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CN106431401A - Magnetic-optical material and preparation method thereof - Google Patents

Magnetic-optical material and preparation method thereof Download PDF

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Publication number
CN106431401A
CN106431401A CN201610807911.4A CN201610807911A CN106431401A CN 106431401 A CN106431401 A CN 106431401A CN 201610807911 A CN201610807911 A CN 201610807911A CN 106431401 A CN106431401 A CN 106431401A
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magneto
preparation
colloidal sol
temperature
optic
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Inventor
张学建
王凤
金维召
刘旺
沈正皓
李春
曾繁明
李永涛
刘景和
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Jilin Jianzhu University
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Jilin Jianzhu University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0036—Magneto-optical materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention provides a magnetic-optical material and a preparation method thereof. The magnetic-optical material is prepared from ceramic adopting composite oxides Tb3Ga5O12 (1) shown in a formula (1) as main components. Experiments show that the grain size in a polycrystal material is small, distribution is uniform, and the material can be used for preparing TGC ceramic. The TGC ceramic prepared from the polycrystal is high in transmittance, low in porosity, small in crystal boundary and capable of being used for manufacturing a magnetic-optical component of a pulse laser with high average power and high energy. The relevance among the Verdet constant, temperature and wavelength in the TGC magnetic-optical ceramic is analyzed, and it is found that the Verdet constant is in inverse proportion to the square of the temperature and the wavelength. The coefficient of thermal expansion, thermo-optical coefficient and other thermal-optical performances are analyzed and discussed, and it is found that the thermal-optical effect of the TGC ceramic component can be effectively restrained by decreasing the temperature.

Description

A kind of magneto-optic memory technique and preparation method thereof
Technical field
A kind of the present invention relates to technical field of magneto-optic memory technique, more particularly, it relates to magneto-optic memory technique and preparation method thereof.
Background technology
In recent years, because high output is possibly realized, the popularization employing the laser machine of optical-fiber laser is notable 's.However, the LASER Light Source being assembled in laser machine is when from outside light incidence, resonance state is unstable, draws Play the disorderly phenomenon of oscillatory regime.When the light being particularly oscillated is reflected by the optical system of midway and returns light source, oscillatory regime Greatly upset.In order to prevent this situation, setting optoisolator generally in face of light source etc..
The light that enters that optoisolator includes Faraday rotor, be configured at Faraday rotor is penetrated the polarizer of side and is configured at method That draws rotor goes out the analyzer that light penetrates side.In addition, applying magnetic field to use Faraday rotor in the direct of travel parallel to light.
Now, the polarized component of light or is advanced in Faraday rotor, or retreats, only in certain orientation rotation.Further Ground, the polarized component that Faraday rotor is adjusted to light is just rotated 45 degree of length.Here, in advance by the polarizer and inspection When the direction of rotation of the partially progressive light of plane of polarization of device offsets 45 degree, the polarized wave of the light of advance due to polarizer position and Analyzer position consistency and pass through.On the other hand, the polarized wave of the light of retrogressing is from analyzer position and the polarizer offseting 45 degree Plane of polarization skew angular direction reversely rotate ground rotation 45 degree.Then, the plane of polarization of the return light at polarizer position is relative In the polarizer plane of polarization offset 45 degree-(- 45 spend)=90 degree it is impossible to pass through the polarizer.So, saturating as the light making advance Cross, project, and the optoisolator that the return light of retrogressing is blocked plays a role.
In the material that can be used as the Faraday rotor constituting above-mentioned optoisolator, known so far have TGG crystal (Tb3Ga5O12) and TSAG crystallization (Tb(3-x)Sc2Al3O12) (JP 2011-213552 publication, JP 2002-293693 public affairs Report (patent document 1,2)).The Verdet constant of TGG crystal is larger, is 40rad/ (T m), widely carries for marking now Accurate fiber laser device.The Verdet constant of TSAG crystal, it is reported that being 1.3 times about of TGG crystal, is similarly to carry Material in fiber laser device.
TGG pottery is structurally similar with crystal, close in performance.And the preparation method of TGG pottery is simple, technique is directly perceived Controlled, easily obtain large-sized magneto-optic pottery.Bigbore bar-shaped, lath-shaped can be met and the design of discoid magneto-optic element will Ask, be expected to replace TGG crystal, be the new direction of magneto-optic memory technique research.
Content of the invention
In view of this, the technical problem to be solved in the present invention is to overcome the defect of prior art, there is provided a kind of magneto-optic Material, includes the composite oxides being represented by following formula (1) as the pottery of principal component,
Tb3Ga5O12(1).
Present invention also offers a kind of preparation method of magneto-optic memory technique, comprise the following steps：Using sol-gel process synthesis Tb3Ga5O12Colloidal sol.
In some embodiments, make Tb3Ga5O12After colloidal sol, also include described Tb3Ga5O12Colloidal sol be dried, grind, The process of polycrystal powder is made after calcining.
In some embodiments, synthesize Tb3Ga5O12Also include after polycrystal powder：By Tb3Ga5O12Polycrystal powder makes magnetic The process of light ceramic.
In some embodiments, synthesize Tb3Ga5O12The detailed process of colloidal sol is：With Tb4O7And Ga2O3For raw material, lemon Acid is complexing agent, carries out complex reaction according to reaction equation (2) and generates Tb3Ga5O12Colloidal sol, 6Tb4O7+20Ga2O3= 8Tb3Ga5O12+3O2(2).
In some embodiments, detailed process is：By Ga2O3It is dissolved in dilute HNO3In solution, Tb4O7It is dissolved in dilute HNO3 Add H afterwards2O2, obtain Ga respectively3+And Tb3+HNO3Solution；By Ga3+HNO3Solution and Tb3+HNO3Make after solution mixing Obtain the first mixed liquor；Citric acid is added in described first mixed liquor, prepared metal cation with citric acid molal weight ratio is 1:1～1:3 the second mixed solution；Agitating heating second mixed solution is obtained Tb3Ga5O12Colloidal sol.
In some embodiments, described heating-up temperature is 60～100 DEG C.
In some embodiments, described Tb3Ga5O12Colloidal sol after 100～140 DEG C of drying 12～36h, be ground, Calcining, calcining heat is divided into three phases to be respectively：800～1000 DEG C, 1000～1200 DEG C, 1000～1200 DEG C, during calcining Between add up for 6h, after calcining, to make Tb3Ga5O12Polycrystal powder.
In some embodiments, described Tb3Ga5O12Add sintering aid to grind in organic solvent in polycrystal powder, Dry-pressing formed after mixing, then cold isostatic compaction；Make magneto-optic pottery by sintered for the ceramic body of cold isostatic compaction.
In some embodiments, described sintering aid is tetraethoxysilance；Described organic solvent is absolute ethyl alcohol；Dry-pressing Shaping detailed process be：Under pressure 15MPa, dwell time 10min, dry-pressing formed；The detailed process of cold isostatic compaction For：Dry-pressing formed ceramic body is put in balloon, vacuumizes, seal, pressurize 900s, isostatic cool pressing under 200MPa pressure Shaping；Described sintering process is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1500 DEG C～1600 DEG C of sintering temperature.
A kind of magneto-optic memory technique and preparation method thereof that the present invention provides with respect to the beneficial effect of prior art is：
Compared with prior art, terbium gallium garnet (molecular formula：Tb3Ga5O12, abbreviation：TGG) pottery has big Fil moral The magneto-optical properties such as constant, high thermal conductivity, and the size of material and device and geometry controlled, process is simple, therefore excellent In and alternative TGG magneto-optical crystal.
Furthermore, sol-gel process makees presoma with the compound containing high chemical active ingredient, under liquid phase, these are former Material uniformly mixes, and is hydrolyzed, is condensed chemical reaction, forms stable vitreosol system in the solution, colloidal sol is aged Slowly it is polymerized between micelle, form the gel of three-dimensional space network structure, between gel network, be filled with the solvent losing flowability, shape Become gel.Gel is through being dried, sintering curing prepares molecule or even the material of nanometer substructure.
Using the polycrystal material of sol-gel process synthesis, prepare the TGG magneto-optic pottery of high-quality.Using XRD, SEM, light splitting The measuring technologies such as photometer, are characterized to the performance of polycrystal material and pottery.Test result indicate that：Crystal grain grain in polycrystal material Footpath is little, be evenly distributed, and can be used for the preparation of TGG pottery.The TGG pottery transmitance being obtained with this polycrystal material is high, the porosity is low, brilliant Boundary is little, can be used for making the magneto-optic element of high-average power and high energy pulse laser instrument.Normal to Fil moral in TGG magneto-optic pottery Number and the correlations of temperature, wavelength are analyzed, discovery Verdet constant respectively with square being inversely proportional to of temperature and wavelength.Also right The thermo-optical property such as thermal coefficient of expansion and thermo-optical coeffecient is analyzed and has been discussed, finds to reduce temperature, can effectively suppress TGG pottery The thermo-optic effect of element.
In sum, the special structure of the present invention, it has the advantages that above-mentioned many and practical value, and in like product In there are no similar method publish or using and really belong to innovation, create handy and practical effect, more existing skill Art has multinomial effect of enhancement, thus being more suitable to practicality, and has extensive industrial value.
Brief description
It should be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore it is not construed as to model The restriction enclosed, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to these Accompanying drawing obtains other related accompanying drawings.
Fig. 1 is the XRD spectrum of the TGG polycrystal powder of synthesis under different temperatures of the present invention；
Fig. 2 is TGG polycrystal powder SEM image of the present invention；
Fig. 2 (a) is TGG polycrystal powder sintering temperature of the present invention is 900 DEG C of SEM image；
Fig. 2 (b) is TGG polycrystal powder sintering temperature of the present invention is 1000 DEG C of SEM image；
Fig. 2 (c) is TGG polycrystal powder sintering temperature of the present invention is 1100 DEG C of SEM image；
Fig. 3 is the H103 resin of TGG pottery of the present invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of described embodiment is shown in the drawings, wherein from start to finish The element that same or similar label represents same or similar element or has same or like function.Below with reference to attached The embodiment of figure description is exemplary it is intended to be used for explaining the present invention, and is not considered as limiting the invention.
In describing the invention it is to be understood that term " length ", " width ", " on ", D score, "front", "rear", The orientation of instruction such as "left", "right", " vertical ", " level ", " top ", " bottom " " interior ", " outward " or position relationship are based on accompanying drawing institute The orientation showing or position relationship, are for only for ease of the description present invention and simplify description, rather than the dress of instruction or hint indication Put or element must have specific orientation, with specific azimuth configuration and operation, therefore it is not intended that limit to the present invention System.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or hint relative importance Or the implicit quantity indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or Implicitly include one or more this feature.In describing the invention, " multiple " are meant that two or more, Unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " being connected ", " connection ", " fixation " etc. Term should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected or integral；Can be that machinery connects Connect or electrically connect；Can be to be joined directly together it is also possible to be indirectly connected to by intermediary, can be in two elements The connection in portion or the interaction relationship of two elements.For the ordinary skill in the art, can be according to concrete feelings Condition understands above-mentioned term concrete meaning in the present invention.
Referring to Fig. 1 to Fig. 3, the invention provides a kind of magneto-optic memory technique, include the combined oxidation being represented by following formula (1) Thing as the pottery of principal component,
Tb3Ga5O12(1).
Present invention also offers a kind of preparation method of magneto-optic memory technique, comprise the following steps：Using sol-gel process synthesis Tb3Ga5O12Colloidal sol.
Above-mentioned, sol-gel process has the advantages that many uniquenesses compared with other methods：
(1) form low viscous solution because raw material used in sol-gel process is dispersed in solvent first, Accordingly, it is possible to obtain the uniformity of molecular level in a short period of time, when forming gel, it is likely between reactant It is uniformly mixed on a molecular scale.
(2) due to through solution reaction step, then mix some trace elements with being just easy to equal and quantitative, realize dividing Uniform Doped in sub- level.
(3) compared with solid phase reaction, chemical reaction is easily carried out, and only needs relatively low synthesis temperature, typically recognizes For being diffused in nanometer range of component in so-gel system, and during solid phase reaction, diffusion of components is in micrometer range, Therefore react and easily carry out, temperature is relatively low.
(4) suitable condition is selected can to prepare various new materials.
It is to be appreciated that in so-gel reaction metallic compound through solution, colloidal sol, gel and solidify, then through low Warm processes and generates nano-particle.It has, and reactant species are more, and product grain is homogeneous, and process is easy to control, are suitable to aoxidize Thing and the preparation of II～VI compounds of group.
Sol-gel method as the important method of synthesizing inorganic compound or inorganic material under low temperature or temperate condition, Critical role is occupied in soft chemical synthesis.Obtain important answering preparing the aspects such as glass, pottery, film, fiber, composite With being more widely used in and preparing nano-particle.
Further, make Tb3Ga5O12After colloidal sol, also include described Tb3Ga5O12Colloidal sol be dried, grind, calcining after make Become the process of polycrystal powder.
Further, synthesize Tb3Ga5O12Also include after polycrystal powder：By Tb3Ga5O12Polycrystal powder makes magneto-optic pottery Process.
Further, the detailed process of synthesis Tb3Ga5O12 colloidal sol is：With Tb4O7And Ga2O3For raw material, citric acid is network Mixture, carries out complex reaction according to reaction equation (2) and generates Tb3Ga5O12 colloidal sol,
6Tb4O7+20Ga2O3=8Tb3Ga5O12+3O2(2).
Further, detailed process is：By Ga2O3It is dissolved in dilute HNO3In solution, Tb4O7It is dissolved in dilute HNO3After add H2O2, obtain Ga respectively3+And Tb3+HNO3Solution；By Ga3+HNO3Solution and Tb3+HNO3It is obtained first after solution mixing Mixed liquor；Citric acid is added in described first mixed liquor, prepared metal cation and citric acid molal weight are than for 1:1～1: 3 the second mixed solution；Agitating heating second mixed solution is obtained Tb3Ga5O12Colloidal sol.
Above-mentioned it is preferable that terbium oxide (Tb with high-purity (5N level)4O7) and gallium oxide (Ga2O3) it is raw material, at 120 DEG C 24h is dried.
Preferably, by Ga2O3It is dissolved in the dilute HNO of 2.5mol/L3In solution, Tb4O7It is dissolved in the dilute HNO of 2.5mol/L3Afterwards plus Enter the H of 10ml 30%2O2, obtain Ga respectively3+And Tb3+HNO3Solution, and two kinds of solution are mixed.
Preferably, citric acid solution being slowly dropped in the first mixed solution prepares in metal cation and citric acid mole Mass ratio is 1:2 the second mixed solution.
Preferably, the second mixed liquor is placed on stirring on magnetic stirring apparatus.
Further, described heating-up temperature is 60～100 DEG C.
Preferably, 80 DEG C are heated to the second mixed solution is light yellow sol.
Further, described Tb3Ga5O12Colloidal sol, after 100～140 DEG C of drying 12～36h, is ground, calcines, calcining Temperature is divided into three phases to be respectively：800～1000 DEG C, 1000～1200 DEG C, 1000～1200 DEG C, calcination time add up be 6h, makes Tb after calcining3Ga5O12Polycrystal powder.
Above-mentioned it is preferable that colloidal sol is dried 24h at 120 DEG C.
Preferably, calcining heat is respectively 900 DEG C, 1000 DEG C, 1100 DEG C, and calcination time is 6h, and the polycrystal material of synthesis is White powder.
Further, described Tb3Ga5O12Add sintering aid to grind in the organic solvent in polycrystal powder, dry after mixing Molded, then cold isostatic compaction；Make magneto-optic pottery by sintered for the ceramic body of cold isostatic compaction.
Further, described sintering aid is tetraethoxysilance；Described organic solvent is absolute ethyl alcohol；Dry-pressing formed tool Body process is：Under pressure 10～20MPa, dwell time 5～20min, dry-pressing formed；The detailed process of cold isostatic compaction For：Dry-pressing formed ceramic body is put in balloon, vacuumizes, seals, under 100～300MPa pressure pressurize 600～ 1000s, cold isostatic compaction；Described sintering process is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, sintering temperature 1500 DEG C～1600 DEG C.
Further, described sintering aid is tetraethoxysilance；Described organic solvent is absolute ethyl alcohol；Dry-pressing formed tool Body process is preferably：Under pressure 15MPa, dwell time 10min, dry-pressing formed；The detailed process of cold isostatic compaction is：Will Dry-pressing formed ceramic body is put in balloon, vacuumizes, seals, pressurize 900s, cold isostatic compaction under 200MPa pressure； Described sintering process is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1500 DEG C～1600 DEG C of sintering temperature.
Present invention also offers with regard to Tb3Ga5O12The XRD phase structure analysis of polycrystal powder：Synthesis under different temperatures The XRD spectrum of TGG nano-powder, as shown in Figure 1.At 900 DEG C, 1000 DEG C and 1100 DEG C, all form TGG crystalline phase.900℃ When, contain a small amount of miscellaneous peak in sample, degree of crystallinity is not high；The sample of 1000 DEG C and 1100 DEG C calcinings, has all formed cube TGG mono- Phase.
Correlation that the degree of crystallinity of powder vary with temperature also can be observed in Fig. 1.With the continuous rising of calcining heat, In XRD spectrum, diffraction maximum becomes sharp, and diffraction peak intensity gradually strengthens, and half-peak breadth relatively narrows.
1. lattice parameter calculates：
TGG crystal belongs to cubic system, and the lattice parameter of crystal calculates as shown in (3) formula：
Wherein, d is interplanar distance, and a is the lattice parameter of family of crystal planes (hkl).The XRD picture of 1100 DEG C of sintering 6h, according to Jade 6.0 software is calculated interplanar distance d=2.7593, crystal face parameter h=4, k=2, l=0, is calculated according to (3) formula Go out lattice parameter a=12.34.
2. the calculating of crystallite dimension：
According to scheller formula：
Wherein, D is average grain size, and K is Scherrer constant, and λ is X-ray wavelength (0.154056nm), and B is sample Diffraction peak width degree, θ is the angle of diffraction.Understand, with the rising of calcining heat, the half-peak breadth of diffraction maximum is gradually reduced, particle diameter There is the trend of increase.
Present invention also offers the Analysis of Surface Topography of Tb3Ga5O12 polycrystal powder, i.e. SEM figure, Tb3Ga5O12Polycrystal powder Last surface topography is as shown in Fig. 2 wherein 900 DEG C of Fig. 2 (a) sintering temperature；1000 DEG C of (b) sintering temperature；(c) sintering temperature 1100 ℃
From SEM image as can be seen that at different temperature, the size of particle diameter differs.When 900 DEG C, at the beginning of sample crystalline phase Step is formed, but grain development is not completely, and powder grain size is less than normal.When 1000 DEG C, preferably, granularity is equal for the activity of sample Even, crystallization is complete, good dispersion, particle diameter about 80nm, cylindrical crystal grain.Crystal grain is distributed in regular and uniform mode, is formed Network-like structure.
In Fig. 2, particle is cylindric, and this is primarily due under the conditions of high-temperature calcination, and multiple spherical particles are reunited one Rise, form columned pattern.The sample of sintering at 1100 DEG C, a footpath is about 100nm, as shown in Fig. 2 particle diameter degree is big The little transparency directly affecting pottery.
Present invention also offers through performance and analysis of Influential Factors
Sample size Φ 40 × 3mm, using Lambda 900 ultraviolets/visible/near infrared spectrophotometer, test sample H103 resin, as shown in Figure 3.From figure 3, it can be seen that with the increase of wavelength, transmitance is gradually increased, the transmitance of 400nm Transmitance for 76%, 700nm is 80%.According to Rayleigh equation：
Wherein, S is scattering strength, and d is the radius of scattering particles, and λ is incident wavelength, n1For the refractive index of scattering particles, n2 Refractive index for ceramic base.S and λ be can be seen that by equation (5)4It is inversely proportional to, that is, with the increase of wavelength, scattering strength is gradually Reduce, therefore transmitance gradually rises.In addition, it is also seen that TGG pottery exists at 308nm, 314nm and 488nm from Fig. 3 Strong absworption peak.
Present invention also offers the Verdet constant of TGG pottery
The thermal conductivity of TGG pottery is high, and the shape of material and physical dimension are controlled, and have big Verdet constant.As (6) Shown in formula：
V=θ/HL (6)
Wherein, V is Verdet constant, and θ is the light vector anglec of rotation, and H is magnetic field intensity, and L is object length, from (6) formula It can be seen that the product of V and H and L is inversely proportional to.
Present invention also offers the functional relation of the Verdet constant of TGG pottery and temperature
Theory and practice finds that Verdet constant is inversely proportional to temperature.At low temperatures, Verdet constant and temperature Functional relation is as shown in (7) formula：
Wherein, C1It is the constant relevant with material, T is temperature.With the reduction of temperature, Verdet constant increases, liquid helium At a temperature of Verdet constant be under room temperature 87 times.
Present invention also offers the functional relation of the Verdet constant of TGG pottery and wavelength
Theory and practice finds, in TGG pottery, Verdet constant and wavelength have dependence, Verdet constant and wavelength Square it is inversely proportional to, as shown in (8) formula：
Wherein, C2It is the constant relevant with material, λ is the wavelength of incident light.
The present invention is analyzed further to the thermo-optical property of TGG pottery：
Object has breathing phenomenon because temperature changes, and under pressure, the length of object, area or volume are with temperature The rate of change of degree, i.e. line, face, three kinds of thermal coefficient of expansions of body, as shown in (9) formula：
α1=Δ L/ (L Δ T) α2=Δ S/ (S Δ T) α3=Δ V/ (V Δ T) (9)
Wherein, L be initial length, S be initial area, V be initial volume；Δ L is length change, Δ S is area change, Δ V is Volume Changes, Δ T changes for object temperature；α1For linear expansion coefficient, α2For superficial expansivity, α3For the coefficient of volume expansion.
Wherein, TGG pottery thermal coefficient of expansion variation with temperature relationship analysis be：
Thermal coefficient of expansion is the function of temperature within the scope of larger temperature, when temperature change is not very big, can be near Seemingly constant must be regarded as.Within the temperature range of 300～500K, the functional relation of the ceramic thermal coefficient of expansion of TGG magneto-optic and temperature, As shown in (10) formula：
α (T)=Aexp (- B/T) (10)
Wherein, A=1.23 × 10-5K-1, B=166.7K.Can be seen that the increase with temperature, thermal coefficient of expansion presses e index Rule decline.During 300K, the thermal coefficient of expansion of TGG pottery is 7 × 10-6K-1.
The thermo-optical coeffecient of TGG pottery：
Thermo-optical coeffecient, is the temperature coefficient of refractive index again, generally represents the refractive index (n) of material with temperature with ε=dn/dT Rate of change.Because Refractive Index of Material can vary with temperature, the thermo-optical coeffecient of different materials is different.
Within the temperature range of 300～500K, the thermo-optical coeffecient (dn/dT) of TGG magneto-optic pottery is with temperature dependent letter Number relation, as shown in (11) formula：
Wherein, M0=-4.0002 × 10-6K-1, M1=-1.4612 × 10-7K-2, M2=-3.3083 × 10-10K-3And M3= 2.9108×10-13K-4.
The Faraday magneto-optical element made with TGG pottery, carries out depolarising analysis, hot optical parameter Q to its thermal lensing effect And P, as shown in (12), (13) formula：
Wherein, n0For refractive index, v is Poisson's ratio.P11And P12For photoelastic constant, it indicates double when calculating thermal stress One group of constant of refraction size, relevant with thermal stress, relevant with material, the photoelastic coefficient of different materials is different.
If n0=1.966, v=0.22, P11=0.02, P12=0.08[20].Under room temperature, α=7.0 × 10-6K-1、dn/ DT=17.5 × 10-6K-1, by (12), (13) formula, hot optical parameter | Q |=12.4 × 10 can be obtained-7K-1, P=15.4 × 10- 6K-1.
It is assumed that v and photoelastic constant P in calculating process11And P12Do not vary with temperature, then hot optical parameter Q and P are with temperature Degree rising and increase.The hot light efficiency of TGG ceramic component in high-average power laser when this means sub-cooled, can be suppressed Should.
In sum, using sol-gel process, synthesized epigranular, unidirectional TGG nano-multicrystal powder, polycrystal powder End is powder, and this powder can be used as the raw material of TGG magneto-optic pottery.
Shaping reasonable in design and sintering process, have been carried out the preparation research of TGG pottery, have been entered by methods such as XRD, SEM Row characterizes.Synthesize the porosity low, crystal boundary is little, the TGG pottery of transmitance up to 80%.Propose large scale TGG ceramic material The prospect being widely used in high-average power laser and high energy pulse laser instrument.
With the correlation of temperature, wavelength, theory analysis is carried out to the Verdet constant of TGG pottery, finds that Verdet constant divides It is not inversely proportional to temperature, square being inversely proportional to of wavelength.
TGG pottery thermal coefficient of expansion (α) and thermo-optical coeffecient (dn/dT) are carried out with theoretic analysis and studies, draw heat The coefficient of expansion is less, and Verdet constant is bigger, and magneto-optical property is better；Thermo-optical coeffecient is less, and thermal lens is less；Find to reduce temperature Degree, can effectively suppress the thermo-optic effect of TGG ceramic component.
For the ease of understanding the present invention, to further illustrate technical scheme with reference to embodiment.Applicant Statement, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the present invention not office It is limited to above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention should rely on above-mentioned detailed process equipment and technique stream Cheng Caineng is implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, each to product of the present invention former The interpolation of the equivalence replacement of material and auxiliary element, selection of concrete mode etc., all fall within protection scope of the present invention and open model Within enclosing.
Embodiment 1
A kind of preparation method of magneto-optic memory technique, comprises the following steps：
Tb is synthesized using sol-gel process3Ga5O12Colloidal sol；
By described Tb3Ga5O12Colloidal sol be dried, grind, calcining after make polycrystal powder；
By Tb3Ga5O12Polycrystal powder makes magneto-optic pottery；
Wherein Tb3Ga5O12The preparation process detailed process of colloidal sol is：By Ga2O3It is dissolved in the dilute HNO of 2.5mol/L3Solution In, Tb4O7It is dissolved in dilute 2.5mol/L HNO3Add 10ml 30%H afterwards2O2, obtain Ga respectively3+And Tb3+HNO3Solution；Will Ga3+HNO3Solution and Tb3+HNO3First mixed liquor is obtained after solution mixing；Citric acid is added described first mixed liquor In, prepared metal cation and citric acid molal weight are than for 1:1 the second mixed solution；Magnetic stirrer, 60 DEG C add Heat second mixed solution is obtained Tb3Ga5O12Colloidal sol；
Wherein Tb3Ga5O12The preparation process detailed process of polycrystal powder is：Tb3Ga5O12After colloidal sol is dried 12h in 100 DEG C, It is ground, calcines, calcining heat is divided into three phases to be respectively：800 DEG C, 1000 DEG C, 1000 DEG C, calcination time add up be 6h, makes Tb after calcining3Ga5O12Polycrystal powder；
Wherein magneto-optic pottery preparation process detailed process be：Tb3Ga5O12Tetraethoxysilance is added in polycrystal powder, with Under pressure 10MPa, the dwell time, 5min was dry-pressing formed, by dry-pressing formed pottery for after grinding in medium, mixing for absolute ethyl alcohol Porcelain base substrate is put in balloon, vacuumizes, seals, pressurize 600s, cold isostatic compaction under 100MPa pressure；Described sintering process It is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1500 DEG C of sintering temperature.
Embodiment 2
A kind of preparation method of magneto-optic memory technique, comprises the following steps：
Tb is synthesized using sol-gel process3Ga5O12Colloidal sol；
By described Tb3Ga5O12Colloidal sol be dried, grind, calcining after make polycrystal powder；
By Tb3Ga5O12Polycrystal powder makes magneto-optic pottery；
Wherein Tb3Ga5O12The preparation process detailed process of colloidal sol is：By Ga2O3It is dissolved in the dilute HNO of 0.5mol/L3Solution In, Tb4O7It is dissolved in dilute 0.5mol/L HNO3Add 20ml 20%H afterwards2O2, obtain Ga respectively3+And Tb3+HNO3Solution；Will Ga3+HNO3Solution and Tb3+HNO3First mixed liquor is obtained after solution mixing；Citric acid is added described first mixed liquor In, prepared metal cation and citric acid molal weight are than for 1:3 the second mixed solution；Magnetic stirrer, 100 DEG C add Heat second mixed solution is obtained Tb3Ga5O12Colloidal sol；
Wherein Tb3Ga5O12The preparation process detailed process of polycrystal powder is：Tb3Ga5O12After colloidal sol is dried 36h in 140 DEG C, It is ground, calcines, calcining heat is divided into three phases to be respectively：1000 DEG C, 1200 DEG C, 1200 DEG C, calcination time add up be 6h, makes Tb after calcining3Ga5O12Polycrystal powder；
Wherein magneto-optic pottery preparation process detailed process be：Tb3Ga5O12Tetraethoxysilance is added in polycrystal powder, with Under pressure 20MPa, the dwell time, 20min was dry-pressing formed, by dry-pressing formed pottery for after grinding in medium, mixing for absolute ethyl alcohol Porcelain base substrate is put in balloon, vacuumizes, seals, pressurize 1000s, cold isostatic compaction under 300MPa pressure；Described sintered Journey is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1600 DEG C of sintering temperature.
Embodiment 3
A kind of preparation method of magneto-optic memory technique, comprises the following steps：
Tb is synthesized using sol-gel process3Ga5O12Colloidal sol；
By described Tb3Ga5O12Colloidal sol be dried, grind, calcining after make polycrystal powder；
By Tb3Ga5O12Polycrystal powder makes magneto-optic pottery；
Wherein Tb3Ga5O12The preparation process detailed process of colloidal sol is：By Ga2O3It is dissolved in the dilute HNO of 1mol/L3In solution, Tb4O7It is dissolved in dilute 1mol/L HNO3Add 15ml 10%H afterwards2O2, obtain Ga respectively3+And Tb3+HNO3Solution；By Ga3+'s HNO3Solution and Tb3+HNO3First mixed liquor is obtained after solution mixing；Citric acid is added in described first mixed liquor, is obtained Metal cation and citric acid molal weight are than for 1:2 the second mixed solution；Magnetic stirrer, 80 DEG C of heating second mix Close solution and Tb is obtained3Ga5O12Colloidal sol；
Wherein Tb3Ga5O12The preparation process detailed process of polycrystal powder is：Tb3Ga5O12After colloidal sol is dried 24h in 120 DEG C, It is ground, calcines, calcining heat is divided into three phases to be respectively：900 DEG C, 1000 DEG C, 1100 DEG C, calcination time add up be 6h, makes Tb after calcining3Ga5O12Polycrystal powder；
Wherein magneto-optic pottery preparation process detailed process be：Tb3Ga5O12Tetraethoxysilance is added in polycrystal powder, with Under pressure 15MPa, the dwell time, 20min was dry-pressing formed, by dry-pressing formed pottery for after grinding in medium, mixing for absolute ethyl alcohol Porcelain base substrate is put in balloon, vacuumizes, seals, pressurize 800s, cold isostatic compaction under 200MPa pressure；Described sintering process It is specially：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1550 DEG C of sintering temperature.

Claims (10)

1. a kind of magneto-optic memory technique it is characterised in that：Include the composite oxides being represented by following formula (1) as the pottery of principal component Porcelain,
Tb3Ga5O12(1).
2. a kind of preparation method of magneto-optic memory technique is it is characterised in that comprise the following steps：Using sol-gel process synthesis Tb3Ga5O12Colloidal sol.
3. a kind of preparation method of magneto-optic memory technique according to claim 2 is it is characterised in that make Tb3Ga5O12After colloidal sol, Also include described Tb3Ga5O12Colloidal sol is dried, grinds, make the process of polycrystal powder after calcining.
4. a kind of preparation method of magneto-optic memory technique according to claim 3 is it is characterised in that synthesize Tb3Ga5O12Polycrystal powder Last also include：By Tb3Ga5O12Polycrystal powder makes the process of magneto-optic pottery.
5. a kind of preparation method of magneto-optic memory technique according to claim 2 is it is characterised in that synthesize Tb3Ga5O12Colloidal sol Detailed process is：With Tb4O7And Ga2O3For raw material, citric acid is complexing agent, carries out complex reaction life according to reaction equation (2) Become Tb3Ga5O12Colloidal sol,
6Tb4O7+20Ga2O3=8Tb3Ga5O12+3O2(2).
6. a kind of preparation method of magneto-optic memory technique according to claim 5 is it is characterised in that detailed process is：By Ga2O3 It is dissolved in dilute HNO3In solution, Tb4O7It is dissolved in dilute HNO3Add H afterwards2O2, obtain Ga respectively3+And Tb3+HNO3Solution；By Ga3 +HNO3Solution and Tb3+HNO3First mixed liquor is obtained after solution mixing；Citric acid is added in described first mixed liquor, system Metal cation and citric acid molal weight ratio for 1:1～1:3 the second mixed solution；Agitating heating second mixed solution system Obtain Tb3Ga5O12Colloidal sol.
7. a kind of magneto-optic memory technique according to claim 6 preparation method it is characterised in that：Described heating-up temperature be 60～ 100℃.
8. a kind of magneto-optic memory technique according to claim 3 preparation method it is characterised in that：Described Tb3Ga5O12Colloidal sol in After 100～140 DEG C of drying 12～36h, it is ground, calcines, calcining heat is divided into three phases to be respectively：800～1000 DEG C, 1000～1200 DEG C, 1000～1200 DEG C, calcination time adds up for 6h, to make Tb after calcining3Ga5O12Polycrystal powder.
9. a kind of magneto-optic memory technique according to claim 4 preparation method it is characterised in that：Described Tb3Ga5O12Polycrystal powder Add sintering aid to grind in the organic solvent in end, dry-pressing formed after mixing, then cold isostatic compaction；By cold isostatic compaction Ceramic body sintered make magneto-optic pottery.
10. a kind of magneto-optic memory technique according to claim 9 preparation method it is characterised in that：Described sintering aid is just Ethyl silicate；Described organic solvent is absolute ethyl alcohol；Dry-pressing formed detailed process is：Under pressure 10～20MPa, during pressurize Between 5～20min, dry-pressing formed；The detailed process of cold isostatic compaction is：Dry-pressing formed ceramic body is put in balloon, Vacuumize, seal, pressurize 600～1000s, cold isostatic compaction under 100～300MPa pressure；Described sintering process is concrete For：Vacuum sintering technique, vacuum 1 × 10-3Pa, 1500 DEG C～1600 DEG C of sintering temperature.
CN201610807911.4A 2016-09-07 2016-09-07 Magnetic-optical material and preparation method thereof Pending CN106431401A (en)

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CN1735570A (en) * 2003-01-14 2006-02-15 迪亚摩弗股份公司 New glass material and method of preparing said glass
CN102093054A (en) * 2010-12-01 2011-06-15 中国科学院上海光学精密机械研究所 Faraday magnetic rotation transparent ceramic and preparation method thereof
CN102485975A (en) * 2010-12-02 2012-06-06 元亮科技有限公司 Growth method of terbium gallium garnet crystal

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CN1735570A (en) * 2003-01-14 2006-02-15 迪亚摩弗股份公司 New glass material and method of preparing said glass
CN102093054A (en) * 2010-12-01 2011-06-15 中国科学院上海光学精密机械研究所 Faraday magnetic rotation transparent ceramic and preparation method thereof
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