TW503225B - Transparent glass-ceramics based on alpha-and beta-willemite - Google Patents

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 precusor 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 ΣK2O+Na2O ≥ 5. The glass-ceramic may be doped with up to 1 wt.% Cr2O3 to impart optical activity thereto.

Description

503225 A7 B7 2 V. Description of the invention (Related application printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs: October 18, 1999 Japanese company George H. Beall and Linda R. Pinckney applied for US No. 60/160, 〇53 The invention name of the provisional patent application is "TRANSITION-METAL Glass-Ceramics GAIN MEDIA", which relates to doped transition metal glass-ceramic materials, which exhibit characteristics that will make it suitable as a gain medium for use in optical amplifiers and / or Laser pump. October 18, 1999. US company 60/159, 967 patent application by George H. Beall and Linda R. Pinckney of Japan, whose invention name is `` TRANSPARENT (Li, Zn, Mg) ORTHOSILICATE GLASS- "CERAMICS" refers to doped transition metal glass-ceramic materials, which exhibit characteristics that make it suitable as a gain medium for use in optical amplifiers and / or laser pumps. October 18, 1999. Japanese company George H. Beall, Linda R Temporary Patent Application No. 60 / 160,052 filed by William Vockroth and Ji Wang, the invention name is 'GLASS-CERAMIC FIBER AND METHO' D "# About glass-ceramic materials, which contain nanometer crystals and transition metals, and a method for manufacturing the glass-ceramics in the form of optical fibers. October 15, 1999 US 60 /, filed by the Japanese company George H. Beall The temporary invention patent application No. 150, 093 has the invention name " TRANSPARENT FORSTERITE GLASS-CERAMICS ", and U.S. Patent No. 60/174, 012 supplemented by Linda R. Pine-kney on October 18, 1999, which has The same name. October 18, 1999 The beauty of the Japanese company Linda R. Pinckney's application—I ί11 (Please read the precautions on the back before filling this page) The paper size of this edition applies the China National Standard (CNS) A4 specification ( 210X297 mm) Hr 503225 A7 B7 V. Description of the invention (i) Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs of the PRC DuPont No. 60 / 160,138 Patent temporary patent application invention name is " Trans a parent Glass-Ceramics'1 , And Linda R. Pinckney's US Patent No. 60/167, 871 supplemented on November 29, 1999, which have the same name. Field of the Invention: The present invention relates to transparent glass-ceramics, in particular to transparent glass-ceramics, which are mainly transparent glass-ceramics of α and / 3 zinc oxalate crystals. BACKGROUND OF THE INVENTION: Glass-ceramic is a polycrystalline material formed by the crystallization of a precursor glass under controlled conditions. The glass-ceramic manufacturing method generally includes three basic steps: first, forming the glass raw material and melting it; second, cooling the melt to a temperature at least lower than its transition temperature range and the glass object of the required geometry Thirdly, the glass object is heated to a temperature under a controlled condition, the temperature being higher than a range of glass transition to generate crystals therein. Glass objects are usually exposed to a two-stage process. Thus, the glass is initially heated to a temperature within the transition temperature range, or slightly above the transition temperature for a period of time sufficient to promote the formation of crystal nuclei in the glass. As a result, the temperature will increase near the softening point of the glass, or even exceed the softening point of the glass to promote crystal growth on previously formed nuclei. The crystals formed are usually more uniform fine particles and the objects are usually highly crystalline. Internal crystal nuclei enable glass-ceramics to have this beneficial characteristic, such as a very narrow particle size distribution and uniform dispersion throughout the host glass. Transparent glass-ceramics are well known in the industry; for example G · Beall and

IIII 4! (Please read the notes on the back before filling this page) Order 503225 A7 B7 V. Description of the invention () DA Duke, transparent glass-ceramics ", Journal of Materials Science, 4, ρρ · 340-352 ( 1969) Research of the literature. Glass-ceramic objects appear visually transparent when the presence of crystals is less than the wavelength of visible light. In particular, the resulting transparency is usually crystallized to be smaller than ribbed coffee, and the preferred size is as small as 10 nm.

At present, considerable attempts have been made to use transparent glass-ceramics as hosts for optically active dopant transition metals. Proper glass-ceramic hosts must be specifically designed so that the transition elements are preferentially distributed within the crystal. The US patent No. 60/160, 053 of the company BeaH and others, the invention name is "Transition Metal Glass-Ceramics'1" is about doped transition metal glass-ceramics suitable for manufacturing communication gains or pumping laser fibers. Transparent glass-ceramics with a small amount of crystals can be widely used in many cases, where glass easily melts or easily forms a carrier of crystals, but provides highly desirable characteristics such as optical activity. Crystals in glass-ceramics are usually scattered randomly and pointed at In the whole glass object, there is no specific orientation like a single crystal. Irregular orientation and anisotropy are beneficial for many applications. An example is an optical amplifier in which the polarization-dependent gain is necessary. Transparency of doped transition elements Glass-ceramics can combine crystal optical benefits and glass-forming elasticity. For example, monolithic (planar) and fiber forms can be made from these glass-ceramics. Therefore, there is a need for transparent glass-ceramic materials that contain a small amount of tetrahedrons and Gap address, and therefore suitable as a small number of optical masters Dynamic transition elements may be useful hosts. This element contains Cr4 +, Cr3 +, C〇2 +, cu2 +, 4 ...... 1 ί 丨. ^ ^-(Please read the precautions on the back before filling this page ) Consumption Cooperation, Printed by the Society

503225 Α7 Β7 V. Description of the invention (L)

Ni2 +, Mn2 +, Cu2 +, and Ni2 + are not limited to these elements. These elements produce light and fluorescence, forming glass-ceramics containing dopants suitable for use in the optical field. The α- and stone-zinc silicate (ie, orthosilicate (ZmSi〇4)) contains Si04 and Zn04 tetrahedron. Alpha-silicic acid was decided in 1930. It has the same crystal structure as sparite (Be2Si〇4), has an orthorhombic hexahedral space group R 3, and is composed of a Si04 and Zn04 tetrahedron. All Zn2 + ions are located in tetrahedral coordination. Each oxygen atom is linked to one silicon and two rhenium atoms. The Ling-zinc silicate phase has scale quartz and cristobalite which are homogeneous and heterogeneous with silica. Half of the ions are in the tetrahedral coordination, while half are in the interstitial position. Phase equilibrium studies confirm that the α-silicic acid form is the only thermodynamically stable binary compound in the ZnO-SiO2 system. However, metastable wan-silicic acid can quickly reach devitrification products in glass. When the temperature is maintained above 85 ° C, the meso-silicic acid finally transforms into a stable heterogeneous phase. The / 5-zinc oxalate phase provides several useful properties. Unlike α-lithium acid, / 3-silicic acid has a widely different composition, which contains 33 to 67 mole percent ZηΟ. This wide range of solid solution phases can be achieved in a wide variety of glass-ceramic compositions. Central Standard Bureau of the Ministry of Economy Patent No. is about glass-ceramic material containing zinc oxalate as the main crystal phase and specially designed as the matrix in the collective circuit package. Glass-ceramic contains 30-55 Si02, 10-30 Al2 in weight percent. 3, 15-45 Znη, and 3-15 MgO. This paper size is applicable to national standards (CNs) A4 (21 × 297 public attack) η 503225 A7 V. Description of the invention (g) However, the previous technology has not revealed and The present invention discloses a glass-ceramic material that is transparent and suitable for use in the field of fiber optics. Therefore, the main object of the present invention is to provide a glass-ceramic material, which is substantially completely transparent, and includes it. The main crystal phase of Wei Cijing County. Another object of the present invention is to provide the silicic acid glass-ceramic, which can be doped with some components and can produce brightness and / or fluorescence. An important advantage of the glass-ceramic series of the present invention is to provide a material containing a zinc silicate crystal phase, which can coordinate a tetrahedron with a transition metal ion, the metal ion including Cr4 +, 〇λ 醎 〇 / +, and N. In addition, the material is mainly glass, so it provides important elasticity to make the whole (such as a flat substrate) and the form of fibers (such as optical fibers). Other objects and advantages of the present invention will become clear from the following description. To: The present invention provides a transparent glass-ceramic, which contains α- and / or / 5-zinc silicate and the composition is expressed as a percentage by weight of oxide containing 25-60 SiO2, 4-20 AI2O3, 20- 55 ZnO, 0-12 MgO, 0-18 K2O, 0-12 Na2〇, 0-30 Ge〇2, and EK20 + Na2〇-5. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ----. ———— (Please read the precautions on the back before filling this page} In order to obtain the maximum transparency in the final glass-ceramic object, the highest priority component is expressed by weight percentage of oxide, which contains 35-5〇Si〇2, 8 -15

Al2〇3, 30-42 ZnO, 0-5 MgO, 3-10 K2〇, 0-6 Na2〇, 0-5

Ge〇20 In order to obtain optical activity in the zinc silicate glass-ceramic material of the present invention, that is, fluorescence in the transmission wavelength range of 1100 to 1700 nm, the Chinese national standard (CNS) A4 specification can be applied to the mother paper. (210X297 mm) 503225 A7 _ B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (6) _————_—— Revised 91 · 7 · ίβ on the 1st day of the month Added 1% to the glass Weight ratio Cn〇3. The present invention also provides a manufacturing method, which comprises the following steps: a) melting the glass raw material, and expressing the glass composition as an oxide weight ratio, including # 25-60 Si〇2, 4-20Al203, 20-55 ZnO, 0 -12MgO, 0-18 K2O, 0-12% 2〇, 0-30 Ge〇2, and ΣΚ2〇 + Να2〇 ^ 5; b) cooling the glass to a temperature at least below the glass transition temperature range; c) The glass is exposed to a temperature range of 55-95 (rc for a sufficient period of time to promote the production of transparent glass-ceramics and contain silicic acid as the main crystal phase; and d) cool the glass-ceramics to room temperature. Brief description of the drawings: The first figure (Fig. 1) is an X-ray diffraction spectrum of a glass-ceramic powder having Example 2 composition, which is formed by heat treatment at 975 ° C for 2 hours and is shown as α-silicic acid Zinc is the main crystalline phase. The second figure (Figure 2) is a glass-ceramic powder X-ray diffraction spectrum with the composition of Example 2. It is formed by heat treatment at 850 ° C for 2 hours and is shown to be cold-silicic acid as the main crystal phase. . The second figure (Figure 3) shows the glass-ceramic fluorescence spectra of Wu You Examples 2 and 13, which are doped with 0.08% by weight & Detailed description: The transparent silicate glass-ceramic according to the present invention has a composition expressed as a percentage by weight of oxidation, including: 25-60 Si〇2, 4-20 AI2O3, 20-55 ZnO, 0-12 MgO, 0-18K2〇, 0 -12Na2〇, 0-30Ge〇2, and ΣΚ20 +% 20-5. (Please read the precautions on the back before filling in this page) Order f This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 503225 V. Description of invention Π) In order to get the largest in the final glass-ceramic object Transparency, the highest priority is expressed by weight percentage of oxides. Contains 35-50 Si〇2, 8-15 Al203, 30-42 ZnO, 0-5 MgO, 3-10 LO, 0-6 Na2〇, 0- 5 The following table reveals some glass components, expressed in weight units of oxides, which show the parameters of the present invention. The table also reveals the ceramic treatment parameters. C and hours indicate and the crystalline phase observed in the final glass-ceramic material. The sum of the individual components of each glass sample is close to 100. In fact, the values listed in the table can be regarded as weight percentages. The formulated glass raw material composition within the composition range of the present invention may contain any material including oxides or other compounds, as long as it is melted together, it will be converted into the appropriate proportion of oxides as required. Exemplary glass is manufactured in the following manner. The raw materials are mixed, stirred to help obtain a homogeneous melt, and placed in a platinum crucible. The crucible was placed in a high-temperature furnace operating at 1400-1600 ° C, and the raw materials were melted for 4-16 hours. The molten material is cast as a free-form sheet with a thickness of 10 mm), which is then moved to an operation at 550-60 (TC annealing furnace. The glass sheet is then ceramized by placing it in a high-temperature furnace and then ceramics according to the following steps Chemical: 30 ° C / hour to crystallization temperature T ° C, and maintained at T ° C for 1-2 hours, and cooled at the cooling rate of the high temperature furnace. The crystallization temperature T is 550-950 ° C, and manufactured Zinc silicate glass-ceramic. Bensmin composition is self-forming nucleus, which is due to liquid-liquid phase separation and therefore no need to add nucleating agent. In particular, nucleation is formed by an amorphous phase Separated and formed. It is not even necessary to apply the Chinese country when the nucleus is formed) A4 specification (2) _0x297 mm) 503225 A7 B7 9 V. Description of the invention (), in many cases, for example, Ti (K4%) (Weight ratio) crystal nucleating agent will produce more small crystal size and improve transparency. However, care must be taken to avoid instant crystal formation in the annealing furnace. CaO, BaO, SrO, or Ga203 can be added up to 5%. Addition of germanium oxide will tend to make alpha oxalate The polymorph is stable and better than / 5-zinc silicate. The glass-ceramic structure of the present invention contains small crystals of zinc silicate and / or 10,000-silicic acid (size about 10-5). ηπι) In stabilized aluminate glass, the total crystallinity is in the range of 10% to 50% by volume, which depends on the individual components. Fine crystals grow in the main glass during the ceramicization process. The glass-ceramic transparency of the present invention is a function of the microstructure, and it is also a function of the composition. The crystalline structure existing in the glass-ceramic material of the present invention provides only a small number of tetrahedrons and void positions. This property can give fine crystals useful as Small optically active non-limiting transition elements include & 4+, Cr'co2, Cu'Nm, Mn2 +, Cu2 +, and Ni2 + hosts. This transition will produce fluorescence and illuminate at different wavelengths. Some These elements are added in large quantities to the precursor product glass, and the amount used in the glass of the present invention does not exceed 1% by weight. As is well known in the optical and laser industries, it has a tetrahedral coordination Cr4 + crystal produced by the Central Bureau of Economic Affairs. Printed by Employee Consumer Cooperatives ---- · ---------- (Please read the notes on the back before filling out this page) The unique optical characteristics are ordered. Therefore, the present invention incorporates Mixed with $ 金林子 之 透 _ 魏 词 _, Qian He is used in the optics and field laser industry. Specific but non-limiting details include optical amplifiers and pumped lasers. In laboratory tests, examples 2 and 3 Doped with 0.08% by weight of chromium oxide and ordered fluorescent spectrometry. As shown in Figure 2, in the world communication

503225 A7 B7 V. Description of the Invention (q) Strong Cr4 + emission was observed in the transition wavelength range. Although the present invention has been fully described by way of examples, those skilled in the art can make various changes and modifications. These changes and modifications do not depart from the scope of the present invention as defined by the following patent application scope. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 503225

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Claims (1)

503225 A8 B8 ~ ....... _____ ;; ____ Twenty-one. One 丄 ------- one one < one one ί --............- -一., [^ &Amp; Circumferential Days—Additional Lambda 11 11 (Please read the precautions on the back before filling out this page) 1. A transparent glass containing silicic acid crystals. The phase is the main crystal phase- Ceramics, the composition of which is expressed as a percentage by weight, includes: 25 ° / 〇-60 ° / 〇Si〇2, 4% -20 ° / 〇AI2O3, 20 ° / 〇-55 ° / 〇ZnO; 0 ° / 〇- 12 ° / 〇MgO, 0% -18% M), 0% -12% Na2〇, 0% -30% Ge〇2, and ΣΚ2〇 + Na2〇 ^ 5 ° / 〇〇2. According to the scope of the patent application The glass-ceramic of item 1 further includes up to 2% by weight of LiO2. 3. The glass-ceramic according to item 丨 of the patent application scope, wherein the step further comprises up to 5% by weight of at least one oxide selected from CaO, BaO, SrO, and Ga203. 4. The glass-ceramic according to item 1 of the scope of the patent application, wherein the glass-ceramic can coordinate with the tetrahedron of transition metal ions, which are composed of Cr4 +, Cr 'C〇2 +, Cu2 +, Ni2 +, Mn2 +, Cu2 + And Ni2 + is selected to produce optical activity. 5. The glass-ceramic according to item 4 of the scope of patent application, wherein the glass-ceramic contains 1% by weight of Cr203. 6. Glass-ceramics according to item 1 of the scope of patent application, whose composition is expressed as a percentage by weight of oxidation. 35 ° / 〇-50 ° / 〇Si〇2, 8 ° / 〇-15 ° / 〇khOh 30 ° / 〇-42 ° / 〇ZnO, 0 ° / 〇-5 ° / 〇Mg〇, 3% -10 ° / 〇L0, 〇%, 〇%, Ge〇2. Economy ^ Printed by the Consumer Cooperatives of the Central Bureau of Standards 7. Glass-ceramics according to item 6 of the scope of patent application, in which glass-ceramics can coordinate with tetrahedral transition metal ions, which are composed of Cr4 +, Cr3 +, Co2 'Co3 +, Mn2 +, Cu2 + and Ni2 + are selected to produce optical activity. 8. According to the 7th scope of the patent application scope-Tao Jing, which glass? Ceramics contain up to 1% by weight Cr203. The size of wood paper is applicable to China National Standard (CNS) 8-4 specification (2 丨 0X297 mm) 503225 ABCD 2 IX VI. Application for patent scope 9 · Glass-Tauman according to the first scope of patent scope for application, among which silicate crystal size 10-50 ηm, making the glass-Tauman transparent. 10. The glass-ceramic according to item 1 of the scope of patent application, wherein the glass-ceramic has a total crystallinity of 10% to 50%, making the glass-ceramic transparent. 11. A method for manufacturing α- and / 5-zinc silicate crystal-based transparent glass-ceramics, the method includes the following steps: a) melting the glass raw material, and the glass composition contains 25%- 60% Si〇2, 4% -20% AI2O3, 20% -55% ZnO, 0% -12% MgO, 0% -18% K2〇, 0% -12% Na2〇, 0% -30% Ge〇 2, and ΣΚ2〇 + Ν & 0 ^ 5 ° / 〇; b) cooling the glass to a temperature at least lower than the glass transition temperature range; c) exposing the glass to a temperature range of 550-95 (TC for a period of time between charging Part of the time is to promote the production of transparent glass-ceramic and contain zinc silicate as the main crystal phase; and d) cool the glass-ceramic to room temperature. 12. The method according to item 1 of the scope of patent application, wherein the glass contains up to 1% by weight CnO3, which content will cause the glass-ceramic to exhibit optical activity. 1 ^ III ~~ 4— (Please read the precautions on the back before filling out this page) Order ---- Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs g Paper Standards Suitable for Financial Care; (CNS) A4 Specification ( 2Κ} χ297 public attack)