CN115433006B - Terbium-based magneto-optical ceramic and preparation method thereof - Google Patents
Terbium-based magneto-optical ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to terbium-based magneto-optical ceramic and a preparation method thereof, wherein the terbium-based magneto-optical ceramic has a composition general formula of Tb 2+ z Hf x Zr y Ti 2‑x‑y O 7+3z/2 Wherein the values of x, y and z are 0 +.x +.2, 0 +.y +.2, 0 +.x +.y +.2, 0 +.z +.3.
Description
Technical Field
The invention relates to terbium-based magneto-optical ceramic and a preparation method thereof, in particular to pyrochlore-type terbium-based magneto-optical ceramic or defect fluorite-type hafnium, zirconium and titanium composite terbium-based magneto-optical ceramic and a preparation method thereof, and belongs to the technical field of transparent ceramic preparation.
Background
Magneto-optical materials have very important applications in the high-tech fields of optical fiber communication, laser processing, computers, etc. In recent years, the development of high-power lasers has put high demands on the performance of magneto-optical materials, including high Verdet constant, high optical qualityLarge size, high thermal conductivity, high laser damage threshold, etc. Terbium gallium garnet (Tb 3 Ga 5 O 12 Abbreviated as TGG) single crystals are used in high-power lasers, various performance indexes are deteriorated, so that searching for novel magneto-optical materials becomes a research hotspot.
Terbium titanate (Tb) belonging to pyrochlore structure 2 Ti 2 O 7 Abbreviated as TTO) has higher Verdet constant and optical transmittance in visible and near infrared bands, and has lower preparation cost, thereby being potential for becoming a next-generation high-power faraday magneto-optical material. However, the use of a large-sized TTO single crystal is not widely achieved because a large temperature gradient is required in the production of the TTO single crystal, which results in easy cracking of the crystal, and the difficulty in producing the TTO single crystal with high optical quality. The preparation technology of the ceramic does not need larger temperature gradient, the preparation temperature is far lower than that of the single crystal, and the excellent magneto-optical performance of the TTO single crystal can be maintained, so that the TTO magneto-optical ceramic has good application prospect. Tb (Tb) 2 Zr 2 O 7 And Tb 2 Hf 2 O 7 Has a high melting point, and is difficult to grow large-sized and high-quality single crystals.
2013 Fujianfu crystal technology Co., ltd discloses a pyrochlore type A 2 B 2 O 7 Ceramic preparation method, which adopts coprecipitation method to prepare Tb 2 Ti 2 O 7 、Ho 2 Ti 2 O 7 The nano powder is sintered in vacuum to prepare ceramic; since 2014, the Xinyue chemical industry Co.Ltd has published various magneto-optical materials and magneto-optical devices with pyrochlore cubic crystals as the main phase; tb was prepared by 2019 from Japan World Lab company by solid phase reaction sintering 2 Hf 2 O 7 Magneto-optical ceramics, which have a higher optical quality, have subsequently further improved in 2020. The Fu-Si technology Co-precipitation method is adopted by the Fu-Si technology Co-Ltd, and the production efficiency is lower than that of the solid phase method; the sintering temperature adopted by the chemical technical scheme is higher, belongs to non-reactive sintering, and is not beneficial to energy conservation.
Disclosure of Invention
In order to solve the problems, the invention aims to provide terbium-based magneto-optical ceramic and a preparation method thereof, and the terbium-based magneto-optical ceramic has the characteristics of short preparation period, simplicity in operation, good controllability, suitability for large-scale production and the like, and the prepared magneto-optical ceramic has a higher Verdet constant and excellent optical performance.
In a first aspect, the present invention provides a terbium-based magneto-optical ceramic having the compositional formula Tb 2+z Hf x Zr y Ti 2-x-y O 7+3z/2 Wherein the values of x, y and z are 0 +.x +.2, 0 +.y +.2, 0 +.x +.y +.2, 0 +.z +.3.
The invention improves Tb in the material by introducing excessive Tb 3+ The volume concentration of the material is improved, the Verdet constant of the material is improved, the magneto-optical performance is effectively improved, and the same Faraday rotation angle can be obtained with smaller length under the same magnetic field when the material is applied. This reduces optical losses on the one hand and also contributes to miniaturization of the device on the other hand. The length of the material can be controlled to be equal to that of commercial TGG single crystals during application, so that the same Faraday rotation angle can be obtained with smaller magnetic field intensity, and the device is also beneficial to miniaturization.
Preferably, the terbium-based magneto-optical ceramic has a linear transmittance of 10-81% in a band range of 600-1500 nm; the Verdet constant of the terbium-based magneto-optical ceramic is-150 to-225 rad/(T.m) at 633 nm.
Preferably, the terbium-based magneto-optical ceramic is a pyrochlore-based terbium-based magneto-optical ceramic or a defective fluorite-based terbium-based magneto-optical ceramic. More preferably, when the terbium-based magneto-optical ceramic is a single phase, a cubic structure and has no air holes, there is theoretically no birefringence or scattering caused by the second phase, and the optical quality is better.
The reason for the two structures is that the preparation process is the same and the specific application is the same because the chemical components are different in proportion. Both structures belong to the cubic system and do not adversely affect the optical quality of the ceramic. And the two structures are mainly different in the disorder degree of cations, the lattice constants of the two structures are basically consistent, and the pyrochlore or the defect fluorite structure has almost no influence on the Verdet constant of the material. The inventionThe only factors affecting Verdet in the light are the chemical components, specifically: under the condition that the composition of the B phase is certain, the more Tb is excessive, the greater the Verdet constant; under the condition that the excess degree of Tb is the same, the smaller the average ion radius of B site is, the higher the Tb volume concentration is, and the higher the Verdet constant is (ion radius Zr 4+ >Hf 4+ >Ti 4+ )。
In a second aspect, the present invention provides a method for preparing the terbium-based magneto-optical ceramic, comprising: the terbium source, the titanium source, the hafnium source and the zirconium source powder as raw materials are mixed according to a chemical formula Tb 2+z Hf x Zr y Ti 2-x-y O 7+3z/2 Batching to obtain mixed powder; grinding and mixing the mixed powder to obtain mixed slurry or powder; drying, sieving and calcining the obtained mixed slurry to obtain mixed powder; forming the powder into a ceramic biscuit; performing reaction sintering on the ceramic biscuit at 1100-1900 ℃ for 1-50 h; and performing hot isostatic pressing treatment at 1100-1900 ℃ under the pressure of 20-250 MPa for 0.1-50 hours, and finally performing annealing treatment, cutting and polishing to obtain the pyrochlore-type or defect fluorite-type terbium-based magneto-optical ceramic. The method adopts a solid-phase reaction sintering method, has higher production efficiency compared with a liquid-phase method, and adopts a reaction sintering technology, so that the calcining temperature can be effectively reduced, and the method is beneficial to energy conservation and environmental protection. The main inventive point is that the Tb excess is introduced into the composition, and the non-stoichiometric ceramic with higher Verdet constant than the stoichiometric terbium-based pyrochlore can be prepared.
The ball mill can crush aggregates in the raw materials, and fully and uniformly mix the components, so that the optical uniformity of the ceramic is ensured. The sieving can break soft agglomeration in the mixed powder, plays a certain role in granulation, controls the particle size distribution of the powder, and is beneficial to powder forming. The calcination can be performed in air to remove organic pollution, and Tb can be performed in a reducing atmosphere 4+ Reduction to Tb 3+ In addition, the calcination can properly grow nano powder with too small particle size, which is beneficial to preventing abnormal growth of crystal grains and wrapping of air holes in the sintering process. The forming canThe ceramic body is high and uniform in density, low in stress and not easy to crack, pores in the body are reduced as much as possible, and the ceramic body is favorable for sintering into transparent ceramic without pores. The presintering can discharge a large number of air holes in the ceramic to obtain a compact ceramic presintering body, at the moment, certain air holes are still reserved in the ceramic presintering body, and the presintering body also has certain sintering activity. The hot isostatic pressing treatment provides higher driving force for discharging pores in the ceramic under the conditions of high temperature and high pressure, and is favorable for obtaining the transparent ceramic without the pores. The annealing can eliminate oxygen vacancies, tb 4+ 、Ti 3+ And the color center is equal, so that light absorption is reduced, and the optical quality of the ceramic is improved.
Preferably, the terbium source is tetraterbium heptaoxide (Tb 4 O 7 ) Or terbium trioxide (Tb) 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The titanium source is at least one of titanium dioxide, titanium hydroxide and metallic titanium; the hafnium source is hafnium dioxide (HfO) 2 ) At least one of hafnium hydroxide and metal hafnium; the zirconium source is zirconium dioxide (ZrO 2 ) At least one of zirconium hydroxide and zirconium metal.
Preferably, the raw materials further comprise a sintering aid, a binder, a dispersing agent and a plasticizer; the sintering aid is Li 2 O、Na 2 O、K 2 O、MgO、CaO、B 2 O 3 、La 2 O 3 、GeO 2 、SiO 2 、LiF、NaF、MgF 2 、CaF 2 、AlF 3 、YF 3 、TEOS、H 3 BO 3 The adhesive is at least one of polyvinyl alcohol, polyvinyl alcohol Ding Quanzhi and paraffin, the dispersing agent is at least one of stearic acid, fish oil and vegetable oil, and the plasticizer is at least one of palm wax, dioctyl phthalate and ethylene glycol.
Preferably, the mixed slurry is dried for 0.1 to 100 hours and is sieved by a 60 to 300-mesh sieve, and then calcined for 1 to 20 hours at 600 to 1300 ℃ to obtain mixed powder.
Preferably, the annealing temperature is 500-1400 ℃, and the annealing heat preservation time is 1-50 hours.
The beneficial effects are that:
1. the terbium-based magneto-optical ceramic prepared by the method has high Verdet constant and excellent optical quality, is used as a main component in an optical isolator, utilizes Faraday effect, and can keep the safety and stability of a light source.
2. Compared with other methods, the preparation method provided by the invention has the advantages of short production period, high production efficiency, environmental protection and energy conservation.
3. The terbium-based magneto-optical ceramic prepared by the method can be used as a main component of an optical isolator, has potential application in the fields of laser, optical information processing, optical fiber communication, magneto-optical recording and the like, and can make beneficial contribution to national defense industry, national construction and people's life.
Drawings
FIG. 1 is a Tb prepared in example 1 2 HfTiO 7 XRD pattern of magneto-optical ceramic.
FIG. 2 is a Tb prepared in example 1 2 HfTiO 7 A physical diagram of magneto-optical ceramics.
FIG. 3 is a Tb prepared in example 1 2 HfTiO 7 Linear transmittance curve of magneto-optical ceramic.
FIG. 4 is Tb prepared in comparative example 1 2 Hf 2 O 7 XRD pattern of magneto-optical ceramic.
FIG. 5 is a Tb prepared in comparative example 2 2 Zr 2 O 7 XRD pattern of magneto-optical ceramic.
FIG. 6 is a Tb prepared in comparative example 2 2 Zr 2 O 7 Linear transmittance curve of magneto-optical ceramic.
FIG. 7 is a Tb prepared in comparative example 3 2 Ti 2 O 7 XRD pattern of magneto-optical ceramic.
FIG. 8 is Tb prepared in example 2 2 HfZrO 7 XRD pattern of magneto-optical ceramic.
FIG. 9 is a Tb prepared in example 3 2 ZrTiO 7 XRD pattern of magneto-optical ceramic.
FIG. 10 is a Tb prepared in example 4 2 Hf 0.67 Zr 0.67 Ti 0.67 O 7 XRD pattern of magneto-optical ceramic.
FIG. 11 is Tb prepared in example 5 2.45 Hf 2 O 7.68 XRD pattern of magneto-optical ceramic.
FIG. 12 is Tb prepared in example 5 2.45 Hf 2 O 7.68 A physical diagram of magneto-optical ceramics.
FIG. 13 is a Tb prepared in example 5 2.45 Hf 2 O 7.68 Linear transmittance curve of magneto-optical ceramic.
FIG. 14 is Tb prepared in example 5 2.45 Hf 2 O 7.68 FESEM microcosmic photograph of magneto-optical ceramic section.
FIG. 15 is Tb prepared in example 5 2.45 Hf 2 O 7.68 FESEM microscopic morphology photograph of magneto-optical ceramic hot-etched surface.
FIG. 16 is a Tb pre-sintered at 1650 ℃ for 3 hours in example 6 5.3 Hf 2 O 11.9 XRD pattern of ceramic sample.
FIG. 17 is a Tb prepared in example 7 3 Hf 2 O 8.5 XRD pattern of magneto-optical ceramic.
FIG. 18 is a Tb prepared in example 8 3.71 Hf 2 O 9.57 XRD pattern of magneto-optical ceramic.
FIG. 19 is a Tb prepared in example 9 4.67 Hf 2 O 11.01 XRD pattern of magneto-optical ceramic.
FIG. 20 is an XRD pattern of the mixed powder after ball milling of comparative example 1 calcined at 800℃to 1300℃for 4 hours.
Detailed Description
The invention will be further described with reference to the accompanying drawings and the following embodiments, it being understood that the following embodiments are only illustrative of the invention and not limiting thereof.
The invention adopts the sintering technology of ceramics to prepare Tb at relatively low temperature 2 Zr 2 O 7 And Tb 2 Hf 2 O 7 And (3) ceramics. Tb (Tb) 3+ Is the main source of magneto-optic effect of terbium-based magneto-optic material, and improves Tb in ceramics 3+ Will be advantageous for increasing the Verdet constant of magneto-optical ceramicsA number. Tb having a high Verdet constant and a high optical quality can be obtained by compounding Ti, zr, hf and excessive Tb element 2+z Hf x Zr y Ti 2-x-y O 7+3z/2 (wherein, the value range of x, y and z is 0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.2, 0.ltoreq.x+y.ltoreq.2, 0.ltoreq.z.ltoreq.3.3).
The following illustrates the operation steps of the present invention for preparing terbium-based magneto-optical ceramic by solid phase reaction.
Preparing raw materials. The metal ion source is not limited, but preferably contains ions which are difficult to remove, such as Cl - . As an example, terbium heptaoxide (Tb 4 O 7 ) Or terbium trioxide (Tb) 2 O 3 ) Titanium dioxide (TiO) 2 ) Hafnium oxide (HfO) 2 ) Zirconium dioxide (ZrO) 2 ) Powder is taken as raw material and is prepared according to chemical formula Tb 2+z Hf x Zr y Ti 2-x-y O 7+3z/2 The raw material powder used is not particularly limited in source, and may be obtained by weighing raw materials in a predetermined ratio, for example, a self-made powder, a commercial powder purchased or a commercial powder purchased and processed. As another example, additives may be added to the raw materials, which may be sintering aids, binders, dispersants, plasticizers, and the like. The sintering aid selected can be Li 2 O、Na 2 O、K 2 O、MgO、CaO、B 2 O 3 、La 2 O 3 、GeO 2 、SiO 2 、LiF、NaF、MgF 2 、CaF 2 、AlF 3 、YF 3 TEOS (tetraethyl orthosilicate), H 3 BO 3 And the binder may be polyvinyl alcohol, polyvinyl acetal Ding Quanzhi, and the dispersing agent such as stearic acid, fish oil, vegetable oil, and the like, and the plasticizer such as palm wax, dioctyl phthalate, and ethylene glycol. When additives are added into raw materials, powder obtained by ball milling cannot be directly calcined, because the main function of the additives is to make the formed biscuit uniform, compact and crack-free, and the additives are removed after calcination, so that the additives cannot play a role. Thus, the additives are added during ball millingThen, the powder obtained by ball milling is directly molded after being dried and sieved, and then the molded biscuit is calcined (also called glue discharging or degreasing) in an oxidizing atmosphere to remove the additives.
Grinding and mixing to obtain mixed powder. The obtained mixed powder is ground and mixed by adopting the modes of planetary ball milling, roller ball milling, bead milling, jet milling, dry jet milling, hammer milling and the like, so as to obtain mixed slurry or powder.
As an example, 3.7384g Tb is weighed 4 O 7 And 4.2098g HfO 2 The powder was placed in an agate mortar, 5mL of absolute ethanol was added thereto, and the mixture was sufficiently ground to obtain a mixed slurry. Drying the mixed slurry for 0.1-100 h, sieving with a 60-300 mesh sieve, and calcining at 600-1300 ℃ for 1-8 h to obtain mixed powder. The calcination can remove partial impurities and organic matters such as ethanol and the like contained in the raw materials, and simultaneously can slightly grow the nano particles with undersize particles in the powder, thereby being beneficial to the uniform growth of crystal grains and the discharge of air holes in the forming and subsequent sintering processes. The calcination temperature selected should not be too high, which would otherwise lead to a significant reduction in the sintering activity of the powder. Such drying means include, but are not limited to, oven drying, spray drying, microwave drying, and freeze drying; the calcining atmosphere comprises but is not limited to air, hydrogen, ammonia, argon, oxygen or mixed gas, vacuum calcining can be adopted, multiple times of calcining can be carried out by utilizing different atmospheres, and the powder can be calcined after being molded.
As an example, absolute ethanol may be used as the ball milling medium, and ball milling may be performed at a rotational speed of 60 to 300rpm for 2 to 50 hours. Drying the ball-milled slurry in an oven at 50-150 ℃ for 0.1-24 h, sieving with a 60-300 mesh sieve, and calcining at 600-1300 ℃ for 1-8 h to obtain mixed powder.
And forming the mixed powder into a ceramic biscuit. The molding mode can be dry pressing, cold isostatic pressing, casting molding, slip casting, gel casting or electrophoretic deposition, and various molding methods can be combined, such as dry pressing molding combined with cold isostatic pressing.
And (3) performing reaction sintering on the ceramic biscuit. The purpose of sintering is to cause diffusion and reaction between the raw materials,the raw materials are directly reacted to form the required phase, and the phase is discharged from the air holes to densify the ceramic. The reaction: (2+z)/4 Tb 4 O 7 +xHfO 2 +yZrO 2 +(2-x-y)TiO 2 ＝Tb 2+z Hf x Zr y Ti 2-x-y O 7+3z/2 +(2+z)/4O 2 And ≡. As an example, the sintering temperature may be 1100 to 1900 ℃ and the holding time may be 1 to 50 hours. And performing hot isostatic pressing treatment at 1100-1900 ℃ under the pressure of 20-250 MPa for 0.1-50 hours to obtain pyrochlore or defect fluorite magneto-optical ceramic. The purpose of the hot isostatic pressing treatment is to increase the driving force of the pore discharge by using pressure assistance, and further discharge pores in the ceramic pre-sintered body, so as to obtain a pore-free ceramic. The absence of air holes as scattering centers for light is one of the fundamental requirements of ceramics for their higher optical quality. The reaction sintering mode can be air sintering, vacuum sintering, oxygen atmosphere sintering, hydrogen atmosphere sintering, ammonia atmosphere sintering, argon atmosphere sintering or mixed atmosphere sintering, microwave sintering, spark plasma sintering and hot-press sintering.
Annealing, cutting and polishing. Annealing treatment is carried out on pyrochlore type or defect fluorite type magneto-optical ceramics. As an example, the annealing atmosphere may be air, argon, hydrogen, ammonia, oxygen or a mixed atmosphere, vacuum annealing may be used, the annealing temperature may be 500-1400 ℃, the annealing heat-preserving time may be 1-50 h, and the annealing aims at eliminating oxygen vacancies and Tb 4+ 、Ti 3+ The color center is equal, the light absorption is reduced, the optical quality of the ceramic is improved, and the pyrochlore-type or defect fluorite-type terbium-based magneto-optical ceramic with optimized performance is obtained.
According to the rule of thumb, at A 2 B 2 O 7 In the structure, the ionic radius ratio r (a)/r (B) =1.46-1.78 of a and B is the stable range of the pyrochlore phase, and when the ratio is less than 1.46, the structure is a defective fluorite structure. However, this rule of thumb is applicable only to the case where the B site is a single element, is not applicable to the case where the B site is substituted with multiple elements, and is not applicable to the case of a non-stoichiometric ratio where the a element is in excess or in small quantity. Stoichiometric Tb 2 Hf 2 O 7 、Tb 2 Ti 2 O 7 Tb is a pyrochlore structure 2 Zr 2 O 7 Is of a defective fluorite structure, and when z is more than or equal to 0.7, tb is taken as a main material 2 Hf 2 O 7 From the phase diagram of (a) at this time Tb 2.7 Hf 2 O 8.05 The material is of a defect fluorite structure, but when B-site multielement substitution is carried out, especially when Tb is excessively introduced while multielement substitution is carried out, no good theory exists at present to predict that the material belongs to pyrochlore phase or defect fluorite phase. And the current research shows that under the condition of unchanged B-site element, the larger z is due to Tb 3+ The higher the concentration, the higher the Verdet constant of the material, and the Verdet constant is free of mutations at z=0.7.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure.
Example 1
According to Tb 2 HfTiO 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)37.3847g，HfO 2 (99.99%) 21.0490g and commercial analytically pure TiO 2 (AR) 7.9865g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. And (3) after dry-pressing and molding the mixed powder under 40MPa, maintaining the pressure under 250MPa for 5min, and performing cold isostatic pressing and molding to obtain the ceramic biscuit. Presintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum presintering is preferably 1600-1750 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree in the heat preservation stage is better than 1X 10 -3 Pa。
FIG. 1 shows Tb after vacuum pre-sintering at 1600 ℃ for 3 hours 2 HfTiO 7 XRD pattern of the ceramic, which presents characteristic diffraction peaks of pyrochlore. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after pre-sintering at 1750 ℃ for 50 hours, wherein the heat preservation temperature of the hot isostatic pressing is preferably 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Hot isostatic pressingAfter the ceramic sample obtained by treatment is annealed for 10 hours in an ammonia atmosphere at 800 ℃, the two surfaces of the sample are mirror polished to obtain Tb 2 HfTiO 7 The magneto-optical ceramic material is shown in figure 2. FIG. 3 is Tb 2 HfTiO 7 The linear transmittance curve (thickness is 0.8 mm) of the magneto-optical ceramic is more than 60% in the band of 650 nm-1500 nm, which shows that Tb 2 HfTiO 7 Magneto-optical ceramics have a certain transmittance. Tb (Tb) 2 HfTiO 7 The Verdet constant of the magneto-optical ceramic is-200.0 rad/(T.m) at 633nm, which reaches 1.5 times of commercial TGG single crystal, indicating Tb 2 HfTiO 7 The magneto-optical ceramic has better application prospect.
Example 2
According to Tb 2 HfZrO 7 Raw material powder is weighed according to the chemical formula: using commercial high purity Tb 4 O 7 (99.99％)37.3847g，ZrO 2 (99.99％)12.3222g，HfO 2 (99.99%) 21.0490g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is dried and pressed for molding under 40MPa, the mixed powder is pressed for molding under 250MPa for 5min under cold isostatic pressing to obtain a ceramic biscuit, the biscuit is presintered in a vacuum furnace, the heat preservation temperature of vacuum presintering is preferably 1600-1800 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree in the heat preservation stage is better than 1 multiplied by 10 -3 Pa. And (3) carrying out hot isostatic pressing sintering treatment on the sample subjected to vacuum presintering at 1750 ℃ for 10 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Finally, the sample is mirror polished on both sides to obtain Tb 2 HfZrO 7 Magneto-optical ceramics whose XRD patterns are shown in FIG. 8, in which characteristic peaks of pyrochlore are hardly observed, it is considered that Tb 2 HfZrO 7 Belonging to a defective fluorite structure.
Tb obtained in the present example 2 HfZrO 7 The linear transmittance of the magneto-optical ceramic at 633nm is lower than 10%.
The optical quality is closely related to the specific preparation process, the most suitable preparation process of each component ceramic is not completely the same, and the optical quality of the monolithic ceramic cannot directly indicate the advantages and disadvantages of each component.
Example 3
According to Tb 2 ZrTiO 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)37.3847g，ZrO 2 (99.99%) 12.3222g and commercial analytically pure TiO 2 (AR) 7.9865g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is dried and pressed for molding under 40MPa, the mixed powder is subjected to cold isostatic pressing for molding under 250MPa and pressure maintaining for 5min to obtain a ceramic biscuit, the biscuit is presintered in a vacuum furnace, the heat preservation temperature of vacuum presintering is preferably 1550-1800 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree in the heat preservation stage is better than 1 multiplied by 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after pre-sintering at 1750 ℃ for 10 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Annealing the ceramic sample obtained by the hot isostatic pressing treatment for 10 hours in an ammonia atmosphere at 800 ℃, and polishing the double surfaces of the sample to obtain Tb 2 ZrTiO 7 Magneto-optical ceramics whose XRD patterns are shown in FIG. 9 have distinct pyrochlore characteristic peaks.
The optical quality of this embodiment is poor and translucent. Tb obtained in the present example 2 ZrTiO 7 The linear transmittance of the magneto-optical ceramic at 633nm is less than 10%.
Example 4
According to Tb 2 Hf 0.67 Zr 0.67 Ti 0.67 O 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)37.3847g，ZrO 2 (99.99％)8.2148g，HfO 2 (99.99%) 14.0327g and commercial analytically pure TiO 2 (AR) 5.3243g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is dried and pressed for molding under 40MPa, the mixed powder is pressed for molding under 250MPa for 5min under cold isostatic pressing to obtain a ceramic biscuit, the biscuit is presintered in a vacuum furnace, and the heat preservation temperature of vacuum presintering is preferably 1600-1850 DEG CThe heat preservation time is preferably 3-50 h, and the vacuum degree in the heat preservation stage is better than 1X 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after pre-sintering at 1750 ℃ for 10 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Annealing the ceramic sample obtained by the hot isostatic pressing treatment for 10 hours in an ammonia atmosphere at 800 ℃, and polishing the double surfaces of the sample to obtain Tb 2 Hf 0.67 Zr 0.67 Ti 0.67 O 7 Magneto-optical ceramics whose XRD patterns are shown in FIG. 10, have distinct pyrochlore characteristic peaks.
Tb obtained in the present example 2 Hf 0.67 Zr 0.67 Ti 0.67 O 7 The linear transmittance of the magneto-optical ceramic at 633nm is less than 10%.
Example 5
According to Tb 2.45 Hf 2 O 7.68 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99%) 45.8262g and HfO 2 (99.99%) 42.0980g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is dried and pressed for molding under 40MPa, the mixed powder is subjected to cold isostatic pressing under 250MPa and pressure maintaining for 5min to obtain a ceramic biscuit, the biscuit is presintered in a vacuum furnace, the vacuum presintering temperature is 1700 ℃, the heat preservation time is 3h, and the vacuum degree in the heat preservation stage is better than 1 multiplied by 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the pre-sintered ceramic sample, wherein the heat preservation temperature of the hot isostatic pressing is 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. The sample obtained after presintering at 1700 ℃ and HIP treatment is mirror polished to 2mm to obtain Tb 2.45 Hf 2 O 7.68 Magneto-optical ceramics.
The XRD pattern of this sample is shown in FIG. 11, with characteristic peaks of pyrochlore present. The Tb obtained 2.45 Hf 2 O 7.68 The magneto-optical ceramic material graph is shown in FIG. 12, the transmittance curve is shown in FIG. 13, the transmittance of the ceramic reaches 79.4% at 1064nm, the magneto-optical ceramic material has higher optical quality, and the Verdet constant is-165 rad/(T.m) at 633nm, thus achieving the commercial use1.23 times of TGG single crystal, indicating Tb 2.45 Hf 2 O 7.68 The ceramic has better application prospect. Tb (Tb) 2.45 Hf 2 O 7.68 The FESEM microscopic morphology photograph of the magneto-optical ceramic section is shown in fig. 14, and the graph shows that the ceramic fracture mode is mainly through crystal fracture, and meanwhile, certain along crystal fracture exists, which shows that the grain boundary strength is higher. Tb (Tb) 2.45 Hf 2 O 7.68 The FESEM micrograph of the hot etched surface of the magneto-optical ceramic is shown in FIG. 15, with an average grain size of 1.11 μm.+ -. 0.12. Mu.m, with no significant voids and second phases present.
Example 6
According to Tb 5.3 Hf 2 O 11.95 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)59.4675g，HfO 2 (99.99%) 25.2588g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. Calcining the mixed powder for 10h at 800 ℃ in an ammonia gas atmosphere after dry-pressing and molding the mixed powder under 40MPa, then maintaining the pressure under 250MPa for 5min, performing cold isostatic pressing and molding to obtain a ceramic biscuit, pre-sintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum pre-sintering is preferably 1500-1850 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree of the heat preservation stage is better than that of 1X 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after presintering at 1650 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1750 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. The ceramic sample obtained by the hot isostatic pressing treatment is subjected to double-sided mirror polishing to 2.0mm, and finally Tb is obtained 5.3 Hf 2 O 11.95 Magneto-optical ceramics.
XRD testing of ceramic sample after 1650 deg.C x 3h presintered is carried out, its XRD pattern is shown in figure 16, and the pattern shows Tb 5.3 Hf 2 O 11.95 As a two-phase coexisting ceramic, the presence of the second phase severely affects the in-line transmittance and is not preferable.
Example 7
According to Tb 3 Hf 2 O 8.5 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)44.8617g，HfO 2 (99.99%) 33.6784g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. Calcining the mixed powder for 10h at 800 ℃ in an ammonia gas atmosphere after dry-pressing and molding the mixed powder under 40MPa, then maintaining the pressure under 250MPa for 5min, performing cold isostatic pressing and molding to obtain a ceramic biscuit, pre-sintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum pre-sintering is preferably 1500-1850 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree of the heat preservation stage is better than that of 1X 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after presintering at 1650 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1750 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. The ceramic sample obtained by the hot isostatic pressing treatment is subjected to double-sided mirror polishing to 2.0mm, and finally Tb is obtained 3 Hf 2 O 8.5 Magneto-optical ceramics whose XRD patterns are shown in FIG. 17 are defective fluorite phases with no distinct pyrochlore peaks.
Tb obtained in the present example 3 Hf 2 O 8.5 The linear transmittance of the ceramic at 633nm is lower than 10%.
Example 8
According to Tb 3.71 Hf 2 O 9.57 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)48.6001g，HfO 2 (99.99%) 29.4686g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. Calcining the mixed powder for 10h at 800 ℃ in an ammonia gas atmosphere after dry-pressing and molding the mixed powder under 40MPa, then maintaining the pressure under 250MPa for 5min, performing cold isostatic pressing and molding to obtain a ceramic biscuit, pre-sintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum pre-sintering is preferably 1500-1850 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree of the heat preservation stage is better than that of 1X 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after presintering at 1650 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1750 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Ceramic sample obtained by hot isostatic pressing treatment is polished by double-sided mirror surfacesLight to 2.0mm, finally obtaining Tb 3.71 Hf 2 O 9.57 Magneto-optical ceramics whose XRD patterns are shown in FIG. 18 are defective fluorite phases with no distinct pyrochlore peaks.
Tb obtained in the present example 3.71 Hf 2 O 9.57 The linear transmittance of the ceramic at 633nm is lower than 10%.
Example 9
According to Tb 4.67 Hf 2 O 11.01 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)52.3386g，HfO 2 (99.99%) 25.2588g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. Calcining the mixed powder for 10h at 800 ℃ in an ammonia gas atmosphere after dry-pressing and molding the mixed powder under 40MPa, then maintaining the pressure under 250MPa for 5min, performing cold isostatic pressing and molding to obtain a ceramic biscuit, pre-sintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum pre-sintering is preferably 1500-1850 ℃, the heat preservation time is preferably 2-50 h, and the vacuum degree of the heat preservation stage is better than that of 1X 10 -3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after presintering at 1650 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1750 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. The ceramic sample obtained by the hot isostatic pressing treatment is subjected to double-sided mirror polishing to finally obtain Tb 4.67 Hf 2 O 11.01 Magneto-optical ceramics whose XRD patterns are shown in FIG. 19 are defective fluorite phases with no distinct pyrochlore peaks.
Tb obtained in the present example 4.67 Hf 2 O 11.01 The linear transmittance of the ceramic at 633nm is lower than 10%.
Comparative example 1
According to Tb 2 Hf 2 O 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)37.3847g，HfO 2 (99.99%) 42.0980g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After 40MPa dry pressing and molding of the mixed powder, 250MPa pressure maintainingCold isostatic pressing for 5min to obtain ceramic biscuit, pre-sintering the biscuit in a vacuum furnace at 1700 deg.c for 3 hr to obtain vacuum degree superior to 1×1 0-3 Pa. And carrying out hot isostatic pressing sintering treatment on the pre-sintered ceramic sample, wherein the heat preservation temperature of the hot isostatic pressing is 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Mirror polishing the two surfaces of the sample to obtain Tb 2 Hf 2 O 7 Magneto-optical ceramics. Tb of the preparation 2 Hf 2 O 7 The XRD pattern of the magneto-optic ceramic is shown in FIG. 4, in which weaker pyrochlore characteristic peaks can be seen, and thus the presence of the pyrochlore phase can be confirmed. The main reason for the weaker characteristic peaks is that the atomic scattering factors of Tb and Hf are close, so that the pyrochlore phase and the defect fluorite phase are difficult to be distinguished obviously by the conventional X-ray diffraction test means, but the defect fluorite phase cannot be demonstrated by various characterization means. In addition, the mixed powder after ball milling was calcined at 800-1300 ℃ for 4 hours and then subjected to XRD test to investigate the phase formation process of ceramics, as shown in fig. 20. In the mixed powder calcined at 800 ℃ for 4 hours, the main phase is the raw material phase of Hf and Tb, and the raw material powder gradually diffuses and reacts to Tb along with the increase of the calcining temperature 2 Hf 2 O 7 The phase, therefore, verifies that the sintering technique used in the present preparation method is a solid phase reaction sintering technique.
Tb obtained in this comparative example 2 Hf 2 O 7 The magneto-optical ceramic has a linear transmittance of about 10% in the band of 650nm to 1500nm and a Verdet constant of 150 rad/(T.m) at 633 nm.
Comparative example 2
According to Tb 2 Zr 2 O 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99％)37.3847g，ZrO 2 (99.99%) 24.6445g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is subjected to dry pressing at 40MPa and molding at 250MPa, maintaining the pressure for 5min, performing cold isostatic pressing to obtain a ceramic biscuit, and pre-sintering the biscuit in a vacuum furnace, wherein the heat preservation temperature of vacuum pre-sintering is preferably 160The temperature is 0-1750 ℃, the heat preservation time is preferably 3-50 h, and the vacuum degree in the heat preservation stage is better than 1X 10 -3 Pa. Presintering at 1600 ℃ for 3h to obtain Tb 2 Zr 2 O 7 The XRD pattern of the ceramic is shown in FIG. 5, and the characteristic peaks of the pyrochlore are not present, and the ceramic is considered to belong to the defective fluorite phase. And carrying out hot isostatic pressing sintering treatment on the ceramic sample after pre-sintering at 1600 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is preferably 1700 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Finally, the sample is mirror polished to 2mm to obtain Tb 2 Zr 2 O 7 Magneto-optical ceramics.
As shown in FIG. 6, the transmittance curve shows that the linear transmittance at 1500nm reaches about 58%, indicating Tb 2 Zr 2 O 7 Magneto-optical ceramics already have a certain transmittance, verdet constant of-150 rad/(T.m) at 633 nm.
Comparative example 3
According to Tb 2 Ti 2 O 7 Raw material powder is weighed according to the chemical formula: commercial high purity Tb 4 O 7 (99.99%) 37.3847g and commercial analytically pure TiO 2 (AR) 15.9730g, absolute ethyl alcohol was used as a ball milling medium, and ball milling was carried out at 130rpm for 15 hours. Drying the ball-milled slurry in an oven at 70 ℃ for 2 hours, sieving the slurry with a 200-mesh sieve, and calcining the slurry at 800 ℃ for 4 hours to obtain mixed powder. After the mixed powder is dried and pressed for molding under 40MPa, the mixed powder is subjected to cold isostatic pressing for molding under 250MPa and pressure maintaining for 5min to obtain a ceramic biscuit, the biscuit is presintered in a vacuum furnace, the heat preservation temperature of vacuum presintering is preferably 1300-1600 ℃, the heat preservation time is preferably 3-50 h, and the vacuum degree in the heat preservation stage is better than 1 multiplied by 10 - 3 Pa. And carrying out hot isostatic pressing sintering treatment on the ceramic sample pre-sintered at 1500 ℃ for 3 hours, wherein the heat preservation temperature of the hot isostatic pressing is 1550 ℃, the heat preservation time is 3 hours, and the argon atmosphere pressure in the furnace is 176MPa. Annealing the ceramic sample obtained by the hot isostatic pressing treatment for 10 hours in an argon atmosphere at 900 ℃, and polishing the double surfaces of the sample to obtain Tb 2 Ti 2 O 7 Magneto-optical ceramics whose XRD patterns are shown in FIG. 7 have distinct pyrochlore characteristic peaks.
Tb obtained in this comparative example 2 Ti 2 O 7 The linear transmittance of the magneto-optical ceramic in the wave band range of 650 nm-1500 nm is 10The Verdet constant is-220 rad/(T.m) at 633 nm.
Claims (4)
1. A terbium-based magneto-optical ceramic is characterized in that the terbium-based magneto-optical ceramic has a chemical formula of Tb 2.45 Hf 2 O 7.68 The method comprises the steps of carrying out a first treatment on the surface of the The terbium-based magneto-optical ceramic has a linear transmittance of 79.4% at 1064 nm; the Verdet constant of the terbium-based magneto-optical ceramic is-165 rad/(T.m) at 633 nm;
the preparation method of the terbium-based magneto-optical ceramic comprises the following steps: the terbium source and hafnium source powder as raw materials are mixed according to chemical formula Tb 2.45 Hf 2 O 7.68 Batching to obtain mixed powder; grinding and mixing the mixed powder to obtain mixed slurry or powder; drying, sieving and calcining the obtained mixed slurry to obtain mixed powder; forming the powder into a ceramic biscuit; vacuum pre-sintering the ceramic biscuit at 1700 deg.c for 3 hr to obtain ceramic biscuit with vacuum degree of 1×10 -3 Pa; and performing hot isostatic pressing sintering treatment at 1700 ℃, wherein the argon atmosphere pressure in the furnace is 176MPa, the time is 3 hours, and finally performing annealing treatment, cutting and polishing to obtain the pyrochlore terbium-based magneto-optical ceramic.
2. The terbium-based magneto-optical ceramic according to claim 1, wherein the raw materials further comprise a sintering aid, a binder, a dispersant, a plasticizer; the sintering aid is Li 2 O、Na 2 O、K 2 O、MgO、CaO、B 2 O 3 、La 2 O 3 、GeO 2 、SiO 2 、LiF、NaF、MgF 2 、CaF 2 、AlF 3 、YF 3 、TEOS、H 3 BO 3 The adhesive is at least one of polyvinyl alcohol, polyvinyl alcohol Ding Quanzhi and paraffin, the dispersing agent is at least one of stearic acid, fish oil and vegetable oil, and the plasticizer is at least one of palm wax, dioctyl phthalate and ethylene glycol.
3. The terbium-based magneto-optical ceramic according to claim 1, wherein the mixed slurry is dried for 0.1 to 100 hours and is calcined at 600 to 1300 ℃ for 1 to 20 hours after passing through a 60 to 300 mesh sieve, thereby obtaining a mixed powder.
4. The terbium-based magneto-optical ceramic according to claim 1, wherein the annealing temperature is 500 to 1400 ℃ and the annealing holding time is 1 to 50 hours.
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| CN110240480A (en) * | 2018-03-09 | 2019-09-17 | 信越化学工业株式会社 | Crystalline ceramics, its manufacturing method and magnetooptics equipment |
| CN110386818A (en) * | 2018-04-23 | 2019-10-29 | 中国科学院上海光学精密机械研究所 | Mix zirconium terbium aluminium garnet magnetic rotation crystalline ceramics and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105531619A (en) * | 2013-09-12 | 2016-04-27 | 信越化学工业株式会社 | Magnetooptical material, manufacturing method therefor, and magnetooptical device |
| JP2016169115A (en) * | 2015-03-11 | 2016-09-23 | 信越化学工業株式会社 | Magnetic optical material and magnetic optical device |
| CN110240480A (en) * | 2018-03-09 | 2019-09-17 | 信越化学工业株式会社 | Crystalline ceramics, its manufacturing method and magnetooptics equipment |
| CN110386818A (en) * | 2018-04-23 | 2019-10-29 | 中国科学院上海光学精密机械研究所 | Mix zirconium terbium aluminium garnet magnetic rotation crystalline ceramics and preparation method thereof |
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