WO2008141793A1 - Procédé de production de nanoparticules de type grenat yttrium-aluminium dopées - Google Patents

Procédé de production de nanoparticules de type grenat yttrium-aluminium dopées Download PDF

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Publication number
WO2008141793A1
WO2008141793A1 PCT/EP2008/004012 EP2008004012W WO2008141793A1 WO 2008141793 A1 WO2008141793 A1 WO 2008141793A1 EP 2008004012 W EP2008004012 W EP 2008004012W WO 2008141793 A1 WO2008141793 A1 WO 2008141793A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
deagglomeration
salt
yttrium
doping metal
Prior art date
Application number
PCT/EP2008/004012
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German (de)
English (en)
Inventor
Norbert Roesch
Original Assignee
Clariant Finance (Bvi) Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant Finance (Bvi) Limited filed Critical Clariant Finance (Bvi) Limited
Publication of WO2008141793A1 publication Critical patent/WO2008141793A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to the preparation of doped and fluorescent YAG nanoparticles (yttrium aluminum garnet).
  • YAG is an interesting ceramic material characterized by high hardness and thermal conductivity.
  • the crystalline matrix can be used to pick up dopants that emit fluorescent light when excited.
  • dopants cerium, terbium, europium, cobalt or samarium are described.
  • cerium-doped YAG with a blue fluorescent pigment, it is possible to construct white light-emitting diodes (US 2005/0 136 782; DE 103 16 769).
  • doped YAG material from the respective oxides (KR 2001 0049014) or carbonates is made with admixed dopants by milled dry the starting materials with each other and sintered at 1500 0 C. Disadvantage of this method is the long sintering time (days) and the low fluorescence yield due to the insufficient mixing.
  • the sol-gel method is also based on the metal salts and citric acid. Also in this process, the resulting dried gel (40 0 C for 24 h) must be calcined at 800 - 1000 0 C for 16 h. In the methods described so far, the powder is due to the high calcination temperatures and long residence times in strongly agglomerated form and consisting of large primary particles.
  • the desired molecules are obtained from chemical reactions of a Precursorgases or by rapid cooling of a supersaturated gas.
  • the formation of the particles occurs either through collision or the constant equilibrium evaporation and condensation of molecular clusters.
  • the newly formed particles grow by further collision with product molecules (condensation) and / or particles (coagulation). However, if the coagulation rate is greater than that of the new growth or growth, agglomerates of spherical primary particles are formed.
  • Nanoparticles are formed here by the decomposition of Precursormolekülen in the flame at 1500 - 2500 0 C.
  • Flame reactors are now used industrially for the synthesis of submicroparticles such as carbon black, pigment TiO 2) silica and alumina. Although the resulting powders contain small primary particles due to the low residence time, due to the high temperatures in the flame, very hard agglomerates form.
  • a nanostructured YAG powder can be obtained at 500 ° C., a pressure of 100 Mpa, within 20 hours (T. Takamori, LD David, Am. Ceram. Soc., Bull., 65 (9), 1986). Disadvantage of this method are again the long reaction time and the high expenditure on equipment.
  • the aim of the present invention is to produce fluorescent YAG nanoparticles using a cost-effective method.
  • the invention relates to a method for producing doped
  • Yttrium aluminum garnet nanoparticles which consists in drying an aqueous solution containing aluminum chlorohydrate, an yttrium salt and a doping metal salt, calcining the resulting salt mixture and deagglomerating.
  • the starting point for the process according to the invention is an aqueous solution of aluminum chlorohydrate which has the formula Al 2 (OH) x Cl y, where x is a number from 2.5 to 5.5 and y is a number from 3.5 to 0.5 and the sum of x and y is always 6.
  • an yttrium salt and a doping metal salt are then dissolved.
  • the commercially available salts are suitable, such as, for example, the chloride, nitrate or acetate.
  • Suitable doping salts are the salts of rare earths and salts of transition metals, for example cerium, dysprosium, gadolinium, europium, terbium, praseodymium, neodymium or cobalt salts. These salts can also be used in the form of their chlorides, nitrates or acetates.
  • the amounts of aluminum chlorohydrate, yttrium salt and doping metal salt with the cation M are chosen so that the molar ratio of the sum of the cations of Y and M to Al is about 0.6: 1, corresponding to the sum formal Y3AI5O12.
  • the amount of doping metal salt having the cation M is generally selected so that the amount of cation M is 0.01 to 6, preferably 0.01 to 2 wt .-%, based on the total amount of cation M and yttrium.
  • the resulting powder mixture containing all the salts in homogeneous distribution is calcined, preferably in a rotary kiln or chamber furnace, to convert the metal salts into the granate-type compound oxide.
  • the calcination is carried out at about 800 - 1500 0 C, preferably at 900-1000 0 C.
  • the residence time is less than 30 min, preferably 10 min.
  • Another possibility is to inject the salt solution directly into a calcination apparatus without separate predrying. In this case, the drying and calcining takes place within a process step.
  • a doped YAG powder consisting of agglomerates of nanoparticles is obtained. From these agglomerates, the nanoparticles must be released. This is preferably done by grinding or by treatment with ultrasound. According to the invention, this deagglomeration is carried out in the presence of a solvent and preferably in the presence of a coating agent, preferably a silane or siloxane, which saturates the resulting active and reactive surfaces during the milling process by a chemical reaction or physical addition, thus preventing reagglomeration.
  • a coating agent preferably a silane or siloxane, which saturates the resulting active and reactive surfaces during the milling process by a chemical reaction or physical addition, thus preventing reagglomeration.
  • the nano-mixed oxide remains as a small particle. It is also possible to add the coating agent after deagglomeration.
  • the agglomerates are preferably comminuted by wet grinding in a solvent, for example in an attritor mill, bead mill or stirred mill.
  • a solvent for example in an attritor mill, bead mill or stirred mill.
  • doped YAG nanoparticles which have a crystallite size of less than 1 ⁇ m, preferably less than 0.2 ⁇ m, more preferably between 0.001 and 0.1 ⁇ m.
  • Another possibility of deagglomeration is sonication.
  • deagglomeration can be carried out in the presence of the coating agent, for example by adding the coating agent to the mill during milling.
  • a second possibility consists of first destroying the agglomerates of the nanoparticles and then treating the nanoparticles, preferably in the form of a suspension in a solvent, with the coating agent.
  • Suitable working medium for deagglomeration are both water and customary solvents, preferably those which are also used in the paint industry, such as, for example, C 1 -C 4 -alcohols, in particular methanol, ethanol or isopropanol, acetone, tetrahydrofuran, butyl acetate.
  • an inorganic or organic acid such as HCl, HNO 3 , formic acid or acetic acid should be added to stabilize the resulting nanoparticles in the aqueous suspension.
  • the amount of acid may be 0.1 to 5 wt .-%, based on the garnet.
  • aqueous suspension of the acid-modified nanoparticles is then preferably the grain fraction having a particle diameter of less than 20 nm separated by centrifugation.
  • the coating agent preferably a silane or siloxane
  • the nanoparticles thus treated precipitate are separated and dried to a powder, for example by freeze-drying.
  • Suitable coating agents are preferably silanes or siloxanes or mixtures thereof.
  • suitable coating agents are all substances which can physically bind to the surface of the mixed oxides (adsorption) or which can bond to form a chemical bond on the surface of the garnet particles. Since the surface of the garnet particles is hydrophilic and free hydroxy groups are available, suitable coating agents are alcohols, compounds having amino, hydroxyl, carbonyl, carboxyl or mercapto functions. Examples of such coating compositions are polyvinyl alcohol, mono-, di- and tricarboxylic acids, amino acids, amines, waxes, surfactants, hydroxycarboxylic acids.
  • Suitable silanes or siloxanes are compounds of the formulas
  • n is an integer meaning 1 ⁇ n ⁇ 1000, preferably 1 ⁇ n ⁇ 100
  • m is an integer 0 ⁇ m ⁇ 12
  • p is an integer 0 ⁇ p ⁇ 60
  • q is an integer 0 ⁇ q ⁇ 40
  • r is an integer 2 ⁇ r ⁇ 10 and s is an integer 0 ⁇ s ⁇ 18 and
  • Y is a reactive group, for example ⁇ , ⁇ -ethylenically unsaturated groups, such as (meth) acryloyl, vinyl or allyl groups, amino, amido, ureido,
  • X is a .functional oligomer with t an integer 2 ⁇ t ⁇ 8 and Z in turn a residue
  • the t-functional oligomer X is preferably selected from:
  • radicals of oligoethers are compounds of the type - (C a H 2a -O) b - C a H 2a - or O- (C a H2a-O) b -CaH 2 aO with 2 ⁇ a ⁇ 12 and 1 ⁇ b ⁇ 60, z.
  • Examples of residues of Oligoestem are compounds of the type -C b H 2b - (C (CO) CaH 2a - (CO) OC b H 2 b) c- or -OC b H 2 b- (C (CO) C 3 H 23 - (CO) OC b H 2b -) c -O- where a and b are different or equal to 3 ⁇ a ⁇ 12, 3 ⁇ b ⁇ 12 and 1 ⁇ c ⁇ 30, z.
  • silanes of the type defined above are, for. Hexamethyldisiloxane, octamethyltrisiloxane, other homologous and isomeric compounds of the series Si n O n -I (CH 3 ) 2n + 2 , where n is an integer 2 ⁇ n ⁇ 1000, e.g. Polydimethylsiloxane 200® fluid (20 cSt).
  • Dihydrohexamethytrisiloxane, Dihydrooctamethyltetrasiloxan other homologous and isomeric compounds of the series H - [(Si-O) n (CH 3 ) 2 n] -Si (CH 3 ) 2 -H, where n is an integer 2 ⁇ n ⁇ 1000, are preferred the ⁇ , ⁇ -dihydropolysiloxanes, e.g. B. polydimethylsiloxane (hydride end groups, M n 580).
  • ⁇ -OH groups are also the corresponding difunctional compounds with epoxy, isocyanato, vinyl, AIIyI- and di (meth) acryloyl used, for.
  • R is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R 1 is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R 1 is a cycloalkyl n is an integer from 1 to 20 x + y 3 x 1 or 2 y 1 or 2.
  • Preferred silanes are the silanes listed below: triethoxysilane, octadecyltimethoxysilane,
  • 3-aminopropyltriethoxysilanes 3-aminopropyltrimethoxysilanes, 2-aminoethyl-3-aminopropyltrimethoxysilanes.
  • Triaminofunctional propyltrimethoxysilanes (DYNASYLAN ® triamino Fa. Degussa), N- (n-butyl-3-aminopropyltrimethoxysilane, 3-Aminopropylmethyldiethoxysilane.
  • the coating compositions are preferably added in molar ratios of YAG nanoparticles to silane of from 1: 1 to 10: 1.
  • the amount of solvent in the deagglomeration is generally 20 to 90 wt .-%, based on the total amount of YAG nanoparticles and solvent.
  • the deagglomeration by grinding and simultaneous modification with the coating agent is preferably carried out at temperatures of 20 to 150 0 C, more preferably at 20 to 90 0 C. If the deagglomeration by grinding, the suspension is then separated from the grinding beads.
  • the suspension can be heated to complete the reaction for up to 30 hours. Finally, the solvent is distilled off and the remaining residue is dried. It may also be advantageous to leave the modified YAG nanoparticles in the solvent and to use the dispersion for other applications. It is also possible to suspend the YAG nanoparticles in the corresponding solvents and to carry out the reaction with the coating agent after deagglomeration in a further step.
  • the images of the SEM image taken showed crystallites in the range 10 - 80 nm (estimate from SEM image), which are present as agglomerates.
  • the residual chlorine content was only a few ppm.
  • this doped YAG powder were suspended in 150 g of water.
  • 0.5 g of trimethoxy-octylsilane was added to the suspension and fed to a vertical stirred ball mill from Netzsch (type PE 075).
  • the grinding beads used consisted of zirconium oxide (stabilized with yttrium) and had a size of 0.3 mm. After three hours, the suspension was separated from the milling beads and boiled under reflux for a further 4 h.
  • the suspension of the fluorescent YAG nanoparticles was subsequently optically characterized.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production de nanoparticules de type grenat yttrium-aluminium dopées. Ce procédé est caractérisé en ce qu'on sèche une solution aqueuse renfermant un chlorhydrate d'aluminium, un sel d'yttrium et un sel métallique dopé, et en ce qu'on calcine et désagrège le mélange salin obtenu.
PCT/EP2008/004012 2007-05-24 2008-05-20 Procédé de production de nanoparticules de type grenat yttrium-aluminium dopées WO2008141793A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007024338.5 2007-05-24
DE102007024338A DE102007024338A1 (de) 2007-05-24 2007-05-24 Verfahren zur Herstellung von dotierten Yttriumaluminiumgranat-Nanopartikeln

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WO2008141793A1 true WO2008141793A1 (fr) 2008-11-27

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DE102009012698A1 (de) * 2009-03-11 2010-09-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Partikel mit einer lumineszierenden anorganischen Schale, Verfahren zur Beschichtung von Partikeln sowie deren Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0666239A1 (fr) * 1993-08-11 1995-08-09 Sumitomo Chemical Company, Limited Poudre d'oxyde metallique composite et procede de production
US20040109808A1 (en) * 2003-11-25 2004-06-10 Lee Heedong Yttrium aluminum garnet powders and processing
WO2007009577A1 (fr) * 2005-07-16 2007-01-25 Clariant International Ltd Procede pour realiser un corindon colore de taille nanometrique
US7175778B1 (en) * 2002-05-10 2007-02-13 Nanocrystals Technology Lp Self-aligning QCA based nanomaterials

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
KR100319461B1 (ko) 1999-11-30 2002-01-12 대한민국(관리청:특허청장, 승계청:기술표준원장) 야그 형광체 및 그 제조방법
DE10316769A1 (de) 2003-04-10 2004-10-28 Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH Leuchtstoffbassierte LED und zugehöriger Leuchtstoff
TWI229462B (en) 2003-12-22 2005-03-11 Solidlite Corp Improved method of white light LED
TWI265916B (en) 2004-12-31 2006-11-11 Ind Tech Res Inst Process of making YAG fluorescence powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0666239A1 (fr) * 1993-08-11 1995-08-09 Sumitomo Chemical Company, Limited Poudre d'oxyde metallique composite et procede de production
US7175778B1 (en) * 2002-05-10 2007-02-13 Nanocrystals Technology Lp Self-aligning QCA based nanomaterials
US20040109808A1 (en) * 2003-11-25 2004-06-10 Lee Heedong Yttrium aluminum garnet powders and processing
WO2007009577A1 (fr) * 2005-07-16 2007-01-25 Clariant International Ltd Procede pour realiser un corindon colore de taille nanometrique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SU, L. T.; TOK, A. I. Y.; BOEY, F. Y. C.; WOODHEAD, J. L.: "Chemical gelation of cerium (III)-doped yttrium aluminium oxide spherical particles", JOURNAL OF MATERIALS RESEARCH, vol. 21, no. 10, October 2006 (2006-10-01), pages 2510 - 2515, XP002494832 *

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