CN1008110B - Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores - Google Patents

Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores

Info

Publication number
CN1008110B
CN1008110B CN86104658.7A CN86104658A CN1008110B CN 1008110 B CN1008110 B CN 1008110B CN 86104658 A CN86104658 A CN 86104658A CN 1008110 B CN1008110 B CN 1008110B
Authority
CN
China
Prior art keywords
terbium
yttrium
mixture
fusing assistant
sio
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.)
Expired
Application number
CN86104658.7A
Other languages
Chinese (zh)
Other versions
CN86104658A (en
Inventor
埃莫克·阿巴萨里
拉茨洛·巴拉斯
弗伦克尼·克希科尔
恩德里尼·科罗斯
加伯尔·萨约
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.)
Tungsram Rt
Original Assignee
Tungsram Rt
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 Tungsram Rt filed Critical Tungsram Rt
Publication of CN86104658A publication Critical patent/CN86104658A/en
Publication of CN1008110B publication Critical patent/CN1008110B/en
Expired legal-status Critical Current

Links

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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77742—Silicates

Landscapes

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

Abstract

Proper quantity of yttrium compound, silicon dioxide and terbia are mixed and added with a fluxing agent, and then the mixture and the fluxing agent are homogenized, the homogenized mixture is annealed for 1 to 3 hours under a temperature of 1000 to 1400 DEG C, and then the annealed material is smashed. The key point of the method is that a fluorine compound is added according to the standard of 0.01 to 0.07 mol F / mol SiO-(2) to act as a fluxing agent and then an annealing in a neutral protective air containing 20 ppm water vapor and 100 ppm oxygen at most is conducted. The method can produce green luminescent material with high efficiency and fewer steps compared with previous technique.

Description

Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores
The invention relates to the production method of terbium activatory yttrium silicate fluorescent material, particularly green luminophores.The known steps that this area produces luminescent material has: by the selected a kind of yttrium compound of suitable proportion, silicon-dioxide and terbium sesquioxide, each selected compound, add fusing assistant, mixture and fusing assistant homogenizing, with homogenizing mixture anneal 1 to 3 hour in 1000 ℃ to 1400 ℃ temperature ranges, the material that will anneal is then pulverized.
Several years ago doing many effort aspect the development new type light source, producing meticulously by three kinds of twinkler compositions and mixed three bands of a spectrum luminescent lamps that constitute and the so-called pocket structure luminescent lamp that constitutes by two kinds of twinkler constituents mixts.In described these products, be included in and be subjected to the twinkler that the exciting radiation induction can produce visible light down.Add the visible light that a kind of green composition can produce required spectrum composition in the light-emitting admixture, this green composition should produce wavelength at 540 light in the 560nm scope, and guarantees to have high efficiency of conversion.This type of twinkler is usually used among the low-pressure gaseous discharge lamp system of highly stable efficient of requirement and very high colour-stable performance.
In order to find best solution, the many possible prescription of green glow composition many researchs have been done.Recently, have that many to have obtained various ways patent and that apply for a patent all known, wherein proposed to come the various crystalline structure of activatory with different ions.Crystalline structure comprises aluminate, borate, phosphoric acid salt and silicates.
A kind of possible green composition be T.E.Peters at US-PS3,758,413(1973 licensed to his September 11) the terbium activatory yttrium silicate of proposition.The formula of the twinkler component in the patent specification is
（Y 2O 3）y·（SiO 2）x∶Tb
Wherein ratio x/y is 1 to 3 scope, and the concentration of terbium is: an atom Tb is to 1 to 15 yttrium atom.
The production method of the luminophore that Peters proposes is: the nitrate of yttrium oxide or yttrium and silicon-dioxide, terbium sesquioxide mixes mutually with a kind of suitable fusing assistant, and fusing assistant is to carry out easily with the diffusion process between the solid-state composition that exists in order to make when the high-temperature fusion attitude.The example of fusing assistant has: yttrium fluoride (YF 3) or Neutral ammonium fluoride (NH 4And be every mole SiO F), 2With 0.4 to 1.2 mole fusing assistant, then mixture is annealed under 1300 ℃ of temperature.This patent does not disclose any more parameters such as composition of relevant annealed time or protective atmosphere.
M. water that primary (transferee are Tokyo Shibaura Elecfric Co.) such as (M.Watanabe) discloses another and has produced the usability methods of green shiner.License to his US Letters Patent No4 on June 17th, 1980,208,611(United States Patent (USP) certificate number) in to disclose one be the luminophore of feature with the following formula
Ln2（1-x-y）O 3·z Si O 2∶Ce2x Tb2y
Wherein Ln is the Y from group of the lanthanides, L, and Ga, a kind of lanthanon of selecting among the Lu, and each numerical value is:
X=1 * 10 -3To 3 * 10 -1Grammeatom/grammeatom total rare earth (TRE) metal
Y=3 * 10 -2To 3 * 10 -1Grammeatom, to the total rare earth (TRE) metal of every grammeatom, and
Z=0.8 to 2.2 mole, to every mole rare-earth oxide.
Proposed to use KF, YF 3, Gd F 3, Li Br, Li Cl, Li F, Zn F 2, Al F 3, Mg F 2, Ba F 2With La F 3As fusing assistant, and when annealing use in 1000 to 1350 ℃ of temperature ranges by H 2Or H 2And N 2Restitutive protection's atmosphere of forming.
The feature of above-mentioned luminophore is complicated prescription.Similar MacAlister in addition, the U.S.Letters Patent No3 that (Mc Allister W.A.) (transferee is Westinghouse Electric Co.) authorized on August 4th, 1970,523,091(United States Patent (USP) certificate number) disclosed, or disclosed silicate-base luminophore that can green light under suitable exciting among the Japanese Patent No56-5883 of the Japanese patent application No54-82493 that submits to based on Dainippon Tokyo K.K..
The material of having annealed be by fusing assistant gluing granulometric composition.Here it is why pulverization process itself can not be enough to the reason of the luminescent material that obtains conforming to quality requirements.Pulverizing the granularity that reaches like this is obsolete when producing light source, therefore need reduce granularity to the too thick particle of great majority.This can finish with grinding, and still, the green luminophore of known various luminophores, especially the above-mentioned type is highstrung for the intensive mechanical treatment.Owing to improving the grinding that granularity carries out and to belong to a kind of intensive mechanical treatment, can a large amount of losses induce light intensity and efficient under the induction after handled by intense mechanical in order to reduce big particle.This loss can be up to 20%.But the luminophore of the mechanical treatment of process reduction granularity can not be used for luminescent lamp, and this is because its adhesion property to glass is very poor.
The present invention is based on such understanding, the consumption that is exactly fusing assistant is a factor that influences granularity, and the fusing assistant of low consumption does not disturb the annealed physical process in a unexpected method, still obtained the composition of necessity of luminophore, and, the material that obtains under this condition is doing promptly to can be applicable to luminescent lamp after simple the pulverizing, does not need it is carried out handling for the grinding and other the intense mechanical that reduce granularity.
The objective of the invention is to develop a kind of method, only do not need with annealing to grind in view of the above to produce terbium activatory yttrium silicate fluorescent material, particularly green luminophore.In other words, the purpose of this invention is to provide a kind of like this method, can use in view of the above than before processing method technological step industrialization ground still less and produce described luminescent material.
According to method provided by the invention, terbium activatory yttrium silicate luminophore be with yttrium silicate be the base, if necessary,, can use the lanthanum silicate yttrium, gadolinium siliate lanthanum or their any combination by different modes for the composition of transmitting green light.The step that comprises in institute's extracting method is with suitable yttrium compound, and silicon-dioxide and terbium sesquioxide are that base is made this original stock, and fusing assistant is added in the original stock, and the mixture that obtains is like this carried out homogenizing.With homogenizing mixture in 1000 to 1400 ℃ of temperature ranges, annealed 1 to 3 hour, will move back the mixture that overdoes then and pulverize.According to the present invention, fusing assistant is a fluorochemicals, particularly Neutral ammonium fluoride or yttrium fluoride, and addition is from 0.01 to 0.07 mole of fluorine/mole SiO 2, this amount is lacked a lot than employee in the known processes, then contain at the most the 20ppm water vapor and at the most the protective atmosphere of 100ppm oxygen for example carry out annealing operation one time in the nitrogen.
In the embodiment preferably of institute of the present invention extracting method, starting material mix to be finished with lanthanum trioxide or gadolinium sesquioxide before homogenizing.
Some of the inventive method embodiment preferably can characterize with following each example:
Example 1
With 3.704 gram NH 4The F homogenizing is by 200.4 gram Y 2O 3With 42.06 gram Tb 4O 7The original stock of forming.Grinding in ball grinder made in 1 hour contain 66.09 the gram SiO 2The homogenizing mixture.With homogenizing mixture sieve, will sieve then particle in alumina container, anneal.Annealing temperature is 1300 ℃ and the time is 1 hour.Annealing is to contain 5ppmH 2O and 10ppm O 2Nitrogen in carry out.The mixture that to anneal with method commonly used is pulverized and is not needed and grinds, and pulverizes the sieve of back with 10 types, thereby obtains the particle that mean diameter is 11.4 μ m.
Example 2
Compound Y 2O 3And Tb 4O 7Consumption with example 1, but the add-on of fusing assistant is example 1 half, i.e. NH 4The F consumption is 1.704 grams.Method shown in the use-case 1 prepares luminescent material under simulated condition.The finished product are that mean diameter is the particle of 6.0 μ m.
Example 3
At the Y of consumption by example 2 decisions 2O 3, Tb 4O 7And NH 4In the mixture that F forms, add 61.29 gram SiO again 2With homogenizing mixture under 1400 ℃ of temperature, annealed 1 hour.When the luminophore that obtains like this was used for light modulation, when thickness was 4.5mg/cm, optical efficiency was 130 lumens/watt.
Example 4
To contain 189.1 gram Y 2O 3, 16.29 gram La 2O 3, 42.06 gram Tb 4O 7, 61.29 gram SiO 2With 1.852 gram NH 4The mixture of F homogenizing 1 hour in ball mill.Then mixture was placed in the protective atmosphere identical under 1400 ℃ of temperature annealing 1 hour with example 1.
Example 5
Make and contain 378.2 gram Y 2O 3, 18.13 gram Gd 2O 3, 42.06 gram Tb 4O 7, 61.29 gram SiO 2With 1.852 gram NH 4The mixture of F changes it into luminescent material according to the method for example 4.
Example 6
Basal component is 198.4 gram Y 2O 3, 2.432 YF 3, 42.06 gram Tb 4O 7With 61.29 gram SiO 2, change it into luminescent material according to the method for example 5.
Done check from the green luminophore that several respects are made the inventive method.The X-ray diffraction analysis causes our attention to the other advantage of this material, because the luminescent material that its proof is produced with present method has the represented Y of ICPDS21-1456 collection of illustrative plates 2SiO 5The feature of monoclinic crystal structure.Do not find to represent in the ICPDS21-1465 collection of illustrative plates to the deleterious crystalline texture of optical characteristics.Patent was not in the past done to measure to crystalline structure.
Table 1 has provided some measuring results, can find some character numerical value of the luminescent material of proposition from table.
Table 1
The efficient of the particle mean size of the luminescent material that obtains according to the present invention and the luminescent lamp produced with it, thickness is 4.5mg/cm and has used different fusing assistant consumptions.
Fusing assistant d, I, LF efficient
Moles/mole SiO 2μ m % % 1m/W
0.125 14 95.0 101.6 108.0
0.100 11.4 92.0 99.1 110.0
0.075 9.4 91.0 101.5 111.0
0.050 6.0 76.0 100.9 118.0
The symbol of gauge outfit is:
D-Coulter Counter device(Coulter counting mechanism) integration particle distribution metering defines the particle diameter that accounts for 50W%;
I-is with respect to being made up of cerium-magnesium alumina and having activated the relative intensity of reference shiner material with terbium, and ionization meter is with known sensitivity function V(λ) photosensor carry out;
The luminous power that LF-represents with intensity, and be used in the reflectance value that wavelength 254nm records and done correction.
The minimizing of the bright fusing assistant ratio of this illness that has not attacked the vital organs of the human body makes the particulate size that sizable reduction be arranged.This can show with the decline of the intensity of particulate sintering process and process of growth.
Can produce quite high efficient when very meaningfully the luminescent material that obtains of the method according to this invention is applied to various luminescent lamp.With the Confirmation Of Number of 1m/W unit than known materials and Yan Shiyou big progress.Explanation to these numerical value that record is when particle has less diameter, and it just has better adhesion to the surface of luminescent lamp.The another one factor is the not needs grinding of luminescent material that obtains according to the present invention, and as above-mentioned, process of lapping all can have passive influence to the optics and the physical properties of luminophore.
The optimum efficiency that studies have shown that luminescent lamp reaches 1301m/W(as shown in example 3)
Use much simpler that processing method can obtain to produce the luminophore of green glow than known processing method according to the present invention.

Claims (1)

1, prepare the method for terbium yttrium silicate twinkler alive, this method may further comprise the steps: preparation is based on the raw mix of suitable yttrium compound, silicon-dioxide and terbium sesquioxide (III), and its consumption is equivalent to formula (Y 2O 3) Y(SiO 2) x: Tb, wherein X/Y is 1～3, content be 1～15 atom %, a kind of fusing assistant is added in the raw mix, and, grinds burnt mixture then 1000～1400 ℃ of homogenizing calcining mixts 1～3 hour, it is characterized in that adding a kind of fluorine cpd or yttrium fluoride (III) as fusing assistant, its add-on is 0.01～0.07 mole of fluorine/mole SiO 2, and containing at the most the 20ppm water vapor and carrying out one-step calcination technology under the inert protective atmosphere of 100ppm oxygen (preferably constituting by nitrogen) at the most.
CN86104658.7A 1985-07-12 1986-07-09 Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores Expired CN1008110B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU2685/85 1985-07-12
HU852685A HUT41436A (en) 1985-07-12 1985-07-12 Process for producing yttrium-silicate luminous powders activated with terbium

Publications (2)

Publication Number Publication Date
CN86104658A CN86104658A (en) 1987-02-04
CN1008110B true CN1008110B (en) 1990-05-23

Family

ID=10960625

Family Applications (1)

Application Number Title Priority Date Filing Date
CN86104658.7A Expired CN1008110B (en) 1985-07-12 1986-07-09 Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores

Country Status (10)

Country Link
JP (1) JPS6264885A (en)
CN (1) CN1008110B (en)
CS (1) CS274655B2 (en)
DD (1) DD247461A5 (en)
DE (1) DE3620987A1 (en)
FI (1) FI862831A (en)
FR (1) FR2584731B1 (en)
GB (1) GB2177714B (en)
HU (1) HUT41436A (en)
NL (1) NL8601569A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2508697Y2 (en) * 1991-08-05 1996-08-28 株式会社安川電機 Electronic device cooling device
US5824393A (en) * 1995-10-26 1998-10-20 Nakamura Label Inc. Forgery-preventing textured emblem
KR100450792B1 (en) 1999-12-23 2004-10-01 삼성에스디아이 주식회사 Phosphors based on yttrium silicate for driving at a low voltage
WO2010108317A1 (en) * 2009-03-25 2010-09-30 海洋王照明科技股份有限公司 Green light-emitting glass and method of preparing the same
ITAN20120058A1 (en) * 2012-05-18 2013-11-19 I T S Innovative Tech Syste Me Sa METHOD FOR THE REALIZATION OF MATERIAL IN INCOERFUL SHAPE WITH PHOTOSTIMULATED LUMINESCENCE

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5927787B2 (en) * 1977-04-13 1984-07-07 株式会社東芝 UV-excited phosphor
JPS5552378A (en) * 1978-10-09 1980-04-16 Toshiba Corp Preparation of fluorescent material
JPS565883A (en) * 1979-06-29 1981-01-21 Dainippon Toryo Co Ltd Method of producing fluorescent material

Also Published As

Publication number Publication date
GB2177714B (en) 1989-01-18
GB2177714A (en) 1987-01-28
HUT41436A (en) 1987-04-28
FR2584731A1 (en) 1987-01-16
CS448786A2 (en) 1991-04-11
NL8601569A (en) 1987-02-02
FI862831A (en) 1987-01-13
GB8616839D0 (en) 1986-08-20
FR2584731B1 (en) 1988-08-19
DD247461A5 (en) 1987-07-08
JPS6264885A (en) 1987-03-23
CN86104658A (en) 1987-02-04
DE3620987A1 (en) 1987-01-22
FI862831A0 (en) 1986-07-03
CS274655B2 (en) 1991-09-15

Similar Documents

Publication Publication Date Title
WO1998042798A1 (en) Silicate phosphor with a long afterglow and manufacturing method thereof
CN108218417A (en) A kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof
CN104818023A (en) Rare earth luminescent material preparation method containing crystal defect repair technology and product thereof
CN114958351B (en) Ultraviolet excited blue-violet fluorescent powder, preparation method thereof and light-emitting device
Yu et al. Enhanced photoluminescence of Ba2GdNbO6: Eu3+/Dy3+ phosphors by Li+ doping
Concas et al. Nano-and microcrystalline Lu2O3: Eu phosphors: variations in occupancy of C2 and S6 sites by Eu3+ ions
JP2992254B2 (en) Method for producing high-speed excitation / high-brightness / low-attenuation luminescent material
CN1008110B (en) Method of producing terbium activitated yttrium silicate fluorescent materials, especially green luminophores
CN114874769A (en) Preparation method of thermoluminescent color-changing fluorescent powder
US7846354B2 (en) Method of making red-emitting borate phosphor
CN1974718A (en) Cerium activated ultraviolet emitting RE phosphate phosphor and its prepn process
US6419852B1 (en) Use as phosphor dot in a plasma or x-ray system of a lanthanum phosphate comprising thulium
US3577350A (en) Europium and manganese activated sodium or potassium aluminate phosphors
EP0057499B1 (en) Phosphor, process for the preparation thereof and a fluorescent screen having the phosphor
CN1397624A (en) Yttrium aluminium garnet (YAG) type fluorescent powder and its preparing process and application
CN104804736B (en) A kind of long after glow luminous material with defect as the centre of luminescence and preparation method thereof
JPH0523316B2 (en)
CN1208423C (en) Red luminescent powder mixed with europium and its method
Hamdy et al. Spectroscopic properties and luminescence behavior of γ-irradiated Sm3+ doped oxy-fluoride phosphate glasses
CN1810921A (en) Red long afterglow luminescent material and its prepn
CN1546606A (en) Violet or ultraviolet ray inspired borophosphate luminescent powder and its preparation method
JP7037082B2 (en) Rare earth aluminate phosphor manufacturing method, rare earth aluminate phosphor and light emitting device
Nehru et al. Ce3+-doped stillwellites: a new luminescent system with strong ion lattice coupling
JP3264045B2 (en) Phosphor manufacturing method
CN1276406A (en) Efficient green phosphor of rare-earth phosphate and its preparing process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C13 Decision
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee