CN108483902A - High V values and low-temperature coefficient heavy metal borate glass and preparation method and application - Google Patents

High V values and low-temperature coefficient heavy metal borate glass and preparation method and application Download PDF

Info

Publication number
CN108483902A
CN108483902A CN201810266445.2A CN201810266445A CN108483902A CN 108483902 A CN108483902 A CN 108483902A CN 201810266445 A CN201810266445 A CN 201810266445A CN 108483902 A CN108483902 A CN 108483902A
Authority
CN
China
Prior art keywords
heavy metal
borate glass
optic
magneto
metal borate
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.)
Granted
Application number
CN201810266445.2A
Other languages
Chinese (zh)
Other versions
CN108483902B (en
Inventor
钱鹏远
王双保
王宇杰
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.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
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 Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201810266445.2A priority Critical patent/CN108483902B/en
Publication of CN108483902A publication Critical patent/CN108483902A/en
Application granted granted Critical
Publication of CN108483902B publication Critical patent/CN108483902B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
    • C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths

Landscapes

  • 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

The present invention provides a kind of high V values and low-temperature coefficient heavy metal borate glass and preparation method and applications.Preparation method is by PbO, B2O3Or H3BO3And Bi2O3It is melted and is clarified after being sufficiently mixed, can also add rare earth oxide or transition metal oxide, and be stirred homogenizing, high V values and low-temperature coefficient heavy metal borate glass are prepared by melt casting method.There is heavy metal borate glass low manufacture cost provided by the invention high Verdet constants and very low temperature dependency, the heavy metal borate glass can be widely used for the design of all kinds of magnetic-optic devices and need not take technique for temperature compensation.There is such glass excellent magnetic rotation optical property, near-infrared transmitance can reach 85%, be suitble to prepare all kinds of magnetic-optic devices such as magneto-optic current transducer, magneto-optic shutter, magneto-optic modulator and magneto optic isolator.

Description

High V values and low-temperature coefficient heavy metal borate glass and preparation method and application
Technical field
The present invention relates to high magneto-optic glass fields, more particularly, to a kind of weight of high magneto-optical property and low-temperature coefficient Metal borate glass.
Background technology
Magneto-optic memory technique refers to that Faraday effect can occur when externally-applied magnetic field is oriented parallel to polarization optical transmission direction Substance, Faraday effect is found in 1845 earliest, but up to date decades with photoelectric technology development, to tool There is the object Quality Research of this characteristic just to achieve major progress.Magneto-optic memory technique is now widely used for magneto optic isolator, magneto-optic In the devices such as sensor and magneto-optic shutter.The magneto-optic memory technique of early stage mainly based on magneto-optical crystal, but in preparation process they Raw material be difficult to congruent melting and obtain larger monocrystalline, lead to complex process and expensive.Compared with magneto-optical crystal, magnetic Light glass is affected by temperature smaller, and the manufacture craft of magneto-optic glass is also more convenient, it is easier to the larger finished product of volume, cost be made It is lower.
Contain Pb2+、Bi3+、Ge2+、Te4+Etc. the magneto-optic glass of diamagnetisms ion be referred to as diamagnetism glass, with addition paramagnetic Property ion magneto-optic glass compare, the Verdet constants of common diamagnetism glass are slightly smaller, but can obtain better temperature and stablize Property.(such as optical fiber) in practical applications, smaller this disadvantage of Verdet constants can be carried out by using longer light path It makes up, although the temperature dependency of magneto-optic glass performance also has a degree of amplification at this time, magnetic-optic devices may be influenced Accuracy, but as long as ensureing there is sufficiently small temperature coefficient, diamagnetism magneto-optic glass just has more than paramagnetism magneto-optic glass Good development prospect.
Invention content
The present invention solves that diamagnetism magneto-optic glass Verdet constants in the prior art are small, temperature dependency in practical application High and low near infrared band transmitance technical problem.
According to the first aspect of the invention, a kind of preparation method of high magneto-optical property heavy metal borate glass is provided, Include the following steps：
(1) by PbO, B2O3And Bi2O3It is uniformly mixed, obtains mixture A；Or by PbO, H3BO3And Bi2O3It is uniformly mixed Afterwards, heating makes H therein3BO3Dehydration generates B2O3, obtain mixture A；Mixture A is heated to 950 DEG C -1200 DEG C, makes institute It states mixture A to melt and clarify, 1h-1.5h is kept in this temperature range, and be carried out at the same time stirring homogenizing, obtain molten liquid；
(2) molten liquid that step (1) obtains is poured into and is preheated in 250 DEG C -280 DEG C of mold, mold is put into 250 2h-2.5h is kept the temperature in DEG C -280 DEG C of annealing furnace, 10 DEG C -20 DEG C is then naturally cooled to, obtains heavy metal borate glass.
Preferably, the mixture A further includes rare earth oxide.
Preferably, the rare earth oxide is Tb2O3、Er2O3、Dy2O3、Ce2O3And Pr2O3At least one of.
Preferably, the ratio that the amount of the PbO substances accounts for the amount of the mixture A substances is 50%-70%；The B2O3 The ratio that the amount of substance accounts for the amount of the mixture A substances is 20%-40%；The Bi2O3The amount of substance accounts for the mixture A The ratio of the amount of substance is 5%-15%.
Preferably, molten liquid described in step (2) imports before mold, further includes that the temperature of molten liquid is down to it to melt Point.
Preferably, the mixture A further includes other metal oxides；
Preferably, other metal oxides are ZnO, Fe2O3、MgO、Al2O3At least one of with CuO.
It is another aspect of this invention to provide that a heavy metal species borate glass is provided, it is any described by claim 1-6 Method is prepared.
It is another aspect of this invention to provide that providing heavy metal borate glass as claimed in claim 7 as magneto-optic The application of device.
Preferably, the application is the application in terms of magneto-optic current transducer, magneto optic isolator or magneto-optic modulator.
It is not necessarily to it is another aspect of this invention to provide that providing heavy metal borate glass as claimed in claim 7 and being used as The application of the fiber medium material of temperature-compensating.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below Technological merit：
(1) heavy metal borate glass provided by the invention is at low cost, and high Verdet constants and low temperature dependence make The heavy metal borate glass is used to be obtained without need for the excellent magnetic rotation optical property of temperature compensation system in magnetic-optic devices.With The existing borate doped salt glass of heavy metal is different, and heavy metal borate glass provided by the invention is by PbO and B2O3Oxide glass Appropriate Bi is added in glass substrate2O3And micro other metal oxides (such as other rare earth oxides or transiting metal oxidations Object), using PbO as the structure of glass, coordinate a small amount of Bi2O3Realize the Verdet for the paramagnetism magneto-optic glass that can match in excellence or beauty Constant value size.Sample passes through Raman spectrum analysis, BO3And BO4Group has been changed into the modified body of glass from glass structures, Ensure that glass has preferable visible waveband transmitance and glass forming ability, while the transition metal oxide added can be further Playing reduces the function of near infrared band absorptivity.And the sample for adulterating micro paramagnetic rare-earth oxide can obtain it is splendid Temperature stability, (such as optical fiber) can not depend on temperature compensation means completely in long light-path application.
(2) heavy metal borate glass Verdet constant values provided by the invention are more than 0.17min/Gcm, and titanium dioxide The Verdet constant values of silica glass are 0.031min/Gcm, and common diamagnetism borosilicate glass is 0.083min/Gcm left The right side, paramagnetism silicate glass and phosphate glass are respectively 0.144min/Gcm and 0.104min/Gcm or so, this hair Bright heavy metal borate glass can provide the rotary light performance much larger than conventional diamagnetism magneto-optic glass.
(3) rate of temperature change of the Verdet values of rare-earth free heavy metal borate glass provided by the invention is less than 0.27%/DEG C, when temperature change is within the scope of 10 DEG C, the variation of Verdet values controls within 3%, has lower magneto-optic Performance temperature dependence；The rate of temperature change of the Verdet values of rear-earth-doped heavy metal borate glass be less than 0.06%/DEG C, when When temperature change is within the scope of 10 DEG C, the variation of Verdet values controls within 0.6%, has extremely low temperature dependency.
(4) near-infrared transmitance is up to 85%, be suitble to prepare magneto-optic current transducer, magneto-optic modulator or magneto-optic every From magnetic-optic devices such as devices.
(5) heavy metal borate glass provided by the invention also has good at glass properties, and good thermodynamics is steady Qualitative and mechanical stability is suitble to prepare optical fiber and the glass matrix as rear-earth-doped glass.
Description of the drawings
Fig. 1 is the Verdet constant values of glass prepared by embodiment 1,2 and 3 and its varies with temperature curve.
Fig. 2 is the near infrared band transmitance of glass prepared by embodiment 1,2 and 3.
Fig. 3 is the Verdet constant values of glass prepared by embodiment 4 and 5 and its varies with temperature curve.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below It does not constitute a conflict with each other and can be combined with each other.
Embodiment 1
A kind of preparation method of high magneto-optical property heavy metal borate glass, by high-purity reagent PbO, H3BO3And Bi2O3, It weighs after recipe calculation by the 1st row in table 1 and fully shakes up mixing, be put into high purity alumina crucible, in Muffle furnace It is heated to 200 DEG C and keeps 20-60min, so that H3BO3Generate B2O3, it is heated to 950 DEG C later and is melted and is clarified, one opens It is to clarify bubble, keep 1h in the process and be stirred, cool to 900 later that beginning, which is heated to temperature more higher than fusing point, DEG C, it cools the temperature to cool down faster when fusing point is to pour at this time.Molten liquid is poured into and is preheating to 280 DEG C of mold in advance In, it is put into the annealing furnace of same temperature and keeps the temperature 1.5h, cooled to room temperature (10-20 DEG C) after then powering off finally uses Tool carries out sanding and polishing and cutting to sample.
Table 1
Embodiment 2
According to the ingredient of the oxide of the 2nd row in table 1, preparation process is consistent the present embodiment with embodiment 1.
Embodiment 3
According to the ingredient of the oxide of the 3rd row in table 1, preparation process is consistent the present embodiment with embodiment 1.
Embodiment 4
The present embodiment according to the oxide of the 4th row in table 1 ingredient, i.e., in addition to PbO, Bi2O3And H3BO3Except, also add Rare earth oxide Dy2O3With transition metal element ZnO, weighing and burden simultaneously fully shakes up mixing, is put into high-purity alpha-alumina It in crucible, is heated to 1150-1200 DEG C and is clarified, keep 1.5h and continue to stir, 1050 DEG C are cooled to later, by glass metal It pours into and is preheating in 250-280 DEG C of mold in advance, be put into the annealing furnace of same temperature and keep the temperature 2h, then power off natural cooling To room temperature (10-20 DEG C), finally tool is used to carry out sanding and polishing and cutting to sample.
Embodiment 5
According to the ingredient of the oxide of the 5th row in table 1, preparation process is consistent the present embodiment with embodiment 4.
The Verdet constant values of rare-earth free heavy metal borate glass in the present invention and its vary with temperature song Line is illustrated in fig. 1 shown below, it can be seen that the temperature dependency of magneto-optic glass shows with temperature rise, Verdet constant values with Decline, i.e., magneto-optical property weaken；Curve fall is big, and temperature dependency is high, and curve fall is small, temperature dependency It is low.With PbO and Bi2O3Content increase, the very low sample of temperature dependency, V values when the Datong District Zhi Hen V can be obtained and existed 0.17min/Gcm or more, rate of temperature change less than -0.27%/DEG C, be very suitable for as magneto-optic current transducer and magneto-optic every From the rotatory device in device.
The near-infrared transmitance of rare-earth free heavy metal borate glass in the present invention is illustrated in fig. 2 shown below, from figure It can be seen that can decline as wavelength increases transmitance, but embodiment 2 and the 3 minimum transmitances for remaining to obtain 50% or more, and It can get 90% or more transmitance close to visible light wave range.
It selects the sample formulations that transmitance is best in above-described embodiment to carry out trace rare-earth doping, transition metal element is added Further weaken infrared absorption, improve mechanical performance, obtains rear-earth-doped heavy metal borate magneto-optic glass as shown in Figure 3 Verdet constant alternating temperature curves, rate of temperature change less than -0.06%/DEG C, for alternating temperature curve close to level, temperature dependency is extremely low, It is suitable as the fiber medium materials'use without temperature-compensating facility.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include Within protection scope of the present invention.

Claims (10)

1. the preparation method of a heavy metal species borate glass, which is characterized in that include the following steps：
(1) by PbO, B2O3And Bi2O3It is uniformly mixed, obtains mixture A；Or by PbO, H3BO3And Bi2O3After mixing, add Heat makes H therein3BO3Dehydration generates B2O3, obtain mixture A；Mixture A is heated to 950 DEG C -1200 DEG C, makes the mixing Object A is melted and is clarified, and 1h-1.5h is kept in this temperature range, and is carried out at the same time stirring homogenizing, obtains molten liquid；
(2) molten liquid that step (1) obtains is poured into and is preheated in 250 DEG C -280 DEG C of mold, mold is put into 250 DEG C -280 DEG C annealing furnace in keep the temperature 2h-2.5h, then naturally cool to 10 DEG C -20 DEG C, obtain heavy metal borate glass.
2. the preparation method of heavy metal borate glass as described in claim 1, which is characterized in that the mixture A is also wrapped Include rare earth oxide.
3. the preparation method of heavy metal borate glass as claimed in claim 2, which is characterized in that the rare earth oxide is Tb2O3、Er2O3、Dy2O3、Ce2O3And Pr2O3At least one of.
4. the preparation method of heavy metal borate glass as described in claim 1, which is characterized in that the amount of the PbO substances The ratio for accounting for the amount of the mixture A substances is 50%-70%；The B2O3The amount of substance accounts for the amount of the mixture A substances Ratio is 20%-40%；The Bi2O3The ratio that the amount of substance accounts for the amount of the mixture A substances is 5%-15%.
5. the preparation method of heavy metal borate glass as described in claim 1, which is characterized in that melted described in step (2) Melt liquid to import before mold, further includes that the temperature of molten liquid is down to its fusing point.
6. the preparation method of heavy metal borate glass as described in claim 1, which is characterized in that the mixture A is also wrapped Include other metal oxides；
Preferably, other metal oxides are ZnO, Fe2O3、MgO、Al2O3At least one of with CuO.
7. a heavy metal species borate glass, which is characterized in that be prepared by any the methods of claim 1-6.
8. application of the heavy metal borate glass as claimed in claim 7 as magnetic-optic devices.
9. application as claimed in claim 8, which is characterized in that the application is in magneto-optic current transducer, magneto optic isolator Or the application in terms of magneto-optic modulator.
10. application of the heavy metal borate glass as claimed in claim 7 as the fiber medium material without temperature-compensating.
CN201810266445.2A 2018-03-28 2018-03-28 High V value and low-temperature coefficient heavy metal borate glass and preparation method and application Expired - Fee Related CN108483902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810266445.2A CN108483902B (en) 2018-03-28 2018-03-28 High V value and low-temperature coefficient heavy metal borate glass and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810266445.2A CN108483902B (en) 2018-03-28 2018-03-28 High V value and low-temperature coefficient heavy metal borate glass and preparation method and application

Publications (2)

Publication Number Publication Date
CN108483902A true CN108483902A (en) 2018-09-04
CN108483902B CN108483902B (en) 2019-09-27

Family

ID=63317034

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810266445.2A Expired - Fee Related CN108483902B (en) 2018-03-28 2018-03-28 High V value and low-temperature coefficient heavy metal borate glass and preparation method and application

Country Status (1)

Country Link
CN (1) CN108483902B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062467A (en) * 2020-06-18 2020-12-11 天津工业大学 Rare earth ion doped Er3+Preparation method of zirconium magnesium borate glass

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100499A (en) * 2008-10-27 2010-05-06 Konica Minolta Opto Inc Molding mold and method of manufacturing glass molded body
CN107643560A (en) * 2017-10-20 2018-01-30 河南工业大学 A kind of method that magneto-optic glass base ion exchange prepares magneto-optic slab guide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010100499A (en) * 2008-10-27 2010-05-06 Konica Minolta Opto Inc Molding mold and method of manufacturing glass molded body
CN107643560A (en) * 2017-10-20 2018-01-30 河南工业大学 A kind of method that magneto-optic glass base ion exchange prepares magneto-optic slab guide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李婧等: "磁光玻璃的研究进展", 《材料导报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062467A (en) * 2020-06-18 2020-12-11 天津工业大学 Rare earth ion doped Er3+Preparation method of zirconium magnesium borate glass

Also Published As

Publication number Publication date
CN108483902B (en) 2019-09-27

Similar Documents

Publication Publication Date Title
Mo et al. Luminescence properties of magneto-optical glasses containing Tb3+ ions
Chen et al. Magneto optical properties of rare earth Tb2O3 doped PbO-Bi2O3-B2O3 glass
US9593039B2 (en) Nanostructured glasses and vitroceramics that are transparent in visible and infra-red ranges
Bellanger et al. Fluorophosphate glasses with high terbium content for magneto-optical applications
Yin et al. Wavelength dependence of Tb3+ doped magneto-optical glass Verdet constant
CN104529166A (en) Ce: YAG microcrystalline glass and application thereof in white-light LED
CN105220232A (en) There is secondary electro-optic crystal and the preparation and application method thereof of graded index effect
CN108483902B (en) High V value and low-temperature coefficient heavy metal borate glass and preparation method and application
CN101088946A (en) Er-doped transparent glass ceramics containing nanometer sodium yttrium fluoride crystal and its prepn and use
Li et al. Surface plasmon resonance effect, nonlinearity and faraday rotation properties of magneto optical glass: Influence of diamagnetic Ag@ ZrO2 nanoparticles
Zhang et al. Microstructure and Faraday effect of Tb2O3‐Al2O3‐SiO2‐B2O3 glasses for fiber‐based magneto‐optical applications
US4999321A (en) Optical glass composition
Taha et al. Structure, optical and magnetic properties of barium sodium borate/cobalt oxide glass structures
CN101182118B (en) Alkali metal lanthanum bismuthate gallate infrared optical glass and method for making same
CN108911502B (en) Fluorine-sulfur phosphate laser glass and preparation method and application thereof
CN107488874A (en) A kind of design method of temperature field structure for rare earth crystal growth technique and the growth technique of low-cost rare earth crystal
CN110204209A (en) A kind of upper conversion glass ceramic composite material of the rear-earth-doped scandium base fluorinated nano crystalline substance of selectivity
CN107721184A (en) A kind of antimagnetic glass system for preparing single mode magneto-optic glass fiber
CN1955129A (en) Transparent oxyfluoride glass ceramic and its preparation method
CN100486923C (en) Quick flashing glass and its preparation process
Bogomolova et al. Use of electron paramagnetic resonance for investigating glasses and raw materials
JP2018118870A (en) Glass material and method for producing the same
CN110228948A (en) A kind of novel photoluminescent transparent glass ceramics and preparation method thereof
Ren et al. Effect of microwave heat-treatment on up-conversion luminescence of Er3+/Yb3+ co-doped NaYF4 oxy-fluoride glass-ceramics
CN107986632B (en) Single-mode magneto-optical glass fiber core and shell inverse magnetic glass system component and preparation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190927