TWI228106B - Transparent lithium zinc magnesium orthosilicate glass-ceramics - Google Patents

Abstract

A glass-ceramic which is substantially and desirably totally transparent, and which contains a predominant, orthosilicate crystal phase whose composition lies 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: 35-72 SiO2, 0-25 Al2O3, 0-40 ZnO, 0-18 MgO, 1-15 Li2O, 0-18 K2O, 0-8 Na2O, 0-8 P2O5, with the condition that Sigma(ZnO+MgO) >= 7. The glass-ceramic may be doped with up to 1 wt.% chromium oxide to impart optical activity thereto.

Description

2 2 A7 Consumption cooperation of employees of the Central Bureau of Standards, Ministry of Economic Affairs, printed by 1228106 B7 __ Five 'invention description (丨> Related applications: October 18, 1999 Japanese company GeOrge H. BeAll and Linda R. PincKney applied for the 60/160, 053 patent provisional patent application invention name is "TRANSITION-META1 Glass-Ceramics GAIN MEDIA" is about 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 US Patent No. 60 / 160,138 filed by the Japanese company Linda R. PincKney for the provisional patent application " Transparent Glass-Ceramics " -Zinc silicate glass-ceramic, which can be doped with transition-metal to produce optical activity in it. October 15, 1999 Japanese company GeOrge Η. BeAll applied for US Patent 60/150, 093 temporary patent application invention name For " TRANSPARENT FORSTER ITE GLASS-CERAM I CSn is about transparent forsterite glass-ceramic, which is doped with transition-metal to produce optical activity in it October 18, 1999. Japanese company GeOrge H. BeAll, Linda R. WilLiam VOcKrOth and Ji Wang applied for US Patent No. 60/160, 052 temporary patent application invention name is "GLASS-CERAMIC FIBER AND METHOD" Ceramic material containing nanometer crystals and transition metals, and a method for manufacturing the glass-ceramic in the form of optical fibers. The present invention is US Patent 60 / 159,967 to GeOrge H. BeAll and Linda R. PincKney The provisional application name is "TRANs-PARENT (Li, Zn, Mg) ORTHOSILICATE GLASS-CERAMICS, 1 and ORTHOSILICATE glass-CERAMICS, and GeOrge H. BeAll and this paper standard (CNS) A4 specification ( 210X297 Male f (Please read the notes on the back before filling this page)

1228106 A7 Printed by the Central Bureau of Quasi-Ministry of Economic Affairs—Industrial and Consumer Cooperatives B7_ 5. Description of the Invention (:) ^^^ US Patent No. 6 0/174, 012, filed on October 18, 1999 by Linda R. PincKney, It has the same name. FIELD OF THE INVENTION The present invention relates to transparent glass ceramics, and more particularly to transparent glass-ceramics, which are mainly ternary MgzSiO4-ZmSiOrLhSiO4 polycrystalline orthosilicate crystals. BACKGROUND OF THE INVENTION: Glass-ceramics are polycrystalline materials formed by the controlled crystallization of the precursor glass. The method of manufacturing the glass-ceramic usually includes three basic steps: first forming the glass raw material and melting it; second, the molten material is simultaneously cooled to a temperature that is at least lower than its transition temperature range and the glass object of the required geometry; And third, 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 higher than 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 such beneficial properties as, for example, a very narrow particle size distribution and uniform dispersion throughout the host glass. Transparent glass-ceramics are well known in the industry; for example, GH BeAll and DA DuKe's "transparent Glass-Ceramics' JOurNAl" This paper size is applicable to Chinese national standards (CNS> A4 specification (2l0x2)) (Please read the back first (Please note this page before filling in this page) Order. — * ♦ · Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 1228106 A7 B7 Five 'Invention Note (3)

Of MateriAls Science, 4, PP. 340-352 (1969). Glass-ceramic objects appear visually transparent when crystals are present below the wavelength of visible light. In particular, transparency typically results in crystals smaller than 50 nm, and preferentially 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 company has U.S. Patent No. 60 / 160,053 and the invention name is "1 ^ 如 31 乜 〇11"

MetAl Glass-Ceramics’1 is about doped transition metal glass-ceramics suitable for manufacturing communication gain or pumping laser fibers. Transparent glass-ceramics containing a relatively small amount of crystals can be widely used in Bento's case, where glass easily melts or easily forms a crystal carrier, but provides highly desirable characteristics such as optical activity. Crystals in glass-ceramics usually face the entire glass object irregularly, unlike single crystals with a specific orientation. Irregular orientation and anisotropy are beneficial for many applications. An example is an optical amplifier in which the polarization-dependent gain is necessary. Transparent glass ceramics doped with transition elements can combine the optical benefits of crystals with the complexity of glass formation. For example, monoliths (flat surfaces) and dishes can be made from these glass-ceramics. 'Thus, there is a need for transparent glass-ceramic materials that contain a small amount of tetrahedrons and interstitial sites, and are therefore suitable as hosts where a small amount of optically active transition elements may be useful. This element contains Cr4 +, Cr3 + Co2 + Cu2 + ΝΛΜγΛ FeV Fe 'Cu +, but it is not limited to these elements. , -------: __ 1 ## >. (Please read the notes on the back before filling in this page), ^ τ

1228106 Five 'invention description (a) These elements generate luminescence and fluorescence, forming glass-ceramics containing dopants suitable for use in the field of optics. Many crystalline phases consisting of polycrystalline materials and a wide range of solid phase solutions are generated in the composition defined by MgzSiOrZmSiO4-LhSi04. These crystalline phases have a unique crystalline phase structure, which differs from the crystalline structure of the end components Mg2Si〇4 (magnesium lanolin VZrnSiO4 (zinc oxalate), and Li4Si〇4. The crystal structure 2 is mainly hexagonal closed Arrange oxygen atoms, all metal ions (ie Zn2 +, Mg2, and Li +) are tetrahedral coordination. The different distribution of cations within the tetrahedral site produces very polycrystalline, which is therefore classified as no—and ^ —forms Structure. In the / 3 form structure, the tetrahedral connection will make each corner of each tetrahedron share with the other three tetrahedrons, which are quite close to the edges of some tetrahedrons in the 7 form structure. The crystal structure characteristics have not been well understood, However, it exhibits orthorhombic or similar orthorhombic (monoclinic) symmetry. / When many of these crystal phases and their stable side 6 have been explained in Shi Guang physical science and phase balance literature, it is not produced in In the ternary Mg2SiQ4—Zn2Si〇4—LhSiO4 system, crystal-based transparent glass-ceramic. Therefore, the main object of the present invention is to provide a glass-ceramic material, which is substantially and completely ground-turned, and its containing There is mainly a crystal phase of orthosulfate, and its composition is in the ternary MgzS i OrZmS i OrL i A 〇4 system. Printed by the consumer cooperation agency of the Central Government Bureau of the Ministry of Economic Affairs (printed on the back) (Fill in this page again.) Another object of the present invention is to provide the orthosilicate glass ceramic, which can be doped with some components that generate ambiguity / money. The advantages of the series of glass-ceramics of the present invention are that it provides Contains orthotite helioside material, the crystal contains tetrahedral coordination sites, and there are some transition metal ions, the ions include Cr4 +, Cr3 \ Co2 +, Cu2 +, Ni2 +, Mn2 +,

1228106 A7 B7 Five 'Invention Description (f) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Fe3 + ’Fe2 +, and C-core materials are glass-based materials that provide important elasticity and are manufactured in the form of monoliths (such as flat substrates) and fibers (such as optical fibers). Other objects and advantages of the present invention will be explained in detail as follows. Summary of the invention: The present invention provides transparent positive Wei salt glass _ pottery change, good crystal composition Lg & lZmSl (VLi4SiH_. The glass _ pottery of the present invention has the following composition based on the predecessor "Lai Cheng, Fine Oxygen« Percent Parts: 35-72 Si〇2, G-25 Α1Λ, G-40 ZnO, 0-18 MgO, 1-15 Li2〇, 0-18 κ2〇, 〇-8 Na2〇, 〇-8 p2〇5, and E (Zn〇 + MgO) g7. 'In order to obtain maximum transparency in glass-ceramic objects, the Mg2Si〇4-ZmSiO4-LuSiO4 system has the highest priority. The oxide basis is 40-65'Si〇2,5- ISA · 8-36ZnO, (H2MgO, 1 12 LhO, 8-14 10, 0 ~ 5 return, 0-6 PA where Σ (ZηΟ + MgO) ^ l0. In the present invention, a salt surface-shout material towel is presented 11GG to 1700nm f signal transmission wavelength range _ to obtain optical activity, that is, fluorescence-the method is glass-ceramic material doped with up to 1% heavy chrome oxide and preferentially doped 003-0. 3% weight ratio. -, The method for manufacturing the glass-breaking method of the present invention also includes the following steps: aMw surface raw material, which is expressed by weight percentage of oxide 3 5-72 Si〇2, 〇 ~ 25 Abo% 〇-4〇ZnO, 0- 18 MgO,; [-1 5 LiA 0-18L0, 〇: 8Na2〇, 〇—sp2〇5, and Σ (Zη〇_) miscellaneous package This paper size is applicable (Please read the precautions on the back before filling this page)

Consumer Co-operation of the Central Standards Bureau of the Ministry of Economic Affairs Du Yinzhuang 1228106 Λ7 B7 V. Description of the Invention (fc) -7 〇 b) Cooling the glass to a temperature lower than the glass transition range; c) Exposing the glass to the temperature range of 550-950 ° C lasted for a sufficient period of time, which was sufficient to promote the production of glass-ceramics that were transparent and contained a major crystalline phase of orthosilicate within the ternary Mg2Si〇4_Zn2Si〇4-Li4Si〇4 system; and d) The glass-ceramic was cooled to room temperature. Brief description of the drawings: The first diagram, the second diagram, and the third diagram (Figs. 1,2 and 3) are X-ray diffraction spectra of the powders of Examples 1, 10, and 17 in the following composition table. The fourth, fifth, and sixth graphs (Figures 1, 10, and 17) are the Cr4 + glass-ceramic fluorescence curves of Examples 1, 10, and 17 in the following composition table. Detailed description: The rhenium component of the present invention is transparent orthoxate glass-ceramic ware, which is expressed in terms of oxide weight ratio and includes: Si〇2 35-72, Al203 0-25, ZnO (M0, MgO, 18, E (ZnO + MgO) > 7, Li2〇1 -15, K2O (M8, Na2 0-8, P2 0-5, Nanda 5% CaO, GaO, PbO, or SrO or up to 20% Ga2 〇3 or Ge〇2 can also be added. In order to obtain the greatest degree of transparency in glass-ceramic objects, the most preferred composition range is expressed by weight percentage of oxides. Contains: SiO2 40-65, Al205--18 , Zn0 8-36, MgO〇-12, E (ZnO + MgO) ^ 10, Li2〇8-14, LO 0-5, Na2〇-5, P205 0-6. The following list reveals some glass The composition, which is expressed in units of oxide weight, shows the parameters of the present invention. The table also reveals the ceramic treatment parameters

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1228106 A7 Γ —_________ B7 V. Description of the invention ("]) It is expressed in c and hours, and the transparency of each glass-ceramic material formed. The transparency of the sample with a thickness of 5-10 mm is graded from (clear) to 4 (water-white transparent). The sum of the individual components of each glass sample close to the actual listed values can be considered as a weight percentage. The composition of the formulated glass raw materials within the composition range of the present invention may include any material including oxides or other compounds, and as long as they are melted together, they will be converted into the appropriate proportion of oxides as required. The exemplary glass was produced in the following manner. The raw materials are mixed, stirred to help obtain a homogeneous melt, and placed in a platinum crucible. Tsunami was then placed in a high-temperature shot at _-16, and the raw materials were melted for 4-16 hours. · The object is washed as a free-form sheet (5-10 mil thickness), which is then moved to an operation at 550-600. (: In an annealing furnace. The glass is thin > 1 and then ceramicized by being placed in a high temperature furnace and then ceramicized according to the following steps: 30 (Tc / hour to crystallization temperature rc, and maintained at T ° C It lasted for 1-2 hours and cooled at a high temperature furnace rate. The crystallization temperature T was 550-950 ° C, and a transparent orthosilicate glass-ceramic was produced. In another embodiment, the sample was first heated to a temperature of Between 575 and 〇〇, it was kept for 2 hours, and then processed at -75G ° C and kept for 4 hours to obtain a transparent orthophosphate glass-ceramic. Consumption by the Central Standards Bureau of the Ministry of Economic Affairs The cooperative prints the constituent self-forming nucleus formation system of the present invention due to liquid-liquid phase separation and therefore does not require the addition of a nucleating agent. In particular, nucleation is formed by amorphous phase separation. However, even When crystal nucleation is not required, the addition of, for example, Ti〇2, Zr〇2, and p205 in the case of noon will produce a smaller scale structure and improve the roll. Adding TiQ2, Ti02 + zr02 Paper Scales and Financial V. Inventive Notes & PΛ Crystal Nuclei Examples of the ingredients are listed in the table. The secret material is widely used as crystals to form in the oxygen brain. ^: Lithium has been made of lithium to make Wei salt glass. The money may form Qiantian, which in turn makes heterostructured oxalic acid. Salt crystal nucleation. It is believed that phosphate acts as an effective crystal nucleating agent for the normal Wei salt phase in the glass pin of the present invention, because the t substance is represented by y? And r polycrystalline U3P04. The glass-ceramic material formed The crystal phase is identified using x-ray powder diffraction. Examples 1, 10, and 17 are representative diffraction patterns shown in Figures 2 and 3. In the glass-ceramic of the present invention, transparency is a function of microstructure, which is also It is a function of composition and heat treatment. The glass-ceramic microstructure of the present invention includes a fine structure of orthosparite (size about 10-50 nm) is a stabilized osate or metallo-alumina silicate glass. The crystallinity is in the range of 10% to volume ratio, and it depends on the individual components. The fine crystals of the orthosilicate constituting the crystalline phase grow in the main glass during the ceramization process. Small tetrahedrons and void locations. This feature gives a fine knot There may be a small optical land initiative of non-limiting transition element contains Cr4 +, Cr3 +, Co2 +, Cu2 +, Ni2 +, +, FV +, Ministry of Economic Affairs Su consumer cooperation Uu quasi-workers printed Mn2

Fe, and the host of cu +. In particular, the microcrystalline phase concentrates the transition metal ions into tetrahedral coordination to produce optical activity. As is well known in the optics and laser industries, having tetrahedral coordination Cr4 + crystals produces unique optical characteristics. Therefore, in one possible application, the transparent orthosilicate glass-ceramic doped with transition metal ions of the present invention is not suitable for use in the optical and laser industries. Specific applications include optical amplifiers and pumped lasers. The size of the wood paper is applicable to the Chinese National Standard (CNS) A4 specification (IlOXf297 mm 1228106 B7 Five 'invention description) In the experiment, the examples 1, 7 and 10 were doped with 0.06% by weight chromium oxide and the amount of fluorescence As shown in Figures 4, 5 and 6, strong Cr4 + emissions were observed in the communication transition wavelength range of 1100-1700nm. Although the present invention has been fully explained by way of example, those skilled in the art can make various changes. And changes. These changes and changes do not depart from the scope of the present invention as defined by the following patent application scope. The Central Standards Bureau of the Ministry of Economic Affairs ^: Industrial paper printed by the Consumer Cooperative Cooperative is applicable to _ 家 标准 (cns) A4 specifications Thin) 丨 1

Claims (1)

1228106 Α8 Β8 C8 D8, patent application scope 1_ A transparent glass ceramic containing an orthosilicate crystal phase, the composition of which is located in the ternary Mg2Si〇4_Zn2Si〇4-Li4Si〇4 system and expressed in weight percent of oxides contains: 35 % -72% Si〇2, 0% -25% Ah〇3, 0% -40% ZnO, 0 ° / 〇-18 ° / 〇MgO, 1 ° / 〇-15 ° / 〇Li2〇, 0 ° / 〇-18 ° / 〇K2O, 0% -8 ° / 〇Na2〇, 〇% -8% P205, and Σ (ZnO + MgO)-7%. 2. The glass-ceramic according to item 1 of the scope of patent application, wherein the composition further comprises 1% by weight of chromium oxide expressed as a percentage of the amount of oxides of the child. 3. Glass Taoman according to item 2 of the scope of patent application, wherein the composition contains 0.003% to 0.3% by weight of chromium oxide. 4. Glass ceramics according to item 1 of the scope of patent application, in which the orthosilicate crystal phase concentrates the transition metal ions at the tetrahedral coordination or small interface position, and thus gets active in the glass ceramics. The transition metal ions are made of Cr4 + , Cr3 +, Co2 +, Cu2 +, Ni2 +, Mn2 +, Fe3 +, Fe2 +, and Cu + are selected. 5. Glass ceramics according to item 丨 of the scope of patent application, where the composition based on oxides contains 40% -65% SiO2, 5% -18% Α12〇3, 8% -36% ZnO, 0 % -12% MgO, 1% -12% Li20, 8% -14% K2O, 0% -5% Na2O, 0% -6% P205, of which Σ (ZnO + MgO) g is 10%. 6. The glassware according to item 5 of the scope of patent application, the composition of which is further printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. One step contains 1% by weight of chromium oxide based on the weight percentage of oxides. 7. The glass ceramics according to item 5 of the scope of the patent application, wherein the composition contains a complex oxide of 0.003% to 0.3% by weight. 8. According to the glass Taoman according to item 5 of the scope of the patent application, the orthosilicate crystal phase concentrates the transition metal ions at the tetrahedral coordination or small interface position, and the Chinese national standard (CNS) Α4 specification is applicable for the paper size (210 × 297 mm) 1228106 A8 B8 C8 D8 6. The scope of patent application is used to obtain activity in glass ceramics. The transition metal ion is selected from Cr4 +, cr3 +, Co, Cu, Ni2 +, Mn2 +, Fe3 +, Fe2 +, and Cu +. 9. The glassware according to the first patent claim, wherein the ortho-acid salt crystal phase is composed of fine crystals with a size of 10 nm to 50 nm. 10. The glass-ceramic according to item 1 of the patent application, wherein the orthosilicate crystal phase is composed of 10% to 50% by volume glass-ceramic. 11. A method for manufacturing a transparent glass ceramic containing orthoxate crystal phase, the composition of which is located in a ternary Mg2Si〇4-ZmSiO4-Li4Si〇4 system, the method includes the following steps: a) molten glass raw material, the raw material Expressed in weight percent of oxides containing 35% -72% Si〇2, 0% -25% Αία, 0% -40% ZnO, 0% -18% MgO, 1% -15% Li2〇, K2O, -8 % Na2〇, 0% -8% ⑽ I (ZnO + MgO) ^ 7%; b) cooling the glass to a temperature at least lower than the glass transition range; c) exposing the glass to a temperature range of 550-950 ° C for a period of time In sufficient time, it is sufficient to promote the production of glass ceramics which are transparent and which contain the orthosilicate main crystal phase within the ternary Mg2Si〇4-Zn2Si〇4-Li4Si〇4 system; and d) the glass ceramic Cool to room temperature. Printed by the Central Government Bureau of the Ministry of Economic Affairs for consumer cooperation and social printing (please read the precautions on the back before filling out this page) 12 · According to the method of item 11 of the scope of patent application, where the glass is initially exposed to a temperature of 575-700 ° C It lasted for 1-2 hours and was then exposed to a temperature of 650-750 ° C for 4 hours. 13. The method according to item 11 of the scope of patent application, wherein the glass ceramic is doped with chromium oxide up to 1% by weight. Long paper size applies to China National Standard (CNS) 8-4 specifications (210 X 297 mm) 1228106 A8 B8 C8 D8 6. Application for patent scope 14. Method according to item 13 of the scope of patent application, in which glass ceramic is doped with 0.003 % -0 · 3% by weight chromium oxide. i i ^ — 41 ^ — (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The paper size of the paper applies the Chinese National Standard (CNS) A4 (210X297 mm)