CN106747398A - A kind of preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate - Google Patents
A kind of preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate Download PDFInfo
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- CN106747398A CN106747398A CN201611108063.4A CN201611108063A CN106747398A CN 106747398 A CN106747398 A CN 106747398A CN 201611108063 A CN201611108063 A CN 201611108063A CN 106747398 A CN106747398 A CN 106747398A
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- Prior art keywords
- copper
- magnesium aluminate
- aluminum bar
- cladding aluminum
- luminescent material
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- 239000011777 magnesium Substances 0.000 title claims abstract description 83
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 63
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000005253 cladding Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 18
- 239000011240 wet gel Substances 0.000 claims abstract description 18
- 239000000499 gel Substances 0.000 claims abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 35
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 18
- 229910002651 NO3 Inorganic materials 0.000 description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000000889 atomisation Methods 0.000 description 6
- 230000001413 cellular effect Effects 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011029 spinel Substances 0.000 description 3
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
-
- 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
- C04B35/624—Sol-gel processing
-
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- 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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- 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
Abstract
The present invention discloses a kind of preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate, belongs to luminescent material preparing technical field.The present invention uses improved sol gel processing --- collosol and gel microcell complexometry, with Mg (NO3)2·6H2O、Cu(NO3)2·3H2O、Al(NO3)3·9H2O and C2H2O4·2H2O prepares wet gel for raw material, and wet gel is through drying, calcining, ball milling, base, shaping, high temperature sintering, you can prepare the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate of spinel-type.The tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate prepared by the method for the invention is in ultraviolet light（280nm）Under shooting condition, 470nm（Blue light region）And 720nm（Red light district）Transmitting peak intensity can be adjusted by the doping of copper；Intrinsic magnesium aluminate is luminous main in red light district, and Copper-cladding Aluminum Bar magnesium aluminate can suitably strengthen 470nm and suitably weaken 720nm transmitting peak intensities so that two peak intensities are approached, and realize the tuning of blue light and feux rouges.Therefore, spinel-type Copper-cladding Aluminum Bar magnesium aluminate ceramic material is the Novel submarine for preparing visible light wave range tunable solid laser part in material.
Description
Technical field
The present invention relates to a kind of tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate and its improved preparation method, belong to luminous material
Material preparing technical field.
Background technology
Magnesium aluminate ceramics have good physical property and chemical property, and such as chemical stability is good, wear-resisting, corrosion-resistant, heat
The coefficient of expansion is small, the crystalline material of good insulation preformance, while having good mechanical property, heat shaken stability and slag resistance
Deng.Can be applied to the fields such as refractory material, optical material, catalyst and moisture sensor.
In magnesium aluminate ceramic preparation, sol-gel process is relatively common preparation method.Traditional collosol and gel
Method be by organic or inorganic compound by solution, colloidal sol, gel, drying, the process such as heat treatment and prepare magnesium aluminate
A kind of method.The raw material of the method is usually simple metal and alcohol or metal alkoxide, the phase of both sol gel courses of reaction
It is the hydrolysis based on metal alkoxide with point, realizes the step, deionized water, therefore the speed that adds water must be introduced in reaction system
Control it is solidifying on colloidal sol-gel process and form the particle diameter of powder and have vital influence, and finally influence magnesium aluminate
The performance of ceramics.In addition, this method has shortcomings in that：The prices of raw materials are expensive, and preparation flow is complicated, colloidal sol-solidifying
Gel process and diameter of particle are difficult to effectively control, large amount of organic or other metal salt anions（Such as Cl-）Presence make
Obtain wet gel and be difficult to removal etc. completely in drying, calcination stage.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate, the material with
Mg(NO3)2·6H2O、Cu(NO3)2·3H2O、Al(NO3)3·9H2O and C2H2O4·2H2O is raw material, using collosol and gel microcell
Complexometry prepares wet gel, and wet gel is through drying, calcining, ball milling, base, shaping, high temperature sintering, you can obtain Cu y Mg1- y Al2O4（0.1% ≤ y≤ 1.0%）Tunable luminescent material；The tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate prepared by the present invention
Tunable luminescent material is in ultraviolet light（280nm）Under shooting condition, 470nm（Blue light region）And 720nm（Red light district）Transmitting peak intensity
Degree can be adjusted by the doping of copper；Intrinsic magnesium aluminate is luminous main in red light district, and Copper-cladding Aluminum Bar magnesium aluminate can suitably strengthen
470nm simultaneously suitably weakens 720nm transmitting peak intensities so that two peak intensities are approached, and realize the tuning of blue light and feux rouges；Cause
This, spinel-type Copper-cladding Aluminum Bar magnesium aluminate ceramic material is the Novel submarine for preparing visible light wave range tunable solid laser part in material
Material.
The preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate of the present invention, specifically includes following steps：
（1）Using new sol-gel microcell complexometry, with Mg (NO3)2·6H2O、Cu(NO3)2·3H2O and Al
(NO3)3·9H2O is raw material, absolute ethyl alcohol is dissolved in proportion and obtains solution A, by C2H2O4·2H2O is dissolved in absolute ethyl alcohol and adds
Dispersant obtains solution B, is added in solution A after solution B is atomized, and solution C is obtained after being well mixed, and C is stirred at room temperature molten
Liquid makes it fully react, and then heating makes ethanol evaporation can obtain wet gel, before the wet gel drying that will be obtained overnight is obtained
Drive body, wherein C2H2O4·2H2O is 1.0 ~ 1.2 with the mol ratio of total metal ion；
（2）Presoma is placed in kiln roasting, after furnace cooling, ball milling obtains Copper-cladding Aluminum Bar magnesium aluminate powder in 1 ~ 2 hour；
（3）Then powder is obtained into the Copper-cladding Aluminum Bar magnesium aluminate tunable luminescent material of ceramics after base, shaping, high temperature sintering, its
Expression formula is Cu y Mg1-y Al2O4, whereiny=0.1%~1.0%。
Preferably, step of the present invention（1）It is middle to be added in solution A solution B with atomised form, and completed at 30 minutes,
Fully it is complexed in microcell.
Preferably, dispersant of the present invention is ethylene glycol and usage amount is 0.4 ~ 0.6ml of every 100ml reaction solutions addition
Ethylene glycol.
Preferably, step of the present invention（1）The middle reaction time is 4 ~ 6h, and the condition of etoh solvent evaporation is 70~80 DEG C of stirrings
1~3 hour.
Preferably, step of the present invention（2）The sintering temperature of middle roasting is 700 ~ 900 DEG C, and roasting time is 4 ~ 6 hours.
Preferably, step of the present invention（3）Described base is to be pressurized to 10 ~ 30Mpa by slow on tablet press machine, pressurize 1 ~
Unloading, the demoulding are that can obtain pie base substrate after 2 minutes.
Preferably, step of the present invention（3）High temperature sintering temperature is 1400 ~ 1600 DEG C, and sintering time is 4 ~ 6 hours.
Principle of the invention：
（1）Shortcoming of the present invention for common sol-gel method is improved, and work is prepared using the sol-gel after improvement
Skill --- sol-gel microcell complexometry has prepared the spinelle tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate；Using cheap easy
The nitrate compound and solvent for obtaining, Mg (NO3)2·6H2O、Cu(NO3)2·3H2O and Al (NO3)3·9H2O.Advantage includes it
One, because ethyl alcohol boiling point is low, wet gel ethanol when drying for 120 DEG C can volatilize rapidly, form the cellular xerogel of fritter, molten
Agent dries more thorough；Second, C2H2O4·2H2O simple structures, main chain only has two carbon atoms, when calcining for 700 ~ 900 DEG C,
C2H2O4·2H2O and nitrate ion can completely become gas and discharge, noresidue, and the fritter for being formed in addition is cellular to be also beneficial to
C2H2O4·2H2The removal of O and nitrate ion；Third, flow is simple and reliable.
（2）Using C2H2O4·2H2O as microcell complexing agent, by a certain amount of C2H2O4·2H2O is dissolved in absolute ethyl alcohol
In, it is subsequently adding appropriate dispersant --- ethylene glycol, solution A is added to after atomization and was completed at 30 minutes, this is sol-gel
The key point of microcell complexometry；Under magnetic stirring, C2H2O4·2H2Forming small drop after O atomizations has the sufficient time
Fully reaction, complexing, the gelation in microcell with solution A, the process is referred to as the complexing of sol-gel microcell, and the method can be more
Plus effective control forms the particle diameter of particle so that the split particle diameter of preparation is evenly, careful, favorably reaches atom level and uniformly mixes
Close.
Beneficial effects of the present invention：
（1）The method of the invention significantly more efficient can control to form the particle diameter of particle so that the split particle diameter of preparation evenly,
It is careful, favorably reach atom level and uniformly mix.
（2）The ultraviolet excitation of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate prepared by the method for the invention in 280nm
Under, 470nm（Blue light region）And 720nm（Red light district）Transmitting peak intensity can be adjusted suitably so that two peak intensities are approached, and are realized
The tuning of blue light and feux rouges；In consideration of it, spinel-type Copper-cladding Aluminum Bar magnesium aluminate ceramic material prepared by the method is to prepare visible light wave
The Novel submarine of section tunable solid laser part is in material.
（4）Copper-cladding Aluminum Bar aluminic acid magnesium material in the method for the invention, which part Mg rooms only replace to form solid solution by Cu
Body, realizes the regulation of magnesium aluminate device for Optical Properties of Materials.
Brief description of the drawings
Fig. 1 is 900 DEG C of XRDs of the magnesium aluminate powder of the different Cu doping concentration of roasting；
Fig. 2 is 1500 DEG C of XRDs of the magnesium aluminate ceramics of the different Cu doping concentration of sintering 5h；
Fig. 3 is 1500 DEG C of launching light spectrograms of the magnesium aluminate ceramics of the different Cu doping concentration of sintering 5h.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
The Cu of the present embodiment y Mg1-y Al2O4（y=0.1%）The preparation of ceramics is comprised the following steps and carried out：
（1）Press（n Mg+n Cu）:n Al= 1 :2 molar ratio weighing 2.5614g Mg (NO3)2·6H2O、0.0024g Cu
(NO3)2·3H2O and 7.5026g Al (NO3)3·9H2O, is dissolved in three 60ml absolute ethyl alcohols and obtains A solution；Weigh
C2H2O4·2H2O is dissolved in the absolute ethyl alcohol of 40ml（C2H2O4·2H2O is 1.0 with total metal ion mol ratio）, and add 0.6mL
Dispersant（Ethylene glycol）, it is uniformly mixed and obtains B solution；To be added in A solution after B solution atomizations with atomizer
And completed at 30 minutes, obtain C solution after being well mixed；80 DEG C of constant temperature stirring 2h after C solution 5h are stirred at room temperature, steam
Light blue wet gel is can obtain after hair ethanol, wet gel to dry that overnight can obtain cellular fritter fluffy at 120 DEG C
Xerogel, i.e. presoma.
（2）By step（1）The presoma of the magnesium aluminate for obtaining is placed in chamber type electric resistance furnace, and 5h is calcined in 900 DEG C, cold with stove
But to taking-up after room temperature, ball milling obtains the magnesium aluminate powder that copper volume is 0.1% for 1 hour in placing into ball mill.
（3）Take appropriate step（2）The aluminic acid magnesium dust for obtaining is poured into mould, is then slowly pressurized on tablet press machine
30Mpa, unloading, the demoulding are that can obtain pie base substrate after pressurize 1min；Pie base substrate, the aluminium that sintering 5h is obtained are sintered in 1500 DEG C
Sour magnesium ceramics.
Under identical preparation condition, take respectivelyy=0%,y=0.3%,y=0.5%,y=1.0%, prepare different aluminic acids
Magnesium ceramics.
Fig. 1 is 900 DEG C of XRDs of the magnesium aluminate powder of the different Cu doping concentration of roasting, as can be seen from Figure 1, at 900 DEG C
Under roasting, Copper-cladding Aluminum Bar magnesium aluminate powder has formd single-phase spinel structure, and powder halfwidth hands over narrow, crystallinity compared with
It is high.
Fig. 2 is 1500 DEG C of XRDs of the magnesium aluminate ceramics of the different Cu doping concentration of sintering 5h, as can be seen from Figure 2, the powder
Body has knot very high by the Copper-cladding Aluminum Bar magnesium aluminate ceramics prepared after calcining, ball milling, base, shaping, high temperature sintering treatment
Brilliant degree, and be single Spinel, with purity very high.
Fig. 3 is 1500 DEG C of launching light spectrograms of the magnesium aluminate ceramics of the different Cu doping concentration of sintering 5h, can from Fig. 3
Go out, gradually increase with Cu doping concentrations, 470nm（Blue light region）Transmitting peak intensity first increases and then decreases, is 0.5% in Cu dopings
When reach maximum, Cu doping MgAl2O4The intensity of ceramic 470nm emission peaks saturation；Cu doping MgAl2O4Ceramic 720nm
（Red light district）The linear taper with the increase of Cu volumes of emission peak.
Embodiment 2
The Cu of the present embodiment y Mg1-y Al2O4（y=0.3%）The preparation of ceramics is comprised the following steps and carried out：
（1）Press（n Mg+n Cu）:n Al= 1 :2 molar ratio weighing 2.5563g Mg (NO3)2·6H2O、0.0072g Cu
(NO3)2·3H2O and 7.5026g Al (NO3)3·9H2O, is dissolved in three 60ml absolute ethyl alcohols and obtains A solution；
Weigh C2H2O4·2H2O is dissolved in the absolute ethyl alcohol of 40ml（C2H2O4·2H2O is 1.0 with total metal ion mol ratio）, and
Add the dispersant of 0.6mL（Ethylene glycol）, it is uniformly mixed and obtains B solution；To be added to after B solution atomizations with atomizer
Completed in A solution and at 30 minutes, C solution is obtained after being well mixed；75 DEG C of constant temperature after C solution 5h are stirred at room temperature
Stirring 1.5h, light blue wet gel is can obtain after ethanol evaporation, wet gel dried at 120 DEG C overnight can obtain it is cellular
The fluffy xerogel of fritter, i.e. presoma.
（2）By step（1）The presoma of the magnesium aluminate for obtaining is placed in chamber type electric resistance furnace, and 6h is calcined in 700 DEG C, cold with stove
But to taking-up after room temperature, ball milling obtains copper volume for 1 hour for 0.3% magnesium aluminate powder in placing into ball mill.
（3）Take appropriate step（2）The aluminic acid magnesium dust for obtaining is poured into mould, is then slowly pressurized on tablet press machine
30Mpa, unloading, the demoulding are that can obtain pie base substrate after pressurize 1min；Pie base substrate, the aluminium that sintering 6h is obtained are sintered in 1400 DEG C
Sour magnesium ceramics.
Embodiment 3
The Cu of the present embodiment y Mg1-y Al2O4（y=0.5%）The preparation of ceramics is comprised the following steps and carried out：
（1）Press（n Mg+n Cu）:n Al= 1 :2 molar ratio weighing 2.5512g Mg (NO3)2·6H2O、0.0121g Cu
(NO3)2·3H2O and 7.5026g Al (NO3)3·9H2O, is dissolved in three 60ml absolute ethyl alcohols and obtains A solution；Weigh
C2H2O4·2H2O is dissolved in the absolute ethyl alcohol of 40ml（C2H2O4·2H2O is 1.1 with total metal ion mol ratio, and adds 0.6mL's
Dispersant（Ethylene glycol）, it is uniformly mixed and obtains B solution；To be added to after B solution atomizations in A solution simultaneously with atomizer
Completed at 30 minutes, C solution is obtained after being well mixed；80 DEG C of constant temperature stirring 2h, evaporation after C solution 6h are stirred at room temperature
Light blue wet gel is can obtain after ethanol, wet gel is dried at 120 DEG C and overnight can obtain that cellular fritter is fluffy to be done
Gel, i.e. presoma.
（2）By step（1）The presoma of the magnesium aluminate for obtaining is placed in chamber type electric resistance furnace, and 6h is calcined in 800 DEG C, cold with stove
But to taking-up after room temperature, ball milling obtains the magnesium aluminate powder that copper volume is 0.5% for 1 hour in placing into ball mill.
（3）Take appropriate step（2）The aluminic acid magnesium dust for obtaining is poured into mould, is then slowly pressurized on tablet press machine
10Mpa, unloading, the demoulding are that can obtain pie base substrate after pressurize 2min；Respectively at 1600 DEG C of examination sintering pie base substrates, 4h is sintered
The magnesium aluminate ceramics for obtaining.
Embodiment 4
The Cu of the present embodiment y Mg1-y Al2O4（y=1.0 %）The preparation of ceramics is comprised the following steps and carried out：
（1）Press（n Mg+n Cu）:n Al= 1 :2 molar ratio weighing 2.5384g Mg (NO3)2·6H2O、0.0242g Cu
(NO3)2·3H2O and 7.5026g Al (NO3)3·9H2O, is dissolved in three 60ml absolute ethyl alcohols and obtains A solution；Weigh
C2H2O4·2H2O is dissolved in the absolute ethyl alcohol of 40ml（C2H2O4·2H2O is 1.2 with total metal ion mol ratio）, and add 0.6mL
Dispersant（Ethylene glycol）, it is uniformly mixed and obtains B solution；To be added in A solution after B solution atomizations with atomizer
And completed at 30 minutes, obtain C solution after being well mixed；70 DEG C of constant temperature stirring 3h after C solution 4h are stirred at room temperature, steam
Light blue wet gel is can obtain after hair ethanol, wet gel to dry that overnight can obtain cellular fritter fluffy at 120 DEG C
Xerogel, i.e. presoma.
（2）By step（1）The presoma of the magnesium aluminate for obtaining is placed in chamber type electric resistance furnace, and 5h is calcined in 850 DEG C, cold with stove
But to taking-up after room temperature, ball milling obtains the magnesium aluminate powder that copper volume is 1.0% for 1 hour in placing into ball mill.
（3）Take appropriate step（2）The aluminic acid magnesium dust for obtaining is poured into mould, is then slowly pressurized on tablet press machine
20Mpa, unloading, the demoulding are that can obtain pie base substrate after pressurize 1min；In 1600 DEG C of examination sintering pie base substrates, sintering 5h is obtained
Magnesium aluminate ceramics.
In sum, the preparation method for being provided using the present invention has prepared the spinel structure of high-purity, high-crystallinity
Copper-cladding Aluminum Bar magnesium aluminate ceramic material, show the present invention offer improved method be effective.Additionally, the Copper-cladding Aluminum Bar magnesium aluminate is made pottery
Under the ultraviolet excitation of 280nm, we can artificially to 470nm for ceramic material（Blue light region）And 720nm（Red light district）Emission peak
Intensity carries out appropriate regulation so that two peak intensities are approached, and realize the tuning of blue light and feux rouges.In consideration of it, spinel-type copper
Doping magnesium aluminate ceramic material is the Novel submarine for preparing visible light wave range tunable solid laser part in material.
Claims (7)
1. a kind of preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate, it is characterised in that comprise the following steps：
（1）Using new sol-gel microcell complexometry, with Mg (NO3)2·6H2O、Cu(NO3)2·3H2O and Al (NO3)3·
9H2O is raw material, absolute ethyl alcohol is dissolved in proportion and obtains solution A, by C2H2O4·2H2O is dissolved in absolute ethyl alcohol and adds dispersant to obtain
To solution B, it is added in solution A after solution B is atomized, solution C is obtained after being well mixed, C solution is stirred at room temperature fills it
Divide reaction, then heating makes ethanol evaporation can obtain wet gel, the wet gel drying that will be obtained overnight obtains presoma, wherein
C2H2O4·2H2O is 1.0 ~ 1.2 with the mol ratio of total metal ion；
（2）Presoma is placed in kiln roasting, after furnace cooling, ball milling obtains Copper-cladding Aluminum Bar magnesium aluminate powder in 1 ~ 2 hour；
（3）Then powder is obtained into the Copper-cladding Aluminum Bar magnesium aluminate tunable luminescent material of ceramics after base, shaping, high temperature sintering, its
Expression formula is Cu y Mg1-y Al2O4, whereiny=0.1%~1.0%。
2. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate according to claim 1, it is characterised in that：Step
（1）It is middle to be added in solution A solution B with atomised form, and completed at 30 minutes, fully it is complexed in microcell.
3. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate according to claim 1, it is characterised in that：Described
Dispersant is ethylene glycol and usage amount is every 100ml reaction solutions addition 0.4 ~ 0.6ml ethylene glycol.
4. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate according to claim 1, it is characterised in that：Step
（1）The middle reaction time is 4 ~ 6h, and the condition of etoh solvent evaporation is 70~80 DEG C and stirs 1~3 hour.
5. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate according to claim 1, it is characterised in that：Step
（2）The sintering temperature of middle roasting is 700 ~ 900 DEG C, and roasting time is 4 ~ 6 hours.
6. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate as claimed in claim 1, it is characterised in that：Step
（3）Described base is to be pressurized to 10 ~ 30Mpa by slow on tablet press machine, and pressurize is unloaded after 1 ~ 2 minute, the demoulding is that can obtain
Pie base substrate.
7. the preparation method of the tunable luminescent material of Copper-cladding Aluminum Bar magnesium aluminate according to claim 1, it is characterised in that：Step
（3）High temperature sintering temperature is 1400 ~ 1600 DEG C, and sintering time is 4 ~ 6 hours.
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