WO2010114403A1 - Nanotubes luminescents à base d'aluminate de béryllium, de magnésium, de calcium, de strontium ou de baryum dopés avec du cérium (iii) et co-dopés avec d'autres ions de lanthanides m(1-x-y)n2o4: cex, lny - Google Patents
Nanotubes luminescents à base d'aluminate de béryllium, de magnésium, de calcium, de strontium ou de baryum dopés avec du cérium (iii) et co-dopés avec d'autres ions de lanthanides m(1-x-y)n2o4: cex, lny Download PDFInfo
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
- C01F17/34—Aluminates, e.g. YAlO3 or Y3-xGdxAl5O12
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
- C01P2004/136—Nanoscrolls, i.e. tubes having a spiral section
Definitions
- the present invention relates to new luminescent of beryllium, magnesium, calcium, strontium or barium aluminate nanotubes doped with cerium (III) and co-doped with other ions from the Lanthanide Series of Elements (Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm and Lu) , inorganic nanomaterials of which present multifunctional properties, namely optical features (ex. thermo-, cathode-, piezo-, sono- and photo-luminescence ⁇ .
- nanotubes are obtained by a synthesis process comprising a thermal treatment of post-annealing of precursor micro- and nano-particles (ex.: BaAl 2 O 4 :Ce 3v , Eu 2 ' of commercial source) , under a temperature range of 573 Kelvin, or more, for a minimum time of 30 minutes, in air atmosphere, nanotubes of which present optical features with the respective emission bands in the (near) infrared and (visible) ultraviolet regions of the electromagnetic spectrum, wherein said emission bands are modified according the composition of the M ⁇ _ >: - Y )N 7 O 4 : Ce x , Ln y formula employed, where 0 ⁇ x ⁇ l and O ⁇ y ⁇ l, wherein said nanotubes are useful for applications in optical materials, devices, sensors and products with afterglow luminescence.
- precursor micro- and nano-particles ex.: BaAl 2 O 4 :Ce 3v , Eu 2 ' of commercial source
- CNTs carbon nanotubes
- AlO aluminate nanotubes
- aluminate nanotubes of alkaline-earth-metals ex. MgAl 2 O 4 , SrAl 2 O 4 and BaAl 2 O 4
- said nanotubes are different from those in the present invention because they are not doped with rare-earths metals while the present invention describe beryllium, magnesium, calcium, strontium or barium aluminate nanotubes ever doped with rare-earths metals, which are characterized by comprising the photoluminescence property in the (near) infrared an (visible) ultraviolet regions with typical light emission derived from the doping of Lanthanide Series of Elements.
- the nanotubes of the present invention being obtained by a synthesis process that comprises the post-annealing of precursor micro- and nano-particles that might be previously synthesized by different ways, such as solid-state reactions or sol-gel method,
- Ln 2 O 3 Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm and Lu
- rare-earth ions with the same valence and a ionic radius comparable to Sr 2+ (1.21 A), such as Eu 2 ' (1.20 A) [3], Dy 31 (1.17 A), and other lanthanide-doped (ex. Ce, Tm, Pr and Nd) can substitute sites with minor local distortion of the crystal lattice, and actuate as luminescent centres.
- the state-of-the-art relates many ways of synthesis of luminescent strontium aluminate oxide doped with rare-earth metals [Sr( 1 - X - Y )Al 2 O 11 : Eu x Ln y ] , experimented to obtain this material with the persistent luminescence property (ex.
- the present invention provides the development of new luminescent beryllium, magnesium, calcium, strontium or barium aluminate nanotubes doped with rare-earth ions from the Lanthanide Series of Elements (Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm and Lu) .
- the luminescent strontium, barium and calcium aluminate nanotubes are always doped with cerium (III) .
- luminescent is applied to said nanotubes to attribute their “luminescence property", that is defined as the photon emission after energy absorption, including all luminescence classifications, in function of the excitation source, such as cathode-, sono-, thermo-, or photo-luminescence .
- the nanotubes of the present invention might be called photoluminescent because they present the photoluminescence property, i.e., the nanotubes present photon emission after excitation and energy absorption from an electromagnetic radiation, without restrictions about the generality of their others optical luminescence features.
- the nanotubes of the present invention are obtained by a new process of synthesis consisting in a thermal treatment of post-annealing (beryllium recrystaliization) of precursor micro- and nano-particles under a temperature range of 573 Kelvin, or more, for a minimum time of 30 minutes.
- the said process comprises the post-annealing of precursor micro- and nano-particles with general composition expressed by the chemical formula Mji- X . ⁇ N-O 4 ICe x , Ln y , where M is an alkaline-earth-metal cation from the HA Family of the Periodic Table of Elements comprising Be, Mg, Ca, Sr, Ba, or a mixture thereof, N is Al, which particles are doped by a combination of elements from the Lanthanide Series that act as (co) activators of luminescent centres, where 0 ⁇ x ⁇ l and O ⁇ y ⁇ l.
- the said process of synthesis of luminescent beryllium, magnesium, calcium, strontium or barium aluminate nanotubes includes the utilization of any composition of micro- and nano-particles satisfying its generic formula.
- the present invention comprises the utilization of precursor particles from commercial sources, such as:
- MgAl 2 O 4 Pr J % MgAl 2 O 4 : Pr 3 % Eu 2* or MgAl 2 O ⁇ Pr 1+ , Eu + ,
- the precursor (micro and nano) particles might be synthesized by different ways, satisfying the generic formula, for later be processed in furnaces (oven with laboratorial or industrial operation) , under a thermal treatment of post-annealing (recrystallization) monitored under a temperature range of 573 Kelvin, or more, to obtain the said nanotubes, in large-scale, with repetitive and economically viable production.
- the present invention might be incorporated in the preparation of new nanomaterials and derivative products, nano-functionalized, in massive or surface-shaped, accepting a mechanical deposition or pressing treatments.
- the luminescent beryllium, magnesium, calcium, strontium or barium aluminate nanotubes doped with rare-earth ions from the Lanthanide Series of Elements might be useful for several applications in nanotechnology, namely m optical devices, such biomarkers and sensors.
- FIG 1 is a micrograph obtained by transmission electron microscopy (TEM) of a precursor
- a laboratorial metallic mould that may be optionally used for mechanical deposition and pressing of precursor micro- and nano-particles in pellet-shaped during synthesis process of luminescent nanotubes.
- TEM transmission electron microscopy
- TEM transmission electron microscopy
- SAED select area electron diffraction
- EDX energy-dispersive X-ray spectroscopy
- FIG 11 is a micrograph obtained by high-resolution transmission electron microscopy (HR-TEM) of a concentrated region with luminescent nanotubes SrAl 2 O 4 :Ce 3+ , Eu 2 ', Dy Jt obtained by the thermal treatment of post-annealing at 1273 K.
- HR-TEM high-resolution transmission electron microscopy
- FIG 12 presents comparative excitation spectra by steady- state photoluminescence spectroscopy of SrAl 2 O 4 : Ce 3+ , Eu 2 ', Dy 3+ nanotubes: (a) precursor micro- and nano- particles, monitored at 525 nm; (b) and (c) nanotubes obtained at 1273 and 1473 K, respectively, and monitored at 495 nm; (d) and (e) nanotubes obtained onto a ceramic template at 1273 and 1473 K, respectively, and monitored at 495 nm, presenting the 2 F$ /? -* 2 F 7/2 transition of cerium (III) doped.
- FIG 13 presents comparative emission spectra by steady- state photoluminescence spectroscopy of SrAl 7 O 4 : Ce 3+ , Eu 2f , Dy 3+ nanotubes: (a) precursor micro- and nano- particles, excited at 360 ran; (b) and (c) nanotubes obtained at 1273 and 1473 K, respectively, excited at 390 nm; (d) and ⁇ e) nanotubes obtained onto a ceramic template at 1273 and 1473 K, respectively, excited at 390 nm.
- the luminescent nanotubes objects of the present invention might be prepared from typical luminophor materials, popularly known as phosphors, of commercial source, said particles of beryllium, magnesium, calcium, strontium or barium aluminates doped with rare-earths.
- the photoluminescent nanotubes of the present invention are prepared using precursor micro- and nano- particles of these aluminates always doped with ions from the Lanthanide Series (ex.: SrAl 2 O ⁇ Ce 3+ , Eu ⁇ + , Dy 3+ ) , which particles are post-annealed to obtain the exclusive luminescent nanotubes.
- Lanthanide Series ex.: SrAl 2 O ⁇ Ce 3+ , Eu ⁇ + , Dy 3+
- M ( I - X - Y jN 2 O 4 :Ce x , Ln y , where 0 ⁇ x ⁇ l and O ⁇ y ⁇ l, M consists in Be, Mg, Ca, Sr or Ba, or mixture thereof, N is Al, such as: a) Solid state reactions; b) Sol-gel method (i.e. "Pequini method”); c) Combustion method (ex.: mixture of metallic nitrates with combustive agent) .
- the invention demonstrates one of many possible ways of the synthesis of precursor particles, namely by solid state reaction (Eqs. 1 and 2), considering that there are no restrictions related to the other synthesis ways that may be selected to obtain the said particles in this synthesis process of luminescent nanotubes:
- the invention admits a large particle size distribution ⁇ diameter) between 60 e 150 ⁇ m, from the example of measurements executed with microparticles of SrAi 2 O 4 :Ce J* , Eu 2+ , Dy 3+ (equipment: Coulter, LS Fraunhofer PIDS) .
- the said precursor SrAl 2 O 4 : Ce 34 , Eu 2+ , Dy 34 (micro and nano) particles might be employed from commercial source, with monoclinic structure ( ⁇ -phase) , for example, presenting cathode-, piezo-, thermo-, sono- and photo-luminescence [8,9,10] .
- Table 1 presents the typical chemical composition of: (a) precursor micro- and nano-particles of Eu 24
- K is the number of moles of "e ⁇ " transferred per mole of oxidant or reductant in the balanced half-reaction, and the number of valence state to spin changing.
- micro- and nano-particles present crystallographic linear defects in the host lattice, with isotropic or anisotropic distribution (FIG 1 and FIG 2) .
- One-dimension (ID) linear defects are predecessor of the formation of SrAl 2 O 4 nanotubes, as suggested by Ye et al.
- precursor micro- and nano-particles of this synthesis process are characterized in:
- An optional step to obtain the mentioned nanotubes in planar templates (substrates), compacted, is provided by pressing the precursor micro- and nano-particles in pellets, using mould (FIG. 3), accepting many shapes and layers, that might be prepared with distinct compositions.
- the process presents the characteristics of low cost and easy reproducibility, providing new luminescent nanotubes M ⁇ i- x -y)N ? ⁇ 4 :Ce x , Ln y applications.
- a preparation of aluminosilicate comprising 65%SiO 2 -21%Al 2 O 3 -14% alkali-oxides (particle diameter between 5 and 30 ⁇ m) can be used as a ceramic template of thin layer of SrAIgO,?: Ce 3+ , Ex/ ⁇ Dy 3 " precursor micro- and nano-particles by mechanical deposition, pressing and respective nanotube overgrowth system.
- the pressed samples can be prepared in mono-, double- or multi-layered systems, depending of the final aimed properties such as, (i.e. and, respectively) synthesized nanoparticles (powders) onto the template.
- laboratorial samples were prepared using 0.10 g of precursor micro- and nano-particles and 0.25 g of ceramic oxides by mechanical deposition and dry- pressing into pellets (Equipment: U.S. Craver Laboratorial Press, ⁇ 490 MPa) .
- the thermal treatment of post-annealing of the precursor micro- and nano-particles is inherent to this synthesis process of luminescent nanotubes, and is recommended the use of furnaces with a maximum temperature of about 2000 K, being of laboratorial or industrial operation.
- the post-annealing (recrystallization) of precursor micro- and nano-particles must be executed in temperature range from 573 to 2000 Kelvin, in controlled atmosphere, for a minimum time of 30 minutes.
- the post- annealing might be executed during a time period over 30 minutes, preferentially more than 1 hour.
- optical features of nanotubes may be controlled according to the post-annealing executed in air (oxidative), inert or reductive (non-oxidative) atmosphere.
- the thermal treatment of recrystallization must be preferentially monitored over and above the temperature of crystalline host lattice phase transformation for a better control of the final properties.
- the precursor micro- and nano- particles of SrAl 2 O 4 ICe 3 ', Eu 2t , Dy 3+ present phase transformation from monoclinic to hexagonal when post-annealed over a temperature range of about -923 Kelvin and this transition can be verified by X-ray diffraction analysis (FIG 4) .
- the first luminescent strontium aluminate nanotubes doped with cerium (III) were synthesized at Ceramic and Glass Engineering Department, and the synthesis process of these nanotubes involved the post-annealing of precursor micro- and nano-particles synthesized by solid state reaction, as claimed by this invention.
- the synthesis process of luminescent beryllium, magnesium, calcium, strontium and barium is realized with the said aluminates always doped with cerium (III), accepting the co-doping with other lanthanide ions.
- nanotubes represents an important improvement in the field of luminescent materials at nanoscale (less than 100 nm) because the same can be obtained by a synthesis process, in large scale, that comprises a solid state reaction of micro- and nano- particles (ex. with monoclinic structure) and post- annealing, under a temperature range over about 573 Kelvin.
- these nanotubes may be obtained in diverse templates, by mechanical deposition, pressing and post- annealing, employing laboratorial or industrial techniques that result in this extraordinary nanostructure .
- the luminescent beryllium, magnesium, calcium, strontium and barium alurainate nanotubes doped with rare-earths, namely with ions from the Lanthanide Series of Elements, Ln y , are a new shape of these inorganic nanomaterials that present preferential ID growth (nanoscale), with the growth of a longitudinal hole and luminescence property.
- This new morphology may be used in several applications with light emission after finish the atomic excitation, with short or long afterglow lifetime.
- the final properties of luminescence might be influenced by the synthesis process, and some photoluminescence measurements are described in the topic 5.
- the new luminescent aluminate nanotubes doped, with rare- earth ions from the Lanthanide Series of Elements are characterized in having a preferential one-dimensional (ID) growth, in one direction, from a curving and seaming process of a surface (tubular geometry) and in comprising a dimension from about 1 ran to less than about 10 microns.
- ID one-dimensional
- these nanotubes are characterized in comprising a dimension from about 1 nm to less than about 150 nm.
- the SrAIj-O 4 : Ce 3 ', Eu 2+ , Dy 3+ nanotubes are characterized in presenting photoluminescence and nanoporous (FIG. 5) .
- these nanotubes overcome extraordinarily the state-of-the-art because they were obtained by the recrystallization of precursor micro- and nano-particles synthesized by solid state reaction.
- the optical properties of the luminescent nanotubes are influenced by their process of synthesis, which the main factors are correlated:
- the atomic photoconductivity of these luminescent nanomaterials can be characterized in function of post- annealing temperature, were the formation of nanotubes process may produces changes on the charging process during the energy transfer among the luminescent centres Ce 3 % Eu ?+ and Dy 3 ' ions from the Lanthanide Series in their electronic states.
- the luminescent nanotubes SrAl 2 O 4 ICe" 3" / Eu 2+ , Dy 3+ were characterized by photolurainescence spectroscopy, where the measurements obtained at room temperature ( ⁇ 300 K) are used to compare the temperature dependence of recrystallization of the precursor micro- and nano-particles with the optical properties of nanotubes obtained by post-annealing temperatures of 1273 and 1473 Kelvin.
- the photoluminescence excitation spectra of SrAl 2 O 4 :Ce 3+ , Eu 2 ', Dy iA nanotubes are obtained with typical transitions of the Ce 3f cation intra-4f 1 , [4f !* ⁇ Sd"], when monitored with emission peak at 495 ran and at 525 nut (FIG. 12) .
- the said luminescent nanotubes were characterized by visible ultraviolet, and they also have electromagnetic emissions in the ultraviolet and infrared regions.
- the photolum ⁇ nescence emission is certainly different between the precursor micro- and nano-particles (curve a) and their nanotubes obtained (curves b-d) , as shown in FIG 13.
- the photoluminescence emission spectra reveal:
- Precursor micro- and nano-particles large band between 450 and 650 run, with peak at 525 run;
- Nanotubes doped with Ce 3 * luminescence emission band in the region between 380 and 450 nm in the visible ultraviolet, characterized by a series of electronic transitions typical of the Ce 31 cation intra-4f 1 e
- Example 2 Process of synthesis of luminescent beryllium aluminate nanotubes doped with cerium, europium and terbium (BeAl 2 O 4 :Ce 3+ , Eu 2+ , Tb 3+ ), comprising the following steps:
- Photoluminescent strontium aluminate nanotubes doped with cerium (III) are characterized by an exclusive energy transfer and electronic configurations from Ce 3+ cation.
- Example 1 Process of synthesis of luminescent strontium aluminate nanotubes doped with cerium, europium and dysprosium (SrAl 2 O ⁇ Ce " ' * , Eu 2t , Dy 3+ ), comprising the following steps: powder mixture in a specific atmosphere ⁇ reductive of 12% N ? + H 2 ), in a temperature range between 1573 and 1773 Kelvin, for 4 hours;
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Abstract
Cette invention concerne des nanotubes luminescents à base d'aluminate dopés avec des terres rares, c'est-à-dire provenant de la série des lanthanides (Ln est La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm et Lu), dont la formule s'avère être M(1-x-y) N2O4:Cex, Lny. Dans la formule, M comprend un cation de métal alcalino-terreux constitué par Be, Mg, Ca, Sr, Ba ou des mélanges de ceux-ci, et N est Al. Lesdits nanotubes luminescents acceptent également le co-dopage avec une combinaison de (co)-activateurs de luminescence du type ions de lanthanides, où Q <x ≤ 1 et 0 ≤ y ≤ 1. Ces nanotubes sont obtenus par un procédé de synthèse consistant en un traitement thermique de post-recuit de micro- et de nanoparticules précurseurs à une température de l'ordre d'environ 573 degrés Kelvin, ou plus, pendant un temps minimum de 30 minutes, pour obtenir des émissions dans les domaines du (proche) infrarouge et de l'ultraviolet (visible), lesdits nanotubes trouvant de larges applications dans des dispositifs optiques, du type biomarqueurs et capteurs.
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Cited By (2)
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WO2016200349A1 (fr) * | 2015-06-10 | 2016-12-15 | Fosfortek Fosfor Teknolojileri Sanayi Ve Ticaret Limited Sirketi | Pigments phosphorescents vert jaunâtre de longue durée dans le système des aluminates de strontium [sral2o4] |
CN110075767A (zh) * | 2019-04-18 | 2019-08-02 | 天津大学 | 长余辉水凝胶及制备方法 |
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CN110075767A (zh) * | 2019-04-18 | 2019-08-02 | 天津大学 | 长余辉水凝胶及制备方法 |
CN110075767B (zh) * | 2019-04-18 | 2021-08-27 | 天津大学 | 长余辉水凝胶及制备方法 |
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