CN100360469C - Dual mixed yttrium aluminium garnet transparent ceramic material and it preparation process - Google Patents

Dual mixed yttrium aluminium garnet transparent ceramic material and it preparation process Download PDF

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CN100360469C
CN100360469C CNB2005100264744A CN200510026474A CN100360469C CN 100360469 C CN100360469 C CN 100360469C CN B2005100264744 A CNB2005100264744 A CN B2005100264744A CN 200510026474 A CN200510026474 A CN 200510026474A CN 100360469 C CN100360469 C CN 100360469C
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purity
powder
sintering
yag
transparent ceramic
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CN1724465A (en
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李江
吴玉松
邱发贵
潘裕柏
郭景坤
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to a dual doped transparent yttrium aluminium garnet ceramic material and a preparation method thereof, which is characterized in that 1) for a system of Cr<4+> and Nd<3+>: YAG, the doped quantity of Cr ions is 0.02 to 0.5 at%, and the doped quantity of Nd ions is 0.5 to 4.0 at%; 2) for a system of Cr<4+> and Yb<3+>: YAG, the doped quantity of Cr ions is 0.01 to 0.5 at%, and the doped quantity of Yb ions is 5 to 30 at%. The preparation method is characterized in that after powder materials are evenly mixed, biscuit which is formed by dry press, cooling and isostatic press is directly sintered in a vacuum sintering furnace or is divided into two steps for sintering, and then annealing processing is carried out to the biscuit after the biscuit is sintered. The transmissivity of the dual doped transparent YAG material provided by the present invention is more than 70%, and the dual doped transparent YAG material can be used for the work material of a self Q-regulating solid laser.

Description

The yttrium aluminum garnet transparent ceramic material and the preparation method of codope
Technical field
The present invention relates to the yttrium aluminum garnet transparent ceramic and the preparation method of codope, relate to Cr or rather 4+, Nd 3+: YAG and Cr 4+, Yb 3+: YAG self-regulated Q laser transparent ceramic and preparation method belong to the laser transparent ceramic technical field of material.
Background technology
Photoelectronic industry is the mainstay industry of 21st century, and laser technology is the core integral part of photoelectron technology.As the main body of solid statelaser, laserable material is the mainstay of Solid State Laser technology.At present, the Nd:YAG laserable material is monocrystalline on the market, because its growth cycle is grown, cost an arm and a leg, size is little, doping content is low, and its performance and range of application are restricted.Researcher is attempted to substitute monocrystalline with glass, glass-ceramic as working-laser material for many years.Though glass is easy to accomplish large size, its thermal conductance is than the low order of magnitude of monocrystalline.Glass-ceramic is the material of heterojunction structure, has the thermal expansivity of very low (even negative value), good thermal shock, but lasing efficiency is compared with monocrystal material and is unsatisfactory.Scientist begins just to attempt using Dy:CaF in the sixties in 20th century 2, polycrystalline ceramicss such as NDY are as the operation material of solid statelaser, but effect is all undesirable.Since patent JP05-286761, JP05-286762, JP05-294722, JP05-294723, JP05-294722, after JP05-235462 delivered, the Nd:YAG transparent polycrystalline ceramics had caused people's very big interest as working-laser material, with the Nd:YAG crystalline ceramics be the solid statelaser of operation material also to the development of high-power, high-level efficiency, the Nd:YAG crystalline ceramics becomes the competitive laserable material that is used for substituting monocrystalline probably.
The Nd:YAG monocrystalline has good machinery, optics and chemical heat stability, so the passive Q-adjusted gain media of LD pumping is generally the Nd:YAG monocrystalline.Cr 4+: the YAG crystal is the ideal material of passive Q-adjusted switch, because it at the big absorption cross in 1 μ m place, is the important saturable absorber of Nd laser, and two Cr that mix 4+, Nd 3+: the YAG crystal be a kind of excellent property from the Q-switch material.With mix Nd 3+Laser transparent ceramic is compared, and mixes Yb 3+The YAG crystalline ceramics because its quantum defective is little, and can realize Yb 3+High-concentration dopant and do not reduce its fluorescence lifetime basically, its spectral response curve ratio is mixed Nd 3+To get well, use Cr 4+: YAG has realized the passive Q-adjusted output of Yb:YAG crystalline as passive Q-adjusted opening the light.Simultaneously, having reported that Chinese Academy of Sciences's Shanghai ray machine grows mixes Cr altogether 4+, Yb 3+: the YAG monocrystalline, and realized the output of self-regulated Q laser.
From Nd:YAG laser transparent ceramic and Cr 4+, Nd 3+: YAG and Cr 4+, Yb 3+: the present Research of YAG monocrystalline and progress, two Cr that mix 4+, Nd 3+: YAG and Cr 4+, Yb 3+: the YAG crystalline ceramics will have very big strength and business potential as the micro-slice laser of self-regulated Q.While Cr 4+, Yb 3+: the YAG crystalline ceramics will have crucial meaning to efficient, the superpower of realizing passive Q-regulaitng laser, integrated, miniaturization, compact construction and useization.
Summary of the invention
The objective of the invention is to be to provide the yttrium aluminum garnet transparent ceramic and the preparation method of two kinds of codopes, relate in particular to Cr 4+, Nd 3+: YAG and Cr 4+, Yb 3+: YAG crystalline ceramics and preparation method, expectation realizes the output of self-regulated Q laser.
Preparation method of the present invention comprises the technological processs such as selection, ball milling mixing, drying, moulding, vacuum sintering and anneal of raw material and sintering aid as shown in Figure 1, and each technological process is characterised in that:
(1) raw material can be:
(a) Shang Yong high-purity α-Al 2O 3, Y 2O 3, Cr 2O 3, Nd 2O 3And Yb 2O 3Powder;
(b) Shang Yong high-purity γ-Al 2O 3, Y 2O 3, Cr 2O 3, Nd 2O 3And Yb 2O 3Powder;
(c) Shang Yong high-purity α-Al 2O 3, γ-Al 2O 3, Y 2O 3, Cr 2O 3, Nd 2O 3And Yb 2O 3Powder;
(d) Shang Yong high-purity α-Al 2O 3, Cr 2O 3, Nd 2O 3, Yb 2O 3And high-purity Y of wet chemistry method (comprising the precipitator method, sol-gel method, combustion synthesis method etc.) preparation 2O 3Nano-powder;
(e) Shang Yong high-purity γ-Al 2O 3, Cr 2O 3, Nd 2O 3, Yb 2O 3And high-purity Y of wet chemistry method (comprising the precipitator method, sol-gel method etc.) preparation 2O 3Nano-powder;
(f) Shang Yong high-purity Y 2O 3, Cr 2O 3, Nd 2O 3, Yb 2O 3And high-purity Al of wet chemistry method (comprising the precipitator method, sol-gel method etc.) preparation 2O 3Nano-powder;
(g) high-purity Al of wet chemistry method (comprising the precipitator method or sol-gel method) preparation 2O 3, Y 2O 3Nano-powder and commercial high-purity Cr 2O 3, Nd 2O 3, Yb 2O 3Powder;
(h) Y of heterogeneous precipitation method preparation 2O 3Parcel Al 2O 3Powder and commercial high-purity Cr 2O 3, Nd 2O 3, Yb 2O 3Powder;
(i) Al of heterogeneous precipitation method preparation 2O 3Parcel Y 2O 3Powder and commercial high-purity Cr 2O 3, Nd 2O 3, Yb 2O 3Powder;
(j) high-purity YAG nano-powder and commercial high-purity Cr of wet chemistry method (comprising the precipitator method or sol-gel method etc.) preparation 2O 3, Nd 2O 3, Yb 2O 3Powder;
(k) high-purity N d:YAG and Yb:YAG nano-powder and commercial high-purity Cr of wet chemistry method (comprising the precipitator method or sol-gel method etc.) preparation 2O 3Powder.
(2) sintering aid of Tian Jiaing can be Li 2O, Na 2O, K 2O, CaO, MgO, SiO 2And among the TEOS (tetraethoxy) one or both, the addition of sintering aid is 10 2～10 6Ppm.
Above-described commercial material purity is 99.95-99.99%, carries out weighing, mixing by adulterated proportioning.
(3) ball milling hybrid technique:
(a) ball grinder uses tetrafluoroethylene or high-purity alumina ceramic material;
(b) abrading-ball uses high-purity agate ball, high-purity zirconia Ceramic Balls or high-purity alumina ceramic ball;
(c) ball-milling medium uses dehydrated alcohol or deionized water;
(d) use planetary ball mill, rotating speed is 100～400rpm, and the ball milling time is 2～20 hours.
(4) ball milling blended slurry is dried in 90-100 ℃ baking oven, grinds 100 mesh sieves.
(5) moulding process:
(a) the axial unidirectional pressuring method that adopts in the dry-pressing formed process, pressure is 50～100MPa, 0.5～3 minute dwell time;
(b) biscuit after dry-pressing formed after vacuum packaging, cold isostatic compaction under the pressure of 200～400MPa, 1～5 minute dwell time, making biscuit density is 45～65% of component theoretical density.
(6) in the vacuum sintering technology:
(a) can directly carry out vacuum sintering to the biscuit that dry-pressing adds cold isostatic compaction, heat-up rate is 1～20 ℃/mim, and sintering temperature is 1650～1850 ℃, and soaking time is 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa;
(b) biscuit that maybe can add cold isostatic compaction to dry-pressing is at vacuum oven sintering in two steps.The first step was 1000～1500 ℃ of pre-burnings 2～20 hours, and heat-up rate is 1～20 ℃/mim, and vacuum tightness is 10 -2～10 -4Pa; The two or two step, heat-up rate was 1～20 ℃/mim 1700～1850 ℃ of insulations 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa;
(c) maybe can the biscuit that dry-pressing adds cold isostatic compaction not had pressure presintering in the Si-Mo rod stove of oxidizing atmosphere: heat-up rate is 1～20 ℃/mim, and sintering temperature is 800～1200 ℃, and the pre-burning time is 2～20 hours; Place the base substrate after the presintering vacuum sintering furnace to carry out double sintering, sintering temperature is 1650～1850 ℃, and soaking time is 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa.The agglomerating key is to get rid of pore, grows crystal grain, prevents that pore from being wrapped up by crystal grain.
(7) with the Cr of vacuum sintering, Nd:YAG and Cr, Yb:YAG pottery carry out anneal in the Si-Mo rod stove of oxidizing atmosphere: annealing temperature is 800～1600 ℃, and annealing time is 2～40 hours, mainly eliminates carbon impurity and oxygen defect.At last to the Cr of vacuum sintering, Nd:YAG and Cr, Yb:YAG pottery carry out that the plane grinds and polished finish.
The Cr of resulting vacuum sintering, Nd:YAG and Cr, Yb:YAG ceramic body relative density is greater than 99.9%, and average grain size is 1～100 μ m.
The concrete component of codope yttrium aluminum garnet transparent ceramic provided by the present invention is:
(1) for Cr 4+, Nd 3+: the YAG system, Cr ionic doping is 0.02～0.5at%, Nd ionic doping is 0.5～4.0at%; Preferential Cr ion and Nd ionic doping of recommending is respectively 0.05-0.1at% and 0.5-1.5at%;
(2) for Cr 4+, Yb 3+: the YAG system, Cr ionic doping is 0.01～0.5at%, Yb ionic doping is 5～30at%; Preferential Cr ion and Yb ionic doping of recommending is respectively 0.01-0.1at% and 5-10at%.
Can prepare the straight line transmitance height (＞70%) of 1064nm optical maser wavelength, two Cr that mix of satisfactory mechanical property according to technology of the present invention 4+, Nd 3+: YAG, Cr 4+, Yb 3+: the YAG crystalline ceramics can be used as the operation material of self-regulated Q solid statelaser.
Description of drawings
The technical process of provided by the invention pair of doped yttrium aluminium garnet transparent ceramic of Fig. 1.
Fig. 2 polishes back 0.1at%Cr 4+, 1.0at%Nd 3+: the photo in kind of YAG pottery 1mm sheet.
The 0.1at%Cr that Fig. 3 embodiment 1 is provided 4+, 1.0at%Nd 3+: the transmittance curve of YAG pottery.
Fig. 4 polishes back 0.025at%Cr 4+, 5.0at%Yb 3+: the photo in kind of YAG pottery 1mm sheet.
The 0.025at%Cr that Fig. 5 embodiment 16 is prepared 4+, 5.0at%Yb 3+: the fracture apperance of YAG pottery.
Embodiment
Embodiment 1:
With 25.4645g purity α-Al of 99.99% 2O 3Powder, 33.4778g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0280g purity are 99.99% CaO powder, and 0.0380g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2976g puts into the tetrafluoroethylene ball grinder, adds high-purity agate ball 180g, dehydrated alcohol 22ml, and ball milling is 10 hours then.In 90 ℃ baking oven, after the oven dry, ground 100 mesh sieves.To unidirectional pressurization, be pressed into the disk of Φ 20 with the forcing spindle of 100MPa, again under the pressure of 300MPa isostatic cool pressing with further increase biscuit density.Sintering is to carry out in vacuum sintering furnace, and sample is placed in the molybdenum crucible.The temperature rise rate of stove is: room temperature to 1150 ℃ is 30 ℃/min, and 1150 ℃ to 1780 ℃ is 10 ℃/min, and 1780 ℃ of soaking times are 10 hours.1780 ℃ to 1500 ℃ with 5 ℃/min cooling, furnace cooling below 1500 ℃.It is thick pottery to be ground and is polished to 1mm with surface grinding machine and diamond paste at last.The ceramic relative density that sintering obtains is＞99.9%, polishing back 0.1at%Cr 4+, 1.0at%Nd 3+: the photo in kind of YAG pottery 1mm sheet is seen Fig. 2, and its transmittance curve is seen Fig. 3.In optical maser wavelength (1064nm) straight line transmitance up to 71%.
The 0.1at%Cr that sintering under the similarity condition is obtained 4+, 1.0at%Nd 3+: the YAG pottery carries out anneal, and mechanism of anneal is: room temperature to 1450 ℃ heat-up rate is 5 ℃/min, is cooled to 450 ℃ with 1 ℃/min after 1450 ℃ of soaking times are 20 hours, then furnace cooling.It is thick with surface grinding machine and diamond paste the pottery of annealed processing to be ground and be polished to 1mm.
Embodiment 2:
With 25.4645g purity α-Al of 99.99% 2O 3Powder, 33.4778g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0280g purity are 99.99% CaO powder, and 0.0380g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2976g puts into the tetrafluoroethylene ball grinder, adds high-purity agate ball 180g, dehydrated alcohol 22ml, and ball milling is 10 hours then.In 90 ℃ baking oven, after the oven dry, ground 100 mesh sieves.To unidirectional pressurization, be pressed into the disk of Φ 20 with the forcing spindle of 100MPa, again under the pressure of 300MPa isostatic cool pressing with further increase biscuit density.Sintering is to carry out in vacuum sintering furnace, and sample is placed in the molybdenum crucible.The intensification mechanism of stove is: room temperature to 1200 ℃ is 30 ℃/min, and 1200 ℃ to 1770 ℃ is 10 ℃/min, and 1770 ℃ of soaking times are 30 hours.1770 ℃ to 1500 ℃ with 5 ℃/min cooling, furnace cooling below 1500 ℃.It is thick pottery to be ground and is polished to 1mm with surface grinding machine and diamond paste at last.The ceramic relative density that sintering obtains is＞99.9%, polishing back 0.1at%Cr 4+, 1.0at%Nd 3+: the transmitance of YAG pottery is greater than 70%, and grain-size is tens of microns.
Embodiment 3:
With 25.4645g purity α-Al of 99.99% 2O 3Powder, 33.4778g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0280g purity are 99.99% CaO powder, and 0.0380g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2976g puts into the tetrafluoroethylene ball grinder, adds high-purity agate ball 180g, dehydrated alcohol 22ml, and ball milling is 10 hours then.In 90 ℃ baking oven, after the oven dry, ground 100 mesh sieves.To unidirectional pressurization, be pressed into the disk of Φ 20 with the forcing spindle of 100MPa, again under the pressure of 300MPa isostatic cool pressing with further increase biscuit density.Biscuit is 800 ℃ of presintering in silicon carbide rod furnace, and temperature rise rate is 5 ℃/min.The presintering body continues to carry out sintering in vacuum sintering furnace then, and sample is placed in the molybdenum crucible.The temperature rise rate of stove is: room temperature to 1200 ℃ is 30 ℃/min, and 1200 ℃ to 1750 ℃ is 5 ℃/min, and 1750 ℃ of soaking times are 30 hours.1750 ℃ to 1000 ℃ with 5 ℃/min cooling, furnace cooling below 1500 ℃.It is thick pottery to be ground and is polished to 1mm with flat and grinding machine and diamond paste at last.The ceramic relative density that sintering obtains is＞99.9%, polishing back 0.1at%Cr 4+, 1.0at%Nd 3+: the transmitance of YAG pottery is greater than 70%, and grain-size is tens of microns.
Embodiment 4: weighing 25.44849g purity is α-Al of 99.99% 2O 3Powder, 33.5004g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0168g purity are 99.99% CaO powder, and 0.0076g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2976g, ball milling mix, dry, sieve, forming of green body, sintering, anneal, grind, polished finish technology is identical with embodiment 1, obtains 0.02at%Cr 4+, 1.0at%Nd 3+: the YAG crystalline ceramics.This pottery relative density＞99.9%, up to 70%, average grain size is tens of microns in optical maser wavelength (1064nm) straight line transmitance.
Embodiment 5: weighing 25.3626g purity is α-Al of 99.99% 2O 3Powder, 33.4778g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0280g purity are 99.99% CaO powder, and 0.1900g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2978g, other technology is identical with embodiment 1, obtains 0.5at%Cr 4+, 1.0at%Nd 3+: the YAG crystalline ceramics.This pottery relative density＞99.9%, up to 65%, average grain size is tens of microns in optical maser wavelength (1064nm) straight line transmitance.
Embodiment 6: weighing 25.4645g purity is α-Al of 99.99% 2O 3Powder, 33.4778g purity are 99.99% Y 2O 3Powder, 0.5047g purity are 99.95% Nd 2O 3Powder, 0.0202g purity are 99.99% MgO powder, and 0.0380g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.2975g, other technology is identical with embodiment 1, obtains 0.1at%Cr 4+, 1.0at%Nd 3+: the YAG crystalline ceramics.
Embodiment 7:25.4645g purity is γ-Al of 99.99% 2O 3Powder, Y 2O 3, Nd 2O 3, CaO, Cr 2O 3The addition of high-purity TEOS is identical with embodiment 1, and ball milling mixing, drying and screening and forming of green body technology are all identical with embodiment 1.Sintering also carries out in vacuum sintering furnace, and sample is placed in the molybdenum crucible.The intensification mechanism of stove is identical with embodiment 1, is 30 hours 1800 ℃ of soaking times, lowers the temperature furnace cooling below 1200 ℃ then from 1800 ℃ to 1200 ℃ with 5 ℃/min.Grind at last, polishing is identical with embodiment 1 with annealing treating process, obtains 0.1at%Cr at last 4+, 1.0at%Nd 3+: the YAG crystalline ceramics.
Embodiment 8: be α-Al of 99.99% with 20.3716g purity 2O 3Powder is γ-Al of 99.99% with 5.0929g purity 2O 3Powder, Y 2O 3, Nd 2O 3, CaO, Cr 2O 3Identical with embodiment 1 with the addition of high-purity TEOS powder, other process is identical with embodiment 1.
Embodiment 9: take by weighing the specpure Y (NO of 169.6220g 3) 36H 2The specpure NH of O and 105.0305g 4HCO 3, be configured to the Y (NO of 0.15M respectively 3) 3The NH of solution and 2.0M 4HCO 3Solution.At room temperature while stirring toward the NH of 2.0M 4HCO 3Slowly drip the Y (NO of 0.15M in the solution 3) 3Solution, the white precipitate that obtains after ageing in 12 hours with deionized water wash 3 times to remove the free mineral ion, then with absolute ethanol washing 2 times to remove moisture.The precipitation of gained is transferred to 90 ℃ oven drying after filtering for a long time.The dry powder of gained ground 200 mesh sieves, and carried out calcination processing at 800 ℃ and obtain Y 2O 3Nano-powder.This Y of weighing 2O 3Nano-powder 33.4778g, α-Al 2O 3, Nd 2O 3, CaO, Cr 2O 3Identical with embodiment 1 with the addition of high-purity TEOS, other process is identical with embodiment 1.
Embodiment 10: take by weighing the specpure NH of 266.7634g 4Al (SO 4) 212H 2The specpure NH of O and 186.0965g 4HCO 3, be configured to the NH of 0.25M respectively 4Al (SO 4) 2The NH of solution and 2.0M 4HCO 3Solution.At room temperature while stirring toward the NH of 2.0M 4HCO 3Slowly drip the NH of 0.25M in the solution 4Al (SO 4) 2Solution, the white precipitate that obtains after ageing in 12 hours with deionized water wash 3 times to remove the free mineral ion, then with absolute ethanol washing 2 times to remove moisture.The precipitation of gained is transferred to 90 ℃ oven drying after filtering for a long time.The dry powder of gained ground 200 mesh sieves, and carried out calcination processing at 1000 ℃ and obtain Al 2O 3Nano-powder.This Al of weighing 2O 3Nano-powder 25.4645g, commercial Y 2O 3, Nd 2O 3, CaO, Cr 2O 3Identical with embodiment 1 with the addition of high-purity TEOS, other process is identical with embodiment 2.
Embodiment 11: according to embodiment 4 preparation Y 2O 3Nano-powder is according to embodiment 4 preparation Al 2O 3Nano-powder.Take by weighing this Y respectively 2O 3Nano-powder 33.4778g, Al 2O 3Nano-powder 25.4645g, commercial high-purity N d 2O 3, CaO, Cr 2O 3Identical with embodiment 1 with the addition of TEOS, other process is identical with embodiment 2.
Embodiment 12: take by weighing the specpure Y (NO of 113.5713g 3) 36H 2The specpure NH of O and 140.6477g 4HCO 3, be configured to the Y (NO of 0.15M respectively 3) 3The NH of solution and 2.0M 4HCO 3Solution.Take by weighing 25.4645g purity and be α-Al of 99.99% 2O 3Powder is distributed to NH 4HCO 3In the solution, stirred 1 hour.At room temperature while stirring toward being dispersed with α-Al 2O 3The NH of powder 4HCO 3Slowly drip the Y (NO of 0.15M in the solution 3) 3Solution is then according to the step process coated powder among the embodiment 4.According to gained Y 2O 3Parcel α-Al 2O 3The quality of composite granule, corresponding interpolation high-purity N d 2O 3, CaO, Cr 2O 3And TEOS, other process is identical with embodiment 1.
Embodiment 13: take by weighing 226.4332g spectroscopically pure NH 4Al (SO 4) 212H 2The specpure NH of O and 315.9236g 4HCO 3, be configured to the NH of 0.25M respectively 4Al (SO 4) 2The NH of solution and 2.0M 4HCO 3Solution.Take by weighing 33.4778g purity and be 99.99% Y 2O 3Powder is distributed to NH 4HCO 3In the solution, stirred 1 hour.At room temperature while stirring toward being dispersed with Y 2O 3The NH of powder 4HCO 3Slowly drip the NH of 0.25M in the solution 4Al (SO 4) 2Solution is then according to the step process coated powder among the embodiment 5.According to gained Al 2O 3Parcel Y 2O 3The quality of composite granule, corresponding interpolation high-purity N d 2O 3, CaO, Cr 2O 3And TEOS, other process is identical with embodiment 2.
Embodiment 14: with the specpure Al (NO of 281.3475g 3) 39H 2Specpure Y (the NO of O and 172.3680g 3) 36H 2O is dissolved in the deionized water, Al 3+And Y 3+Concentration be respectively 0.25M and 0.15M, this mixing salt solution slowly is added drop-wise to contains tensio-active agent (polyoxyethylene glycol, PEG1000) in the ammonia soln, the amount of tensio-active agent is 1% of aluminium and a yttrium inorganic salt solution weight, regulate about pH value to 9 with ammoniacal liquor, obtain white precipitate, the treating processes of presoma is identical with embodiment 5.And carry out calcination processing at 1000 ℃ and obtain pure YAG phase nano-powder.According to the quality of gained YAG powder, corresponding interpolation high-purity N d 2O 3, CaO, Cr 2O 3And TEOS, other process is identical with embodiment 1.
Embodiment 15: with the specpure Al (NO of 47.3940g 3) 39H 2O, the specpure Y (NO of 29.0360g 3) 36H 2O and 42.4060g citric acid are dissolved in the deionized water, stir to form uniform solution.The beaker that fills this solution is placed on the magnetic stirring apparatus, do not stop to stir evaporating solns, finally form lurid transparent jelly at 80 ℃.Gel is put into 200 ℃ silicon carbide rod furnace thermal treatment, form lurid loose precursor powder.Precursor powder generates pure YAG phase powder through 850 ℃ of calcinings.According to the quality of gained YAG powder, corresponding interpolation high-purity N d 2O 3, CaO, Cr 2O 3And TEOS, other process is identical with embodiment 1.
Example 16: be α-Al of 99.99% with 25.4839g purity 2O 3Powder, 32.1638g purity are 99.99% Y 2O 3Powder, 2.9556g purity are 99.95% Yb 2O 3Powder, 0.007g purity are 99.99% CaO powder, and 0.0095g purity is 99.99% Cr 2O 3The high-purity TEOS of powder and 0.3031g puts into poly-recessed vinyl fluoride ball grinder, adds high-purity agate ball 180g, dehydrated alcohol 22ml, and ball milling is 10 hours then.In 90 ℃ baking oven, after the oven dry, ground 100 mesh sieves.To unidirectional pressurization, be pressed into the disk of Φ 20 with the forcing spindle of 100MPa, again under the pressure of 300MPa isostatic cool pressing with further increase biscuit density.Sintering is to carry out in vacuum sintering furnace, and sample is placed in the molybdenum crucible.The intensification mechanism of stove is: room temperature to 1150 ℃ is 30 ℃/min, and 1150 ℃ to 1770 ℃ is 10 ℃/min, and 1770 ℃ of soaking times are 10 hours.1780 ℃ to 1500 ℃ with 5 ℃/min cooling, furnace cooling below 1500 ℃.It is thick pottery to be ground and is polished to 1mm with surface grinding machine and diamond paste at last.The ceramic relative density that sintering obtains is＞99.9%, polishing back 0.025at%Cr 4+, 5.0at%Yb 3+: the YAG pottery carries out anneal, and mechanism of anneal is: room temperature to 1450 ℃ heat-up rate is 5 ℃/min, is cooled to 450 ℃ with 1 ℃/min after 1450 ℃ of soaking times are 20 hours, then furnace cooling.It is thick with surface grinding machine and diamond paste the pottery of annealed processing to be ground and be polished to 0.5mm.Polishing back 0.025at%Cr 4+, 5.0at%Yb 3+: the photo in kind of YAG pottery 0.5mm sheet is seen Fig. 4, and the appearance structure of its fracture is seen Fig. 5.This ceramic relative density＞99.9%, up to 75%, average grain size is 40 microns in optical maser wavelength (1064nm) straight line transmitance.
Example 17:25.4648g purity is α-Al of 99.99% 2O 3Powder, 32.1215g purity are 99.99% Y 2O 3Powder, 2.9556g purity are 99.95% Yb 2O 3Powder, 0.0280g purity are 99.99% CaO powder, and 0.0380g purity is 99.99% Cr 2O 3Powder and the high-purity TEOS of 0.303 1g, other technology is all identical with embodiment 1.Obtain the thick 0.075at%Cr of 1mm after the polishing 4+, 5.0at%Yb 3+: the YAG sheet of transparent ceramic.

Claims (8)

1, the yttrium aluminum garnet transparent ceramic material of codope is characterized in that: for Cr 4+, Nd 3+: the YAG system, Cr ionic doping is 0.02～0.5at%, Nd ionic doping is 0.5～4.0at%.
2, by the yttrium aluminum garnet transparent ceramic material of the described codope of claim 1, it is characterized in that: for Cr 4+, Nd 3+: the YAG system, Cr ionic doping is 0.05～0.1at%, Nd ionic doping is 0.5～1.5at%.
3, by the yttrium aluminum garnet transparent ceramic material of claim 1 or 2 described codopes, it is characterized in that average grain size is 1-100 μ m.
4, a kind of method for preparing yttrium aluminum garnet transparent ceramic material as claimed in claim 1 or 2 comprises selection, ball milling mixing, drying, moulding, sintering and the annealing process step of raw material and sintering aid,
It is characterized in that concrete processing step is:
Step 1: carry out weighing by claim 1 or 2 described proportionings; The sintering aid that is made is Li 2O, Na 2O, K 2O, CaO, MgO, SiO 2Or in the tetraethoxy one or both, addition is 10 2Ppm;
Step 2: the mixing in planetary ball mill with described powder of step 1 and sintering aid, working medium is dehydrated alcohol or deionized water;
Step 3:90-100 ℃ of oven dry slurry, grinding is sieved, and dry-pressing adds cold isostatic compaction;
Step 4: vacuum sintering:
1. the biscuit that dry-pressing is added cold isostatic compaction directly carries out vacuum sintering, and heat-up rate is 1～20 ℃/mim, and sintering temperature is 1650～1850 ℃, and soaking time is 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa;
2. or the biscuit that dry-pressing is added cold isostatic compaction at vacuum oven sintering in two steps, the first step was 1000～1500 ℃ of pre-burnings 2～20 hours, heat-up rate is 1～20 ℃/mim, vacuum tightness is 10 -2～10 4Pa; Second step, heat-up rate was 1～20 ℃/mim 1700～1850 ℃ of insulations 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa;
3. or the biscuit that dry-pressing is added cold isostatic compaction in the Si-Mo rod stove of oxidizing atmosphere, do not have pressure presintering: heat-up rate is 1～20 ℃/mim, and sintering temperature is 800～1200 ℃, and the pre-burning time is 2～20 hours; Place the base substrate after the presintering vacuum sintering furnace to carry out double sintering, sintering temperature is 1650～1850 ℃, and soaking time is 5～40 hours, and vacuum tightness is 10 -2～10 -4Pa;
Step 5: with the Cr of vacuum sintering, the Nd:YAG pottery carries out anneal in the Si-Mo rod stove of oxidizing atmosphere: annealing temperature is 800～1600 ℃, and annealing time is 2～40 hours.
5, by the yttrium aluminum garnet transparent ceramic preparation methods of the described codope of claim 4, the selection that it is characterized in that raw material be in following (a)～(k) any one:
(a) Shang Yong high-purity α-Al 2O 3, Y 2O 3, Cr 2O 3And Nd 2O 3Powder;
(b) Shang Yong high-purity γ-Al 2O 3, Y 2O 3, Cr 2O 3And Nd 2O 3Powder;
(c) Shang Yong high-purity α-Al 2O 3, γ-Al 2O 3, Y 2O 3, Cr 2O 3And Nd 2O 3Powder;
(d) Shang Yong high-purity α-Al 2O 3, Cr 2O 3, Nd 2O 3High-purity Y with the wet chemistry method preparation 2O 3Nano-powder;
(e) Shang Yong high-purity γ-Al 2O 3, Cr 2O 3, Nd 2O 3High-purity Y with the wet chemistry method preparation 2O 3Nano-powder;
(f) Shang Yong high-purity Y 2O 3, Cr 2O 3, Nd 2O 3High-purity Al with the wet chemistry method preparation 2O 3Nano-powder;
(g) high-purity Al of wet chemistry method preparation 2O 3, Y 2O 3Nano-powder and commercial high-purity Cr 2O 3, Nd 2O 3Powder;
(h) Y of heterogeneous precipitation method preparation 2O 3Parcel Al 2O 3Powder and commercial high-purity Cr 2O 3, Nd 2O 3Powder;
(i) Al of heterogeneous precipitation method preparation 2O 3Parcel Y 2O 3Powder and commercial high-purity Cr 2O 3, Nd 2O 3Powder;
(j) high-purity YAG nano-powder and commercial high-purity Cr of wet chemistry method preparation 2O 3, Nd 2O 3Powder;
(k) high-purity N d:YAG nano-powder and commercial high-purity Cr of wet chemistry method preparation 2O 3Powder;
Above-described commercialization powder purity high-purity or the wet chemistry method preparation is 99.95-99.99%.
6, by the yttrium aluminum garnet transparent ceramic preparation methods of the described codope of claim 5, it is characterized in that: described wet chemistry method is a kind of in the precipitator method or the sol-gel method.
7, by the yttrium aluminum garnet transparent ceramic preparation methods of the described codope of claim 4, it is characterized in that described planetary ball mill rotating speed is 100-400rpm, the ball milling time is 2-20 hour.
8, by the yttrium aluminum garnet transparent ceramic preparation methods of the described codope of claim 4, it is characterized in that described moulding is:
(a) the axial unidirectional pressuring method that adopts in the dry-pressing formed process, pressure is 50～100MPa, 0.5～3 minute dwell time;
(b) biscuit after dry-pressing formed after vacuum packaging, cold isostatic compaction under the pressure of 200～400MPa, 1～5 minute dwell time, making biscuit density is 45～65% of component theoretical density.
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