CN106830935A - A kind of yttria-base laser ceramics of Nd sensitizations and preparation method thereof - Google Patents
A kind of yttria-base laser ceramics of Nd sensitizations and preparation method thereof Download PDFInfo
- Publication number
- CN106830935A CN106830935A CN201710025333.3A CN201710025333A CN106830935A CN 106830935 A CN106830935 A CN 106830935A CN 201710025333 A CN201710025333 A CN 201710025333A CN 106830935 A CN106830935 A CN 106830935A
- Authority
- CN
- China
- Prior art keywords
- compound
- nitrate
- yttria
- yttrium
- hours
- 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.)
- Granted
Links
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
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
- C04B35/505—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds based on yttrium 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
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/62615—High energy or reactive ball milling
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62815—Rare earth metal oxides
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62892—Coating the powders or the macroscopic reinforcing agents with a coating layer consisting of particles
-
- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- 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
- C04B2235/3227—Lanthanum 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- 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
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
Abstract
The yttria-base laser ceramics of Nd sensitizations disclosed by the invention, its crystal grain has core shell structure, and stratum nucleare is (Y, Nd, M)2O3Phase, shell are (Y, N)2O3Phase, wherein M are rare earth luminous ion, N is sintering aid.Preparation process is as follows：The compound of yttrium, the compound of neodymium are mixed with the compound of M first, is calcined (Y, Nd, M)2O3Powder, then the compound of yttrium is mixed with the compound of N, calcine (Y, N)2O3Powder, then mixes above two powder；Or (Y, Nd, M) is directly added into after the compound of yttrium is mixed with the compound of N2O3Powder mixing, calcining；Mixed powder isostatic pressing, the vacuum-sintering that will be obtained, cool down after annealing.The present invention is using sintering character excellent (Y, N)2O3Thin layer is to (Y, Nd, M)2O3Mutually coated, distortion of lattice can be reduced on the basis of ceramic post sintering performance is improved, so as to obtain excellent laser activity.
Description
Technical field
The present invention relates to a kind of yttria-base laser ceramics and preparation method thereof, especially the yttria-base laser of Nd sensitizations
Ceramics and preparation method thereof, belong to materials science field.
Background technology
Yittrium oxide is cubic system crystal, with excellent light transmission, and with fusing point is high, chemistry and photochemistry is steady
Qualitative good, thermal conductivity is high, optical transparence wide ranges (0.23~8.0 μm) the advantages of, particularly in region of ultra-red, with 80%
Theoretical transmission above；Its phonon energy is low, easily realizes the doping vario-property of rare earth ion, can suppress without spoke to a certain extent
Transition is penetrated, the probability of radiation transistion is improved, is as the important base of solid laser medium material so as to improve luminous quantum efficiency
Material.
Y2O3Melt temperature be up to 2430 DEG C, a polycrystalline phase transformation for opposite hexagonal phase is also occurred that cube at 2280 DEG C, because
This is difficult to grow Y using traditional czochralski method2O3Monocrystalline.Using traditional ceramics technique, can be far below Y2O3At a temperature of fusing point
Crystalline ceramics is prepared, production cost, improve production efficiency is saved, it is often more important that ceramic preparation technology easily realizes active ions
It is highly doped, can greatly improve laser output power so that refractory oxide be used as optical medium and laser medium
It is possibly realized.The sintering temperature of yttrium oxide transparent ceramic is general more than 2000 DEG C, is prepared using vacuum-sintering and nano-powder
After technology, sintering temperature drops to 1700 DEG C, lower than its melt temperature 700 DEG C.Ceramic material is polycrystal, its crystal boundary, stomata
The scattering loss that can all increase light with the imperfection of lattice etc. causes the opacity of material, for Y2O3Base transparent ceramic
Research discovery, La3+And Zr4+Doping can be effectively improved Y2O3The sintering character of base transparent ceramic, improves Y2O3The densification of base ceramics
Degree, so as to improve its transmitance.
Rear-earth-doped Y2O3The laser activity of base transparent ceramic has been widely studied, and it is dense that such as Lu prepares doping
It is the Nd of 1.5 at% to spend:Y2O3Crystalline ceramics, the LD with 807 nm is pumping source, under the pump power of 742 mW, is obtained
The laser output of 160 mW.Akira first reported the Yb of diode pumping:Y2O3Femtosecond ceramic laser, is absorbing 2.6 W
Draw power when, obtain the laser output of centre wavelength 1076.5 nm, the mW of mean power 420.Kong utilizes Yb:Y2O3Pottery
Porcelain laser, realizes the laser output of the nm of wavelength 1078, the W of peak power 4.2.Further to improve Y2O3The burning of crystalline ceramics
Knot performance and luminescent properties, the red seminars of Shanghai University Yang Qiu are with La2O3It is sintering aid, using low-temperature sintering method in nothing
The good yttrium lanthanum oxide laser ceramic of the transparency is prepared under pressure reducing atmosphere, the La of addition is found2O3Effectively improve Y2O3Thoroughly
The sintering character of bright ceramics, and with good laser spectrum performance.US military laboratory reports in Er first3+:Y2O3
2.71 μm of mid-infrared laser output is obtained in crystalline ceramics, at room temperature the mW of peak power output 380.
Although yttria-base laser ceramics has obtained extensive research report, from the point of view of current present Research both at home and abroad,
When doping concentration of rare earth ion is relatively low, lasing efficiency is relatively low；Although in theory can be rare earth ion doped dense by increasing
Degree come improving laser performance, but correlative study show laser ceramics with the raising of rear-earth-doped concentration occur scattering increase,
The problems such as beam quality factor is reduced.Because the directionality of laser is extremely strong, any small refraction can all cause light to reflect and draw
Play error and loss.Therefore, Y is being kept2O3On the premise of the good chemistry and photochemistry performance of base transparent ceramic, it is to avoid it goes out
Now big distortion of lattice, reduction scattering loss, is Y while keeping good sintering character2O3Base laser ceramics more extensively should
Key.
The content of the invention
Yttria-base laser ceramics it is an object of the invention to provide a kind of Nd sensitizations and preparation method thereof, makes yttria-base
The crystal grain of laser ceramics has core shell structure, and stratum nucleare solid solution enters the rare earth ion of Nd sensitizations, and shell solid solution enters sintering aid, so that
On the basis of distortion of lattice is reduced, beneficial to the sintering character and laser activity that improve yttria-base laser ceramics.
The yttria-base laser ceramics of Nd sensitizations of the invention, it is characterised in that the crystal grain of ceramics has core shell structure, core
Layer is (Y1-x-yNdxMy)2O3Phase, shell are (Y1-zNz)2O3Phase, wherein 0.01≤x≤0.1,0.005≤y≤0.1,
0.05≤z≤0.2, M is the one kind in rare earth luminous ion Er and Dy, N be sintering aid La, Zr, Ti, Mn, Al, Ca,
One or more in Zn and Mg, shell material is 0.01~0.2 with the mol ratio of stratum nucleare material:1.
The preparation method of the yttria-base laser ceramics of Nd sensitizations of the present invention, there is following two schemes：
Scheme 1：
The method for preparing the yttria-base laser ceramics of Nd sensitizations, comprises the steps：
(1) compound of the compound of yttrium, the compound of neodymium and M element is weighed by the amount of stratum nucleare material, and is put into deionized water
In be well mixed, then with zirconia ball for mill be situated between, ball milling mixing 4~24 hours, dry after again 1250~1550 DEG C calcine
2~8 hours, obtain Nd and enter Y with M solid solutions2O3In (Y, Nd, M)2O3Phase powder；
(2) weigh the compound of yttrium and the compound of N element by the amount of shell material, and be put into deionized water and be well mixed,
It is subsequently adding (Y, Nd, the M) of step (1) synthesis2O3Phase powder, ball milling mixing 4~24 hours, is then sprayed mixture
Dry, remove deionized water；
(3) powder obtained after spray drying is put into mould, in the forming under the pressure of 10~40 MPa, is then warmed up to
1050~1250 DEG C are incubated 1~4 hour, are placed into after cooling in isostatic pressing machine, and isostatic pressed is carried out under 180~300 MPa；
(4) product after isostatic pressed is put in a vacuum furnace, 4~24 hours is incubated at 1550~1750 DEG C, exist again after cooling
Annealed 2~8 hours in 900~1500 DEG C of air, obtain the yttria-base laser ceramics of Nd sensitizations.
In this programme, the compound of described yttrium is one or more in yittrium oxide, yttrium nitrate and acetic acid yttrium；Described
The compound of neodymium is one or more in neodymia, neodymium nitrate and acetic acid neodymium；The compound of described M element be erbium oxide,
One kind in erbium nitrate, acetic acid erbium, dysprosia, dysprosium nitrate and acetic acid dysprosium；The compound of described N element is lanthanum nitrate, acetic acid
Lanthanum, zirconium nitrate, acetic acid zirconium, butyl titanate, Titanium Nitrate, manganese nitrate, manganese acetate, aluminum nitrate, aluminum acetate, calcium nitrate, calcium acetate,
One or more in zinc nitrate, zinc acetate, magnesium nitrate and magnesium acetate.
Scheme 2：
The method for preparing the yttria-base laser ceramics of Nd sensitizations, comprises the steps：
(1) compound of the compound of yttrium, the compound of neodymium and M element is weighed by the amount of stratum nucleare material, and is put into deionized water
In be well mixed, then with zirconia ball for mill be situated between, ball milling mixing 4~24 hours, dry after again 1250~1550 DEG C calcine
2~8 hours, obtain Nd and enter Y with M solid solutions2O3In (Y, Nd, M)2O3Phase powder；
(2) weigh the compound of yttrium and the compound of N element by the amount of shell material, and be put into deionized water and be well mixed,
Then it is situated between by mill of zirconia ball, ball milling mixing 4~24 hours is calcined 1~4 hour at 1050~1250 DEG C again after drying, and is obtained
Obtain N solid solutions and enter Y2O3In (Y, N)2O3Phase powder；
(3) powder that above-mentioned steps (1) are prepared with step (2) is mixed, is put into ball grinder, be mill with zirconia ball
It is situated between, ball milling mixing 4~24 hours obtains mixed powder；
(4) it is compressing after above-mentioned mixed powder is dried, by the isostatic cool pressing of 180~300 MPa, then it is placed on vacuum drying oven
In, 4~24 hours are incubated at 1550~1750 DEG C, annealed 2~8 hours in 900~1500 DEG C of air again after cooling, obtain
To the yttria-base laser ceramics of Nd sensitizations.
In this programme, the compound of described yttrium is one or more in yittrium oxide, yttrium nitrate and acetic acid yttrium；Described
The compound of neodymium is one or more in neodymia, neodymium nitrate and acetic acid neodymium；The compound of described M element be erbium oxide,
One kind in erbium nitrate, acetic acid erbium, dysprosia, dysprosium nitrate and acetic acid dysprosium；The compound of described N element is lanthana, nitric acid
Lanthanum, lanthanum acetate, zirconium oxide, zirconium nitrate, acetic acid zirconium, titanium oxide, butyl titanate, Titanium Nitrate, manganese oxide, manganese nitrate, manganese acetate,
Aluminum oxide, aluminum nitrate, aluminum acetate, calcium oxide, calcium nitrate, calcium acetate, zinc oxide, zinc nitrate, zinc acetate, magnesia, magnesium nitrate
With one or more in magnesium acetate.
The invention has the advantages that：The compound of the compound of yttrium, the compound of neodymium and M first is carried out into ball milling to mix
Close, then in 1250~1550 DEG C of calcinings, you can obtain Nd and enter Y with M solid solutions2O3In (Y, Nd, M)2O3Phase powder, because Nd is
Sensitizer, M are rare earth luminous ions（One kind in Er and Dy）, the structure has good luminescent properties；Then by the change of yttrium
Compound is coated on (Y, Nd, M) with the compound of N2O3Around phase powder, or the compound of yttrium is mixed with the compound ball milling of N
Merge and obtain (Y, N) by 1050~1250 DEG C of calcinings2O3After powder, then with (Y, Nd, M)2O3Phase powder mixes, because N is
Sintering aid ion（One or more in La, Zr, Ti, Mn, Al, Ca, Zn, Mg）, therefore (Y, N)2O3Mutually there is good sintering
Activity；(Y,Nd,M)2O3The synthesis temperature of powder is 1250~1550 DEG C, (Y, N)2O3The synthesis temperature of powder be 1050~
1250 DEG C, due to the difference of synthesis temperature so that (Y, N)2O3Diameter of particle is than (Y, Nd, M)2O3Diameter of particle is tiny to be obtained
It is many, when both powders are mixed, by both ratios of control, can obtain tiny (Y, N)2O3Powder is surrounded
At thick (Y, Nd, M)2O3Circumgranular structure, it is (Y, Nd, M) that can obtain stratum nucleare after shaping with sintering2O3Phase, shell
It is (Y, N)2O3The yttria-base ceramics of phase.With (Y, Nd, M)2O3It is stratum nucleare, (Y, N)2O3It is the structure of shell, realizes sensitization
Ion/light emitting ionic separates doping with sintering aid ion, thereby reduces distortion of lattice, improves the laser of ceramics
Can, simultaneously because (Y, the N) of sintering aid doping2O3Mutually there is good sintering character, the consistency and printing opacity of ceramics is effectively improved
Performance, so that yttria-base of the invention ceramics have good laser activity.Preparation process is simple of the present invention is controllable.
Specific embodiment
With reference to example, the invention will be further described.
Embodiment 1：(Y0.84Nd0.08Er0.08)2O3-0.01(Y0.95La0.05)2O3（X=0.08, y=0.08, z=0.05, M=
Er, N=La）
Weigh during the yttrium nitrate of 0.84 mol, the neodymium nitrate of 0.08 mol, the erbium nitrate of 0.08 mol are put into deionized water and mix
Uniformly, then it is situated between by mill of zirconia ball, ball milling mixing 4 hours is calcined 2 hours at 1550 DEG C again after drying, obtain (Y, Nd,
Er)2O3Phase powder.Weigh during the yttrium nitrate of 0.0095 mol, the lanthanum nitrate of 0.0005 mol are put into deionized water and be well mixed,
It is subsequently adding (Y, Nd, the Er) of above-mentioned synthesis2O3, then be spray-dried for mixture by phase powder, ball milling mixing 4 hours, is removed
Fall deionized water.The powder obtained after spray drying is put into mould, in the forming under the pressure of 10 MPa, is then warmed up to
1050 DEG C are incubated 4 hours, are placed into after cooling in isostatic pressing machine, and isostatic pressed is carried out under 300 MPa；By the product after isostatic pressed
Thing is put in a vacuum furnace, and 4 hours are incubated at 1750 DEG C, is annealed 2 hours in 1500 DEG C of air again after cooling, that is, obtain this
The yttria-base laser ceramics of the Nd sensitizations of invention.
Embodiment 2：(Y0.985Nd0.01Dy0.005)2O3-0.2(Y0.88La0.09Zr0.03)2O3（X=0.01, y=0.005, z=
0.12, M=Dy, N=La, Zr）
Weigh yittrium oxide, the yttrium nitrate of 0.085 mol, the neodymium nitrate of 0.01 mol, the acetic acid dysprosium of 0.005 mol of 0.45 mol
It is put into deionized water and is well mixed, is then situated between by mill of zirconia ball, ball milling mixing 24 hours, again at 1250 DEG C after drying
Calcining 8 hours, obtains (Y, Nd, Dy)2O3Phase powder.Weigh yttrium nitrate, the lanthanum nitrate of 0.018 mol, 0.006 of 0.176 mol
The zirconium nitrate of mol is well mixed in being put into deionized water, is then situated between by mill of zirconia ball, ball milling mixing 24 hours, after drying
Calcined 1 hour at 1050 DEG C again, obtained (Y, La, Zr)2O3Phase powder.By (Y, Nd, the Dy) of above-mentioned preparation2O3Phase powder with
(Y,La,Zr)2O3Phase powder is mixed, and is put into ball grinder, is situated between by mill of zirconia ball, and ball milling mixing 24 hours is mixed
Close powder；Will above-mentioned mixed powder dry after it is compressing, by the isostatic cool pressing of 180 MPa, then put in a vacuum furnace,
1550 DEG C are incubated 24 hours, are annealed 8 hours in 900 DEG C of air again after cooling, that is, obtain the oxygen of Nd sensitizations of the invention
Change yttrium base laser ceramics.
Embodiment 3：(Y0.8Nd0.1Er0.1)2O3-0.1(Y0.8La0.1Ti0.05Al0.05)2O3（X=0.1, y=0.1, z=0.2, M=
Er, N=La, Ti, Al）
Weigh the yittrium oxide of 0.25 mol, the yttrium nitrate of 0.15 mol, the acetic acid yttrium of 0.15 mol, the neodymium nitrate of 0.1 mol,
The acetic acid erbium of 0.1 mol is well mixed in being put into deionized water, is then situated between by mill of zirconia ball, and ball milling mixing 12 hours is done
Calcined 6 hours at 1500 DEG C again after dry, obtained (Y, Nd, Er)2O3Phase powder.Weigh yttrium nitrate, 0.04 mol of 0.04 mol
Acetic acid yttrium, the lanthanum acetate of 0.01 mol, the butyl titanate of 0.005mol, the aluminum nitrate of 0.005mol be put into deionized water
It is well mixed, it is subsequently adding (Y, Nd, the Er) of above-mentioned synthesis2O3Phase powder, ball milling mixing 12 hours, is then carried out mixture
Spray drying, removes deionized water.The powder obtained after spray drying is put into mould, in the forming under the pressure of 20 MPa,
Then 1250 DEG C are warmed up to and are incubated 2 hours, placed into after cooling in isostatic pressing machine, isostatic pressed is carried out under 200 MPa；Will etc.
Product after static pressure is put in a vacuum furnace, and 8 hours are incubated at 1650 DEG C, and annealing 5 is small in 1200 DEG C of air again after cooling
When, that is, obtain the yttria-base laser ceramics of Nd sensitizations of the invention.
Embodiment 4：(Y0.87Nd0.05Dy0.08)2O3-0.1(Y0.9Zr0.04Mn0.03Ca0.03)2O3（X=0.05, y=0.08, z=
0.1, M=Dy, N=Zr, Mn, Ca）
Weigh yittrium oxide, 0.1 mol yttrium nitrates, 0.17 mol acetic acid yttriums, acetic acid neodymium, 0.08 of 0.05 mol of 0.3 mol
The acetic acid dysprosium of mol is well mixed in being put into deionized water, is then situated between by mill of zirconia ball, ball milling mixing 10 hours, after drying
Calcined 7 hours at 1450 DEG C again, obtained (Y, Nd, Dy)2O3Phase powder.Weigh acetic acid yttrium, the vinegar of 0.004 mol of 0.09 mol
Sour zirconium, the manganese acetate of 0.003 mol, the calcium acetate of 0.003 mol are well mixed in being put into deionized water, then with zirconia ball
For mill is situated between, ball milling mixing 12 hours is calcined 2 hours at 1150 DEG C again after drying, and is obtained (Y, Zr, Mn, Ca)2O3Phase powder.Will
(Y, Nd, the Dy) of above-mentioned preparation2O3Phase powder and (Y, Zr, Mn, Ca)2O3Phase powder is mixed, and is put into ball grinder, with oxygen
Change zirconium ball for mill is situated between, ball milling mixing 8 hours obtains mixed powder；It is compressing after above-mentioned mixed powder is dried, by 250
The isostatic cool pressing of MPa, then puts in a vacuum furnace, 12 hours is incubated at 1600 DEG C, after cooling again in 1300 DEG C of air
Annealing 3 hours, that is, obtain the yttria-base laser ceramics of Nd sensitizations of the invention.
Embodiment 5：(Y0.88Nd0.08Er0.04)2O3-0.15(Y0.88La0.1Zn0.01Mg0.01)2O3（X=0.08, y=0.04, z=
0.12, M=Er, N=La, Zn, Mg）
Weigh during the yttrium nitrate of 0.88 mol, the acetic acid neodymium of 0.08 mol, the acetic acid erbium of 0.04 mol are put into deionized water and mix
Uniformly, then it is situated between by mill of zirconia ball, ball milling mixing 24 hours is calcined 7 hours at 1350 DEG C again after drying, obtain (Y,
Nd,Er)2O3Phase powder.Weigh the yttrium nitrate of 0.132 mol, the lanthanum nitrate of 0.015 mol, the zinc acetate of 0.0015 mol,
The magnesium acetate of 0.0015 mol is well mixed in being put into deionized water, is subsequently adding (Y, Nd, the Er) of above-mentioned synthesis2O3Phase powder,
, then be spray-dried for mixture by ball milling mixing 6 hours, removes deionized water.The powder obtained after spray drying is put
Enter in mould, in the forming under the pressure of 15 MPa, be then warmed up to 1100 DEG C and be incubated 3 hours, isostatic pressing machine is placed into after cooling
In, isostatic pressed is carried out under 200 MPa；Product after isostatic pressed is put in a vacuum furnace, 20 hours are incubated at 1550 DEG C, it is cold
But annealed 3 hours in 1450 DEG C of air again after, that is, obtain the yttria-base laser ceramics of Nd sensitizations of the invention.
Claims (10)
1. the yttria-base laser ceramics that a kind of Nd is sensitized, it is characterised in that the crystal grain of ceramics has core shell structure, and stratum nucleare is
(Y1-x-yNdxMy)2O3Phase, shell are (Y1-zNz)2O3Phase, wherein 0.01≤x≤0.1,0.005≤y≤0.1,0.05
≤ z≤0.2, M is the one kind in rare earth luminous ion Er and Dy, and N is sintering aid La, Zr, Ti, Mn, Al, Ca, Zn and Mg
In one or more, the mol ratio of shell material and stratum nucleare material is 0.01~0.2:1.
2. the method for preparing the yttria-base laser ceramics that the Nd described in claim 1 is sensitized, it is characterised in that including following steps
Suddenly：
(1) compound of the compound of yttrium, the compound of neodymium and M element is weighed by the amount of stratum nucleare material, and is put into deionized water
In be well mixed, then with zirconia ball for mill be situated between, ball milling mixing 4~24 hours, dry after again 1250~1550 DEG C calcine
2~8 hours, obtain Nd and enter Y with M solid solutions2O3In (Y, Nd, M)2O3Phase powder；
(2) weigh the compound of yttrium and the compound of N element by the amount of shell material, and be put into deionized water and be well mixed,
It is subsequently adding (Y, Nd, the M) of step (1) synthesis2O3Phase powder, ball milling mixing 4~24 hours, is then sprayed mixture
Dry, remove deionized water；
(3) powder obtained after spray drying is put into mould, in the forming under the pressure of 10~40 MPa, is then warmed up to
1050~1250 DEG C are incubated 1~4 hour, are placed into after cooling in isostatic pressing machine, and isostatic pressed is carried out under 180~300 MPa；
(4) product after isostatic pressed is put in a vacuum furnace, 4~24 hours is incubated at 1550~1750 DEG C, exist again after cooling
Annealed 2~8 hours in 900~1500 DEG C of air, obtain the yttria-base laser ceramics of Nd sensitizations.
3. it is according to claim 2 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that it is described
The compound of yttrium is one or more in yittrium oxide, yttrium nitrate and acetic acid yttrium.
4. it is according to claim 2 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that it is described
The compound of neodymium is one or more in neodymia, neodymium nitrate and acetic acid neodymium.
5. it is according to claim 2 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that described M
The compound of element is the one kind in erbium oxide, erbium nitrate, acetic acid erbium, dysprosia, dysprosium nitrate and acetic acid dysprosium.
6. it is according to claim 2 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that described N
The compound of element is lanthanum nitrate, lanthanum acetate, zirconium nitrate, acetic acid zirconium, butyl titanate, Titanium Nitrate, manganese nitrate, manganese acetate, nitre
One or more in sour aluminium, aluminum acetate, calcium nitrate, calcium acetate, zinc nitrate, zinc acetate, magnesium nitrate and magnesium acetate.
7. the method for preparing the yttria-base laser ceramics that the Nd described in claim 1 is sensitized, it is characterised in that including following steps
Suddenly：
(1) compound of the compound of yttrium, the compound of neodymium and M element is weighed by the amount of stratum nucleare material, and is put into deionized water
In be well mixed, then with zirconia ball for mill be situated between, ball milling mixing 4~24 hours, dry after again 1250~1550 DEG C calcine
2~8 hours, obtain Nd and enter Y with M solid solutions2O3In (Y, Nd, M)2O3Phase powder；
(2) weigh the compound of yttrium and the compound of N element by the amount of shell material, and be put into deionized water and be well mixed,
Then it is situated between by mill of zirconia ball, ball milling mixing 4~24 hours is calcined 1~4 hour at 1050~1250 DEG C again after drying, and is obtained
Obtain N solid solutions and enter Y2O3In (Y, N)2O3Phase powder；
(3) powder that above-mentioned steps (1) are prepared with step (2) is mixed, is put into ball grinder, be mill with zirconia ball
It is situated between, ball milling mixing 4~24 hours obtains mixed powder；
(4) it is compressing after above-mentioned mixed powder is dried, by the isostatic cool pressing of 180~300 MPa, then it is placed on vacuum drying oven
In, 4~24 hours are incubated at 1550~1750 DEG C, annealed 2~8 hours in 900~1500 DEG C of air again after cooling, obtain
To the yttria-base laser ceramics of Nd sensitizations.
8. it is according to claim 7 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that it is described
The compound of yttrium is one or more in yittrium oxide, yttrium nitrate and acetic acid yttrium；The compound of described neodymium is neodymia, nitric acid
One or more in neodymium and acetic acid neodymium.
9. it is according to claim 7 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that described M
The compound of element is the one kind in erbium oxide, erbium nitrate, acetic acid erbium, dysprosia, dysprosium nitrate and acetic acid dysprosium.
10. it is according to claim 7 prepare Nd sensitization yttria-base laser ceramics method, it is characterised in that it is described
The compound of N element is lanthana, lanthanum nitrate, lanthanum acetate, zirconium oxide, zirconium nitrate, acetic acid zirconium, titanium oxide, butyl titanate, nitre
Sour titanium, manganese oxide, manganese nitrate, manganese acetate, aluminum oxide, aluminum nitrate, aluminum acetate, calcium oxide, calcium nitrate, calcium acetate, zinc oxide, nitre
One or more in sour zinc, zinc acetate, magnesia, magnesium nitrate and magnesium acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710025333.3A CN106830935B (en) | 2017-01-13 | 2017-01-13 | Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710025333.3A CN106830935B (en) | 2017-01-13 | 2017-01-13 | Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106830935A true CN106830935A (en) | 2017-06-13 |
| CN106830935B CN106830935B (en) | 2020-01-24 |
Family
ID=59124351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710025333.3A Active CN106830935B (en) | 2017-01-13 | 2017-01-13 | Nd-sensitized yttrium oxide-based laser ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106830935B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359271A (en) * | 2018-02-23 | 2018-08-03 | 中国科学院包头稀土研发中心 | A kind of high temperature resistant purple rare-earth ceramic colorant and preparation method thereof |
| CN110342907A (en) * | 2019-07-22 | 2019-10-18 | 中国科学院上海光学精密机械研究所 | A kind of Y2O3The preparation method of-MgO Nanocomposite infra-red china |
| CN113549446A (en) * | 2021-07-09 | 2021-10-26 | 上海大学 | Neodymium-sensitized rare earth luminescent multilayer core-shell structure material, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897358A (en) * | 1971-03-01 | 1975-07-29 | Gen Electric | Polycrystalline ceramic lasers |
| JPH05294709A (en) * | 1992-04-13 | 1993-11-09 | Kunio Yoshida | Polycrystalline transparent ceramic for laser |
| CN103864409A (en) * | 2014-01-28 | 2014-06-18 | 中国科学院上海光学精密机械研究所 | Preparation method of neodymium-doped yttrium aluminum garnet transparent ceramic |
| CN105565810A (en) * | 2015-12-27 | 2016-05-11 | 西南技术物理研究所 | Preparation method of rare-earth-doped yttrium oxide laser ceramic optical fiber |
| CN105601277A (en) * | 2015-12-23 | 2016-05-25 | 江苏师范大学 | Preparation method of yttrium oxide-based transparent ceramic |
-
2017
- 2017-01-13 CN CN201710025333.3A patent/CN106830935B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897358A (en) * | 1971-03-01 | 1975-07-29 | Gen Electric | Polycrystalline ceramic lasers |
| JPH05294709A (en) * | 1992-04-13 | 1993-11-09 | Kunio Yoshida | Polycrystalline transparent ceramic for laser |
| CN103864409A (en) * | 2014-01-28 | 2014-06-18 | 中国科学院上海光学精密机械研究所 | Preparation method of neodymium-doped yttrium aluminum garnet transparent ceramic |
| CN105601277A (en) * | 2015-12-23 | 2016-05-25 | 江苏师范大学 | Preparation method of yttrium oxide-based transparent ceramic |
| CN105565810A (en) * | 2015-12-27 | 2016-05-11 | 西南技术物理研究所 | Preparation method of rare-earth-doped yttrium oxide laser ceramic optical fiber |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108359271A (en) * | 2018-02-23 | 2018-08-03 | 中国科学院包头稀土研发中心 | A kind of high temperature resistant purple rare-earth ceramic colorant and preparation method thereof |
| CN110342907A (en) * | 2019-07-22 | 2019-10-18 | 中国科学院上海光学精密机械研究所 | A kind of Y2O3The preparation method of-MgO Nanocomposite infra-red china |
| CN110342907B (en) * | 2019-07-22 | 2023-02-14 | 中国科学院上海光学精密机械研究所 | Preparation method of Y2O3-MgO nano complex phase infrared ceramic |
| CN113549446A (en) * | 2021-07-09 | 2021-10-26 | 上海大学 | Neodymium-sensitized rare earth luminescent multilayer core-shell structure material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106830935B (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ikesue et al. | Synthesis of Nd3+, Cr3+‐codoped YAG ceramics for high‐efficiency solid‐state lasers | |
| CN106673652A (en) | Yttrium oxide-based laser ceramics with core-shell structure and preparation method thereof | |
| CN101284733B (en) | Yttrium aluminium garnet and yttria double crystal transparent ceramic and method for making same | |
| CN111205081B (en) | Single-structure type low-color-temperature high-color-rendering-index fluorescent ceramic and preparation method and application thereof | |
| CN104557041B (en) | Preparation method of yttria-base transparent ceramic | |
| Yu et al. | Fabrication of Nd: YAG transparent ceramics using powders synthesized by citrate sol-gel method | |
| CN108751991B (en) | Preparation of Tb: Lu by laser sintering2O3Method for producing ceramic | |
| CN105601277A (en) | Preparation method of yttrium oxide-based transparent ceramic | |
| CN110885684B (en) | Rare earth doped barium scandium aluminate up-conversion luminescent material and preparation method thereof | |
| CN106830935A (en) | A kind of yttria-base laser ceramics of Nd sensitizations and preparation method thereof | |
| CN101148357A (en) | Method for preparing Yb3+ mixed lanthanum yttrium oxide upconversion luminous transparent laser ceramic | |
| CN113773081A (en) | Transparent ceramic and preparation method thereof | |
| CN106631022A (en) | Tm sensitized yttria-based laser ceramic and preparation method | |
| CN106800410A (en) | A kind of yttria-base laser ceramics of Yb sensitizations and preparation method thereof | |
| CN115557787B (en) | Sesquioxide transparent ceramic and preparation method thereof | |
| CN106800412A (en) | A kind of yttria-base transparent ceramics with core shell structure and preparation method thereof | |
| CN100447106C (en) | Method for preparing transparent polycrystal ceramics and laser ceramics in Y2O3 base with La3+ being mixed into | |
| CN103073295B (en) | Preparation method of Er3+ and Tm3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material | |
| CN104830344B (en) | A kind of Er3+,Yb3+The preparation method being co-doped with YOF redness upconverting fluorescent material | |
| CN102515751A (en) | Upconversion luminescent transparent ceramic material and preparation method thereof | |
| Jiang et al. | Synthesis and properties of Yb: Sc2O3 transparent ceramics | |
| CN104150904A (en) | Preparation method of Er<3+>-single-doped yttrium lanthanum oxide transparent ceramic for middle infrared lasers | |
| CN109354496B (en) | Preparation method of yttrium vanadate transparent ceramic | |
| CN106810256B (en) | Yttria-based powder with core-shell structure and preparation method thereof | |
| CN107573071B (en) | Monodisperse spherical Y2O3And Al2O3Powder preparation (Y)1-xYbx) Method for preparing AG transparent ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |