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DE1596855B2 - COMPOSITIONS FOR THE MANUFACTURING OF OPAQUE GLASS CERAMICS WITH SPECIFICALLY ADJUSTABLE COEFFICIENTS OF EXPANSION BETWEEN 9 AND 75 10 TO THE MAXIMUM 7 DEGREES C. - Google Patents

COMPOSITIONS FOR THE MANUFACTURING OF OPAQUE GLASS CERAMICS WITH SPECIFICALLY ADJUSTABLE COEFFICIENTS OF EXPANSION BETWEEN 9 AND 75 10 TO THE MAXIMUM 7 DEGREES C.

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Publication number
DE1596855B2
DE1596855B2 DE19671596855 DE1596855A DE1596855B2 DE 1596855 B2 DE1596855 B2 DE 1596855B2 DE 19671596855 DE19671596855 DE 19671596855 DE 1596855 A DE1596855 A DE 1596855A DE 1596855 B2 DE1596855 B2 DE 1596855B2
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compositions
glass ceramics
glass
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DE1596855A1 (en
Inventor
Werner Dr.; Scheidler Herwig Dipl.-Ing.; Petzoldt Jürgen Dipl.-Chem. Dr.; 6500 Mainz Sack
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Schott AG
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Jenaer Glaswerk Schott and Gen
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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
    • C03C10/0018—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 monovalent metal oxide as main constituents
    • C03C10/0027—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 monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

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

Description

1 21 2

Die Erfindung bezieht sich auf Zusammensetzungen Al2O3 14,5 bis 22,0,The invention relates to compositions Al 2 O 3 14.5 to 22.0,

zum Herstellen von undurchsichtiger Glaskeramik, Li2O 1,5 bis 2,8,for the production of opaque glass ceramic, Li 2 O 1.5 to 2.8,

vielfach auch als Glas-Kristall-Mischkörper bezeich- CaO O bis 1,9,often also referred to as a glass-crystal mixed body - CaO O to 1.9,

net, welche durch eine Wärmebehandlung der aus BaO O -bis 7,0,net, which by a heat treatment of the BaO O -to 7.0,

den Zusammensetzungen erschmolzenen Glasgegen- 5 mindestens eines der Oxidethe compositions fused glass against at least one of the oxides

stände oberhalb der Transformationstemperatur mindestens eines der Uxidewould be above the transformation temperature at least one of the Uxides

(Zähigkeit i/ < 1013·5 Poise) durch eine gesteuerte MgO O bis 7,5 und(Toughness i / < 10 13 · 5 poise) controlled by a MgO O to 7.5 and

Kristallisation erhalten werden, und welche Wärme- ZnO , O bis 12,0 sowieCrystallization can be obtained, and what heat- ZnO, O to 12.0 as well

dehnungskoeffizienten zwischen 75 und 9 · 10~7/°C P2O5 O bis 8,0,expansion coefficients between 75 and 9 · 10 ~ 7 / ° CP 2 O 5 O to 8.0,

im Temperaturbereich von 20 bis 300° C haben. Diese io TiO2 0,6 bis 1,8,in the temperature range from 20 to 300 ° C. This io TiO 2 0.6 to 1.8,

Glaskeramiken werden aus Gläsern hergestellt, welche ZrO2 1,8 bis 4,0,Glass ceramics are made from glasses containing ZrO 2 1.8 to 4.0,

aus SiO2, B2O3, Li2O, CaO, BaO, MgO, ZnO, P2O5, As2O3 0,15 bis 0,30,made of SiO 2 , B 2 O 3 , Li 2 O, CaO, BaO, MgO, ZnO, P 2 O 5 , As 2 O 3 0.15 to 0.30,

TiO2, ZrO2 und As2O3 bestehen. P2O5, TiO2 und , . f , , o , u . , : TiO 2 , ZrO 2 and As 2 O 3 exist. P 2 O 5 , TiO 2 and,. f ,, o , u . , :

ZrO2 wirken als Keimbildner und dienen zur Ein- wobei folSende Summen einzuhalten sind:ZrO 2 act as nucleating agents and are used to input wherein fol S end totals are observed:

leitung und damit zur Förderung der Kristallisation. 15 CaO + BaO + MgO + ZnOline and thus to promote crystallization. 15 CaO + BaO + MgO + ZnO

As2O3 dient zur Läuterung der Glasschmelzen. Die = 7,5 bis 19 Gewichtsprozent,As 2 O 3 is used to refine the glass melt. The = 7.5 to 19 percent by weight,

übrigen Komponenten bestimmen durch das jeweilige P2O5 + TiO2 + ZrO2 the other components are determined by the respective P 2 O 5 + TiO 2 + ZrO 2

Mischungsverhältnis die während des Keramisierungs- = 3,6 bis 11,6 Gewichtsprozent.Mixing ratio during the ceramization = 3.6 to 11.6 percent by weight.

prozesses sich ausscheidenden Kristallphasen undprocess separating crystal phases and

damit die Eigenschaften der so entstandenen Glas- 20 Von den bekannten Glaskeramiken unterscheidenso that the properties of the glass-ceramics produced in this way differ from the known glass-ceramics

keramiken. sich die Glaskeramiken gemäß der Erfindung durchceramics. the glass ceramics according to the invention

Derartige Glaskeramiken sind im allgemeinen durch andere Zusammensetzungen mit einem deutlich eine höhere mechanische Festigkeit, durch höhere höheren Gehalt an den zweiwertigen Metalloxiden Gebrauchstemperaturen und durch höhere oder CaO, BaO, MgO, ZnO und durch einen niedrigen niedrigere Wärmedehnungskoeffizienten als die 25 Gehalt an Li2O und SiO2. Die Gläser sind aus. ursprünglichen Gläser gekennzeichnet und sind bei- diesem Grunde in guter Qualität zwischen 1560 spielsweise beschrieben in der deutschen Patentschrift und 1580° C schmelzbar und lassen sich im Gegensatz 1 045 056 (transparente und undurchsichtige Glas- zu den bekannten Glaskeramiken bei tieferen Temkeramiken), deutsche Patentschrift 1 159 142 (trans- peraturen verarbeiten, weil sie im schmelzflüssigen parente Glaskeramik), deutsche Auslegeschrift 3° Zustand weniger zäh sind. Ein weiterer Unterschied 1 090 397 (transparente Glaskeramik), französische besteht im kristallinen Phasengehalt nach der UmPatentschrift 1 300 614 (transparente und undurch- Wandlung (Keramisierung). Während die bisherigen sichtige Glaskeramiken) und USA.-Patentschrift Li2O-haltigen undurchsichtigen Glaskeramiken vor-3 241 985 (transparente Glaskeramik). wiegend die Lithiummineraleß-Eukryptit (Li2O Al2O3:Such glass ceramics are generally due to other compositions with a significantly higher mechanical strength, due to a higher higher content of the divalent metal oxides service temperatures and due to higher or CaO, BaO, MgO, ZnO and a lower, lower coefficient of thermal expansion than the 25 content of Li 2 O and SiO 2 . The glasses are off. original glasses and are for this reason in good quality between 1560, for example, described in the German patent and 1580 ° C meltable and, in contrast to 1 045 056 (transparent and opaque glass to the known glass ceramics for lower temp ceramics), German patent specification 1 159 142 (process temperatures because they are less tough in the molten parent glass ceramic), German Auslegeschrift 3 ° condition. Another difference 1 090 397 (transparent glass ceramics), French is in the crystalline phase content according to the UmPatentschrift 1 300 614 (transparent and opaque conversion (ceramization). While the previous visible glass ceramics) and USA. Patent Li 2 O-containing opaque glass ceramics vor-3 241 985 (transparent glass ceramic). predominantly the lithium mineral ß-eucryptite (Li 2 O Al 2 O 3 :

Zur Herstellung dieser bekannten Glaskeramiken 35 SiO2 = 1 : 1 : 2) und h-Spodumen (Li2O : Al2O3 : SiO2 To produce these known glass ceramics 35 SiO 2 = 1: 1: 2) and h-spodumene (Li 2 O: Al 2 O 3 : SiO 2

waren sowohl hohe Schmelz- wie Verarbeitungstem- = 1:1:4) als kristalline Phase enthalten, sind in denwere both high melting and processing rates = 1: 1: 4) as a crystalline phase, are in the

peraturen erforderlich. Ferner lagen die Umwand- erfindungsgemäßen Glaskeramiken neben ß-Eukryp-temperatures required. Furthermore, the conversion glass ceramics according to the invention were next to ß-Eukryp-

lungstemperaturen ebenfalls sehr hoch. titmischkristallen noch Zinkspinell (ZnO · Al2O3)temperatures are also very high. titanium mixed crystals still zinc spinel (ZnOAl 2 O 3 )

Aufgabe der vorliegenden Erfindung sind Zusam- und/oder Celsian (BaO -Al2O3 -2SiO2) und/oder mensetzungen zum Herstellen von undurchsichtigen, 40 ZrO2-Keimphase als Kristallphasen vorhanden. Als neben Beta-Eukryptit-Mischkristallen als weitere ein besonderer Vorteil ist schließlich die tiefe Um-Kristallphasen mindestens noch Zinkspinell und/oder Wandlungstemperatur zwischen 720 und 820° C anzu-Celsian und/oder ZrO2-Keimphase enthaltenden sprechen, wodurch eine Deformation der Formkörper Glaskeramiken mit gezielt einstellbaren, zwischen 9 während der Keramisierung vermieden wird. Nach und 75 ■ 10~7/°C (20 bis 30O0C) liegenden Aus- 45 dem Stand der Technik mußten bisher dafür Temdehnungskoeffizienten durch eine Wärmebehandlung peraturen bis zu 1300° C angewendet werden, wobei zwischen 720 und 820° C der aus den Zusammen- für alle auf dem Markt bekannten Produkte die Endsetzungen erschmolzenen Glasgegenstände. stufe der Umwandlung über 1000° C liegt.The object of the present invention are compositions and / or celsian (BaO-Al 2 O 3 -2SiO 2 ) and / or compositions for producing opaque, 40 ZrO 2 seed phase as crystal phases. Another particular advantage besides beta-eucryptite mixed crystals is the deep um-crystal phases containing at least zinc spinel and / or conversion temperature between 720 and 820 ° C to-Celsian and / or ZrO 2 seed phase, which causes deformation of the shaped body Glass ceramics with specifically adjustable, between 9 is avoided during the ceramization. According to the state of the art lying at 75 · 10 ~ 7 / ° C (20 to 30O 0 C), thermal expansion coefficients of up to 1300 ° C had to be used for this purpose, with temperatures of between 720 and 820 ° C being used the ends of melted glass objects for all products known on the market. conversion stage is above 1000 ° C.

Diese Aufgabe wird erfindungsgemäß gelöst durch In der Tabelle 1 sind zur weiteren Erläuterung der folgenden Zusammensetzungsbereich in Gewichts- 50 Erfindung die Zusammensetzungen von 16 Glasprozent: keramikgrundgläsern aufgeführt. Tabelle 2 enthältAccording to the invention, this object is achieved by Table 1 for further explanation of the the following composition range in weight - 50 invention the compositions of 16 glass percent: ceramic base glasses listed. Table 2 contains

verschiedene Eigenschaftswerte der Gläser und derdifferent property values of the glasses and the

SiO2 54,0 bis 62,0, entsprechenden keramisierten Produkte zusammenSiO 2 54.0 to 62.0, corresponding ceramized products together

B2O3 O bis 6,4, mit den kristallinen Phasengehalten.B 2 O 3 O to 6.4, with the crystalline phase contents.

Tabelle 1
Gewichtsprozent-Zusammensetzungen der Glaskeramikgrundgläser 1 bis 16Table 1
Weight percent compositions of the glass ceramic base glasses 1 to 16

Nr.No. SiO2 SiO 2 B2O3 B 2 O 3 Al2O3 Al 2 O 3 Li2OLi 2 O BaOBaO CaOCaO MgOMgO ZnOZnO TiO2 TiO 2 ZrO2 ZrO 2 P2O5 P 2 O 5 As2O3 As 2 O 3 11 54,054.0 6,46.4 17,017.0 2,82.8 4,24.2 12,012.0 1,81.8 1,81.8 0,150.15 22 54,054.0 0,60.6 17,017.0 2,02.0 4,04.0 3,03.0 12,012.0 0,60.6 4,04.0 2,82.8 0,300.30 33 54,054.0 0,60.6 17,017.0 2,82.8 7,07.0 12,012.0 1,01.0 3,63.6 2,02.0 0,300.30 44th 54,754.7 1,11.1 22,022.0 2,82.8 7,57.5 1,81.8 1,81.8 8,08.0 0,300.30 55 54,754.7 22,022.0 2,02.0 7,57.5 1,91.9 1,81.8 1,81.8 8,08.0 0,300.30 66th • 60,5• 60.5 14,514.5 2,02.0 3,03.0 12,012.0 1,01.0 2,82.8 4,24.2 0,300.30


SiO,
SiO, B2O.,B 2 O., 33 U2OU 2 O 1 5961 596 855855 BaOBaO CaOCaO MgOMgO ZnOZnO TiO,TiO, 44th ZrO2 ZrO 2 IM)5 IM) 5 As2O.,As 2 O., 54,754.7 2,82.8 7,57.5 1,11.1 1,81.8 1,81.8 8,08.0 0,300.30 62,062.0 Al2O,Al 2 O, 1,51.5 Fortsetzungcontinuation 3,03.0 12,012.0 1,01.0 1,81.8 4,24.2 0,300.30 Nr.No. 61,561.5 22,022.0 2,02.0 3,03.0 12,012.0 1,01.0 1,81.8 4,24.2 0,300.30 77th 54,054.0 3,63.6 14,514.5 2,82.8 7,07.0 12,012.0 1,01.0 2,62.6 0,150.15 88th 61,061.0 14,514.5 2,5.2.5. 1,901.90 3,03.0 12,012.0 1,81.8 1,81.8 0,300.30 99 55,655.6 17,017.0 2,82.8 7,07.0 12,012.0 1,01.0 2,62.6 2,02.0 0,150.15 1010 56,956.9 16,016.0 1,51.5 7,07.0 12,012.0 1,01.0 2,62.6 2,02.0 0,150.15 1111th 54,054.0 0,60.6 17,017.0 2,02.0 7,07.0 12,012.0 0,60.6 4,04.0 2,82.8 0,300.30 1212th 61,061.0 17,017.0 2,52.5 3,03.0 12,012.0 1,01.0 1,81.8 2,72.7 0,300.30 1313th 54,054.0 17,017.0 2,82.8 7,07.0 12,012.0 1,01.0 2,62.6 3,63.6 0,150.15 1414th 16,016.0 Tabelle 2Table 2 1515th 17,017.0 1616

; Eigenschaften der Zusammensetzungsbeispiele 1 bis 16 von Tabelle 1 im glasigen und keramisierten Zustand . nach einer Wärmebehandlung von 2 Stunden 72O0C + 3 Stunden 820°C; Properties of composition examples 1 to 16 of Table 1 in the vitreous and ceramized state. after a heat treatment of 2 hours 72O 0 C + 3 hours 820 ° C

Austhe end GlasGlass Dichte"Density" Austhe end Dichtedensity Keramisiertes ProduktCeramized product kristalline Phasencrystalline phases dehnungselongation (g/ccm)(g / ccm) dehnungselongation (g/ccm)(g / ccm) Nr.No. koeffizientcoefficient koeffizientcoefficient prozentualepercentage u · 107 u 10 7 7VnUSn 7 VnUSn 2,672.67 a ■ Wa ■ W 2,882.88 Dichtedensity /J-Eukryptitmischkristalle,/ J-eucryptite solid solution, (20 bis 300° C)(20 to 300 ° C) i/~ 1013·5Ρi / ~ 10 13 5 Ρ 20 bis 300° C)20 to 300 ° C) änderungmodification Zinkspinell, ZrO2-KeimphaseZinc spinel, ZrO 2 seed phase 4242 2,722.72 7575 2,822.82 Quarz, Zinkspinell, Celsian,Quartz, zinc spinel, celsian, 11 600600 7,877.87 ZrO2-KeimphaseZrO 2 seed phase 3737 2,772.77 7575 2,862.86 /S-Eukryptitmischkristalle,/ S-eucryptite solid solution, 22 634634 3,683.68 Celsian, ZrO2-KeimphaseCelsian, ZrO 2 seed phase 4343 2,482.48 6767 2,532.53 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 33 607607 3,253.25 ZrO2-KeimphaseZrO 2 seed phase 4141 2,502.50 2929 2,582.58 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 44th 670670 2,022.02 ZrO2-KeimphaseZrO 2 seed phase 3737 2,622.62 2424 2,732.73 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 55 683683 3,203.20 Zinkspinell, ZrO2-KeimphaseZinc spinel, ZrO 2 seed phase 3636 2,502.50 2424 2,552.55 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 66th 629629 4,204.20 ZrO2-KeimphaseZrO 2 seed phase 4141 2,602.60 2323 2,692.69 /J-Eukryptitmischkristalle,/ J-eucryptite solid solution, 77th 666666 2,002.00 ZrO2-KeimphaseZrO 2 seed phase 3333 2,612.61 2020th 2,692.69 /J-Eukryptitmischkristalle,/ J-eucryptite solid solution, 88th 650650 3,463.46 Zinkspinell, ZrO2-KeimphaseZinc spinel, ZrO 2 seed phase 3535 2,472.47 1818th 2,862.86 /S-Eukryptitmischkristalle,/ S-eucryptite solid solution, 99 628628 3,063.06 Celsian, ZinkspinellCelsian, zinc spinel 4343 2,662.66 1616 2,742.74 /S-Eukryptitmischkristalle,/ S-eucryptite solid solution, 1010 585585 4,394.39 ZinkspinellZinc spinel 3939 2,762.76 1515th 2,832.83 /S-Eukryptitmischkristalle,/ S-eucryptite solid solution, 1111th 634634 3,023.02 ZrO2-KeimphaseZrO 2 seed phase 4545 2,752.75 1313th 2,832.83 /S-Eukryptitmischkristalle,/ S-eucryptite solid solution, 1212th 637637 2,542.54 ZrO2-KeimphaseZrO 2 seed phase 3636 2,782.78 1212th 2,842.84 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 1313th 662662 2,902.90 ZrO2-KeimphaseZrO 2 seed phase 4040 2,622.62 1010 2,672.67 ß-Eukryptitmischkristalle,ß-eucryptite solid solution, 1414th 630630 2,162.16 Zinkspinell, ZrO2-KeimphaseZinc spinel, ZrO 2 seed phase 3737 2,752.75 1010 2,802.80 ^-Eukryptitmischkristalle,^ -Eucryptite solid solution, 1515th 632632 1,921.92 Celsian, ZrO2-KeimphaseCelsian, ZrO 2 seed phase 3939 99 1616 627627 1,821.82

Claims (1)

Patentanspruch:Claim: Zusammensetzungen zum Herstellen von undurchsichtigen, neben Beta-Eukryptit-Mischkristallen als weitere Kristallphasen mindestens noch Zinkspinell und/oder Celsian und/oder ZrO2-Keimphase enthaltenden Glaskeramiken mit gezielt einstellbaren, zwischen 9 und 75 · 10 ~Ί/° C (20 bis 300° C) liegenden Ausdehnungskoeffizienten, gekennzeichnet durch folgenden Bereich in Gewichtsprozent, berechnet auf Oxidbasis:Compositions for the production of opaque glass ceramics containing at least zinc spinel and / or Celsian and / or ZrO 2 seed phase in addition to beta-eucryptite mixed crystals as further crystal phases with specifically adjustable, between 9 and 75 · 10 ~ Ί / ° C (20 to 300 ° C), characterized by the following range in percent by weight, calculated on the oxide basis: SiO2..
B2O3 .
Al2O3.
Li2O .SiO 2 ..
B 2 O 3 .
Al 2 O 3 .
Li 2 O. 54,054.0 bisuntil 62,0,62.0, 00 bisuntil 6,4,6.4, 14,514.5 bisuntil 22,0,22.0, 1,51.5 bisuntil 2,8,2.8,
CaO CaO BaO BaO mindestens eines d,er Oxideat least one d, er oxides MgO MgO ZnO ZnO P2O5 P 2 O 5 TiO2 TiO 2 ZrO2 ZrO 2 As2O3 0,15 bis 0,30,As 2 O 3 0.15 to 0.30, wobei folgende Summen einzuhalten sind:whereby the following sums are to be adhered to: CaO + BaO + MgO + ZnO = 7,5 bis 19 Gewichtsprozent,CaO + BaO + MgO + ZnO = 7.5 to 19 percent by weight, P2O5 + TiO2 + ZrO2 = 3,6 bis 11,6 Gewichtsprozent.P 2 O 5 + TiO 2 + ZrO 2 = 3.6 to 11.6 percent by weight. OO bisuntil 1,9,1.9, OO bisuntil 7,0,7.0, IQC
OIQC
O bisuntil 7,5 und7.5 and OO bisuntil 12,0 sowie12.0 as well as OO bisuntil 8,0,8.0, 0,60.6 bisuntil 1,8,1.8, 1,81.8 bisuntil 4,0,4.0,
DE19671596855 1967-03-29 1967-03-29 COMPOSITIONS FOR THE MANUFACTURING OF OPAQUE GLASS CERAMICS WITH SPECIFICALLY ADJUSTABLE COEFFICIENTS OF EXPANSION BETWEEN 9 AND 75 10 TO THE MAXIMUM 7 DEGREES C. Withdrawn DE1596855B2 (en)

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DEJ0033321 1967-03-29
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DE19671596863 Withdrawn DE1596863B1 (en) 1967-03-29 1967-11-11 COMPOSITIONS FOR THE MANUFACTURING OF CLEAR GLASKERA MIKEN AND PROCESS FOR THEIR MANUFACTURING

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BE (1) BE744573Q (en)
CH (1) CH502278A (en)
DE (2) DE1596855B2 (en)
FR (1) FR1562377A (en)
GB (1) GB1221851A (en)
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GB2159514B (en) * 1984-05-23 1987-12-02 Zeiss Stiftung Glass ceramic with specific thermal expansion behaviour
US5968857A (en) * 1997-03-31 1999-10-19 Corning Incorporated Glass-ceramics
US6197429B1 (en) 1998-02-26 2001-03-06 Corning Incorporated Method for making transparent glass-ceramics with high temperature dimensional stability
EP0997445B1 (en) 1998-10-27 2004-03-10 Corning Incorporated Low expansion glass-ceramics
CN105899469B (en) 2013-08-30 2020-03-10 康宁股份有限公司 Ion-exchangeable glass, glass-ceramic and method of making the same
FR3067345B1 (en) 2017-06-07 2020-09-25 Eurokera LOW LITHIUM QUARTZ-BETA TRANSPARENT VITROCERAMICS
WO2020018408A1 (en) * 2018-07-16 2020-01-23 Corning Incorporated Methods for ceramming glass with nucleation and growth density and viscosity changes
KR20210101269A (en) 2018-12-12 2021-08-18 코닝 인코포레이티드 Ion-exchangeable lithium-containing aluminosilicate glass
CN111620566B (en) * 2020-05-15 2021-10-22 华南理工大学 A kind of multiphase transparent ceramic, multiphase transparent ceramic optical fiber and preparation method and application thereof

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GB1010513A (en) * 1962-02-02 1965-11-17 Fuji Photo Film Co Ltd Improvements in or relating to crystalline glass and to methods of making the same
FR1382060A (en) * 1962-03-31 1964-12-18 Nippon Electric Glass Co Acid Resistant and Low Thermal Expansion Ceramic Glass Manufacturing Method

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DE1596863B1 (en) 1972-01-13
FR1562377A (en) 1969-04-04
CH502278A (en) 1971-01-31

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