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CN86106629A - Glass of high refractive index - Google Patents

Glass of high refractive index Download PDF

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Publication number
CN86106629A
CN86106629A CN198686106629A CN86106629A CN86106629A CN 86106629 A CN86106629 A CN 86106629A CN 198686106629 A CN198686106629 A CN 198686106629A CN 86106629 A CN86106629 A CN 86106629A CN 86106629 A CN86106629 A CN 86106629A
Authority
CN
China
Prior art keywords
glass
oxide
dioxide
zro
replace
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN198686106629A
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Chinese (zh)
Inventor
胡和方
林凤英
林光荣
袁逸波
朱永明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Optics and Fine Mechanics of CAS
Original Assignee
Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Optics and Fine Mechanics of CAS filed Critical Shanghai Institute of Optics and Fine Mechanics of CAS
Priority to CN198686106629A priority Critical patent/CN86106629A/en
Publication of CN86106629A publication Critical patent/CN86106629A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C03C12/00—Powdered glass; Bead compositions

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

Abstract

A kind of glass of high refractive index that is used to make glass microballon, its mole percentage composition are TiO 250-70, BaO 12-30, B 2O 3+ SiO 22-10, Bi 2O 30-10, Sb 2O 30-5, La 2O 3+ ZrO 2+ Nb 2O 52-20, La wherein 2O 30-10, ZrO 20-15, Nb 2O 50-8.This glass refraction has anti-preferably devitrification behavior and good physical and chemical performance greater than 2.1, and available crucible is founded.The glass microballon that this glass is made can be used for making high brightness traffic sign and high-brightness reflective film.

Description

The invention relates to specific refractory power greater than 2.1, the chemical constitution of crown glass.It is suitable for making the high-refraction glass bead as retroreflecting material especially.These microballons can be used for making high brightness traffic sign, sign and high-brightness reflective film.
In invention in the past, adopt plumbous oxide and titanium dioxide to make specific refractory power greater than 2.1 high-refraction glass bead, as English Patent GB-1130284, what U.S. Pat P-3293051 etc. introduced usually as the main component of glass.Its shortcoming be glass smelting with become the pearl process in because the volatilization of leaded component and dispersing in the material can cause in the atmosphere plumbous pollution and operator's lead poisoning; High lead content also damages platinum crucible easily in the glass; In addition, this class glass microballon easily with atmosphere in the sulfurous gas reaction, make the transmittance decline of microballon.Introduced in U.S. Pat P-3419403 in titanium dioxide-barium oxide system and introduced bismuthous oxide bismuth trioxide, manufacturing specific refractory poweres such as antimonous oxide are the glass microballon of 1.8-2.5.But barytic content was higher during the glass that should invent employing was formed, titanium dioxide is 0.9-2.2 with barytic molar content ratio in the glass, barytic a large amount of existence that the part specific refractory power is lower are unfavorable for improving the specific refractory power of glass, have in glass, introduce a large amount of antimonous oxide and bismuthous oxide bismuth trioxide for improving specific refractory power, but the existence of a large amount of antimonous oxides and bismuthous oxide bismuth trioxide produces injurious effects to platinum crucible easily, and the anti-devitrification behavior of these glass is still relatively poor in addition.
The objective of the invention is to seek and be suitable for making the composition of specific refractory power greater than 2.1 high refracting glass.These glass can be with common technology flux in platinum crucible, and have anti-preferably devitrification behavior.
Consider the above-mentioned shortcoming of flint glass, we select titanium dioxide and barium oxide for use is the main ingredient of glass.In this system, the part specific refractory power of titanium dioxide is higher, and increases with the increase of titanium dioxide with barytic molar content ratio, and its value is 2.2-2.48, and barytic part specific refractory power is lower, is 1.87.Obtain specific refractory power greater than 2.1 glass, should make titanium dioxide higher than as far as possible with barytic molar content.But simple binary is formed the very difficult glass that forms.In this class is formed, introduce network formers such as silicon-dioxide and boron trioxide and can obviously improve its glass forming ability, but the part specific refractory power of most of network formers that comprises silicon-dioxide, boron trioxide is all very low, should reduce the low refraction of this class components contents in the glass as far as possible for this reason.Bismuthous oxide bismuth trioxide and antimonous oxide can promote the formation of glass, and can obviously improve the specific refractory power of glass, but the existence of a large amount of antimonous oxides and bismuthous oxide bismuth trioxide produces injurious effects to platinum crucible easily, and the content of these two kinds of components in glass also be should give control.Also be mixed with part specific refractory power high rare earth oxides such as lanthanum trioxide, niobium oxides or zirconium dioxide in the glass to improve the anti-devitrification behavior of ba titanate glass, reduce the painted of glass, they at high temperature can not produce injurious effects to platinum crucible yet.
Glass of the present invention is to serve as main the composition with titanium dioxide and barium oxide, and titanium dioxide is 2.3 to 5 with barytic molar content ratio in the glass, and the molar content that its glass is formed is:
The component molecular fraction
TiO 250-70
BaO 12-30
B 2O 3+SiO 22-10
Bi 2O 30-10
Sb 2O 30-5
La 2O 3+ZrO 2+Nb 2O 52-20
Wherein:
La 2O 30-10
ZrO 20-15
Nb 2O 60-8
Titanium dioxide is 2.5 to 4 with barytic molar content ratio in forming, and the glass that meets following compositing range can obtain more satisfied result.
The component molecular fraction
TiO 255-65
BaO 15-25
B 2O 3+SiO 22-7
Bi 2O 32-10
Sb 2O 30-3
La 2O 3+ZrO 2+Nb 2O 53-15
Wherein:
La 2O 31-5
ZrO 22-10
Nb 2O 30-5
Can make the transparent glass that specific refractory power is 2.1-2.4 from above-mentioned composition, to yellow, density is less from little Huang for color, is about the 5.0-5.5 gram per centimeter 3, and having anti-preferably devitrification behavior and other good physical and chemical performance, the high temperature viscosity of glass melt is little, and platinum crucible is not had tangible harmful effect, is suitable for making specific refractory power greater than 2.1 glass microballon.
During above-mentioned glass is formed, available strontium oxide, calcium oxide or alkalimetal oxide replace partial oxidation barium, silicon-dioxide and boron trioxide can partly or entirely be used germanium dioxide, network formers such as aluminium sesquioxide replace, lanthanum trioxide can replace with other rare earth oxide, and zirconium dioxide and niobium oxides are then distinguished available consanguinity hafnium oxide, and tantalum oxide replaces.
Provided the embodiment of a collection of glass of high refractive index of the present invention in the following table.
NO TiO 2BaO CaO B 2O 3SiO 2Sb 2O 3Bi 2O 3La 2O 3ZrO 2Nb 2O 3
1 52 21 2.5 7 3 0 0 4 8 2.5
2 55 20 4 5 5 0 5 3 3 0
3 55 17 2 2 2 1 7 3 10 1
4 55 17 2 2 2 1 7 8 5 1
5 56 15 2 1.5 1.5 1 10 3 6 4
6 60 24 0 2 2 1 5 2 2 2
7 60 13 0 2 2 2 10 2 1 8
8 62 15 0 2 2 5 9 5 0 0
9 63 20 0 2 2 2 7 4 0 0
10 63 20 2 3 2 0 0 3 5 2
11 65 16 0 2 2 2 7 3 2 1
12 68 15 0 2 2 1 7 2 2 1
These glass can be founded at platinum crucible or other suitable fire proofed wood material as container with usual method.Wherein barium oxide and other alkaline earth metal oxide, and alkalimetal oxide is introduced with corresponding carbonate or nitrate, titanium dioxide, antimonous oxide, bismuthous oxide bismuth trioxide, niobium oxides, zirconium dioxides etc. are introduced with oxide compound usually, rare earth oxides such as lanthanum trioxide can be introduced with oxide compound or nitrate form, and silicon-dioxide is introduced with glass sand, and boron trioxide is then introduced with boric acid.The admixtion that is mixed with in required ratio with these raw materials is founded in globars electric furnace or other High Temperature Furnaces Heating Apparatus with platinum crucible after fully mixed, and glass melting temperature is 1250-1400 ℃, and the smelting furnace planted agent keeps oxidizing atmosphere.After admixtion melted fully, the melt quenching that can in all sorts of ways after abundant homogenizing made little Huang to the xanchromatic transparent glass.The specific refractory power 2.1～2.4 of these glass, density 5.0～5.5 gram per centimeters 3About, transition temperature 600-700 ℃, and have anti-preferably devitrification behavior and good physicochemical property.These transparent glasses are ground into certain granularity, can make no devitrification with commonly used one-tenth pearl method, specific refractory power is greater than 2.1 glass microballon.These glass melt high temperature viscosities are little, and platinum crucible is not had tangible harmful effect, are suitable for directly making microballon from melt.

Claims (4)

  1. It is 1, a kind of that what be used to make glass microballon serves as the main glass of high refractive index of forming with titanium dioxide and barium oxide, contain silicon-dioxide and boron trioxide, it is characterized in that titanium dioxide is 2.3 to 5 with barytic molar content ratio in the glass, it is high that this glass also contains at least a part specific refractory power, as lanthanum trioxide, heavy metal oxides such as niobium oxides and zirconium dioxide.
  2. 2, a kind of glass according to claim 1 is characterized in that consisting of of this glass:
    The component molecular fraction
    TiO 250-70
    BaO 12-30
    B 2O 3+SiO 22-10
    Bi 2O 30-10
    Sb 2O 30-5
    La 2O 3+ZrO 2+Nb 2O 52-20
    Wherein:
    La 2O 30-10
    ZrO 20-15
    Nb 2O 30-8
  3. 3, a kind of glass according to claim 2 is characterized in that consisting of of this glass:
    The component molecular fraction
    TiO 255-65
    BaO 15-25
    B 2O 3+SiO 22-7
    Bi 2O 32-10
    Sb 2O 30-3
    La 2O 3+ZrO 2+Nb 2O 33-15
    Wherein:
    La 2O 31-5
    ZrO 22-10
    Nb 2O 30-5
  4. 4, a kind of glass according to claim 2 or 3, it is characterized in that the available calcium oxide of a said barytic part, or strontium oxide or alkalimetal oxide replace, said silicon-dioxide, boron trioxide can partly or entirely replace with network formers such as germanium dioxide or aluminium sesquioxides, said lanthanum trioxide can replace with other rare earth oxide, and said zirconium dioxide, niobium oxides can replace with consanguinity hafnium oxide, tantalum oxide respectively.
CN198686106629A 1986-09-27 1986-09-27 Glass of high refractive index Pending CN86106629A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN198686106629A CN86106629A (en) 1986-09-27 1986-09-27 Glass of high refractive index

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN198686106629A CN86106629A (en) 1986-09-27 1986-09-27 Glass of high refractive index

Publications (1)

Publication Number Publication Date
CN86106629A true CN86106629A (en) 1988-04-06

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Family Applications (1)

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CN198686106629A Pending CN86106629A (en) 1986-09-27 1986-09-27 Glass of high refractive index

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CN (1) CN86106629A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071721C (en) * 1997-09-18 2001-09-26 中国科学院感光化学研究所 High-refractive index transparent ceramic micro-bead and its manufacture method and use
CN100337955C (en) * 2002-12-25 2007-09-19 日本电气硝子株式会社 Optical glass for molding shape
CN101407376B (en) * 2008-11-05 2010-06-02 江西盛富莱定向反光材料有限公司 High brightness glass microbeads and preparation technique thereof
CN101200127B (en) * 2006-12-15 2011-04-20 中国科学院合肥物质科学研究院 Lanthanum zirconic acid/yttrium titanate film material and method for making same
US7960300B2 (en) 2006-09-14 2011-06-14 Japan Aerospace Exploration Agency Titanium-containing oxide glass and method for production thereof
CN101538114B (en) * 2001-08-02 2011-07-13 3M创新有限公司 Article comprising metal oxide glasses and method of making same
CN101319100B (en) * 2007-07-18 2011-09-14 朱建新 Reflecting beads for road mark line
EP2467342A1 (en) * 2009-08-21 2012-06-27 3M Innovative Properties Company Pavement markings, reflective elements, and methods of making microspheres
EP2467341A1 (en) * 2009-08-21 2012-06-27 3M Innovative Properties Company Pavement markings, reflective elements, and methods of making microspheres

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071721C (en) * 1997-09-18 2001-09-26 中国科学院感光化学研究所 High-refractive index transparent ceramic micro-bead and its manufacture method and use
CN101417860B (en) * 2001-08-02 2012-01-18 3M创新有限公司 Method of making articles from glass and glass ceramic articles so produced
CN101538114B (en) * 2001-08-02 2011-07-13 3M创新有限公司 Article comprising metal oxide glasses and method of making same
US8003217B2 (en) 2001-08-02 2011-08-23 3M Innovative Properties Company Metal oxide ceramic and method of making articles therewith
CN100337955C (en) * 2002-12-25 2007-09-19 日本电气硝子株式会社 Optical glass for molding shape
US8030232B2 (en) 2006-09-14 2011-10-04 Japan Aerospace Exploration Agency Titanium-containing oxide glass and method for production thereof
US7960300B2 (en) 2006-09-14 2011-06-14 Japan Aerospace Exploration Agency Titanium-containing oxide glass and method for production thereof
CN101516795B (en) * 2006-09-14 2013-03-27 独立行政法人宇宙航空研究开发机构 Titanium-containing oxide glass and method for production thereof
CN101200127B (en) * 2006-12-15 2011-04-20 中国科学院合肥物质科学研究院 Lanthanum zirconic acid/yttrium titanate film material and method for making same
CN101319100B (en) * 2007-07-18 2011-09-14 朱建新 Reflecting beads for road mark line
CN101407376B (en) * 2008-11-05 2010-06-02 江西盛富莱定向反光材料有限公司 High brightness glass microbeads and preparation technique thereof
EP2467342A1 (en) * 2009-08-21 2012-06-27 3M Innovative Properties Company Pavement markings, reflective elements, and methods of making microspheres
EP2467341A1 (en) * 2009-08-21 2012-06-27 3M Innovative Properties Company Pavement markings, reflective elements, and methods of making microspheres
EP2467342A4 (en) * 2009-08-21 2014-08-13 3M Innovative Properties Co Pavement markings, reflective elements, and methods of making microspheres
EP2467341A4 (en) * 2009-08-21 2014-08-20 3M Innovative Properties Co Pavement markings, reflective elements, and methods of making microspheres

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