167,871 Linda R.Pinckney.
Invention field
The present invention relates to the transparent glass ceramics body, particularly based on α-and the glass-ceramic of the substantially transparent of β-willemite.
Background technology
Glass-ceramic is the polycrystalline material that is formed by precursor glass controlled crystallization.The method of making this glass-ceramic generally includes three basic steps: the first, and the raw material of fusing form glass; The second, melt is cooled to be lower than at least the temperature of its transition range simultaneously, form vitreum thus with required geometrical shape; The 3rd, in a controlled manner vitreum is heated to the temperature more than the transition range of glass, produce crystal on the spot.
Usually vitreum is carried out second-stage treatment.Therefore, reach in its transition range or the temperature that exceeds slightly to glass heats earlier, be enough to make the time that produces nucleus in the glass.Then, be warming up to approaching or even surpass the temperature of glass softening point so that crystal is grown on preformed nucleus.The normally comparatively uniform particulate of the crystal that produces, its goods are generally the height crystalline.Inner nucleogenesis makes glass-ceramic have the extremely narrow and uniformly dispersed high good quality of size-grade distribution of whole glass body.
Transparent glass ceramics is as known in the art; Classics research to it is outstanding in " Transparent Glass-Ceramics (transparent glass ceramics), Journal of MaterialsScience (Materials science magazine), 4, the 340-352 page or leaf (1969) of G.H.Beall and D.A.Duke.When the crystal that exists in the glass-ceramic is littler when many than visible wavelength, it demonstrates the transparency for human eye.More particularly, the transparency is by producing less than 50 nanometers, preferred little crystal to 10 nanometer sizes.
Recently, many researchs have been done about the field of the transition metal that will be used to serve as the optical activity dopant as the transparent glass ceramics of main body.Must repair suitable glass-ceramic, so that transition element can priority allocation be gone in the crystal.The co-pending application sequence number is 60/160,053, the application that is entitled as " Transition Metal Glass-Ceramics (transition-metal glass-ceramic) " that together transfers the same beneficiary of the application such as Beall relates to the glass-ceramic that is mixed with transition metal that is suitable for forming telecommunications gain or pumping fiber optics, all is incorporated herein by reference.
It is extremely useful under the situation of the easy fusing or the vehicle that easily is shaped that the less transparent glass ceramics of crystalline content provides for crystal at precursor glass.Crystal itself may be difficult to synthetic or synthetic expense height, but it can provide the feature that suits the requirements very much, as optical activity.Crystal in the glass-ceramic is random orientation in whole glass body usually, and definite orientation is arranged unlike monocrystalline.Random orientation and the anisotropy that therefore produces are favourable for many application.An example is the purposes of optical amplifier, and it must have the gain of the polarized action of not relying on (polarization-independent).
The transparent glass ceramics that is mixed with transition element can combine the crystalline optical efficiency with the shaping handiness of glass.For example, these glass-ceramic not only can be made into bulk (plane) form but also can be made into fibers form.
Therefore, need contain little position, four sides and position, gap, therefore be suitable for use as transparent glass-stupalith that the main body of potential value is arranged for little optically active transition element.This element is including, but not limited to Cr 4+, Cr 3+, Co 3+, Co 2+, Cu 2+, Mn 2+, Cu 2+And Ni 2+These elements provide luminous and fluorescence for the glass-ceramic material of this blending, so that they are applicable to application in the optical field industry.
α-and β-willemite (be orthosilicic acid zinc (Zn 2SiO 4)) crystalline structure all be by SiO 4And ZnO 4Tetrahedral structure is formed.
The structure of α-willemite was determined in nineteen thirty.It and phenakite (Be 2SiO 4) isostructure, it has rhombus spacer R3, and by the SiO that links to each other 4And ZnO 4Tetrahedron is formed.All Zn 2+Ion all occurs with tetrahedral coordination.Each Sauerstoffatom links to each other with two zinc atoms with a Siliciumatom.
β-willemite has and the policrystalline silicon type thing tridymite crystalline structure relevant with cristobalite mutually.Half of zinc atom is tetrahedral coordination, and remaining half be in aperture position.Balance each other and determine, α-willemite form is unique thermodynamically stable binary compound in the ZnO-SiO2 system.But being easy in glass with devitrification (devitrification) product is that metastable state β-willemite obtains.When the temperature that β-willemite is statically placed in more than 850 ℃, it finally can be converted into the alpha-polymorphic thing of stable state.
β-willemite provides some potentially useful performances.Different with α-willemite is that β-willemite can have the very big composition that can go bad, from 33-67 mole %ZnO range changing.This making on a large scale of sosoloid can obtain to form the phase that alters a great deal in the glass-ceramic.
Contain Zn 2SiO 4The glass-ceramic of form α-willemite is known, particularly as the electronic application material.U.S. Patent No. 4,714,687 relate to and contain the glass-ceramic material of willemite as main crystalline phase, this material be for the base material of unicircuit plug-in unit specially designed.This glass-ceramic is in the weight percentage of oxide compound, basically by the SiO of 30-55 2, 10-30 Al 2O 3, the ZnO of 15-45 and 3-15 MgO form.
But what prior art did not disclose and disclosed by the present invention is to be applicable to the transparent silicon zinc ore glass-ceramic material of optical fiber industry.
Therefore, primary and foremost purpose of the present invention provide basically and preferably fully transparent, and mainly contain the glass-ceramic material of willemite crystalline phase.
Another object of the present invention provides and the willemite glass-ceramic that luminous and epipolic composition fusion can be provided for it.
The significant advantage of glass-ceramic class of the present invention is that it provides the material that contains the willemite crystalline phase that can cooperate with the transition metal ion tetrahedron, and wherein transition metal ion is including, but not limited to Cr 4+, Cr 3+, Co 3+, Co 2+, Cu 2+, Mn 2+, Cu 2+And Ni 2+In addition, this material is a glass-based, therefore can provide important handiness for making body form (as planar substrate) and fibers form (as optical fiber).
Can understand other purpose of the present invention and advantage from following description.
The invention summary
According to the present invention, provide and contained α-and/or β-willemite principal crystalline phase and have the transparent glass ceramics of following composition, it forms the weight percentage in oxide compound, is the SiO of 25-60 substantially 2, 4-20 Al 2O 3, 20-55 ZnO and the MgO of 0-12, the K of 0-18 2The Na of O, 0-12 2The GeO of O, 0-30 2, condition is ∑ K 2O+Na 2O 〉=5.
For making final glass-ceramic article obtain best transparency, highly preferred composition is the SiO of 30-55 in the weight percentage of oxide compound substantially 2, 8-15 Al 2O 3, 30-42 ZnO and the MgO of 0-5, the K of 3-10 2The Na of O, 0-6 2The GeO of O, 0-5 2
For making willemite glass-ceramic material of the present invention obtain optical activity, promptly can in precursor glass, add Cr up to 1 weight % in the fluorescence of the communication transmission wavelength scope of 1100-1700 nanometer 2O 3
Manufacture method also is provided, and it may further comprise the steps:
A) fusing has the preparing glass charge of following composition: in the weight percentage of oxide compound, be the SiO of 25-60 substantially 2, 4-20 Al 2O 3, 20-55 ZnO and the MgO of 0-12, the K of 0-18 2The Na of O, 0-12 2The GeO of O, 0-30 2, condition is ∑ K 2O+Na 2O 〉=5.
B) with the temperature of this glass cools to the transition range that is lower than glass at least.
C) make glass expose for some time between about 550-950 ℃ temperature, exposure duration will be enough to the glass-ceramic that produces substantially transparent and contain the willemite principal crystalline phase; With
D) make the glass-ceramic cool to room temperature.
The accompanying drawing summary
Fig. 1 is that it demonstrates α-willemite principal crystalline phase by the powder x-ray diffraction spectrum of the glass-ceramic of making in 2 hours 975 ℃ of following thermal treatments with embodiment 2 compositions.
Fig. 2 is that it demonstrates β-willemite principal crystalline phase by the powder x-ray diffraction spectrum of the glass-ceramic of making in 2 hours 850 ℃ of following thermal treatments with embodiment 2 compositions.
Shown in Figure 3 for being mixed with 0.08 weight %Cr 2O 3Embodiment 2 and the fluorescence spectrum of 13 glass-ceramic.
Detailed Description Of The Invention
The present invention is that the willemite glass ceramics of substantially transparent has following composition, take the percetage by weight of oxide substantially as
SiO 2                                 25-60
Al 2O 3                               4-20
ZnO                                   20-55
MgO                                   0-12
K 2O                                  0-18
Na 2O                                 0-12
∑K 2O+Na 2O                          ≥5
GeO 2?????????????????????????????????0-30
For making final glass-ceramic article obtain maximum transparency, best compositing range in the weight percentage of oxide compound is substantially
SiO 2?????????????????????????????????35-50
Al 2O 3???????????????????????????????8-15
ZnO???????????????????????????????????30-42
MgO???????????????????????????????????0-5
K 2O??????????????????????????????????3-10
Na 2O?????????????????????????????????0-6
GeO 2?????????????????????????????????0-5
Following table has displayed the multiple glass of representing with the weight part of oxide compound to be formed, and parameter of the present invention has been described.Following table give with ℃ and the potting process (ceramming schedule) of hour expression and final glass-ceramic in observed crystalline phase.
Because the sum of each composition therefore for practical purpose, can think that tabular numerical value has reflected weight percentage near 100 in each described glass.The food ingredient of the manufacturing glass in compositing range of the present invention can comprise oxide compound or other compound of any material, as long as they are in case melt the required oxide compound that just can change into proper ratio mutually.
Tabulation
???1 ???2 ???3 ???4 ???5 ???6 ???7 ???8 ???9 ???10 ???11 ???12 ???13 ???14 ???15 ???16
????SiO 2 ??39.1 ??41.5 ??40.5 ??40.5 ??41.5 ??41.5 ??41.5 ??40.6 ??41.7 ??42.4 ??38.7 ??28.0 ??40.0 ??40.7 ??42.7 ??44.7
????Al 2O 3 ??9.7 ??11.9 ??11.5 ??10.9 ??13.6 ??11.9 ??10.5 ??11.5 ??11.4 ??12.2 ??11.9 ??11.9 ??11.0 ??12.5 ??12.5 ??12.5
????ZnO ??43.8 ??36.5 ??36.0 ??36.5 ??34.3 ??36.5 ??36.5 ??36.5 ??40.2 ??36.5 ??35.2 ??30.5 ??40.0 ??30.0 ??26.0 ??22.0
????K 2O ??4.3 ??8.7 ??12.0 ??8.7 ??8.6 ??8.5 ??8.5 ??8.5 ???- ??3.8 ??8.6 ??8.6 ??8.0 ??11.8 ??11.8 ??11.8
????Na 2O ??3.1 ??1.6 ???- ??1.6 ??1.5 ??1.5 ??1.5 ??1.0 ??6.9 ??4.9 ??1.6 ??1.6 ???- ???- ????- ???-
????P 2O 5 ???- ???- ???- ??2.0 ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ????- ???-
????Li 2O ???- ???- ???- ???- ??0.5 ???- ???- ???- ???- ???- ???- ???- ???- ???- ????- ???-
????NaCl ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ????- ???-
????BaO ???- ???- ???- ???- ???- ??1.5 ??1.5 ???- ???- ???- ???- ???- ???- ???- ????- ???-
????CaO ???- ???- ???- ???- ???- ???- ???- ??1.0 ???- ???- ???- ???- ???- ???- ????- ???-
????GeO 2 ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ??4.0 ??19.5 ???- ???- ????- ???-
????MgO ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ???- ??1.0 ??5.0 ???7.0 ??9.0
℃-hour ??850- ???2 ??850- ???2 ??850- ???2 ??850- ???2 ??850- ???2 ??750- ???2 ??750- ???2 ??750- ???2 ??750- ???2 ??750- ???2 ??750- ???2 ??750- ???2 ??900- ???2 ??800- ???2 ???800- ????2 ??800- ???2
Crystalline phase ???β ???β ???β ???β ??β+ ???α ???β ???β ???β ???β ???α ???β+ ???α ???α ???α ???β+ ???α ???β+ ???α ??β+ ??α
The glass that exemplifies is made by following method.Prepare batching, they are mixed mutually,, put into platinum crucible then to help to obtain even melt.Crucible is put into process furnace with 1400-1600 ℃ temperature operation, making batching fusing 4-16 hour.Melt is toppled over into free " little cake (patties) ", and it is transferred in the annealing furnace with about 550-600 ℃ operation.
The little cake of glass is placed process furnace, and heat-treat according to following process, to carry out potting circulation: 300 ℃/hour up to Tc T ℃, left standstill under T ℃ 1-2 hour, and cool off with stove speed (furnace rate).Tc T changes between 650-900 ℃, obtains the willemite glass-ceramic of substantial transparent thus.
Composition of the present invention is because liquid-liquid phase separation so be spontaneous nucleation, therefore need not to add nucleator.In particular, the promotes of amorphous phase nucleation.Even do not need nucleator, but add such as TiO in many cases 2The nucleator of (4 weight %) can produce trickleer crystallographic dimension and improve transparency: but must carefully avoid spontaneous crystallization in annealing furnace.
Can add Li up to 2% 2O, or up to 5% CaO, BaO, SrO or Ga 2O 3Adding germanium oxide makes α-willemite polymorphic form with respect to β-willemite polymorphic form stabilization easily.
The crystalline phase of gained glass-ceramic material can be determined by X-ray powder derivatization method.Representational diffraction pattern is shown in Fig. 1 and Fig. 2, and Fig. 1 is by the glass of making in 2 hours 975 ℃ of following thermal treatments that embodiment 2 forms that has, and Fig. 2 is the glass that embodiment 2 forms that has by making in 2 hours 850 ℃ of following thermal treatments.
The structure of glass-ceramic of the present invention is to contain α-and/or β-willemite crystallite (size for 10-50 nanometer) in stable alkaline sillico aluminate glass, and overall crystallinity is about 10-50 volume % and does not wait according to each composition.In the potting circulation, crystallite is grown in substrate glass.The transparency of glass-ceramic of the present invention is the function of microtexture, thereby also is the function of forming.
Crystalline structure in the glass-ceramic material of the present invention only provides little position, four sides and position, gap.This feature makes crystal provide the main body of potentially useful for little optical activity transition element, and these transition element are including, but not limited to Cr 4+, Cr 3+, Co 3+, Co 2+, Cu 2+, Mn 2+, Cu 2+And Ni 2+These transition element can fluoresce and luminescence at different wave length.Though some these element of volume more can be blended into precursor glass, their consumptions in glass of the present invention are no more than about 1 weight % usually.
As known in optics and the laser field, contain the Cr of tetrahedral coordination 4+The ionic crystal can provide unique optical characteristics.Therefore, in a possible application, the transparent silicon zinc ore glass-ceramic that is mixed with transition metal ion of the present invention is applicable to the application in optics and the laser industry.Specifically use including, but not limited to optical amplifier and pumping light.
In breadboard test, the chromic oxide fusion of embodiment 2 and 3 and 0.08 weight %, and carry out fluorescence and measure.As shown in Figure 2, can be observed the strong Cr of two kinds of glass-ceramic on the communication transmission wavelength scope of 1100-1700 nanometer 4+Emission.
Though by embodiment, intactly described the present invention, should notice and to have carried out various changes and improvement to it that this is tangible to those of skill in the art.Therefore, as long as scope of the present invention is not run counter in these changes and improvement, they all should be regarded as and are included in this scope.

Claims (12)

1. contain the willemite crystalline phase as principal crystalline phase and have the glass-ceramic of the substantial transparent of following composition, the weight percentage that it is formed in oxide compound is essentially
SiO 2????????????????????????????????25-60
Al 2O 3??????????????????????????????4-20
ZnO??????????????????????????????????20-55
MgO??????????????????????????????????0-12
K 2O?????????????????????????????????0-18
Na 2O????????????????????????????????0-12
K 2O+Na 2O???????????????????????????≥5
GeO 2????????????????????????????????0-30。
2. glass-ceramic as claimed in claim 1, it also comprises the Li up to 2 weight % 2O.
3. glass-ceramic as claimed in claim 1, it also comprises and is selected from CaO, BaO, SrO and Ga up to 5 weight % 2O 3In at least a oxide compound.
4. glass-ceramic as claimed in claim 1, it is characterized in that described glass ceramic body can be selected from Cr 4+, Cr 3+, Co 3+, Co 2+, Cu 2+, Mn 2+, Cu 2+And Ni 2+The transition metal ion tetrahedral coordination, so that optical activity to be provided.
5. glass-ceramic as claimed in claim 4 is characterized in that described glass-ceramic contains the Cr up to 1 weight % 2O 3
6. contain the willemite crystalline phase as principal crystalline phase and have the glass-ceramic of the substantial transparent of following composition, the weight percentage that it is formed in oxide compound is essentially
SiO 2???????????????????????????????35-50
Al 2O 3?????????????????????????????8-15
ZnO?????????????????????????????????30-42
MgO?????????????????????????????????0-5
K 2O????????????????????????????????3-10
Na 2O???????????????????????????????0-6
GeO 2???????????????????????????????0-5。
7. glass-ceramic as claimed in claim 6, it is characterized in that described glass-ceramic can be selected from Cr 4+, Cr 3+, Co 3+, Co 2+, Cu 2+, Mn 2+, Cu 2+And Ni 2+The transition metal ion tetrahedral coordination, so that optical activity to be provided.
8. glass-ceramic as claimed in claim 7 is characterized in that described glass-ceramic contains the Cr up to 1 weight % 2O 3
9. glass-ceramic as claimed in claim 1 is characterized in that described willemite crystallographic dimension is the 10-50 nanometer, so that described glass-ceramic is transparent basically.
10. glass-ceramic as claimed in claim 1 is characterized in that the overall crystallinity of described glass-ceramic is about 10-50%, so that described glass-ceramic is transparent basically.
11. based on α-and the manufacture method of β-willemite crystalline transparent glass ceramics, it may further comprise the steps:
A) fusing has the preparing glass charge of following composition: in the weight percentage of oxide compound, be essentially the SiO of 25-60 2, 4-20 Al 2O 3, 20-55 ZnO and the MgO of 0-12, the K of 0-18 2The Na of O, 0-12 2The GeO of O, 0-30 2, condition is ∑ K 2O+Na 2O 〉=5;
B) with the temperature of described glass cools to the transition range that is lower than glass at least;
C) make described glass expose for some time between about 550-950 ℃ temperature, exposure duration will be enough to the glass-ceramic that produces substantial transparent and contain the willemite principal crystalline phase; With
D) make the glass-ceramic cool to room temperature.
12. method as claimed in claim 11 is characterized in that described glass also comprises the Cr up to 1 weight % 2O 3, its consumption makes described glass-ceramic show optical activity.
CNB008143374A 1999-10-18 2000-10-12 Transparent glass-ceramics based on alpha-and beta-willemite Expired - Fee Related CN1184157C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16013899P 1999-10-18 1999-10-18
US60/160,138 1999-10-18

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CN1379742A true CN1379742A (en) 2002-11-13
CN1184157C CN1184157C (en) 2005-01-12

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CN102892724A (en) * 2010-05-10 2013-01-23 日本电气硝子株式会社 Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler
CN103194229A (en) * 2013-03-29 2013-07-10 华南理工大学 Near-infrared long-afterglow florescent powder and preparation method thereof
CN103466949A (en) * 2013-08-21 2013-12-25 中国计量学院 Glass-ceramic precipitating Zn1.7SiO4 nanocrystalline and preparation method thereof
CN103833228A (en) * 2014-01-23 2014-06-04 中国计量学院 Tetravalent-chromium-ion-doped microcrystalline glass and preparation method thereof

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CN102844271A (en) * 2010-04-22 2012-12-26 日本电气硝子株式会社 Fire-resistant filler powder, adhesive material, and method for producing fire-resistant filler powder
CN102892724A (en) * 2010-05-10 2013-01-23 日本电气硝子株式会社 Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler
US8871664B2 (en) 2010-05-10 2014-10-28 Nippon Electric Glass Co., Ltd. Refractory filler, sealing material using same, and manufacturing method for refractory filler
CN102892724B (en) * 2010-05-10 2015-04-01 日本电气硝子株式会社 Fire-resistant filler, sealing material using same, and method for producing fire-resistant filler
CN103194229A (en) * 2013-03-29 2013-07-10 华南理工大学 Near-infrared long-afterglow florescent powder and preparation method thereof
CN103466949A (en) * 2013-08-21 2013-12-25 中国计量学院 Glass-ceramic precipitating Zn1.7SiO4 nanocrystalline and preparation method thereof
CN103466949B (en) * 2013-08-21 2015-10-28 中国计量学院 A kind of precipitation Zn 1.7siO 4nanocrystalline devitrified glass and preparation method thereof
CN103833228A (en) * 2014-01-23 2014-06-04 中国计量学院 Tetravalent-chromium-ion-doped microcrystalline glass and preparation method thereof
CN103833228B (en) * 2014-01-23 2015-10-28 中国计量学院 Chromium ion-doped devitrified glass of a kind of tetravalence and preparation method thereof

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CA2387951A1 (en) 2001-04-26
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