CN101328018A - Lead free and cadmium free diamagnetic magnetic rotation glass - Google Patents

Lead free and cadmium free diamagnetic magnetic rotation glass Download PDF

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Publication number
CN101328018A
CN101328018A CNA2008101504344A CN200810150434A CN101328018A CN 101328018 A CN101328018 A CN 101328018A CN A2008101504344 A CNA2008101504344 A CN A2008101504344A CN 200810150434 A CN200810150434 A CN 200810150434A CN 101328018 A CN101328018 A CN 101328018A
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glass
free
magnetic rotation
lead
diamagnetic
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CN101328018B (en
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祁学孟
祁堃
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Abstract

The invention discloses a lead and cadmium free diamagnetic magnetic rotation glass melted by oxides according to a certain mol percent: Sm2O3, Ta2O5, SiO2, Yb2O3, Nb2O5, B2O3, Sb2O3, Bi2O3, La2O3, WO3, BaO and ZnO using optical glass batch classic melting method. The lead and cadmium free diamagnetic magnetic rotation glass of the invention is not sensitive to temperature with the verdet constant V=+0.20- +0.50min/oe.cm, has excellent chemical stability and thermal stability, good drawing property and high intensity, can be of a block, column, strip or optical fiber shape, which is used in faraday rotation elements and producing magnetic optical current transformer, optical isolator, magnetic optical modulator and laser small angle deflection measuring instrument, improves the measuring sensitivity of the instrument and achieves effective measurement and monitoring.

Description

Lead free and cadmium free diamagnetic magnetic rotation glass
Technical field
The present invention relates to a kind of magnetic rotation glass, be specifically related to a kind of faraday's spinner member lead free and cadmium free diamagnetic magnetic rotation glass.
Background technology
The eighties in 20th century, the country of some advanced technology, as U.S., day, English, method, moral etc., a kind of MOCT technology of having researched and developed, realizing to power industry that automatically-monitored and metering provides may.So this technology obtains the approval of each country rapidly.On being suitable for, this parts are the requirement of satisfying the power industry transmission system, necessarily require extremely low temperature factor and bigger Verdet constant.Because flint glass has unique advantages, the scientific worker has selected SF for use through the exploration of decades 6, SF 57With dense flint glass such as FR-2, the Verdet constant of these glass and composition (wt%) are as following table:
The glass trade mark SiO 2 Na 2O K 2O PbO As 2O 3 V 632.8
SF 6 26.9 0.5 1.0 71.3 0.3 +0.06
SF 57 22.8 0.2 1.5 75 0.5 +0.07
FR-2 20.0 0 1.5 75 0.5 +0.072
As can be known, there are two problems in the opticglass of these trades mark from table: the one, and Verdet constant is on the low side, can not satisfy the requirement of making highly sensitive metering and watch-dog; The 2nd, all contain a large amount of plumbous oxide in the composition.Such as, at SF 57In FR-2 flint glass composition, PbO content at least also has 75wt%.This glass types is not only harmful to HUMAN HEALTH, and serious pollution of ecological environment, especially in this glass process of high temperature melting, will have the PbO of PbO total content 14% to evaporate in the air and go.Therefore, do not meet and on July 1st, 2006 came into force, the regulation of " lead etc. is used in new electronics of putting on market and electric installation restriction " six kinds of objectionable impuritiess in " ROHS instruction case ".And in ZL91112680.5, ZL95106279.4, USP 4,165,989 and USP 4,726,652 patents, described glass is the paramagnetism magnetic rotation glass.Verdet constant varies with temperature bigger, and especially performance variation is very fast in-40～+ 80 ℃ of scopes, is not suitable for the outdoor environment life-time service; The FR-2 of Verdet constant maximum on the other hand, Verdet constant has only+0.072min/oe.cm, so sensitivity is lower, is well-known.
Diamagnetic magnetic rotation glass is the same with paramagnetic glass, is the dielectric material of Faraday magnetooptical effect spinner member.For Fil moral (Verdet) constant of anti-(contrary) magnetic rotation glass that does not contain paramagnetic ion, Becquerel (Becquerel) formula of deriving with classical way V = ( vg 2 mc 2 ) ( dn dv ) Can know that the V value of diamagnetic magnetic rotation glass is temperature independent, only relevant with the chromatic dispersion size.
In the formula: the v-light frequency; The specific refractory power of n-medium; The q-lande g factor; Dn/dv-represents chromatic dispersion.
According to the above, inquire into out the diamagnetic magnetic rotation glass of the lead-free and cadmium-free unharmful substance of big Verdet constant, be that very big Practical significance is arranged.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provide a kind of Verdet constant bigger, glass varies with temperature insensitive, have excellent chemical stability and thermostability, and wire-drawing performance is good, the lead free and cadmium free diamagnetic magnetic rotation glass that intensity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of lead free and cadmium free diamagnetic magnetic rotation glass is characterized in that this magnetic rotation glass is made up of the oxide compound of following molecular fraction:
Sm 2O 3 0～20％ Ta 2O 5 0～5％ SiO 2 2～30％
Yb 2O 3 0～20％ Nb 2O 5 0～20％ B 2O 3 20～70％
La 2O 3 5～30％ Sb 2O 3 0～5％ Bi 2O 3 1～20％
WO 3 1～12％ BaO 0～5％ ZnO 0～5％；
Wherein, SiO 2/ (B 2O 3+ SiO 2)=1/13～1/30, (SiO 2+ B 2O 3)/Bi 2O 3=2～40, ∑ (Nb 2O 5+ Ta 2O 5+ Sb 2O 3)≤30%, ∑ (Sm 2O 3+ Yb 2O 3+ La 2O 3)=9～50%.
Above-mentioned oxide compound WO 3Molecular fraction be 2～8%.
Above-mentioned oxide compound WO 3Molecular fraction be 3～6%.
The Verdet constant V=+0.20 of lead free and cadmium free diamagnetic magnetic rotation glass～+ 0.50min/oe.cm.
Lead free and cadmium free diamagnetic magnetic rotation glass of the present invention adopts the classic melting method of opticglass intermittent type: adopt chemical reagent analytical pure raw material, accurate each raw material of weighing, raw material is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1050～1300 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
In composition, SiO 2, B 2O 3Be that glass network forms oxide compound.SiO 2Be to constitute network skeleton, the effect with stabilized glass structure is a neccessary composition.B 2O 3Being the main component of glass of the present invention, can reducing glass melting temperature, also is the component that makes stabilization.B 2O 3With SiO 2Cooperate the viscosity of may command glass metal by a certain percentage.In the described glass, SiO 2/ (SiO 2+ B 2O 3)=1/13～1/30.If ratio＞1/13, the glass smelting temperature raises, if ratio＜1/30, then glass melting temperature is on the low side, and glass forms bad.
Bi 2O 3Also be requisite composition in the glass ingredient, can reduce temperature of fusion, Bi 2O 3Introducing one be the diamagnetism function that increases glass, the 2nd, make the glass metal good fluidity, and the recrystallization temperature upper limit reduced, help wire drawing.If content＞20mol%, glass colour increases the weight of, and influences the glass transmitance; If content＜1mol% acts on not obvious.In addition, (SiO 2+ B 2O 3)/Bi 2O 3=2～40.If (SiO 2+ B 2O 3)/Bi 2O 3＞40, temperature of fusion raises, and it is big that viscosity becomes, the fusing difficulty; If (SiO 2+ B 2O 3)/Bi 2O 3＜2 glass propertiess become and are difficult to control.
In the glass ingredient of the present invention, contain the La of 5mol% at least 2O 3, the most nearly 30mol% shows as weak paramagnetism, but contains a certain amount of La in borate glass 2O 3Can enlarge glass formation range.But content＞30mol%, the easy crystallization of glass; Content＜5mol% works undesirable.
Glass of the present invention adds a spot of Yb in forming 2O 3, be to La 2O 3Replenishing of effect, favourable to the viscosity of improving glass metal.
WO 3Increase the chromatic dispersion of glass, favourable diamagnetism improves, and can improve glass transition temperature.If content＜1mol%, it is not obvious to work, content＞12mol%, the easy crystallization of glass.Preferred 2～8mol%, most preferably 3～6mol%.
In the composition of lead free and cadmium free diamagnetic magnetic rotation glass of the present invention, add Nb 2O 5And Ta 2O 5Can reduce the coefficient of expansion of glass, a certain amount of Nb 2O 5Avoid the glass work area too narrow, the effect of stabilized glass performance is arranged.Introduce a spot of Ta 2O 5, the effect of stabilized glass component is arranged.The two is favourable to improving the V value simultaneously.
In the described invention glass ingredient, introduce a spot of Sb 2O 3, can quicken the clarification of glass metal, improve favourable to Verdet constant.Introduce a certain amount of ZnO and BaO glass melting temperature is reduced, ZnO has the volatilization of other oxide compound of inhibition in the process of founding.BaO is easier polar oxide compound, helps glass smelting.
The present invention compared with prior art has the following advantages: lead free and cadmium free diamagnetic magnetic rotation glass of the present invention does not contain six kinds of objectionable impuritiess of instruction regulation, performance varies with temperature insensitive, its Verdet constant V=+0.20～+ 0.50min/oe.cm, have excellent chemical stability and thermostability, and wire-drawing performance is good, the intensity height, can be bulk, cylindrical, bar shaped or optical fiber shape, be used for faraday's spinner member, can make magneto-opitcal current transducer, optical isolator, the little angular deflection surveying instrument of magneto-optic modulator and laser etc., the measurement sensitivity of instrument be can improve, effectively metering and monitoring realized.
Below by embodiment, technical scheme of the present invention is described in further detail, but protection scope of the present invention is not limited only to following examples.
Embodiment
Each oxide compound of following examples is all by mole percentage ratio.
Embodiment 1
Each oxide compound is formed (mol%): SiO 23%, B 2O 357%, La 2O 310%, Yb 2O 36%, Sm 2O 32%, Bi 2O 38%, Nb 2O 55%, Ta 2O 52%, Sb 2O 31%, WO 36%.
The preparation method of present embodiment: the raw material of accurate above-mentioned each oxide compound of weighing, it is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1050 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
The Verdet constant V=+0.242min/oe.cm of present embodiment diamagnetic magnetic rotation glass, Tg=660 ℃, Ts=680 ℃, 690～880 ℃ of crystalline ranges are at 950～1050 ℃ of excellent thread forming properties.
Embodiment 2
Oxide compound is formed (mol%): SiO 22.0%, B 2O 358%, La 2O 36%, Yb 2O 33%, Sm 2O 33%, Bi 2O 36%, Sb 2O 35%, Ta 2O 54%, WO 39%, ZnO 2%, and BaO 2%.
The preparation method of present embodiment: the raw material of accurate above-mentioned each oxide compound of weighing, it is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1300 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
It is functional that the Verdet constant V=+0.162min/oe.cm of present embodiment diamagnetic magnetic rotation glass, glass are silk.
Embodiment 3
Oxide compound is formed (mol%): SiO 24%, B 2O 355%, La 2O 38%, Yb 2O 39%, Sm 2O 36%, Bi 2O 313%, WO 35%.
The preparation method of present embodiment: the raw material of accurate above-mentioned each oxide compound of weighing, raw material is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1150 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
The Verdet constant V=+0.40min/oe.cm of present embodiment diamagnetic magnetic rotation glass.
Embodiment 4
Oxide compound is formed (mol%): SiO 24%, B 2O 360%, La 2O 315%, Yb 2O 38%, Sm 2O 33%, Bi 2O 37%, WO 33%.The preparation method of present embodiment: the raw material of accurate above-mentioned each oxide compound of weighing, raw material is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1250 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
The Verdet constant V=+0.28min/oe.cm of present embodiment diamagnetic magnetic rotation glass.
Embodiment 5
Oxide compound is formed (mol%): SiO 22.5%, B 2O 342.5%, La 2O 318%, Yb 2O 316%, Sm 2O 34%, Sb 2O 32%, Bi 2O 310%, WO 35%.
The preparation method of present embodiment: the raw material of accurate above-mentioned each oxide compound of weighing, raw material is mixed, with platinum crucible or high-quality zirconium titanium corundum crucible, in the clean vacuum high-temperature electric furnace of 1050 ℃ of temperature or high frequency vacuum oven, found, to found uniform glass metal after castable, annealing, promptly make the lead free and cadmium free diamagnetic magnetic rotation glass that is used for various spinner members.
The Verdet constant V=+0.50min/oe.cm of present embodiment diamagnetic magnetic rotation glass.
Explanation of nouns: Faraday magnetooptical effect (rotation): a branch of polarized light that is parallel to magnetic field, when passing through transparent magneto-optic glass, it is Faraday effect that polarization plane will rotate to an angle.Angle of rotation: θ=VHL, wherein: V (Verdet)--be the natural characteristics of dielectric material, the size of expression faraday angle of rotation is called Verdet constant, unit: min/oe.cm.According to custom, direction of light forward, faraday's rotation is clockwise, is decided to be negative (-) number, glass is called the paramagnetism magnetic rotation glass; If rotation is anticlockwise, just be decided to be (+) number, glass is called diamagnetic magnetic rotation glass.H--magneticstrength (oe: oersted); L--light passes the light path (cm) of glass.

Claims (4)

1. lead free and cadmium free diamagnetic magnetic rotation glass is characterized in that this magnetic rotation glass is made up of the oxide compound of following molecular fraction:
Sm 2O 3 0～20％ Ta 2O 5 0～5％ SiO 2 2～30％
Yb 2O 3 0～20％ Nb 2O 5 0～20％ B 2O 3 20～70％
La 2O 3 5～30％ Sb 2O 3 0～5％ Bi 2O 3 1～20％
WO 3 1～12％ BaO 0～5％ ZnO 0～5％；
Wherein, SiO 2/ (B 2O 3+ SiO 2)=1/13～1/30, (SiO 2+ B 2O 3)/Bi 2O 3=2～40, ∑ (Nb 2O 5+ Ta 2O 5+ Sb 2O 3)≤30%, ∑ (Sm 2O 3+ Yb 2O 3+ La 2O 3)=9～50%.
2. lead free and cadmium free diamagnetic magnetic rotation glass as claimed in claim 1 is characterized in that described oxide compound WO 3Molecular fraction be 2～8%.
3. lead free and cadmium free diamagnetic magnetic rotation glass as claimed in claim 2 is characterized in that described oxide compound WO 3Molecular fraction be 3～6%.
4. as claim 1,2 or 3 described lead free and cadmium free diamagnetic magnetic rotation glass, it is characterized in that the Verdet constant V=+0.20 of described lead free and cadmium free diamagnetic magnetic rotation glass～+ 0.50min/oe.cm.
CN2008101504344A 2008-07-23 2008-07-23 Lead free and cadmium free diamagnetic magnetic rotation glass Expired - Fee Related CN101328018B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102745901A (en) * 2012-07-10 2012-10-24 陕西科技大学 Preparation method of diamagnetic Faraday rotation glass
US10722845B1 (en) * 2012-07-31 2020-07-28 Raytheon Company Isotope enrichment for improved magnetic materials

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1035549C (en) * 1991-12-29 1997-08-06 中国科学院西安光学精密机械研究所 Magneto-sensitive optical rotary glass and its preparation method
CN1038189C (en) * 1995-06-10 1998-04-29 中国科学院西安光学精密机械研究所 Magnetosensitive optical rotation glass with high fuld constant
DE60100599T2 (en) * 2001-06-21 2004-04-08 Alcatel Optical device with multi-component oxide glass
CN1142111C (en) * 2002-01-23 2004-03-17 天津市硅酸盐研究所 Faraday rotation glass with high weld constant and its prepn

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102745901A (en) * 2012-07-10 2012-10-24 陕西科技大学 Preparation method of diamagnetic Faraday rotation glass
CN102745901B (en) * 2012-07-10 2014-07-30 陕西科技大学 Preparation method of diamagnetic Faraday rotation glass
US10722845B1 (en) * 2012-07-31 2020-07-28 Raytheon Company Isotope enrichment for improved magnetic materials

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