JP2009007434A - Thermo-optic conversion system of rare earth compound - Google Patents
Thermo-optic conversion system of rare earth compound Download PDFInfo
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Abstract
Description
本発明は希土類化合物の熱光変換システムに関する。 The present invention relates to a heat-light conversion system for rare earth compounds.
従来、紫外線領域の発光デバイスとしては、ZnO、GaN等多くの化合物がある(非特許文献1,2)。また、熱からエネルギーを取り出す方法として、熱を電気に変換する熱電素子が存在する。
しかし、上記従来の発光デバイスの化合物からは、該化合物の温度変化により熱エネルギーから光エネルギーを直接取り出すということはできなかった。また、上記従来の熱電素子は、本発明とは原理が異なり、発光はしないし、また、200℃以下では使用できてない。
本発明は、上記従来技術では不可能であった、熱エネルギーを光エネルギーに直接変え得る、また、100℃乃至200℃程度の低温度廃熱から、有効にエネルギーを取り出し得る希土類化合物の熱光変換システムを提供することを解決すべき目的としている。
However, it has not been possible to directly extract light energy from heat energy from the compound of the above conventional light emitting device due to temperature change of the compound. Further, the above-described conventional thermoelectric element is different in principle from the present invention, does not emit light, and cannot be used at 200 ° C. or lower.
The present invention can directly convert heat energy into light energy, which is impossible with the above-described prior art, and can effectively extract energy from low-temperature waste heat of about 100 ° C. to 200 ° C. Providing a conversion system is the purpose to be solved.
第1発明の希土類化合物熱光変換システムは、
希土類化合物を環境下の常温よりも高い温度まで加熱し、5d軌道に集まった電子を、該軌道よりも低いエネルギー準位で空席のある4f軌道に遷移させることにより両者のエネルギー差に相当する光エネルギーを取り出すシステムである。
したがって、第1発明の希土類化合物熱光変換システムによれば、希土類化合物を加熱して該化合物の温度を変化させたとき起こる、電子のエネルギー準位間の遷移を利用して、光エネルギーを直接取り出すことができる。
第2発明の希土類化合物熱光変換システムは、
第1発明の希土類熱光変換システムにより光エネルギーを取り出した後に温度が下がった希土類化合物を、放冷、空冷、水冷またはペルチエ素子等と組み合わせた方法により、環境下の常温程度まで低下させて希土類化合物を元の状態に戻し、これを再度加熱して5d軌道に集まった電子を4f軌道に遷移させることにより両者のエネルギー差に相当する光エネルギーを取り出すシステムである。
本発明で使用する希土類化合物では、環境下の常温(以下「常温」という。)以下で希土類元素の電子は配位する原子の2p軌道に遷移する。これを加熱し、例えば、160℃程度にすると、配位する原子の2p軌道に遷移した電子が、希土類元素の常温での状態から、数eV上にある軌道をほぼ埋めるほど移動する。この変化は可逆的な変化であり、第2発明によれば、希土類化合物の温度を循環的に変化させ、高温時に光エネルギーを取り出せば、熱源のある限り作動する、循環的エネルギー供給システムができるのである。当該熱源には、高温度の廃熱とともに、100乃至200℃の低温度廃熱も利用できるため諸分野の廃熱の有効活用によりエネルギー効率の向上が可能である。
一般に希土類原子においては、電子が存在する軌道としてはf-軌道のエネルギーが最も高く、その数eV上にあるd軌道には電子は存在しない。本発明者らの開発したX線原子軌道解析法(XAO法)を使用して、希土類化合物の電子密度を測定したところ、驚いたことに、f軌道に余席があるにも関わらず、その数eV上にあるd軌道に電子が満席になるまで詰まっていた。常温から100Kまで冷却すると、f電子が配位する分子に移動することは既に本発明者らが発表しているが(非特許文献3)、逆に常温より温度を上げると、配位する分子の電子が希土類原子の前記d軌道に大量に移動したのである。このことは、常温より上まで希土類化合物を加熱し、前記d軌道に集まった電子を、空席のあるf軌道に遷移させると、両者のエネルギー差に相当する紫外光が取り出せることを示している。
Light corresponding to the energy difference between the two rare earth compounds is heated to a temperature higher than ambient temperature in the environment, and electrons collected in the 5d orbital are transferred to a vacant 4f orbital at a lower energy level than the orbital. It is a system to extract energy.
Therefore, according to the rare earth compound thermo-optic conversion system of the first invention, the light energy is directly converted using the transition between the energy levels of electrons that occurs when the rare earth compound is heated to change the temperature of the compound. It can be taken out.
The rare earth compound heat-light conversion system of the second invention is:
The rare earth compound whose temperature has been lowered after taking out the light energy by the rare earth thermal light conversion system of the first invention is reduced to about room temperature in the environment by a method of cooling, air cooling, water cooling, Peltier element, etc. This is a system that takes out the light energy corresponding to the energy difference between the two by returning the compound to its original state and heating it again to transition the electrons collected in the 5d orbit to the 4f orbit.
In the rare earth compound used in the present invention, the electron of the rare earth element transitions to the 2p orbit of the coordinating atom below the ambient temperature in the environment (hereinafter referred to as “room temperature”). When this is heated to, for example, about 160 ° C., the electrons that have transitioned to the 2p orbit of the coordinating atoms move from the state of the rare earth element at room temperature to the extent that the orbit above several eV is almost filled. This change is a reversible change. According to the second invention, if the temperature of the rare earth compound is changed cyclically and light energy is taken out at a high temperature, a cyclic energy supply system that operates as long as the heat source is present can be formed. It is. As the heat source, low-temperature waste heat of 100 to 200 ° C. can be used in addition to high-temperature waste heat. Therefore, energy efficiency can be improved by effectively using waste heat in various fields.
In general, in rare earth atoms, the f-orbital has the highest energy in the orbit where electrons exist, and no electron exists in the d orbital that is several eV above. Using the X-ray atomic orbit analysis method (XAO method) developed by the present inventors, the electron density of the rare earth compound was measured. The electrons were stuck in the d orbit, which was several eV above, until the electrons were full. The inventors have already announced that f electrons move to coordinated molecules when cooled from room temperature to 100K (Non-patent Document 3), but conversely, molecules that coordinate when the temperature is raised from room temperature. This electron has moved to the d orbit of the rare earth atom in large quantities. This indicates that when the rare earth compound is heated to above room temperature and the electrons collected in the d orbital are shifted to the f orbital having a vacant seat, ultraviolet light corresponding to the energy difference between the two can be extracted.
以下、本発明を具体化した実施例を図面を参照しつつ説明する。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will be described below with reference to the drawings.
(1)図1では、配位する分子のひとつである配位分子中の2p電子のエネルギー準位と、5d(j=3/2)軌道のエネルギー準位が近いことを示している。
(2)配位分子中の2p電子が、100K乃至200Kで5d(j=3/2)軌道に遷移する(図21))。
(3)(2)の後、エネルギーの近い対称性が同じである(量子力学的に許容される)5d(j=5/2)軌道に遷移し(図22))、その軌道を満たす。軌道の上の数字はその軌道を占有する電子数(上限は1)である。5d(j=5/2)G8軌道は4重に縮重した軌道であるので、ここには最大4個までの電子が存在でき、この図では合計1x4=4個の電子が存在し、満席状態である。
(3)これまで空席であった5d(j=5/2)G8軌道に電子が、配位する分子から遷移してきたので、本来なら4f(j=5/2)G8軌道の方が4f(j=5/2)G7軌道よりエネルギーが低いのであるが、全く同じ方向に伸びる軌道に負の電荷を持つ電子が満席まで詰まったため、4f(j=5/2)G8軌道が不安定になり、エネルギーが高くなっている(図23))。これは逆に5d(j=5/2)G8軌道に電子が存在することを強く支持する結果である。この図の下から上に向かう矢印(4))はエネルギーが相対的に低くなった、4f(j=5/2)G7軌道から4f(j=5/2)G8軌道に、熱励起により電子が遷移することを示している。(この場合、両軌道を占有する電子数の比から、両者のエネルギー差は、68meVと見積もられる。) したがって、エネルギー発生の仕組みは、希土類化合物内での、温度による分子内電子遷移を利用するものである。そのため、外部から5d(j=5/2)G8軌道と4f(j=5/2)G8軌道のエネルギー差に相当するエネルギーを供給することなく、紫外光が取り出せる。
室温以下では、希土類元素4fG8軌道のエネルギーは、同G7軌道より低いが、希土類元素の4fG8電子の一部がB原子のp軌道に移動する。このp電子が他のp電子と共に、温度上昇に伴い、希土類原子の5dG8に遷移し、同軌道をほぼ満席になるまで占有する。この電子を数eV下にある、Ce4fG8軌道に遷移させれば、その差のエネルギーが取り出せる。この後、結晶を冷却すれば、エネルギーサイクルは完成する。ただし、光を放出した希土類化合物はエネルギーを失い、温度が低下するので、冷却過程は省略することもできる。尚、X線解析法によってのみ、各原子軌道を占有する電子数を特定することができる。また、この解析法はわれわれが独自に開発したものであり、今後一般への普及を図る予定であるが、現在は他の人には同様の解析はできない。
(1) FIG. 1 shows that the energy level of the 2p electron in the coordination molecule, which is one of the coordinated molecules, is close to the energy level of the 5d (j = 3/2) orbital.
(2) 2p electrons in the coordination molecule transition to 5d (j = 3/2) orbitals at 100K to 200K (Fig. 21)).
(3) After (2), transition to a 5d (j = 5/2) orbit having the same energy symmetry (quantum mechanically allowed) (FIG. 22)), and the orbit is satisfied. The number above the orbit is the number of electrons occupying the orbit (upper limit is 1). The 5d (j = 5/2) G 8 orbit is a quadruple degenerate orbit, so there can be up to 4 electrons, and in this figure there are a total of 1x4 = 4 electrons, It is full.
(3) Since electrons have transitioned from the coordinated molecule to the previously unoccupied 5d (j = 5/2) G 8 orbit, the 4f (j = 5/2) G 8 orbit was originally The energy is lower than 4f (j = 5/2) G 7 orbit, but electrons with negative charge are fully packed in the orbit extending in the same direction, so 4f (j = 5/2) G 8 orbit is It is unstable and energy is high (Figure 23)). This is a result that strongly supports the existence of electrons in the 5d (j = 5/2) G 8 orbit. The arrow (4)) from the bottom to the top of this figure shows thermal excitation from 4f (j = 5/2) G 7 orbit to 4f (j = 5/2) G 8 orbit, where the energy is relatively low. Shows that the electrons transition. (In this case, from the ratio of the number of electrons occupying both orbitals, the energy difference between the two is estimated to be 68 meV.) Therefore, the mechanism of energy generation uses intramolecular electronic transition due to temperature in the rare earth compound. Is. Therefore, without supplying energy corresponding to the energy difference between the outside from 5d (j = 5/2) G 8 orbital and 4f (j = 5/2) G 8 track, retrieve the ultraviolet light.
Hereinafter room temperature, the energy of the rare earth element 4FG 8 track is lower than the G 7 trajectory, part of 4FG 8 electrons of the rare earth element is moved to the p-orbital of the B atoms. This p-electron, together with other p-electrons, transitions to the rare earth atom 5dG 8 as the temperature rises, occupying the orbit until it is almost full. If this electron is shifted to the Ce4fG 8 orbit, which is several eV below, the difference energy can be extracted. After this, if the crystal is cooled, the energy cycle is completed. However, since the rare earth compound emitting light loses energy and the temperature decreases, the cooling process can be omitted. The number of electrons occupying each atomic orbital can be specified only by the X-ray analysis method. This analysis method was originally developed by us and is planned to be widely used in the future. However, other people cannot do the same analysis now.
本発明の熱光変換システムは、従来の紫外光の利用法のすべてに応用可能であるが、100乃至200℃程度の低温度廃熱は、工場、発電所等の大規模な廃熱から、家庭からの小規模な廃熱にも適用できる。社会のあらゆるところに存在する廃熱の、徹底的な活用が可能になれば、エネルギー問題および地球環境問題の解決に大きく寄与する。また、発光する紫外線を、太陽光発電システムの光源として活用すれば、太陽光がえられない時間・場所での太陽光発電が可能になる。たとえば、温熱水の通る下水道に本システムを設置すれば、家庭の下水道から取り出される紫外光を照射して発電することにも利用可能性がある。 The heat-light conversion system of the present invention can be applied to all conventional methods of using ultraviolet light, but low-temperature waste heat of about 100 to 200 ° C. is from large-scale waste heat of factories, power plants, etc. It can also be applied to small-scale waste heat from households. If exhaust heat that exists in every part of society can be used thoroughly, it will greatly contribute to solving energy and global environmental problems. In addition, if ultraviolet rays that emit light are used as a light source of a solar power generation system, it is possible to generate solar power at times and places where sunlight cannot be obtained. For example, if this system is installed in a sewer through which hot water passes, it may be used to generate power by irradiating ultraviolet light extracted from the home sewer.
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JP2000096034A (en) * | 1998-09-22 | 2000-04-04 | Sumitomo Metal Mining Co Ltd | Sun radiation screening material, coating solution for sun radiation screening membrane and sun radiation screening membrane |
JP2004059875A (en) * | 2002-07-31 | 2004-02-26 | Sumitomo Metal Mining Co Ltd | Masterbatch containing heat ray shielding ingredient, heat ray shielding transparent resin molding applied with the masterbatch and laminate thereof |
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