CN110550945B - Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic - Google Patents
Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic Download PDFInfo
- Publication number
- CN110550945B CN110550945B CN201810565772.8A CN201810565772A CN110550945B CN 110550945 B CN110550945 B CN 110550945B CN 201810565772 A CN201810565772 A CN 201810565772A CN 110550945 B CN110550945 B CN 110550945B
- Authority
- CN
- China
- Prior art keywords
- luag
- transparent ceramic
- powder
- sintering
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
-
- 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
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- 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
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a preparation method of LuAG-Ce transparent ceramic and the LuAG-Ce transparent ceramic, wherein the preparation method of the transparent ceramic comprises the following steps: preparation of Ce-containing 3+ A cerium salt solution of (a); mixing Lu 2 O 3 And Al 2 O 3 Respectively pretreating the nano-powder; mixing Ce in proportion 3+ Cerium salt solution and pretreated Lu 2 O 3 And Al 2 O 3 Mixing the nano powder evenly and then carrying out ball milling; drying the ball-milled mixture, and then calcining; pressing the calcined powder into a green body and presintering; and sintering the pre-sintered blank in vacuum to obtain the ceramic material. The invention can solve the technical problems that in the prior art, the LuAG-Ce transparent ceramic has low transmittance in the visible light range, and the preparation is limited by high sintering temperature in large-scale application, and the prior preparation method cannot adopt nano powder with smaller particle size as a raw material, so that the LuAG-Ce transparent ceramic with better quality cannot be obtained.
Description
Technical Field
The invention belongs to the technical field of optical functional ceramic materials, relates to a preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic, and particularly relates to a method for preparing LuAG Ce transparent ceramic by vacuum sintering.
Background
LuAG is short for Lu-aluminum garnet, and its chemical formula is Lu 3 Al 5 O 12 Is prepared from Lu 2 O 3 And Al 2 O 3 The formed solid solution belongs to a cubic crystal system, has a garnet structure, does not have a birefringence effect, and can be prepared into transparent ceramics with excellent optical properties. Simultaneously, the LuAG has high density (6.73 g/cm) 3 94% of BGO density), high melting point (2010 ℃), high effective atomic number (Z) eff 60), good mechanical property, and optical and physicochemical properties stable under long-term radiation, especially rare earth RE 3+ The 5d-4f transition of the ions can generate nanosecond (ns) -level fast luminescence attenuation, up-conversion luminescence or laser, and the like, so the rare earth RE doped LuAG-RE transparent ceramic has important potential application prospects in the fields of scintillation detection, up-conversion luminescence, solid laser and the like. The matrix is added with small amount of rare earth ions (for exampleSuch as Ce 3+ ) As an activator, the fluorescent material is a novel rapid scintillator.
Currently, the solid phase reaction method is one of the main methods for preparing LuAG ceramics. The representative Shanghai silicate research institute in the field adopts self-made 40nm Lu for the first time 2 O 3 And Al having a commercially available average particle diameter of 200nm 2 O 3 、CeO 2 The transparent LuAG Ce ceramic is prepared by a powder solid-phase reaction method under the condition of vacuum sintering at 1760 ℃ for 10 hours, the transmittance of the transparent LuAG Ce ceramic is 56 percent in a visible light range, is only 67 percent of the theoretical transmittance (83.3 percent) of the LuAG, and 30 percent of the transparent LuAG Ce ceramic is scattered by a grain boundary phase and air holes. In addition, the high sintering temperature of 1760 ℃ also limits the large-scale application.
In addition, the quality of the transparent ceramic prepared by the solid-phase reaction method strongly depends on the activity and the morphology of the raw material powder, the smaller the particle size of the powder is, the higher the surface activity is, the more the morphology is close to a sphere, the easier the dispersion is, the more complete the growth of crystal grains during sintering is, and the fewer crystal boundary phases and air holes are. However, the nano-scale powder with small particle size is easy to agglomerate, and needs to be finely dispersed and impurities introduced during dispersion are removed during use. At present, no relevant reports and patents of preparing LuAG: Ce by adopting nano-scale powder with the particle size less than 50nm as a raw material and performing vacuum sintering at low temperature (<1750 ℃ vacuum sintering temperature) are found because the fine dispersion and impurity removal of the powder are difficult to control.
Disclosure of Invention
The following presents a simplified summary of the invention in order to provide a basic understanding of some aspects of the invention. It should be understood that this summary is not an exhaustive overview of the invention. It is not intended to determine the key or critical elements of the present invention, nor is it intended to limit the scope of the present invention. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is discussed later.
The invention provides a preparation method of LuAG-Ce transparent ceramic and the LuAG-Ce transparent ceramic, which aim to solve the technical problems that in the prior art, the LuAG-Ce transparent ceramic has low transmittance in a visible light range, and is limited by high sintering temperature in preparation, and the prior preparation method cannot adopt nano powder with smaller particle size as a raw material, so that the LuAG-Ce transparent ceramic with better quality cannot be obtained.
The technical solution of the invention is as follows:
according to one aspect of the invention, the preparation method of the LuAG-Ce transparent ceramic is realized by the following steps:
preparation of Ce-containing 3+ A cerium salt solution of (a);
mixing Lu 2 O 3 And Al 2 O 3 Respectively pretreating the nano-powder;
mixing Ce in proportion 3+ Cerium salt solution and pretreated Lu 2 O 3 And Al 2 O 3 Mixing the nano powder evenly and then carrying out ball milling;
drying the ball-milled mixture, and then calcining;
pressing the calcined powder into a green body and presintering;
and sintering the pre-sintered blank in vacuum to obtain the LuAG-Ce transparent ceramic.
Further, the Lu 2 O 3 The average particle diameter of the nano powder is 25-35 nm, and the Al is 2 O 3 The average particle size of the nano powder is 20-25 nm.
Further, the formulation contains Ce 3+ The cerium salt solution of (a) is: with Ce (NO) 3 ) 3 ·6H 2 O crystal is taken as a raw material, dissolved in deionized water and filtered to prepare cerium nitrate solution with a certain concentration.
Further, the concentration of the cerium nitrate solution is 0.5-0.8 mol.L -1 。
Further, the pretreatment refers to the step of adding Lu 2 O 3 And Al 2 O 3 The nano powder is firstly calcined at high temperature and then dried.
Further, the Ce is contained 3+ Cerium salt solution and pretreated Lu 2 O 3 And Al 2 O 3 Nano powderAccording to the stoichiometric ratio (Lu) 2.985 Ce 0.015 Al 5 O 12 ) The respective proportional contents are determined.
Further, the ball milling is carried out in two times, and comprises the following steps:
adding high-purity ZrO into the uniformly mixed mixture 2 Performing first ball milling in ethanol of the balls;
and drying and sieving the ball-milled powder, adding a certain amount of sintering aid, and further carrying out secondary ball milling under the ball milling conditions.
Further, the vacuum sintering is carried out in a vacuum furnace, the temperature is increased at a certain sintering temperature increasing speed in the sintering process, the temperature is increased to 1600-1700 ℃ for heat preservation, and the heat preservation time is preferably more than 24 hours.
Further, the pre-sintering time of the blank is 4-6 h, and the temperature is 1200-1250 ℃; and drying the ball-milled mixture, and then calcining for 4-6 h at 1100-1150 ℃.
According to another aspect of the invention, the LuAG-Ce transparent ceramic is prepared by the method.
The method for preparing the LuAG-Ce transparent ceramic is different from the traditional method for preparing the LuAG-Ce transparent ceramic by taking powder as a raw material, and the invention uses Ce (NO) in the invention 3 ) 3 ·6H 2 O crystal and Lu with particle size less than 50nm 2 O 3 And Al 2 O 3 The nanometer powder is used as raw material, and comprises the following steps: the powder and the solution are blended, the means of calcination, presintering and the like are added, and the appropriate time of calcination, presintering and the like is determined, so that the nano powder with smaller particle size can be well dispersed during preparation, and the quality of the transparent ceramic is ensured; meanwhile, the improved process is adopted, so that the vacuum sintering temperature is reduced by about 60-150 ℃, and the large-scale application of the preparation method is enlarged; and the transmittance of the LuAG-Ce transparent ceramic prepared by the method in a visible light range is increased by at least 7 percent compared with that of the existing product.
Drawings
FIG. 1 is a TEM morphology photograph of an original powder;
FIG. 2 is an X-ray diffraction pattern of Ce in LuAG at 1100 ℃ and 4h after high-temperature calcination;
FIG. 3 is a photograph of the appearance of a vacuum sintered sample (1.5mm thick);
FIG. 4 is a line transmittance curve of LuAG: Ce (sample thickness 1.5 mm);
in the figure, Lu 2 O 3 Is 1; al (Al) 2 O 3 Is 2; the product prepared by the method of Shanghai silicate institute is 3; the product prepared by the method of the invention is 4.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the device structures and/or processing steps that are closely related to the scheme according to the present invention are shown in the drawings, and other details that are not so relevant to the present invention are omitted.
According to a preparation method of LuAG: Ce transparent ceramics, the steps included in the method are explained in detail as follows:
step 2, mixing Lu 2 O 3 And Al 2 O 3 Respectively pretreating the nano-powder;
step 5, pressing the calcined powder into a green body and presintering the green body;
and 6, sintering the pre-sintered blank in vacuum to obtain the LuAG-Ce transparent ceramic.
Further, in the present invention, the formulation contains Ce 3+ The cerium salt solution of (a) is: with Ce (NO) 3 ) 3 ·6H 2 O crystal is taken as a raw material, dissolved in deionized water and filtered to prepare cerium nitrate solution with a certain concentration.
In particular, the method comprises the following steps of,
first Ce (NO) 3 ) 3 ·6H 2 Dissolving the O crystal in deionized water, filtering and preparing into 0.5-0.8 mol.L -1 The nitrate solution of (a) is ready for use. The invention adopts cerium nitrate solution to blend with other powder, compared with the prior art which adopts powder to blend Ce 3+ The solution is easier to disperse uniformly and the free Ce 3+ CeO in a relatively +4 valence state 2 The stable particles have stronger reactivity and can more easily enter Lu with small particle size 2 O 3 And Al 2 O 3 Within the crystal lattice of the matrix.
In the present invention, the Lu 2 O 3 The average particle diameter of the nano powder is 25-35 nm, and the Al is 2 O 3 The average particle size of the nano powder is 20-25 nm; the Lu is 2 O 3 Is commercially available in high purity (>99.99%) nano-scale powder, Al 2 O 3 Is commercially available in high purity (>99.99%) nano-level powder, Ce (NO) 3 ) 3 ·6H 2 O is a commercially available analytically pure crystal.
In the present invention, it will be understood by those skilled in the art that the pair Lu 2 O 3 And Al 2 O 3 The pretreatment of the nano powder can be carried out by adopting the technology known in the field, so long as the impurity removal can be achieved, for example, the nano powder can be calcined at high temperature and then dried. The present invention gives specific pretreatment processes below, but is not limited thereto:
will Lu 2 O 3 And Al 2 O 3 The powder is calcined at 700 ℃ and 1000 ℃ for 5h to remove impurities and dried at 120 ℃ for 24h for standby.
In the present invention, for determining the Ce content 3+ Cerium salt solution ofAnd pretreated Lu 2 O 3 And Al 2 O 3 The content of the nanopowder can be determined by a technique known in the art, for example, by a stoichiometric ratio (Lu) 2.985 Ce 0.015 Al 5 O 12 ) The respective proportional contents are determined.
Furthermore, to make the particle size small, Lu 2 O 3 And Al 2 O 3 The nano powder is more uniformly mixed, and the ball milling in the invention is carried out by two times, comprising the following steps:
adding high-purity ZrO into the uniformly mixed mixture 2 Performing first ball milling in ethanol of the balls;
and drying and sieving the ball-milled powder, adding a certain amount of sintering aid, and further carrying out secondary ball milling under the ball milling conditions.
Wherein, the ball material ratio is 1-2: 1, the ratio of material to ethanol is 1: 1 to 3.
The specific ball milling process is given below:
firstly adding high-purity ZrO 2 Ball-milling the ball in ethanol at 200r/min for 12h, and rapidly drying and sieving the ball-milled powder; adding 0.5 wt% of Tetraethoxysilane (TEOS) as a sintering aid, and carrying out secondary ball milling for 12 hours under the original condition.
The invention is realized by two-time ball milling and wet milling in ethanol to ensure that Lu is obtained 2 O 3 And Al 2 O 3 The two phases are mixed as homogeneously as possible, which directly affects the Lu in the pre-firing and sintering process 2 O 3 And Al 2 O 3 The two-phase diffusion and reaction speed greatly influence the quality of a sample, and proper proportion of powder, grinding media and dispersion media and proper ball milling time are necessary conditions for ensuring the uniformity of mixed materials. In addition, the uniform dispersion of the cerium nitrate solution and the aluminum nitrate solution is ensured, and the Lu with smaller particle size is selected based on the raw material of the cerium nitrate solution 2 O 3 And Al 2 O 3 The nano powder can be well applied in the method.
Further, the vacuum sintering is the final step of preparing LuAG: Ce transparent ceramics by solid phase reactionOne step, in the prior art, the powder after ball milling is directly pressed into a green body and then directly sintered in vacuum, while the invention firstly calcines the powder after ball milling twice, then presses the powder into a green body, presintering the green body and finally sintering in vacuum, and the reason and the purpose of adopting the improved process are that: in Lu 2 O 3 And Al 2 O 3 In the course of reaction to produce LuAG, the reaction is microscopically composed of 5 substances and 4 interfaces, and in the initial stage of reaction, the powder is formed from Lu 2 O 3 And Al 2 O 3 Of composition, Lu with increasing temperature 3+ And Al 3+ Interdiffusion occurs due to the concentration gradient, producing LuAM (Lu) 4 Al 2 O 9 ) LuAM and Al 2 O 3 Further reaction produces LuAP (LuAlO) 3 ) Lu of LuAP 3+ With Al 2 O 3 Al of (2) 3+ The invention further diffuses and generates LuAG, the purpose of the invention is to enable the process to take place in advance, on one hand, the invention avoids incomplete reaction on the grain boundary during the later sintering to leave LuAM and LuAP impurity phases to influence the transmittance, on the other hand, the invention correspondingly reduces the sintering temperature; in addition, the calcination function can also remove organic impurities, adsorbed water, free carbon and the like mixed in the raw material after wet grinding, thereby ensuring the purity of the raw material. According to the invention, the green body is further pre-sintered after being pressed, because in the process of pressing the powder into the green body, air is mixed in to cause that the exterior of the green body is tightly sintered when the green body is sintered in a vacuum atmosphere, and the internal gas cannot be discharged in time to cause cracking or deformation.
Further, the vacuum sintering is carried out in a vacuum furnace, the temperature is increased at a certain sintering temperature increasing speed in the sintering process, and the temperature is increased to 1600-1700 ℃ for heat preservation.
Preferably, the heat preservation time exceeds 24h, the invention further prolongs the heat preservation time, can further correspondingly reduce the sintering temperature, and simultaneously finds that the transmittance of the transparent ceramic is improved by prolonging the heat preservation time.
Further, the pre-sintering time of the blank is 4-6 h, and the temperature is 1200-1250 ℃; and drying the ball-milled mixture, and then calcining for 4-6 hours at 1100-1150 ℃.
Specific processes are given below, but not limited thereto:
drying, sieving and calcining the powder after ball milling for 4 hours at 1100 ℃; the calcined powder is molded by bidirectional pressing, the pressing pressure is 200MPa, the diameter of a pressed blank is 16mm, the thickness is 3mm, and the powder is presintered for 4h at 1200 ℃; the vacuum sintering adopts a VSF-7 type vacuum furnace, and the sintering temperature rise speed is 300 ℃ h -1 Heating to 1700 ℃ and preserving heat for 5 hours, wherein the vacuum degree in the furnace is 5 multiplied by 10 -3 Pa。
The following gives specific examples of the preparation of LuAG: Ce transparent ceramics according to the invention:
example 1
Adding Ce (NO) 3 ) 3 ·6H 2 Dissolving O in deionized water, filtering and preparing into 0.5 mol.L -1 The nitrate solution of (a) is ready for use. Mixing Lu 2 O 3 And Al 2 O 3 The powder is calcined at 700 ℃ and 1000 ℃ for 5h to remove impurities and dried at 120 ℃ for 24h for standby. Precision weighing 297.0075gLu 2 O 3 、127.5gAl 2 O 3 Adding 850g of high-purity ZrO into the nano powder and 7.5ml of cerium nitrate solution 2 Ball milling is carried out on the ball for 12 hours in ethanol at room temperature of 200r/min, and powder slurry after ball milling is rapidly dried and sieved. Adding 0.5 wt% of Tetraethoxysilane (TEOS) as a sintering aid, performing secondary ball milling for 12 hours under the original condition, drying and sieving powder slurry after ball milling, and calcining for 4 hours at 1100 ℃; the calcined powder is molded by bidirectional pressing, and the pressing pressure is 200 MPa; pre-sintering the pressed blank for 4 hours at 1200 ℃ with the diameter of 16mm and the thickness of 3 mm; the vacuum sintering adopts a VSF-7 type vacuum furnace; the temperature rising speed of the green body sintering is 300 ℃ h -1 Heating to 1700 ℃ and preserving the temperature for 24 hours, wherein the vacuum degree in the furnace is 5 multiplied by 10 -3 Pa。
Observing the primary particle morphology of the powder by adopting a transmission electron microscope (Philips EM400), grinding the powder for TEM analysis in a mortar, ultrasonically dispersing in absolute ethyl alcohol for 20min, sucking suspended liquid to drop on a copper net, naturally drying, and observing. Study phase composition with an X-ray diffractometer (Xpert Pro X); the transmittance of the transparent ceramic was measured by an ultraviolet-visible-near infrared spectrophotometer (Perkin-Elemer Lambda 950).
Comparative example 1
Ce was prepared according to literature "solid phase reaction: LuAG transparent ceramics "inorganic materials bulletin, 2006, 21 (5): 1161-1166, Ce: and preparing LuAG transparent ceramics.
TEM morphology display Lu of 1 of FIG. 1 2 O 3 The nano powder particle size is about 30nm, but the nano powder particle is in a scaly structure, and the TEM morphology of 2 in figure 1 shows Al 2 O 3 2 the average grain diameter of the powder is about 20nm, the dispersibility is good, the particles are spherical, and the powder is suitable to be used as an initial raw material for preparing transparent ceramics.
The X-ray diffraction pattern of FIG. 2 shows a small amount of LuAM (Lu) after calcination at 1100 deg.C 4 Al 2 O 9 ) And most of LuAP (LuAlO) 3 ) Co-exists with LuAG.
The appearance photograph of fig. 3 shows that the transmittance of product 4 prepared by the method of the present invention is higher than the transmittance of product 3 prepared by the method of shanghai silicate institute.
Ce Linear transmittance curves for LuAG: Ce obtained in the examples of the invention are shown in FIG. 4, where the broad absorption bands at 340nm and 450nm are due to Ce 3+ The maximum light transmittance in a visible light region (380-780nm) caused by the electron transition from the 4f ground state to the 5d excited state is 73.4 percent, which is better than LuAG: Ce (maximum light transmittance in the visible light region: 66 percent) which is obtained by 1760 ℃ vacuum heat preservation of Shanghai silicate research institute for 10 hours.
Features that are described and/or illustrated above with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
The many features and advantages of these embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of these embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
The invention has not been described in detail and is in part known to those of skill in the art.
Claims (7)
1. The preparation method of the LuAG-Ce transparent ceramic is characterized by comprising the following steps:
preparation of Ce-containing 3+ A cerium salt solution of (a);
mixing Lu 2 O 3 And Al 2 O 3 Respectively pretreating the nano-powder;
mixing Ce in proportion 3+ Cerium salt solution and pretreated Lu 2 O 3 And Al 2 O 3 Mixing the nano powder evenly and then carrying out ball milling;
drying the ball-milled mixture, and then calcining for 4-6 h at 1100-1150 ℃;
pressing the calcined powder into a green body and presintering;
sintering the pre-sintered blank in vacuum to obtain LuAG-Ce transparent ceramic;
the average particle size of the Lu2O3 nano powder is 25-35 nm, and the average particle size of the Al2O3 nano powder is 20-25 nm;
the vacuum sintering is carried out in a vacuum furnace, the temperature is increased at a certain sintering temperature-increasing speed in the sintering process, the temperature is increased to 1600 ℃ for heat preservation, and the heat preservation time is more than 24 hours;
the pre-sintering time of the blank is 4-6 h, and the temperature is 1200-1250 ℃.
2. The method for preparing LuAG-Ce transparent ceramic according to claim 1, wherein the formulation contains Ce 3+ Cerium salt ofThe solution is as follows: with Ce (NO) 3 ) 3 ·6H 2 O crystal is taken as a raw material, dissolved in deionized water and filtered to prepare cerium nitrate solution with a certain concentration.
3. The method for preparing LuAG-Ce transparent ceramic according to claim 2, wherein the concentration of the cerium nitrate solution is 0.5-0.8 mol-L -1 。
4. The method for preparing LuAG-Ce transparent ceramic according to any one of claims 1-3, wherein the pretreatment is to add Lu 2 O 3 And Al 2 O 3 The nano powder is firstly calcined at high temperature and then dried.
5. The method for preparing LuAG-Ce transparent ceramic according to claim 4, wherein the Ce is contained 3+ Cerium salt solution and pretreated Lu 2 O 3 And Al 2 O 3 Nano powder Lu according to stoichiometric ratio 2.985 Ce 0.015 Al 5 O 12 The respective proportional contents are determined.
6. The method for preparing LuAG-Ce transparent ceramic according to claim 4, wherein the ball milling is performed in two steps, comprising:
adding high-purity ZrO into the uniformly mixed mixture 2 Performing first ball milling in ethanol of the balls;
and drying and sieving the ball-milled powder, adding a certain amount of sintering aid, and further carrying out secondary ball milling under the ball milling conditions.
7. A LuAG-Ce transparent ceramic, characterized in that it is produced according to the method of any one of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810565772.8A CN110550945B (en) | 2018-06-04 | 2018-06-04 | Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810565772.8A CN110550945B (en) | 2018-06-04 | 2018-06-04 | Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110550945A CN110550945A (en) | 2019-12-10 |
| CN110550945B true CN110550945B (en) | 2022-08-12 |
Family
ID=68736241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810565772.8A Active CN110550945B (en) | 2018-06-04 | 2018-06-04 | Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110550945B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200746A (en) * | 2021-04-30 | 2021-08-03 | 中国科学院上海光学精密机械研究所 | Method for preparing infrared transparent ceramic through pressureless rapid sintering |
| CN113405995A (en) * | 2021-06-24 | 2021-09-17 | 上海洞舟实业有限公司 | Preparation method of light conversion ultraviolet beam analyzer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837142A (en) * | 2006-04-07 | 2006-09-27 | 中国科学院上海硅酸盐研究所 | Luetcium aluminum garnet -base transparent ceramic and process for preparing same |
| CN101514100A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Twinkling transparent ceramics system with garnet structure and preparation method thereof |
| CN105418063A (en) * | 2014-09-22 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | Lutetium-aluminum garnet scintillation ceramic in non-stoichiometric ratio and preparation method for ceramic |
| RU2584187C1 (en) * | 2015-01-19 | 2016-05-20 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ им. Г.Г. Девятых Российской академии наук (ИХВВ РАН) | Method of producing transparent ceramic of yttrium aluminium garnet |
| CN107793152A (en) * | 2016-08-29 | 2018-03-13 | 深圳市光峰光电技术有限公司 | The preparation method and associated light ceramics of a kind of Ce doping YAG luminescent ceramics |
-
2018
- 2018-06-04 CN CN201810565772.8A patent/CN110550945B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837142A (en) * | 2006-04-07 | 2006-09-27 | 中国科学院上海硅酸盐研究所 | Luetcium aluminum garnet -base transparent ceramic and process for preparing same |
| CN101514100A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Twinkling transparent ceramics system with garnet structure and preparation method thereof |
| CN105418063A (en) * | 2014-09-22 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | Lutetium-aluminum garnet scintillation ceramic in non-stoichiometric ratio and preparation method for ceramic |
| RU2584187C1 (en) * | 2015-01-19 | 2016-05-20 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ им. Г.Г. Девятых Российской академии наук (ИХВВ РАН) | Method of producing transparent ceramic of yttrium aluminium garnet |
| CN107793152A (en) * | 2016-08-29 | 2018-03-13 | 深圳市光峰光电技术有限公司 | The preparation method and associated light ceramics of a kind of Ce doping YAG luminescent ceramics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110550945A (en) | 2019-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018045782A1 (en) | Preparation method for ceramic composite material, ceramic composite material, and light source apparatus | |
| Chen et al. | Effect of ball-milling granulation with PVB adhesive on the sinterability of co-precipitated Yb: YAG nanopowders | |
| US20100048378A1 (en) | Sintered polycrystalline yttrium aluminum garnet and use thereof in optical devices | |
| JP4623403B2 (en) | Ceramics, ceramic powder production method and ceramic production method. | |
| CN101993240B (en) | Preparation method of Ce3+doped lutetium silicate (Lu2SiO5) polycrystalline flashing optical ceramic | |
| Yavetskiy et al. | Phase formation and densification peculiarities of Y3Al5O12: Nd3+ during reactive sintering | |
| Sun et al. | Production and optical properties of Ce3+‐activated and Lu3+‐stabilized transparent gadolinium aluminate garnet ceramics | |
| JPWO2017033618A1 (en) | Translucent rare earth aluminum garnet ceramics | |
| CN110550945B (en) | Preparation method of LuAG Ce transparent ceramic and LuAG Ce transparent ceramic | |
| JP2008143726A (en) | Polycrystalline transparent y2o3 ceramics and its production method | |
| CN101844784A (en) | Alpha-Al2O3 nanostructure aggregate material and preparation method thereof | |
| CN108046768B (en) | Gadolinium gallium aluminum scintillation ceramic double doped with rare earth ions and preparation method thereof | |
| Wang et al. | Microwave synthesis of homogeneous YAG nanopowder leading to a transparent ceramic | |
| JP2939535B2 (en) | Manufacturing method of transparent yttrium oxide sintered body | |
| Mohammadi et al. | The effects of ball milling time on the rheological, optical, and microstructural properties of YAG transparent ceramics | |
| Xie et al. | Eu: Lu2O3 transparent ceramics fabricated by vacuum sintering of co-precipitated nanopowders | |
| Ma et al. | Fabrication of Lu2O3: Eu transparent ceramics using powder consisting of mono-dispersed spheres | |
| Xu et al. | Scintillation and luminescent properties of cerium doped lutetium aluminum garnet (Ce: LuAG) powders and transparent ceramics | |
| ZHU et al. | Fine-grained Ce, Y: SrHfO3 scintillation ceramics fabricated by hot isostatic pressing | |
| Van Opdenbosch et al. | Replication of wood into biomorphous nanocrystalline Y 2 O 3: Eu 3+ phosphor materials | |
| Sidorowicz et al. | Precipitation of Tm2O3 nanopowders for application in reactive sintering of Tm: YAG | |
| CN115010503A (en) | Use method of sintering aid for transparent oxide ceramic material | |
| Liu et al. | Fabrication and microstructures of YAG transparent ceramics | |
| CN115215651A (en) | Preparation method of rare earth doped lutetium oxide based composite luminescent ceramic | |
| Osipov et al. | Ce: YAG transparent ceramics based on nanopowders produced by laser ablation method: Fabrication, optical and scintillation properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |