CN101370749A - Method of making a gos ceramic using single-axis hot pressing and a flux aid - Google Patents

Method of making a gos ceramic using single-axis hot pressing and a flux aid Download PDF

Info

Publication number
CN101370749A
CN101370749A CNA2007800026118A CN200780002611A CN101370749A CN 101370749 A CN101370749 A CN 101370749A CN A2007800026118 A CNA2007800026118 A CN A2007800026118A CN 200780002611 A CN200780002611 A CN 200780002611A CN 101370749 A CN101370749 A CN 101370749A
Authority
CN
China
Prior art keywords
hot pressing
agglutinant
fusing assistant
top temperature
carried out
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.)
Pending
Application number
CNA2007800026118A
Other languages
Chinese (zh)
Inventor
C·R·龙达
H·施赖讷马赫尔
G·蔡特勒
N·康拉茨
S·莱韦内
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.)
Koninklijke Philips NV
Original Assignee
Koninklijke Philips Electronics NV
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 Koninklijke Philips Electronics NV filed Critical Koninklijke Philips Electronics NV
Publication of CN101370749A publication Critical patent/CN101370749A/en
Pending legal-status Critical Current

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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • 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
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • 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
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C09K11/7771—Oxysulfides
    • 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
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • 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
    • C04B2235/30—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
    • C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/446—Sulfides, tellurides or selenides
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • 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
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • 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
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/664—Reductive annealing
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • 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
    • 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

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Luminescent Compositions (AREA)

Abstract

The present invention relates to method of producing a fluorescent ceramic having the general formula Gd2O2S doped with M, whereby M represents at least one element selected from the group Ce, Pr, Eu, Tb, Yb, Dy, Sm and/or Ho involving a uniaxial hot-pressing step in the presence of a sintering and/or flux aid.

Description

The hot uniaxial pressing system of utilization and fusing assistant prepare the method for GOS pottery
Technical field
What the present invention relates to be doped with M has a general formula Gd 2O 2The fluorescence ceramics of S, wherein M represents at least a element that is selected from Ce, Pr, Eu, Tb, Yb, Dy, Sm and/or Ho, the invention still further relates to the preparation method of described fluorescence ceramics.
The invention still further relates to the hot uniaxial pressing system of utilization and prepare the method for fluorescence ceramics.
The invention still further relates to the detector that is used to detect ionizing rays.
The invention still further relates to the purposes of the described detector that is used to detect ionizing rays.
Background technology
The fluorescent element that is used to detect high-energy radiation comprises can absorbing radiation and be translated into the fluor of visible light.Consequent luminous be the electron device requirement, and estimate by means of optical sensing system such as photodiode or photomultiplier.Described fluorescent element can be by monocrystal material, as adulterated alkali metal halide preparation.Non-single-crystal material can adopt as the fluor of powdered or with the form of ceramic component prepared therefrom.
The preparation method of described fluorescence ceramics for example is disclosed among WO 2005/110943 A1, by reference it is added herein at this.Yet the shortcoming of this method is for example for some application need high pressure.
Summary of the invention
The preparation method who the purpose of this invention is to provide scintillating ceramic, described scintillating ceramic has the light output of further improvement and the persistence characteristic of improving.
Above-mentioned purpose can realize by claim 1 of the present invention.Therefore, the invention provides the method that the hot uniaxial pressing system of utilization prepares the fluorescence ceramics material, wherein, the inventive method comprises the Gd that selects to be doped with M 2O 2The step of the pigment powder of S, wherein M represents at least a element that is selected from Eu, Tb, Yb, Dy, Sm, Ho, Ce and/or Pr, and described hot pressing is carried out under the following conditions:
-top temperature is 〉=900 ℃ to≤1500 ℃, and/or
-peak pressure is 〉=75MPa is to≤300MPa;
Wherein, in the presence of agglutinant and/or fusing assistant, carry out described hot pressing.
Used term " hot uniaxial pressing system " is extensively known in the art among the present invention, and is understood to be in heating and exerts pressure powder pressing in hard mould on axially single by die head or piston down.
" agglutinant and/or fusing assistant " on the meaning of the present invention means, is described as and/or comprise material or the mixtures of material that especially shows at least a following characteristic:
-be lower than or temperature province in hot pressing in decompose to form actual fusing assistant (for example, Li 2GeF 6Be decomposed into 2LiF and GeF 4).
-some degradation productions are gasiform, thereby they can easily leave mixture to be sintered.
-fusing point is in being used for the temperature province of hot pressing.
-boiling point is being used for outside the temperature province of hot pressing, thereby prevents that fusing assistant is from mixture volatilization to be sintered.
-used Gd 2O 2The S pigment powder has high resolution in the fused fusing assistant.
-on the other hand, fusing assistant is originally in Gd 2O 2Be insoluble or in the S material only with trace soluble.
Thereby-during hot pressing etched surfaces to strengthen the surface reaction acceleration of sintering.
-in the situation of enhanced wetting behavior, guarantee during hot pressing, to be easy to spread by mixture.
-can preferably use with considerably less amount, to prevent the pollution of mixture to be sintered, pollution can cause unfavorable result such as twilight sunset or light productive rate to reduce.
According to an embodiment of the invention, before the hot pressing step, use suitable blending means that agglutinant and/or fusing assistant are added equably; According to another embodiment of the present invention, mixed sintering agent and/or fusing assistant and pigment powder before hot pressing, and vacuum-sealing.
According to an embodiment of the invention, agglutinant and/or fusing assistant comprise fluorochemical.
Term on the meaning of the present invention " fluorochemical " means, is described as and/or comprises material or the mixtures of material that comprises fluorine especially.
According to an embodiment of the invention, agglutinant and/or fusing assistant comprise the fluorochemical of basic metal and/or alkaline-earth metal.
Term on the meaning of the present invention " fluorochemical of basic metal and/or alkaline-earth metal " means, is described as and/or comprises material or the mixtures of material that comprises at least a basic metal and/or alkaline-earth metal and fluorine, with the form of simple fluorochemical or with the form of more complicated structure, for example with form with " two-fluorochemical " of one or more additional metals compounds.
According to an embodiment of the invention, agglutinant and/or fusing assistant comprise LiF and/or Li 2GeF 6And/or Li 2SiF 6And/or Li 3AlF 6
According to an embodiment of the invention, the ratio of the F conversion values of pigment powder and agglutinant and/or fusing assistant (weight: weight) be 〉=50:1 is to≤20000:1.
On meaning of the present invention, term " the F conversion values of agglutinant and/or fusing assistant " is meant the F-ionic amount (weight) that exists in fusing assistant during the hot pressing step.
That is to say, be in the situation of LiF and the LiF that uses 2.6g at agglutinant and/or fusing assistant, and the F conversion values of agglutinant and/or fusing assistant is 1.9g (because the molar mass of LiF is 26g/mole).At agglutinant and/or fusing assistant is Li 2GeF 6And the Li of use 2.00g 2GeF 6Situation in, the F conversion values of agglutinant and/or fusing assistant is that 380mg is (because each Li 2GeF 6Discharge two F-ions, and Li 2GeF 6Molar mass be 200g/mole).
According to an embodiment of the invention, the ratio of the F conversion values of pigment powder and agglutinant and/or fusing assistant (weight: weight) be 〉=1000:1 is to≤10000:1.
According to an embodiment of the invention, the ratio of the F conversion values of pigment powder and agglutinant and/or fusing assistant (weight: weight) be 〉=2000:1 is to≤8000:1.
According to an embodiment of the invention, the ratio of the F conversion values of pigment powder and agglutinant and/or fusing assistant (weight: weight) be 〉=3000:1 is to≤7000:1.
According to an embodiment of the invention, the ratio of the F conversion values of pigment powder and agglutinant and/or fusing assistant (weight: weight) be 〉=4000:1 is to≤6000:1.
According to an embodiment of the invention, hot pressing was carried out under peak pressure and/or top temperature 〉=30 to≤600 minutes.
On meaning of the present invention, term " under peak pressure and/or top temperature " means, is described as and/or comprises especially when reaching peak pressure and/or top temperature and to be described as the press time above-mentioned preset time; Yet according to an embodiment of the invention, whole hot pressing step can be very long, after will describe.
According to an embodiment of the invention, reach peak pressure and top temperature basically at the same time; According to an embodiment of the invention, reach peak pressure and top temperature and have delay.
According to an embodiment of the invention, hot pressing was carried out under peak pressure and/or top temperature 〉=100 to≤400 minutes.
According to an embodiment of the invention, hot pressing was carried out under peak pressure and/or top temperature 〉=150 to≤300 minutes.
According to an embodiment of the invention, hot pressing with factors A be set to 〉=45000 to≤540000 mode carries out, wherein A satisfies formula:
A＝t*T，
T be under peak pressure, carry out hot pressing time and
T be described time t (minute) in top temperature (℃).
Preferably, in time range t, it is constant that temperature T keeps; If in time range t, temperature change, temperature T is the top temperature that is provided with in the time t.
According to an embodiment of the invention, hot pressing with factors A (unit [℃ * minute]) is set to 〉=45000 to≤540000 mode carries out.
According to an embodiment of the invention, hot pressing with factors A be set to 〉=50000 to≤450000 mode carries out.
According to an embodiment of the invention, hot pressing with factors A be set to 〉=60000 to≤400000 mode carries out.
According to an embodiment of the invention, hot pressing with factors A be set to 〉=70000 to≤300000 mode carries out.
According to an embodiment of the invention, hot pressing is carried out under top temperature is 〉=1000 ℃ to≤1400 ℃.
According to an embodiment of the invention, hot pressing is carried out under top temperature is 〉=1100 ℃ to≤1300 ℃.
According to an embodiment of the invention, hot pressing is carried out under top temperature is 〉=1200 ℃ to≤1250 ℃.
According to an embodiment of the invention, hot pressing is carried out to≤300MPa for 〉=75MPa at peak pressure.
According to an embodiment of the invention, hot pressing is carried out to≤150MPa for 〉=90MPa at peak pressure.
According to an embodiment of the invention, hot pressing is carried out to≤125MPa for 〉=100MPa at peak pressure.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=0.1K/min to the heating steps of≤40K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=5K/min to the heating steps of≤25K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=10K/min to the heating steps of≤20K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=0.2K/min to the heating steps of≤5K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=1K/min to the heating steps of≤4K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches top temperature for 〉=1.5K/min to the heating steps of≤2.5K/min by heat-up rate wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by heat-up rate wherein be 〉=0.1K/min extremely≤at least one first heating steps of 40K/min, wherein temperature-resistant stop step then reaches top temperature for 〉=0.2K/min at least one second heating steps of≤5K/min by heat-up rate wherein then.
According to an embodiment of the invention, at least one first heating steps, heat-up rate is 〉=5K/min is to≤25K/min.
According to an embodiment of the invention, at least one first heating steps, heat-up rate is 〉=10K/min is to≤20K/min.
According to an embodiment of the invention, at least one second heating steps, heat-up rate is 〉=1K/min is to≤4K/min.
According to an embodiment of the invention, at least one second heating steps, heat-up rate is 〉=1.5K/min is to≤2.5K/min.
According to an embodiment of the invention, reaching temperature for stopping step after 〉=600 ℃ to≤1100 ℃.
According to an embodiment of the invention, reaching temperature for stopping step after 〉=700 ℃ to≤900 ℃.
According to an embodiment of the invention, reaching temperature for stopping step after 〉=750 ℃ to≤850 ℃.
According to an embodiment of the invention, stop step carry out 〉=5min is to≤30min.
According to an embodiment of the invention, stop step carry out 〉=10min is to≤20min.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches peak pressure for 〉=0.5MPa/min to the pressurization steps of≤10MPa/min by the rate of rise wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches peak pressure for 〉=1MPa/min to the pressurization steps of≤5MPa/min by the rate of rise wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, reaches peak pressure for 〉=1.5MPa/min to the pressurization steps of≤3MPa/min by the rate of rise wherein at least in part.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by blowdown rate wherein be 〉=5MPa/min is to the depressurization steps release peak pressure of≤35MPa/min.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by blowdown rate wherein be 〉=10MPa/min is to the depressurization steps release peak pressure of≤25MPa/min.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=2K/min is to the cooling step reduction top temperature of≤5K/min.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=3K/min is to the cooling step reduction top temperature of≤3.5K/min.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=2K/min is to the cooling step reduction top temperature of≤5K/min, until reaching 〉=300 ℃ to≤600 ℃ temperature.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=3K/min is to the cooling step reduction top temperature of≤3.5K/min, until reaching 〉=300 ℃ to≤600 ℃ temperature.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=2K/min is to the cooling step reduction top temperature of≤5K/min, until reaching 〉=350 ℃ to≤450 ℃ temperature.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=3K/min is to the cooling step reduction top temperature of≤3.5K/min, until reaching 〉=350 ℃ to≤450 ℃ temperature.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=2K/min is to the cooling step reduction top temperature of≤5K/min, until reaching about 400 ℃ temperature.
According to an embodiment of the invention, hot pressing is carried out as follows, at least in part by cooling rate wherein be 〉=3K/min is to the cooling step reduction top temperature of≤3.5K/min, until reaching about 400 ℃ temperature.
According to an embodiment of the invention, carry out hot pressing as follows, after depressurization steps, carry out cooling step.
According to an embodiment of the invention, the particle diameter that is used for the described pigment powder of hot pressing is 〉=1 μ m is to≤20 μ m.
According to an embodiment of the invention, Gd 2O 2The amount of the M that the S pigment powder comprises for 〉=0.1ppm to≤2000ppm (weight part).
In the situation of using more than a kind of element, M represents total adding parts by weight of described element.
Under vacuum after the single shaft hot pressing step, fluorescence ceramics can be further processed by the annealing of the air under 700 ℃ to 1200 ℃ temperature, preferred 800 ℃ to 1100 ℃, more preferably 900 ℃ to 1000 ℃, wherein, the described time that is used for the air anneal is 0.5 hour to 30 hours, preferred 1 hour to 20 hours, more preferably 2 hours to 10 hours, most preferably 2 hours to 4 hours.
Another advantage of the present invention is to have the Gd that median size is 1 μ m to 20 μ m 2O 2The S material can be commercially available with starting material by the manufacturer of fluorescence ceramics, and do not need to be broken for the particulate that is lower than 100nm.In one embodiment, Gd preferably used according to the invention 2O 2The median size that the S pigment powder has is 2 μ m to 10 μ m, more preferably 4 μ m to 6 μ m.And, owing to method of the present invention, not needing special powder process, the powder that obtains can be successfully used to prepare fluorescence ceramics usually.
Can obtain following ceramic parameter by method of the present invention:
-under 500ms twilight sunset 1 * 10 -6To 8 * 10 -5Scope (using the experimental technique of describing among the WO 2005110943A1); And/or
-total transparency of measuring under wavelength 513nm is in the scope of 0-80%, preferred 10-70%, more preferably 20-35%.
Pottery of the present invention can be advantageously used in preparation x-radioluminescence pottery, the starting material during it is produced as medical computerized tomography shadowgraph (CT).
Find advantageously to introduce the vacuum annealing step with the further optical characteristics of improving the gained pottery.In this step, the particle further growth in the pottery further improves transparency owing to the reduction of porosity.Next, owing to particle growth, the extra diffusion of the foreign atom in the oxysulfide lattice has further improved ceramic blinking characteristic.
Therefore, according to an embodiment of the inventive method, between hot pressing and annealing, can carry out following other step: it was included under 1000 ℃ to 1400 ℃ the temperature in the vacuum annealing fluorescence ceramics 0.5 hour to 30 hours.
Preferably, the selective annealing temperature is 1100 ℃-1300 ℃ a scope, more preferably 1200 ℃-1250 ℃.
The time of vacuum annealing preferably can be made as 1 hour to 20 hours, and more preferably 2 hours to 10 hours, most preferably 3 hours to 5 hours.
In another embodiment, be the embodiment of 1 μ m to 20 μ m according to particle diameter, with unadulterated Gd according to the inventive method 2O 2The S powder mixes with the composition of the rare earth element ion that comprises at least a Pr of being selected from, Ce, Eu, Tb, Yb, Dy, Sm and/or Ho.
These technical measures have further been simplified the process of Production of Ceramics, because can use large-scale available materials.For example, when selecting Pr or Ce, can use corresponding salt: PrCl as the anticipation hotchpotch 3, PrBr 3, PrI 3, Pr (NO 3) 3, Pr 2(SO 4) 3, CeCl 3, CeBr 3, CeI 3, Ce (NO 3) 3, Ce 2(SO 4) 3Deng the aqueous solution introduce Pr or Ce ion.Perhaps, can be at mechanically mixing Gd 2O 2The S powder with comprise hotchpotch such as oxide compound, as Pr 6O 11, Pr 2O 3, Ce 2O 3, CeO 2Insoluble composition during introduce dopant ions.
Perhaps, Gd 2O 2The S powder can with the water-insoluble salt of hotchpotch, as PrF 3, Pr 2S 3, Pr 2O 2S, Pr 2(CO 3) 3, Pr 2(C 2O 4) 3, CeF 3, Ce 2O 2S, Ce 2(CO 3) 3, Ce 2(C 2O 4) 3Deng mechanically mixing.
The principle that hotchpotch is introduced can be used to introduce ion such as Tb, Eu and other rare earth element.Additionally, can correspondingly introduce the ion of other element that is not rare earth element ion.Preferably, the suitable agglutinant of co-blended before hot pressing.
The invention still further relates to be doped with M by chemical general formula Gd 2O 2The pottery of S representative, wherein M represents at least a element that is selected from Pr, Ce, Eu, Tb, Yb, Dy, Sm and/or Ho, and wherein said fluorescence ceramics comprises single phase in its volume.
In addition, find that also fluorescence ceramics of the present invention has the productive rate of light relatively or the light output of remarkable increase with respect to the obtainable ceramic fluorescent material in market.Be equal to or greater than 1.5mm for ceramic thickness especially visible difference.The cadmium tungstate crystal of light output ratio same thickness is high 2.3 times.
Gd 2O 2The BET surface-area that the doping pigment powder of S has is at 〉=0.01m 2/ g is to≤1m 2The scope of/g, preferred 〉=0.05m 2/ g is to≤0.5m 2/ g, more preferably 〉=0.1m 2/ g is to≤0.2m 2/ g.
Gd 2O 2S can be by at least a element doping that is selected from Ce, Pr, Eu, Tb, Yb, Dy, Sm and/or Ho.Preferably, Gd 2O 2The S powder is only by a kind of element doping that is selected from Ce, Pr, Eu, Tb, Yb, Dy, Sm and/or Ho.Most preferred Elements C e or the Pr of being to use.
Gd 2O 2The weight part content of Ce in the S powder is 0.1ppm to 100ppm, preferred 5ppm to 50ppm, more preferably 10ppm to 25ppm and/or Gd 2O 2The content of Pr in the S powder is 100ppm to 2000ppm, preferred 300ppm to 1200ppm, more preferably 500ppm to 800
ppm。
Found Gd of the present invention 2O 2The S fluorescence ceramics has significantly reduced twilight sunset, and it is output as 1 * 10 with respect to initial light under 500ms -6To 8 * 10 -5Scope.With respect to initial light output, fluorescence ceramics of the present invention preferably has twilight sunset 1.0 * 10 under 500ms -6To 6 * 10 -5Scope, preferably be 1.0 * 10 under 500ms -6To 5 * 10 -5And more preferably be 1.0 * 10 under 500ms -6To 3.0 * 10 -5
According to a preferred embodiment of the present invention, during hot uniaxial pressing system, the polycrystalline piece preferably is densified to the density value near theoretical density, p Actual99.7%p TheoreticalOwing to this high-density, fluorescence ceramics of the present invention provides the good transparency in the optical range.Therefore, the density that fluorescence ceramics preferably prepared in accordance with the present invention has is 〉=99.0%, and preferred 〉=99.5% is more preferably 〉=99.7% with≤100%.
Find unexpectedly that also fluorescence ceramics prepared in accordance with the present invention has the productive rate of light relatively or the light output of remarkable increase, it is in the scope of 0.74-1.00, preferred 0.80-1.00 and more preferably 0.84-1.00.
With the Gd that is doped with M 2O 2The particle diameter of S particulate initial powder is compared, and the crystalline size of fluorescence ceramics prepared in accordance with the present invention is preferably higher.Preferably, the Gd that is doped with M of fluorescence ceramics 2O 2S crystalline 〉=50%, preferred 〉=70% more preferably 〉=90% should have 1-300 μ m, the crystalline size of preferred 10-100 μ m.
Fluorescence ceramics prepared in accordance with the present invention has texture (texture) in face 001, face 001 is corresponding to the face in the lattice that is basically perpendicular to the direction orientation of exerting pressure during the single shaft compacting.
According to an embodiment of the invention, described method comprises the steps:
A) first solid is placed mould, preferably it is selected from graphite and/or TZM;
B) molybdenum foil is placed on first solid of step a);
C) mixture with pigment powder and agglutinant and/or fusing assistant places on the molybdenum foil of step b);
D) if desired, the other alternating layer of the mixture of molybdenum foil and pigment powder and agglutinant and/or fusing assistant is placed on the mixture of the pigment powder of step c) and agglutinant and/or fusing assistant;
E) or, if desired, the mixture and the other solid alternating layer of molybdenum foil, pigment powder and agglutinant and/or fusing assistant placed on the ceramic powder of step c);
F) layer second from the bottom that piles up of gained is set to molybdenum foil;
G) to be set to the solid of step a) be the solid of same material to last one deck of piling up of gained;
H) cover last one deck with graphite solid;
I) in pressurizing device, produce 〉=1 * 10 -8Bar is to≤1 * 10 -3The vacuum of bar;
J) carry out the hot pressing step as mentioned above.
Fluorescence ceramics prepared in accordance with the present invention for example can be used for:
-be used to detect ionizing rays, the scintillator of the fluorescent element of preferred x-ray, gamma-rays and electron beam, and/or
Device that uses in-the medical field or equipment are preferred for computerized tomography shadowgraph (CT).
Most preferably, at least a fluorescence ceramics prepared in accordance with the present invention can be used to be suitable for the detector or the device of imaging of medical.
Yet fluorescence ceramics prepared in accordance with the present invention can be used for the known any detector of medical field.Described detector for example is x-ray detector, CT-detector, electronics launched field image detector etc.
Parts in above-mentioned parts, claims and used parts are not limited to its size, shape, material and select and technological concept according to the present invention in said embodiment, known choice criteria can be used without restriction in the association area.
The other details of the object of the invention, feature and advantage are disclosed in dependent claims, in accompanying drawing and the following description, two preferred implementations being suitable for device of the present invention and an embodiment of preparation in accordance with the present invention have been shown in an exemplary fashion about drawings and Examples separately.
Description of drawings
Fig. 1 has shown the device that is suitable for according to the inventive method, and it is designed to add in a direction depresses the compacting of hot single shaft.
Fig. 2 has shown another device that is suitable for according to the inventive method, and it is designed to add at both direction depresses the compacting of hot single shaft.
Fig. 3 has shown the hot single shaft pressing step for first embodiment of the invention, and temperature and pressure is with respect to the figure of time.
Fig. 1 shown and has been suitable for according to device of the present invention (1), and it is designed to add in a direction depresses hot single shaft compacting.Described device also is described among the EP 05 110 054.3, adds herein by reference at this.
Piston (2) with pressure transmission to die head (3).Die head (3) is suitable for mould (5) inside.On the bottom of mould (5), be provided with second die head (6) that is positioned at the fixed position.This is arranged by well heater (4) heating.At mould inside, has the layer of a plurality of ceramic powder (9) that contact with molybdenum foil (8).Molybdenum foil layers contacts with the layer of graphite solid (7) in turn.The layer that it should be noted that piston (2), die head (3) and (6), well heater (4), mould (5) and graphite linings (7), molybdenum foil (8) and ceramic powder (9) centers on the vertical axis of symmetry setting in cylindrosymmetric mode.It is also to be noted that the layer of well heater (4), mould (5) and graphite (7), molybdenum foil (8) and ceramic powder (9) centers on the horizontal symmetry axis setting in mirror symmetry mode.
Fig. 2 shown according to another device of the present invention (10), and it is designed to add at both direction depresses hot single shaft compacting.Piston (2) with pressure transmission to die head (3).Die head (3) is suitable for mould (5) inside.On the bottom of mould (5), be provided with movably and pass through another die head (11) of second piston (12) driving.This is arranged by well heater (4) heating.At mould inside, has the layer of a plurality of ceramic powder (9) that contact with molybdenum foil (8).Molybdenum foil layers contacts with the layer of graphite solid (7) in turn.The layer that it should be noted that piston (2) and (12), die head (3) and (11), well heater (4), mould (5), second die head (6) and graphite (7), molybdenum foil (8) and ceramic powder (9) centers on the horizontal symmetry axis setting in cylindrosymmetric mode around the vertical axis of symmetry setting and in mirror symmetry mode.
Will be further understood that the present invention by following embodiment, embodiment has only shown the method for fluorescence ceramics produced according to the present invention in an exemplary fashion.
Embodiment
Embodiment 1
In this embodiment, use the Gd of Pr concentration as the 500-1000 ppm by weight 2O 2The S:Pr pigment powder, wherein Ce exists as impurity with about 20 ppm by weight of concentration.The described pigment powder of 3kg is mixed with LiF as the 0.0055g of agglutinant and/or fusing assistant.
The mixture of pigment powder and LiF is filled in the device as Fig. 1, and carries out hot pressing as shown in Figure 3.
At first, until reaching 800 ℃, carry out 25 minutes stop step with about 20K/min elevated temperature this moment.During the part that stops step, with 2.5MPa/min rising pressure, until reaching about 50MPa.
Subsequently, with 10K/min once more elevated temperature until reaching 1050 ℃, subsequently with 2K/min and 1MPa/min elevated temperature and pressure simultaneously, until reaching 1250 ℃ of peak pressure 150MPa and top temperatures.
At this moment, carried out hot pressing 240 minutes.
After compacting is finished, at first reduce pressure with 5MPa/min, reduce temperature with 3K/min then, until reaching room temperature and normal pressure.
To disclose in order providing completely, and can suitably to increase this specification sheets, the applicant adds this paper with the full content of above-mentioned patent and patent application by reference at this.
The composition in the above-mentioned embodiment and the particular combination of characteristic only are exemplary, can exchange and replace these instructions with other instruction at this, and the present invention also comprise the patent/application that adds this paper by reference.Do not deviating under the spirit and scope of the present invention, one skilled in the art will realize that various change described here, improvement and other embodiment.Therefore, aforesaid specification sheets only is exemplary and not restrictive.Scope of the present invention is limited by claims and Equivalent thereof.And Reference numeral used in this specification sheets does not limit the scope of the invention.

Claims (10)

1. fluorescence ceramics preparation methods, it utilizes hot uniaxial pressing system, and described method comprises the Gd that selects to be doped with M 2O 2The step of the pigment powder of S, wherein M represents at least a element that is selected from Eu, Tb, Yb, Dy, Sm, Ho, Ce and/or Pr, and described hot pressing is carried out under the following conditions:
-top temperature is 〉=900 ℃ to≤1500 ℃, and/or
-peak pressure is 〉=75MPa is to≤300MPa;
Wherein, in the presence of agglutinant and/or fusing assistant, carry out described hot pressing.
2. the method for claim 1, wherein described agglutinant and/or fusing assistant comprise fluorochemical.
3. method as claimed in claim 1 or 2, wherein, described agglutinant and/or fusing assistant comprise LiF and/or Li 2GeF 6And/or Li 2SiF 6And/or Li 3AlF 6
4. as each described method of claim 1-3, wherein, the part by weight of the F conversion values of described pigment powder and described agglutinant and/or fusing assistant is 〉=50:1 is to≤20000:1.
5. as each described method of claim 1-4, wherein, described hot pressing was carried out under described peak pressure and/or top temperature 〉=30 to≤600 minutes.
6. as each described method of claim 1-5, wherein, described hot pressing with factors A be set to 〉=45000 to≤540000 mode carries out, wherein A satisfies formula:
A＝t*T，
T be under peak pressure, carry out time of hot pressing and T be described time t (minute) in top temperature (℃).
7. as each described method of claim 1-6, wherein, described hot pressing is carried out as follows, reaches described top temperature for 〉=0.1K/min to the heating steps of≤40K/min by heat-up rate wherein at least in part.
8. fluorescence ceramics, its by as the described method of one of claim 1-7 prepare.
9. detector, it is used to detect ionizing rays, and described detector comprises fluorescence ceramics as claimed in claim 8.
10. the purposes of detector as claimed in claim 9, it is used for being suitable for the device of imaging of medical.
CNA2007800026118A 2006-01-18 2007-01-08 Method of making a gos ceramic using single-axis hot pressing and a flux aid Pending CN101370749A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06100519.5 2006-01-18
EP06100519 2006-01-18

Publications (1)

Publication Number Publication Date
CN101370749A true CN101370749A (en) 2009-02-18

Family

ID=37945482

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007800026118A Pending CN101370749A (en) 2006-01-18 2007-01-08 Method of making a gos ceramic using single-axis hot pressing and a flux aid

Country Status (3)

Country Link
JP (1) JP2009523689A (en)
CN (1) CN101370749A (en)
WO (1) WO2007083248A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105330289A (en) * 2014-08-14 2016-02-17 清华大学 Sulfur oxide gadolinium (Gd2O2S) scintillation ceramics preparation method

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2577351B1 (en) 2010-05-24 2017-06-14 Koninklijke Philips N.V. Ct detector including multi-layer fluorescent tape scintillator with switchable spectral sensitivity
EP2737340B1 (en) 2011-07-28 2019-04-24 Koninklijke Philips N.V. Terbium based detector scintillator
EP2756151B1 (en) 2011-09-16 2017-06-21 Baker Hughes Incorporated Methods of forming polycrystalline compacts and resulting compacts
EP3173571A1 (en) 2011-09-19 2017-05-31 Baker Hughes Incorporated Methods of forming polycrystalline diamond compacts and resulting polycrystalline diamond compacts and cutting elements

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4224931C2 (en) * 1992-07-28 1995-11-23 Siemens Ag Process for producing a scintillator ceramic and its use
RU2350579C2 (en) * 2004-05-17 2009-03-27 Федеральное Государственное Унитарное Предприятие "Научно-Исследовательский И Технологический Институт Оптического Материаловедения" Всероссийского Научного Центра "Государственный Оптический Институт Им. С.И.Вавилова" Fluorescent ceramics
RU2008106600A (en) * 2005-07-25 2009-09-10 Сэнт-Гобэн Керамикс Енд Пластикс, Инк. (Us) SCINTILLATOR BASED ON RARE-EARTH OXIDE SULFIDES AND METHOD FOR ITS MANUFACTURE

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105330289A (en) * 2014-08-14 2016-02-17 清华大学 Sulfur oxide gadolinium (Gd2O2S) scintillation ceramics preparation method
US9816028B2 (en) 2014-08-14 2017-11-14 Tsinghua University Process for the preparation of gadolinium oxysulfide (Gd2O2S) scintillation ceramics
CN105330289B (en) * 2014-08-14 2018-08-31 清华大学 A kind of gadolinium oxysulfide（Gd2O2S）Scintillating ceramic preparation method

Also Published As

Publication number Publication date
WO2007083248A1 (en) 2007-07-26
JP2009523689A (en) 2009-06-25

Similar Documents

Publication Publication Date Title
CN101107206B (en) Fluorescent ceramic and fabrication method thereof
US5296163A (en) Method for producing a scintillator ceramic
US4473513A (en) Method for sintering high density yttria-gadolinia ceramic scintillators
US4747973A (en) Rare-earth-doped yttria-gadolina ceramic scintillators
US4571312A (en) Preparation of yttria-gadolinia ceramic scintillators by sintering and gas hot isostatic pressing
JPS6359436B2 (en)
JP5686724B2 (en) Solid scintillator, radiation detector, and X-ray tomography apparatus
US4518546A (en) Preparation of yttria-gadolinia ceramic scintillators by sintering and gas hot isostatic pressing
US5518659A (en) Method for manufacturing a phosphor having high translucency
US6967330B1 (en) High-density polycrystalline lutetium silicate materials activated with Ce
CN101370749A (en) Method of making a gos ceramic using single-axis hot pressing and a flux aid
US4518545A (en) Method for sintering high density yttria-gadolinia ceramic scintillators
WO2014168202A1 (en) Fluorescent material, scintillator and radiation conversion panel
US8668844B2 (en) Fluorescent material for use in CT applications
EP0097296B1 (en) Rare earth doped yttria-gadolinia ceramic scintillators and methods for making
US4466929A (en) Preparation of yttria-gadolinia ceramic scintillators by vacuum hot pressing
JP5269634B2 (en) Solid scintillator, radiation detector, radiation inspection apparatus, powder for producing solid scintillator, and method for producing solid scintillator
TW201521685A (en) Scintillator material, radiation detector, and radiographic examination device
Kanai et al. Hot‐Pressing Method to Consolidate Gd 3 (Al, Ga) 5 O 12: Ce Garnet Scintillator Powder for use in an X‐ray CT Detector
EP0097295B1 (en) Rare earth doped yttria-gadolinia ceramic scintillators and methods for making
WO2022202500A1 (en) Scintillator and radiation detector
JPS6359435B2 (en)
JP2016145310A (en) Scintillator material, radiation detector and radiation inspection device
WO2021149670A1 (en) Scintillator and radiation detector
JP2021102716A (en) Scintillator and radiation detector

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication