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WO2016200350A1 - Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4] - Google Patents

Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4] Download PDF

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Publication number
WO2016200350A1
WO2016200350A1 PCT/TR2015/050006 TR2015050006W WO2016200350A1 WO 2016200350 A1 WO2016200350 A1 WO 2016200350A1 TR 2015050006 W TR2015050006 W TR 2015050006W WO 2016200350 A1 WO2016200350 A1 WO 2016200350A1
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WO
WIPO (PCT)
Prior art keywords
violet
long
magenta
proper
mentioned
Prior art date
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Ceased
Application number
PCT/TR2015/050006
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English (en)
Inventor
Bekir KARASU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FOSFORTEK FOSFOR TEKNOLOJILERI SANAYI VE TICARET Ltd SIRKETI
Original Assignee
FOSFORTEK FOSFOR TEKNOLOJILERI SANAYI VE TICARET Ltd SIRKETI
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 FOSFORTEK FOSFOR TEKNOLOJILERI SANAYI VE TICARET Ltd SIRKETI filed Critical FOSFORTEK FOSFOR TEKNOLOJILERI SANAYI VE TICARET Ltd SIRKETI
Priority to PCT/TR2015/050006 priority Critical patent/WO2016200350A1/fr
Publication of WO2016200350A1 publication Critical patent/WO2016200350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K11/7783—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

Definitions

  • This invention is about pigments with phosphorescence specification, having long term luminescence of violet ( magenta) / violet-blue colour in the dark and wide usage areas reguiring optimum specifications in the product obtained
  • Phosphorescence is an event of a insulator to diffuse at room temperature even after exciting (generally UV ray) is suspended. This is a process occuring during trapping or distortion of trapping in specific defected areas of the charge carriers (e - or gaps) formed with this detained light exciting. Phosphorescence event besides luminescence center requires the presence of discrete layers in forbidden bandgap related with chemical and physical defects (contributions and gaps) in the main lattice. Some electrons and gaps occur with excitation are entrapped at these kind of layers. According to these defects and dimensional separation between luminescence centers or more precisely direct re-combination has low possibility in the lack of orbital overlaps. As a result, the trapped charge carriers stay at metastable state unless there is not enough energy to trigger of reunification
  • Phosphorescent pigments absorb a certain wavelength of light and radiate it to surrounding when light source is removed.
  • the long-lasting violet (magenta)/ violet-blue phosphorescent pigments in the dark are generally used in surface coating, mixed with glass, metal, ceramic, resin, polymer, plastic etc. or appropriate additional methods. They have wide usage areas.
  • microtubes consisting of a very little amount of gas tritium in glass. Inner wall of microtube was coated with ZnS which diffuses green light, doped and undoped. The tritium amount used was as little as it can be neglected and radioactive beta particles were not able to go out from the glass they locked in.
  • CaAl 2 O 4: Eu 2+, Nd 3+ phosphors are evaluated in watches, outdoor and dark ambient lighting with their violet/blue emission in the dark.
  • Earth alkali aluminate systems activated with rare earth elements are long-lasting phosphorescent pigment systems. The most important property of them are strong light absorbtion, storage and emmission thanks to their crystal structure, long-afterglow property with high brightness, eventually. According to the light source (generally room light) they show emission for more than 12 hours after the light source is removed. Their brightness and decay times are ten times more than those of well known zinc sulphate phosphors. Earth alkali aluminate systems do not show any harmfull effects to the health not containing radioactive contribution. Apart from this, they are stable and resistant to atmospheric effects unlike zinc sulphate system. Light absorbtion and emission go on continuously.
  • the violet (magenta) / violet-blue colour emitting phosphorescent pigments of calcium aluminates being most common and accomplished in the earth alkali aluminate systems were developed under the lights of previous studies reported in the literature.
  • M Calcium (Ca) element R: Europium (Eu) as emission center, Dysprosium (Dy), Yttrium (Y) or Neodymium (Nd) Yttrium (Y), Praseodymium (Pr), Ytterbium (Yb), Erbium (Er), Gadolinium (Gd), Cerium (Ce), Samarium (Sm), Hafnium (Hf), Thulium (Tm) occur as co-dopant in the structure.
  • the molar ranges of rare earth elements Eux, Dyy, Ndz, Yt, Prk, Ybl, Erm, Gdr, Cea, Smb, Hfc, Tmd which can be added to Sr4Al14O25 , the main phase are as follows:
  • CaAl 2 O 4 Eu x , Dy y , Nd z , Y t , Pr k , Yb l , Er m , Gd r , Ce a , Sm b , Ho c , Tm d 0.0001 ⁇ x, y, z, t, k, l, m, r, a, b, c, d ⁇ 0.5
  • These pigments are able to give diffusion (emission) peak values in the range of 430-460 nm wavelength according to spectrophotometer analysis.
  • the phosphorescent pigments with long lasting violet (magenta) / violet-blue emission have been characterized by synthesizing via solid-state reaction method under reductive nitrogen (N 2 )-hydrogen (H 2 ) gas atmosphere.
  • the synthesizing method and its specification consists of the relevant steps as follows: - Nitrogen (N 2 ) – hydrogen (H 2 ) 90-98.5 % N 2 is mentioned gas atmosphere and 1.5-10 % H 2 is used. - Appropriate raw materials are chosen for solid –state reaction method of the phosphorescence pigment (in oxide, carbonate, hydroxide etc. forms). The determined raw materials are selected with the proper purities ( >99.5 %) - To get long-afterglow phosphorescent pigment by the synthesizing method mentioned wet milling is applied for appropriate time by planetary mill (30 minutes-6 hours).
  • Pigments with phosphorescence ability are used in plating on many product surfaces and can also be mixed with plastic, elastic, polyvinyl chloride (PVC), other synthetic resins and glass.
  • PVC polyvinyl chloride
  • Ceramic glazes doped with phosphorescence pigments have potential usage in apartments, especially with basement ceramic production used in area where the wall and ground intersect. It can be a practical solution in the case of sudden electric cut, afterwards in emergency when the phosphorescent signs are placed beside stairs. Ceramic and glass products with phosphorescence pigment can be used as decor. As a border, glow stone, overlays in kitchen, bathroom or pool, ceramics with phosphorescent pigments containing glazes also provide visual richness which could be of ceramic artists interest.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium (CaAl2O4). L'invention concerne des pigments phosphorescents ayant une luminescence de longue durée de couleur violet (magenta)/bleu violacé dans l'obscurité et offrant de vastes domaines d'utilisation requérant des spécifications optimales dans le produit obtenu.
PCT/TR2015/050006 2015-06-10 2015-06-10 Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4] Ceased WO2016200350A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/TR2015/050006 WO2016200350A1 (fr) 2015-06-10 2015-06-10 Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4]

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2015/050006 WO2016200350A1 (fr) 2015-06-10 2015-06-10 Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4]

Publications (1)

Publication Number Publication Date
WO2016200350A1 true WO2016200350A1 (fr) 2016-12-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2015/050006 Ceased WO2016200350A1 (fr) 2015-06-10 2015-06-10 Pigments phosphorescents violet (magenta)/bleu violacé de longue durée dans le système des aluminates de calcium [caal2o4]

Country Status (1)

Country Link
WO (1) WO2016200350A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8298441B1 (en) * 2007-05-22 2012-10-30 The Sherwin-Williams Company Method for incorporating water soluble, reactive, phosphorescent pigments into a stable waterborne coating through pH buffering

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8298441B1 (en) * 2007-05-22 2012-10-30 The Sherwin-Williams Company Method for incorporating water soluble, reactive, phosphorescent pigments into a stable waterborne coating through pH buffering

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
HOLSA J ET AL: "Persistent luminescence of Eu<2+> doped alkaline earth aluminates, MAl2O4:Eu<2+>", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 323-324, 12 July 2001 (2001-07-12), pages 326 - 330, XP027389893, ISSN: 0925-8388, [retrieved on 20010712] *
HOLSA J ET AL: "Role of defect states in persistent luminescence materials", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 374, no. 1-2, 14 July 2004 (2004-07-14), pages 56 - 59, XP004514895, ISSN: 0925-8388, DOI: 10.1016/J.JALLCOM.2003.11.064 *
QIU ET AL: "Combustion synthesis of long-persistent luminescent MAl2O4: Eu<2+>, R<3+> (M=Sr, Ba, Ca, R=Dy, Nd and La) nanoparticles and luminescence mechanism research", ACTA MATERIALIA, ELSEVIER, OXFORD, GB, vol. 55, no. 8, 6 April 2007 (2007-04-06), pages 2615 - 2620, XP022023964, ISSN: 1359-6454, DOI: 10.1016/J.ACTAMAT.2006.12.018 *
WEI XIE ET AL: "The long Afterglow and Thermoluminescence Properties of MAl<sub>2</sub>O<sub>4</sub> Eu<sup>2+</sup>, Dy<sup>3+</sup>(M=Ca, Sr and Ba) Phosphors Syntheized by Combustion Technique", ADVANCED MATERIALS RESEARCH, vol. 197-198, 1 February 2011 (2011-02-01), pages 318 - 322, XP055224621, DOI: 10.4028/www.scientific.net/AMR.197-198.318 *
XUHUI XU ET AL: "CaAl2O4:Eu2+,Nd3+,Sr2+: A White-Light Phosphor with Yellow-Green Long Afterglow", ELECTROCHEMICAL AND SOLID-STATE LETTERS., vol. 12, no. 4, 1 January 2009 (2009-01-01), US, pages J44, XP055224633, ISSN: 1099-0062, DOI: 10.1149/1.3075902 *

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