CN101717249A - Yttrium aluminum garnet transparent ceramic material double doped with rare earth ions and preparation method thereof - Google Patents

Yttrium aluminum garnet transparent ceramic material double doped with rare earth ions and preparation method thereof Download PDF

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CN101717249A
CN101717249A CN200910263226A CN200910263226A CN101717249A CN 101717249 A CN101717249 A CN 101717249A CN 200910263226 A CN200910263226 A CN 200910263226A CN 200910263226 A CN200910263226 A CN 200910263226A CN 101717249 A CN101717249 A CN 101717249A
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ceramic material
sintering
transparent ceramic
powder
rare earth
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张其土
杨浩
王丽熙
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention relates to a yttrium aluminum garnet transparent ceramic material double-doped with rare earth ions and a preparation method thereof, which is characterized in that the chemical composition general formula of the transparent ceramic material is as follows: 1-x-yYbxNdy)3Al5O12Wherein x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than or equal to 0.005 and less than or equal to 0.05. Weighing and proportioning according to the general formula of the composition, ball-milling and uniformly mixing the raw materials by using commercial high-purity powder or nano powder prepared by a coprecipitation method, forming, vacuum sintering and annealing to obtain Yb, Nd and YAG transparent ceramics with good light transmittance. The purposes of improving the absorption efficiency of pump light and reducing the laser oscillation threshold can be achieved by adopting the Yb and Nd double-doped rare earth ions, and the method has practical application value.

Description

Yttrium aluminum garnet transparent ceramic material of codope rare earth ion and preparation method thereof
Technical field
The present invention relates to a kind of yttrium aluminum garnet transparent ceramic material and preparation method of codope rare earth ion, belong to the advanced ceramics preparation field.
Background technology
Laser is one of human greatest invention of 20th century, and laser technology has been widely used in high-technology fields such as industrial and agricultural production, medical treatment, aerospace.Since nineteen sixty first ruby laser invention, a large amount of new pattern laser materials continue to bring out, and people begin working-laser material is carried out extensively and profoundly research and discovery.
Since 1964, the YAG crystalline of mixing Nd occurs, and is subjected to paying close attention to widely as the large power solid laser material.But mix the YAG crystal of Nd because shortcomings such as the growth cycle length of monocrystalline, crystal growth size, Nd ions dosage have restricted it uses widely.Along with improving constantly of great-power solid laser power, the wait in expectation appearance of new laserable material of people.Nineteen ninety-five, people such as Japanese A.Ikesue have made the polycrystalline Nd:YAG transparent ceramic material of complete densification and excellent optical performance, and obtain laser output.Coming years, especially after 2000, the Nd:YAG crystalline ceramics has obtained fast development, has realized the maximum power output of 67KW at present, has caused international extensive concern.Along with the continuous breakthrough of powder and ceramic preparation science and technology, polycrystalline transparent ceramic becomes the laserable material of the most competitive replacement monocrystalline.
Except Nd doping YAG crystalline ceramics, Yb mixes and has also received concern.Yb 3+Has the simplest level structure, with Nd 3+Compare, intrinsic quantum defective is low, photon efficient height, and the life time of the level is long, and absorption and emmission spectrum are wide.The appearance of the LD pumping source little along with volume, that the life-span is long, efficient is high, Yb 3+As laser active ionic research fast development.Yb particularly 3+Main absorption peak be positioned at 0.9~1.0 μ m, can effectively be coupled with the InGaAs laser diode pumping source of high brightness, and not need strict temperature control.While Yb 3+It also is a kind of high efficiency sensitized ions, sensitized ions can absorb more optical pump energy, and be transferred to active ions, and enlarging and strengthen the absorption spectrum of active ions, the optical pump energy that makes the ionic absorption that originally is not activated obtains utilizing by the effect of sensitized ions.Yb 3+Can absorb sensitizing agent as multiple laser active ionic pump energy, as Nd 3+Deng.Because the LD about 980nm is very general, so use Yb 3+Carry out sensitization and have more practical meaning, can reach raising the assimilated efficiency of pump light and the purpose of reduction laser generation threshold value.Also there are not two mix Yb, the relevant report of the yttrium aluminum garnet transparent ceramic material of Nd rare earth ion at present.
Summary of the invention
This purpose is to provide a kind of codope Yb for the deficiency of the yttrium aluminum garnet transparent ceramic material that further remedies, improves single doping with rare-earth ions, the yttrium aluminum garnet transparent ceramic material of Nd rare earth ion, another object of the present invention provides the preparation method of above-mentioned materials, doping by rare earth ion Yb, can improve the assimilated efficiency of Nd:YAG crystalline ceramics to pump light, and can reduce the laser generation threshold value, have actual application value.
Technical scheme of the present invention is: the yttrium aluminum garnet transparent ceramic material of codope rare earth ion is characterized in that: described transparent ceramic material chemical constitution general formula is: (Y 1-x-yYb xNd y) 3Al 5O 12, 0.01≤x≤0.1,0.005≤y≤0.05 wherein.
The present invention also provides the method for above-mentioned yttrium aluminum garnet transparent ceramic material, and its concrete steps are as follows:
(1) according to the chemical constitution general formula with Y 2O 3, Al 2O 3, Yb 2O 3And Nd 2O 3Powder carries out the weighing proportioning, adds the sintering aid that accounts for total powder quality 0.5~0.8%, and ball milling mixes the back oven dry and sieves;
(2) powder adopts first dry-pressing isostatic cool pressing technological forming again, and wherein dry-pressing pressure is 10~20MPa, and isostatic cool pressing pressure is 200~300MPa;
(3) biscuit of moulding carries out sintering, and the control sintering temperature is 1700~1800 ℃, and soaking time is 5~50h;
(4) the sample anneal behind the sintering prepares the yttrium aluminum garnet transparent ceramic material of codope rare earth ion.Preferred described Y 2O 3, Al 2O 3, Yb 2O 3And Nd 2O 3The purity of powder is 99.9%~99.999%.Sieve order number is 160~200 orders in the above-mentioned step (1).
Described sintering aid is at least a kind of in tetraethoxy, magnesium oxide or the Calcium Fluoride (Fluorspan).
The biscuit of moulding is in hydrogen atmosphere or 10 in the preferred steps (3) -3~10 -4Sintering in the vacuum of Pa; Sample 1300~1550 ℃ of following anneal 2~20h in air in the step (4) behind the sintering.
Beneficial effect:
(1) mixing codope Yb on the YAG crystalline ceramics basis of Nd, Nd rare earth element, Yb 3+Be a kind of high efficiency sensitized ions, sensitized ions can absorb more optical pump energy, and is transferred to active ions Nd 3+, enlarging and strengthen the absorption spectrum of active ions, the optical pump energy that makes the ionic absorption that originally is not activated obtains utilizing by the effect of sensitized ions.Laserable material is needed just for the assimilated efficiency of raising material, and this lays a good foundation for it becomes the large power solid laser material.
(2) technology by optimizing is prepared the YAG transparent ceramic material of the codope rare earth ion of high permeability, and its high permeability reaches 76%.Illustrate that method that this patent provides can prepare the transparent ceramic material of high permeability.The crystalline ceramics that has high permeability simultaneously can effectively reduce the optical loss.
Description of drawings
The Yb that Fig. 1 embodiment 3 is prepared, the surface corrosion electromicroscopic photograph of Nd:YAG crystalline ceramics.
The Yb that Fig. 2 embodiment 3 is prepared, the cross-section morphology of Nd:YAG crystalline ceramics.
The Yb that Fig. 3 embodiment 5 is prepared, Nd:YAG pottery XRD figure spectrum.
Embodiment
Embodiment 1
Take by weighing 10.1961g purity and be α-Al of 99.99% 2O 3Powder, 13.2099g purity are 99.99% Y 2O 3Powder, 0.4729g purity are 99.99% Yb 2O 3Powder and 0.1009g purity are 99.99% Nd 2O 3Powder is put into nylon ball grinder with powder, and adds 100gAl 2O 3Abrading-ball, the analytically pure dehydrated alcohol of 12g, the analytically pure TEOS of 0.19g, ball milling is 12 hours then.To grind 200 mesh sieves after the oven dry of the slurry behind the ball milling.With above-mentioned powder earlier in stainless steel mould with the first one-step forming of 15MPa pressure, be pressed into biscuit through the 200MPa isostatic cool pressing then.Biscuit is placed vacuum tightness 10 -3~10 -4In the vacuum oven of Pa in 1700 ℃ of sintering 6 hours, the 1450 ℃ of anneal 20 hours in air of the sample behind the sintering.The two-sided sanding and polishing of sample after will annealing at last is thick to 1mm.Sintering obtains codope Yb, (the Y of Nd 0.975Yb 0.02Nd 0.005) 3Al 5O 12Crystalline ceramics, the relative density of sample are greater than 99%, and transmitance is 76%.
Embodiment 2
Take by weighing 10.1961g purity and be α-Al of 99.99% 2O 3Powder, 12.7357g purity are 99.99% Y 2O 3Powder, 1.1822g purity are 99.99% Yb 2O 3Powder and 0.2019g purity are 99.99% Nd 2O 3Powder is put into nylon ball grinder with powder, and adds 100gAl 2O 3Abrading-ball, the analytically pure dehydrated alcohol of 12g, the analytically pure TEOS of 0.2g, ball milling is 12 hours then.To grind 200 mesh sieves after the oven dry of the slurry behind the ball milling.With above-mentioned powder earlier in stainless steel mould with the first one-step forming of 15MPa pressure, be pressed into biscuit through the 200MPa isostatic cool pressing then.Biscuit is placed vacuum tightness 10 -3~10 -4In the vacuum oven of Pa in 1720 ℃ of sintering 12 hours, the 1450 ℃ of anneal 10 hours in air of the sample behind the sintering.The two-sided sanding and polishing of sample after will annealing at last is thick to 1mm.Sintering obtains codope Yb, (the Y of Nd 0.94Yb 0.05Nd 0.01) 3Al 5O 12Crystalline ceramics, sample relative density are greater than 99%, and transmitance is 75%, and average grain size is 20 μ m.
Embodiment 3
Take by weighing 10.1961g purity and be α-Al of 99.99% 2O 3Powder, 11.5163g purity are 99.99% Y 2O 3Powder, 2.3645g purity are 99.99% Yb 2O 3Powder and 1.0094g purity are 99.99% Nd 2O 3Powder is put into nylon ball grinder with powder, and adds 100gAl 2O 3Abrading-ball, the analytically pure dehydrated alcohol of 12g, the analytically pure TEOS of 0.2g, ball milling is 12 hours then.To grind 200 mesh sieves after the oven dry of the slurry behind the ball milling.With above-mentioned powder earlier in stainless steel mould with the first one-step forming of 15MPa pressure, be pressed into biscuit through the 200MPa isostatic cool pressing then.Biscuit is placed vacuum tightness 10 -3~10 -4In the vacuum oven of Pa in 1750 ℃ of sintering 6 hours, the 1450 ℃ of anneal 10 hours in air of the sample behind the sintering.The two-sided sanding and polishing of sample after will annealing at last is thick to 1mm.Sintering obtains codope Yb, (the Y of Nd 0.85Yb 0.1Nd 0.05) 3Al 5O 12Crystalline ceramics, sample relative density are greater than 99%, and transmitance is 76%.The Yb that the present invention is prepared, the surface corrosion electromicroscopic photograph of Nd:YAG crystalline ceramics as shown in Figure 1, the Yb that the present invention is prepared, Nd:YAG crystalline ceramics cross-section morphology as shown in Figure 2.Can see that sample does not have tangible pore basically on scheming, ceramic section all is transgranular fractures, and crystal boundary is clean, no crystal boundary phase.
Embodiment 4
Y with rare earth oxide 12.7357g 2O 3Powder, the Yb of 1.1822g 2O 3The Nd of powder and 0.2019g 2O 3Powder is dissolved in the nitric acid, and adds the analytically pure Al (NO of 75.026g 3) 39H 2O, with the mixing salt solution thin up to 1333ml.Get the 80ml strong aqua and add 252.992g bicarbonate of ammonia and be made into compound precipitants, wherein bicarbonate of ammonia concentration is 2mol/L, and precipitation agent is diluted to 1600ml.The salts solution that the mixes speed with 3ml/min is added drop-wise in the precipitation agent of vigorous stirring, generates white gelatinous precipitate.Behind precipitate with deionized water, dehydrated alcohol and washing with acetone, dry 24h in 80 ℃ of baking ovens obtains presoma.Presoma was obtained rear-earth-doped YAG powder in 2 hours 1200 ℃ of calcinings.Burnt powder is put into nylon ball grinder, and add 100gAl 2O 3Abrading-ball, the analytically pure dehydrated alcohol of 16g, the analytically pure TEOS of 0.12g, ball milling is 12 hours then.To grind 200 mesh sieves after the oven dry of the slurry behind the ball milling.With above-mentioned powder earlier in stainless steel mould with the first one-step forming of 15MPa, be pressed into biscuit through the 200MPa isostatic cool pressing then.Biscuit is placed vacuum tightness 10 -3~10 -4In the vacuum oven of Pa in 1750 ℃ of sintering 6 hours, the 1550 ℃ of anneal 2 hours in air of the sample behind the sintering.The two-sided sanding and polishing of sample after will annealing at last is thick to 1mm.Sintering obtains codope Yb, (the Y of Nd 0.94Yb 0.05Nd 0.01) 3Al 5O 12Crystalline ceramics, sample relative density are greater than 99%, and transmitance is 73%.
Embodiment 5
Y with rare earth oxide 11.5163g 2O 3Powder, the Yb of 2.3645g 2O 3The Nd of powder and 1.0094g 2O 3Powder is dissolved in the nitric acid, and adds the analytically pure Al (NO of 75.026g 3) 39H 2O, with the mixing salt solution thin up to 1333ml.Get the 120ml strong aqua and add 252.992g bicarbonate of ammonia and be made into compound precipitants, wherein bicarbonate of ammonia concentration is 2mol/L, and precipitation agent is diluted to 1600ml.The salts solution that the mixes speed with 3ml/min is added drop-wise in the precipitation agent of vigorous stirring, generates white gelatinous precipitate.Behind precipitate with deionized water, dehydrated alcohol and washing with acetone, dry 24h in 80 ℃ of baking ovens obtains presoma.Presoma was obtained rear-earth-doped YAG powder in 2 hours 1200 ℃ of calcinings.Burnt powder is put into nylon ball grinder, and add 100gAl 2O 3Abrading-ball, the analytically pure dehydrated alcohol of 16g, the analytically pure TEOS of 0.12g, ball milling is 12 hours then.To grind 200 mesh sieves after the oven dry of the slurry behind the ball milling.With above-mentioned powder earlier in stainless steel mould with the first one-step forming of 15MPa, be pressed into biscuit through the 200MPa isostatic cool pressing then.Biscuit is placed vacuum tightness 10 -3~10 -4In the vacuum oven of Pa in 1780 ℃ of sintering 6 hours, the 1550 ℃ of anneal 2 hours in air of the sample behind the sintering.The two-sided sanding and polishing of sample after will annealing at last is thick to 1mm.Sintering obtains codope Yb, (the Y of Nd 0.85Yb 0.1Nd 0.05) 3Al 5O 12Crystalline ceramics, sample relative density are greater than 99%, and transmitance is 75%.The Yb that the present invention is prepared, Nd:YAG pottery XRD figure spectrum as shown in Figure 3.Sample is pure YAG phase from scheming as can be seen, does not have other dephasign peak.

Claims (6)

1. the yttrium aluminum garnet transparent ceramic material of codope rare earth ion, it is characterized in that: described transparent ceramic material chemical constitution general formula is: (Y 1-x-yYb xNd y) 3Al 5O 12, 0.01≤x≤0.1,0.005≤y≤0.05 wherein.
2. method for preparing yttrium aluminum garnet transparent ceramic material as claimed in claim 1, its concrete steps are as follows:
(1) according to the chemical constitution general formula with Y 2O 3, Al 2O 3, Yb 2O 3And Nd 2O 3Powder carries out the weighing proportioning, adds the sintering aid that accounts for total powder quality 0.5~0.8%, and ball milling mixes the back oven dry and sieves;
(2) powder adopts first dry-pressing isostatic cool pressing technological forming again, and wherein dry-pressing pressure is 10~20MPa, and isostatic cool pressing pressure is 200~300MPa;
(3) biscuit of moulding carries out sintering, and the control sintering temperature is 1700~1800 ℃, and soaking time is 5~50h;
(4) the sample anneal behind the sintering prepares the yttrium aluminum garnet transparent ceramic material of codope rare earth ion.
3. method according to claim 2 is characterized in that in described Y 2O 3, Al 2O 3, Yb 2O 3And Nd 2O 3The purity of powder is 99.9%~99.999%.
4. method according to claim 2 is characterized in that sieve order number is 160~200 orders in the described step (1).
5. method according to claim 2 is characterized in that described sintering aid is at least a kind of in tetraethoxy, magnesium oxide or the Calcium Fluoride (Fluorspan).
6. method according to claim 2, the biscuit that it is characterized in that moulding in the step (3) is in hydrogen atmosphere or 10 -3~10 -4Sintering in the vacuum of pa; Sample 1300~1550 ℃ of following anneal 2~20h in air in the step (4) behind the sintering.
CN200910263226A 2009-12-17 2009-12-17 Yttrium aluminum garnet transparent ceramic material double doped with rare earth ions and preparation method thereof Pending CN101717249A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101891477A (en) * 2010-07-23 2010-11-24 中国科学院上海硅酸盐研究所 Method for preparing circular rod-shaped RE:YAG laser transparent ceramics
CN102581929A (en) * 2012-02-16 2012-07-18 山东晶鑫晶体科技有限公司 Cake forming method of high-purity alumina powder
CN102659409A (en) * 2012-02-24 2012-09-12 上海大学 Preparation method for Ho<3+>-Yb<3+>-co-doped yttrium lanthanum oxide laser transparent ceramic material
CN104059635A (en) * 2013-03-21 2014-09-24 海洋王照明科技股份有限公司 Neodymium and ytterbium double doping alkali fluoborate up-conversion luminescent material, preparation method and application thereof
CN104099090A (en) * 2013-04-09 2014-10-15 海洋王照明科技股份有限公司 Dysprosium-doped alkali fluosilicic acid glass up-conversion luminescent material, and preparation method and application thereof
CN107253854A (en) * 2017-05-18 2017-10-17 北京科技大学 A kind of laser transparent ceramic of grade doping and preparation method thereof
CN108536993A (en) * 2018-01-04 2018-09-14 广东工业大学 A kind of determination method of raw material proportioning in optical ceramics preparation process

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101891477A (en) * 2010-07-23 2010-11-24 中国科学院上海硅酸盐研究所 Method for preparing circular rod-shaped RE:YAG laser transparent ceramics
CN101891477B (en) * 2010-07-23 2013-01-02 中国科学院上海硅酸盐研究所 Method for preparing circular rod-shaped RE:YAG laser transparent ceramics
CN102581929A (en) * 2012-02-16 2012-07-18 山东晶鑫晶体科技有限公司 Cake forming method of high-purity alumina powder
CN102581929B (en) * 2012-02-16 2014-03-05 山东晶鑫晶体科技有限公司 Cake forming method of high-purity alumina powder
CN102659409A (en) * 2012-02-24 2012-09-12 上海大学 Preparation method for Ho<3+>-Yb<3+>-co-doped yttrium lanthanum oxide laser transparent ceramic material
CN104059635A (en) * 2013-03-21 2014-09-24 海洋王照明科技股份有限公司 Neodymium and ytterbium double doping alkali fluoborate up-conversion luminescent material, preparation method and application thereof
CN104099090A (en) * 2013-04-09 2014-10-15 海洋王照明科技股份有限公司 Dysprosium-doped alkali fluosilicic acid glass up-conversion luminescent material, and preparation method and application thereof
CN107253854A (en) * 2017-05-18 2017-10-17 北京科技大学 A kind of laser transparent ceramic of grade doping and preparation method thereof
CN107253854B (en) * 2017-05-18 2020-10-02 北京科技大学 Gradient doped laser transparent ceramic and preparation method thereof
CN108536993A (en) * 2018-01-04 2018-09-14 广东工业大学 A kind of determination method of raw material proportioning in optical ceramics preparation process

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Application publication date: 20100602