JP3478162B2 - Manufacturing method of thermoelectric material - Google Patents
Manufacturing method of thermoelectric materialInfo
- Publication number
- JP3478162B2 JP3478162B2 JP09442399A JP9442399A JP3478162B2 JP 3478162 B2 JP3478162 B2 JP 3478162B2 JP 09442399 A JP09442399 A JP 09442399A JP 9442399 A JP9442399 A JP 9442399A JP 3478162 B2 JP3478162 B2 JP 3478162B2
- Authority
- JP
- Japan
- Prior art keywords
- molten metal
- cooling roll
- thermoelectric material
- producing
- foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 93
- 239000002184 metal Substances 0.000 claims description 93
- 239000011888 foil Substances 0.000 claims description 83
- 238000001816 cooling Methods 0.000 claims description 82
- 238000002347 injection Methods 0.000 claims description 71
- 239000007924 injection Substances 0.000 claims description 71
- 239000002994 raw material Substances 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 15
- 230000000171 quenching effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 44
- 239000013078 crystal Substances 0.000 description 12
- 239000000155 melt Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Continuous Casting (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱電材料の製造方
法に関し、特に、結晶の配向性が良い、急冷箔粉末等を
形成することができる熱電材料の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoelectric material, and more particularly, to a method for producing a thermoelectric material having good crystal orientation and capable of forming a quenched foil powder or the like.
【０００２】[0002]
【従来の技術】従来、熱電材料の製造方法としては、一
方向凝固させた材料を粉砕して固化成形する方法が知ら
れている。図７（ａ）乃至（ｄ）は従来の熱電材料の製
造方法を示す模式図である。2. Description of the Related Art Conventionally, as a method for producing a thermoelectric material, there has been known a method in which a unidirectionally solidified material is pulverized and solidified. FIGS. 7A to 7D are schematic views illustrating a conventional method for manufacturing a thermoelectric material.
【０００３】先ず、図７（ａ）に示すように、原料１０
１を石英管１００に入れた後、石英管１００を溶断して
封入する。次に、図７（ｂ）に示すように、石英管１０
０を管状炉１０２に入れて溶解し管状炉１０２を揺動し
て攪拌する。次に、図７（ｃ）に示すように、管状炉１
０２内に温度勾配をつけ、結晶方位を配向させながら凝
固させて凝固材１０３を形成する。次に、図７（ｄ）に
示すように、凝固材１０３を粉砕しホットプレス等によ
り固化成形し、固化成形材を作製する。このとき、圧力
の作用方向と垂直方向に低抵抗の結晶方向が成長するた
め、この方向に電流を流すように電極を取りつけてモジ
ュ−ルを作製している。また、凝固材１０３をそのまま
モジュールに使用している。[0003] First, as shown in FIG.
After putting 1 into the quartz tube 100, the quartz tube 100 is melted and sealed. Next, as shown in FIG.
Is melted in a tubular furnace 102, and the tubular furnace 102 is rocked and stirred. Next, as shown in FIG.
A solidified material 103 is formed by solidifying while orienting the crystal orientation while giving a temperature gradient in 02. Next, as shown in FIG. 7D, the solidified material 103 is pulverized and solidified by hot pressing or the like to produce a solidified molded material. At this time, since a crystal direction having a low resistance grows in a direction perpendicular to the direction in which the pressure acts, a module is manufactured by mounting electrodes so that a current flows in this direction. The solidified material 103 is used as it is for the module.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上述の従来の
熱電材料の製造方法では、例えば、凝固材１０３では製
造された熱電材料の結晶粒径が数ｍｍ以上になり、へき
開性があるため脆くなるという問題点がある。また、熱
伝導率が高い。熱電材料の性能指数をＺ、熱起電力を
α、熱伝導率をκ、比抵抗をρとするとき、下記数式１
のように示される。However, according to the above-mentioned conventional method for producing a thermoelectric material, for example, the solidified material 103 has a crystal grain size of several mm or more in the produced thermoelectric material, and is brittle because it has cleavage. There is a problem that becomes. Also, the thermal conductivity is high. When the figure of merit of the thermoelectric material is Z, the thermoelectromotive force is α, the thermal conductivity is κ, and the specific resistance is ρ,
Is shown as
【０００５】[0005]
【数１】Ｚ＝α2／（κ×ρ）## EQU1 ## Z = α 2 / (κ × ρ)
【０００６】数式１で示されるように熱伝導率が高いと
性能の向上に限界がある。[0006] As shown in Equation 1, when the thermal conductivity is high, there is a limit in improving the performance.
【０００７】また、図７の（ｄ）で得られる固形成形材
では粉砕された粉末の大きさが結晶粒径であるため、κ
を低下させるために結晶粒を微細化しても限界がある。
また、粉砕時の粉末の表面酸化又は不純物の混入のため
に比抵抗の増大を招いて、数式１に示されるように性能
指数が低下し、性能が劣化するという問題点がある。In the solid compact obtained in FIG. 7 (d), the size of the pulverized powder is the crystal grain size.
There is a limit even if the crystal grains are refined in order to reduce the crystallinity.
Further, there is a problem that the specific resistance increases due to the surface oxidation of the powder at the time of pulverization or the incorporation of impurities, so that the performance index decreases as shown in Expression 1 and the performance deteriorates.
【０００８】本発明はかかる問題点に鑑みてなされたも
のであって、結晶の配向性が良い、急冷箔粉末を形成す
ることができる熱電材料の製造方法を提供することを目
的とする。The present invention has been made in view of the above problems, and an object of the present invention is to provide a method of manufacturing a thermoelectric material having good crystal orientation and capable of forming a quenched foil powder.
【０００９】[0009]
【課題を解決するための手段】本発明に係る熱電材料の
製造方法は、原料を溶融し、前記原料を溶湯射出ノズル
から冷却ロ−ルに溶湯射出する液体急冷方法により急冷
箔を作製し、この急冷箔をそのまま又は粉砕した後、固
化成形して熱電材料を作製する熱電材料の製造方法にお
いて、前記原料はＢｉ及びＳｂからなる群から選択され
た少なくとも１種の元素と、Ｔｅ及びＳｅからなる群か
ら選択された少なくとも１種の元素と、を含有する組成
を有し、前記溶湯射出の溶湯射出温度をＴＬとし、前記
冷却ロ−ルの回転速度をＲとするとき、前記ＴＬは６０
０乃至１１００℃であり、前記Ｒは２乃至８０ｍ／秒で
あり、前記ＴＬは（２０Ｒ＋４６７６０）／７８乃至
（１００Ｒ＋７７８００）／７８である条件で急冷箔を
製造する工程を有することを特徴とする。According to a method of manufacturing a thermoelectric material according to the present invention, a quenched foil is produced by a liquid quenching method in which a raw material is melted, and the raw material is injected from a molten metal injection nozzle into a cooling roll. In the method for producing a thermoelectric material, in which the quenched foil is directly or pulverized, and then solidified and formed to produce a thermoelectric material, the raw material comprises at least one element selected from the group consisting of Bi and Sb, and Te and Se. The composition has a composition containing at least one element selected from the group consisting of: TL is 60 when the molten metal injection temperature of the molten metal injection is TL, and the rotation speed of the cooling roll is R.
A temperature of 0 to 1100 ° C., R is 2 to 80 m / sec, and TL is (20R + 46760) / 78 to (100R + 77800) / 78.
【００１０】この場合、前記原料は更にＩ、Ｃｌ、Ｈ
ｇ、Ｂｒ、Ａｇ及びＣｕからなる群から選択された少な
くとも１種の元素を含有させて、キャリア密度の制御が
可能である。In this case, the raw materials further include I, Cl, H
The carrier density can be controlled by containing at least one element selected from the group consisting of g, Br, Ag, and Cu.
【００１１】本発明においては、前記冷却ロ−ルの表面
温度をＴＲとするとき、前記ＴＲは５乃至８０℃であ
り、前記ＴＲは（ＴＬ−１００）／１００乃至（ＴＬ＋
２９００）／５０である条件で急冷箔を製造する工程を
有することが好ましい。In the present invention, when the surface temperature of the cooling roll is TR, the TR is 5 to 80 ° C., and the TR is (TL-100) / 100 to (TL +
It is preferable to have a step of manufacturing a quenched foil under the condition of 2900) / 50.
【００１２】また、前記溶湯射出ノズルと前記冷却ロー
ルとの間隔をｄとするとき、前記ｄは０．３乃至２０ｍ
ｍであり、前記Ｒは（８ｄ＋３７）／１９．７乃至（３
０ｄ＋９７６）／１９．７である条件で急冷箔を製造す
る工程を有することが好ましい。When the distance between the molten metal injection nozzle and the cooling roll is d, the distance d is 0.3 to 20 m.
m, and R is (8d + 37) /19.7 to (3
(0d + 976) /19.7.
【００１３】更に、前記溶湯射出の圧力をＰとすると
き、前記Ｐは０．１乃至７ｋｇｆ／ｃｍ2であり、前記
Ｒは（Ｐ＋４．５）／２．３乃至（２５Ｐ＋３７７）／
６．９である条件で急冷箔を製造する工程を有すること
が好ましい。Further, when the pressure of the molten metal injection is P, the P is 0.1 to 7 kgf / cm 2 , and the R is (P + 4.5) /2.3 to (25P + 377) /
It is preferable to have a step of producing a quenched foil under the condition of 6.9.
【００１４】更にまた、前記溶湯射出ノズルの口径をφ
とするとき、前記φは０．１乃至１０ｍｍであり、前記
Ｐは（−０．４φ＋４．９９）／９．９乃至（−２φ＋
６９．５）／９．９である条件で急冷箔を製造する工程
を有することが好ましい。Further, the diameter of the molten metal injection nozzle is φ
Is from 0.1 to 10 mm, and P is (−0.4φ + 4.99) /9.9 to (−2φ +
(69.5) /9.9 It is preferable to have a process of manufacturing a quenched foil under the condition of 9.9.
【００１５】また、前記急冷箔を製造する工程の後工程
として、前記急冷箔を還元ガス雰囲気で熱処理し、固化
成形する工程を有することが好ましい。It is preferable that the method further includes a step of heat-treating the quenched foil in a reducing gas atmosphere and solidifying and forming the quenched foil as a step subsequent to the step of manufacturing the quenched foil.
【００１６】本発明においては、溶湯射出の溶湯射出温
度をＴＬとし、冷却ロ−ルの回転速度をＲとするとき、
ＴＬは６００乃至１１００℃であり、Ｒは２乃至８０ｍ
／秒であり、ＴＬは（２０Ｒ＋４６７６０）／７８乃至
（１００Ｒ＋７７８００）／７８である条件で急冷箔を
製造することにより、低抵抗に配向された結晶を有する
急冷箔を製造することができる。In the present invention, when the molten metal injection temperature of molten metal injection is TL and the rotation speed of the cooling roll is R,
TL is 600 to 1100 ° C., R is 2 to 80 m
/ Sec, and the TL is (20R + 46760) / 78 to (100R + 77800) / 78, whereby a quenched foil having crystals oriented with low resistance can be manufactured.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施例に係る熱電
材料の製造方法について添付の図面を参照して詳細に説
明する。図１は本発明の実施例に係る熱電材料の製造装
置を示す模式図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a thermoelectric material according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a schematic view showing an apparatus for manufacturing a thermoelectric material according to an embodiment of the present invention.
【００１８】本実施例では、冷却ロ−ル１と溶融した原
料を冷却ロ−ル１表面に射出させるノズル２が間隔をｄ
あけて配置されている。このノズル２には溶融した溶湯
３が充填され、溶湯３を射出する口径φの開口部４が形
成されている。また、溶湯３を射出するための溶湯射出
圧力Ｐを作用させる圧力発生手段（図示せず）に接続さ
れている。In the present embodiment, the cooling roll 1 and the nozzle 2 for injecting the molten raw material onto the surface of the cooling roll 1 have a distance d.
It is arranged open. The nozzle 2 is filled with a molten metal 3, and an opening 4 having a diameter φ for injecting the molten metal 3 is formed. Further, it is connected to pressure generating means (not shown) for applying a molten metal injection pressure P for injecting the molten metal 3.
【００１９】この冷却ロ−ル１を周速度をＲで回転さ
せ、冷却ロ−ル１の中心に向けてノズル２から溶湯３を
射出し、冷却ロ−ル１により冷却されて急冷箔５が形成
される。この作製された急冷箔５を還元ガス雰囲気で熱
処理し、固化成形して熱電材料が形成される。なお、冷
却ロ−ル１の材質としては銅、銅合金、鉄、鋼又はチタ
ン合金等を使用することができる。The cooling roll 1 is rotated at a peripheral speed of R, a molten metal 3 is injected from a nozzle 2 toward the center of the cooling roll 1, and is cooled by the cooling roll 1 to form a quenched foil 5. It is formed. The quenched foil 5 thus produced is heat-treated in a reducing gas atmosphere and solidified to form a thermoelectric material. The material of the cooling roll 1 may be copper, copper alloy, iron, steel, titanium alloy or the like.
【００２０】次に、本発明の熱電材料の製造方法の数値
限定理由について説明する。Next, the reasons for limiting the numerical values of the method for producing a thermoelectric material of the present invention will be described.
【００２１】溶湯射出温度：６００乃至１１００℃
溶湯射出温度が６００℃未満では、材料が十分に溶解で
きないか又は溶湯の粘性が高くて射出できない。一方、
溶湯射出温度が１１００℃を超えると、蒸気圧の高いＴ
ｅ及びＳｅが蒸発して組成が変わってしまい熱電材料の
性能が高性能を得ることができない。従って、溶湯射出
温度は６００乃至１１００℃とする。 Melt injection temperature: 600 to 1100 ° C. If the melt injection temperature is lower than 600 ° C., the material cannot be melted sufficiently or the melt cannot be injected due to its high viscosity. on the other hand,
If the molten metal injection temperature exceeds 1100 ° C, T
e and Se evaporate and the composition changes, and the performance of the thermoelectric material cannot be high. Therefore, the molten metal injection temperature is set to 600 to 1100 ° C.
【００２２】冷却ロ−ルの回転速度：２乃至８０ｍ／秒
冷却ロ−ルの回転速度が２ｍ／秒未満では急冷速度が十
分に得ることができず低抵抗方位に配向した超急冷箔を
得ることができない。一方、冷却ロ−ルの回転速度が８
０ｍ／秒を超えると、冷却ロ−ルと溶湯との濡れ性が悪
化し、箔が粉末状になるため、急冷速度を十分に得るこ
とができず、低抵抗方位に配向した超急冷箔が得られな
いと共に、箔の形状が一定化せず、安定した性能を得る
ことができない。従って、冷却ロ−ルの回転速度は２乃
至８０ｍ／秒とする。 Rotation speed of cooling roll: 2 to 80 m / sec When the rotation speed of cooling roll is less than 2 m / sec, a sufficient quenching speed cannot be obtained, and a super-quenched foil oriented in a low resistance direction is obtained. Can not do. On the other hand, when the rotation speed of the cooling roll is 8
If it exceeds 0 m / sec, the wettability between the cooling roll and the molten metal deteriorates, and the foil becomes powdery, so that the quenching speed cannot be sufficiently obtained, and the ultra-quenched foil oriented in the low-resistance direction cannot be obtained. In addition to this, the shape of the foil is not constant and stable performance cannot be obtained. Therefore, the rotation speed of the cooling roll is set to 2 to 80 m / sec.
【００２３】溶湯射出温度：（２０Ｒ＋４６７６０）／
７８乃至（１００Ｒ＋７７８００）／７８
図２は縦軸に溶湯射出温度、横軸に冷却ロールの回転速
度をとり、急冷箔の製造条件を示すグラフ図である。図
２に示すように、下記数式２及び３に示す直線により表
すことができる。 Melt injection temperature: (20R + 46760) /
78 to (100R + 77800) / 78 FIG. 2 is a graph showing production conditions of the quenched foil, with the vertical axis representing the molten metal injection temperature and the horizontal axis representing the rotation speed of the cooling roll. As shown in FIG. 2, it can be represented by a straight line represented by the following mathematical expressions 2 and 3.
【００２４】[0024]
【数２】７８ＴＬ＝２０Ｒ＋４６７６０## EQU2 ## 78TL = 20R + 46760
【００２５】[0025]
【数３】７８ＴＬ＝１００Ｒ＋７７８００## EQU3 ## 78TL = 100R + 77800
【００２６】溶湯射出温度が（２０Ｒ＋４６７６０）／
７８の値未満では溶湯の粘性が高すぎて冷却ロ−ルで十
分に急冷されず急冷速度が十分に得ることができない。
このため、低抵抗方位に配向した超急冷箔を得ることが
できない。一方、溶湯射出温度が（１００Ｒ＋７７８０
０）／７８を超えると、冷却ロ−ルと溶湯との濡れ性が
悪化すると共に、箔が粉末状になるため急冷速度を十分
に得ることができず、低抵抗方位に配向した超急冷箔を
得ることができない。従って、溶湯射出温度：（２０Ｒ
＋４６７６０）／７８乃至（１００Ｒ＋７７８００）／
７８とする。When the molten metal injection temperature is (20R + 46760) /
When the value is less than 78, the viscosity of the molten metal is too high and the quenching is not sufficiently performed by the cooling roll, so that a sufficient quenching speed cannot be obtained.
Therefore, it is not possible to obtain a super-quenched foil oriented in a low resistance orientation. On the other hand, when the molten metal injection temperature is (100R + 7780)
If the ratio exceeds 0) / 78, the wettability between the cooling roll and the molten metal is deteriorated, and the quenching rate cannot be sufficiently obtained because the foil is powdery. Can not get. Therefore, the molten metal injection temperature: (20R
+47760) / 78 to (100R + 77800) /
78.
【００２７】冷却ロ−ルの表面温度：５乃至８０℃
冷却ロ−ルの表面温度が５℃未満では、急冷時に溶湯に
歪が過度に生じ、結晶性が崩れるため、低抵抗の方位に
配向性を揃えることができず、抵抗が高くなり、性能指
数が低下し、高性能の熱電材料を得ることができない。
一方、冷却ロ−ルの表面温度が８０℃を超えると、溶湯
と冷却ロ−ルとの濡れ性が悪化し、低抵抗の配向性を得
ることが難しくなり、高性能の熱電材料を得ることがで
きない。従って、冷却ロ−ルの表面温度は５乃至８０℃
とすることが好ましい。 Surface temperature of the cooling roll: 5 to 80 ° C. If the surface temperature of the cooling roll is less than 5 ° C., the melt is excessively strained during quenching, and the crystallinity is destroyed. The properties cannot be uniform, the resistance increases, the figure of merit decreases, and a high-performance thermoelectric material cannot be obtained.
On the other hand, if the surface temperature of the cooling roll exceeds 80 ° C., the wettability between the molten metal and the cooling roll deteriorates, making it difficult to obtain a low-resistance orientation, and obtaining a high-performance thermoelectric material. Can not. Therefore, the surface temperature of the cooling roll is 5 to 80 ° C.
It is preferable that
【００２８】冷却ロ−ルの表面温度：（ＴＬ−１００）
／１００乃至（ＴＬ＋２９００）／５０
図３は縦軸に冷却ロールの表面温度、横軸に溶湯射出温
度をとり、急冷箔の製造条件を示すグラフ図である。図
３に示すように、下記数式４及び５に示す直線により表
すことができる。 Surface temperature of cooling roll: (TL-100)
/ 100 to (TL + 2900) / 50 FIG. 3 is a graph showing the production conditions of the quenched foil, with the vertical axis representing the surface temperature of the cooling roll and the horizontal axis representing the molten metal injection temperature. As shown in FIG. 3, it can be represented by a straight line represented by the following mathematical expressions 4 and 5.
【００２９】[0029]
【数４】１００ＴＲ＝ＴＬ−１００## EQU4 ## 100TR = TL-100
【００３０】[0030]
【数５】５０ＴＲ＝ＴＬ＋２９００## EQU5 ## 50TR = TL + 2900
【００３１】冷却ロ−ルの表面温度が（ＴＬ−１００）
／１００未満では、急冷時に溶湯に歪が過度に生じ、結
晶性が崩れるため、低抵抗の方位に配向性を揃えること
ができず、抵抗が高くなり、性能指数が低下し、高性能
の熱電材料を得ることができない。一方、冷却ロ−ルの
表面温度が（ＴＬ＋２９００）／５０を超えると、溶湯
と冷却ロ−ルとの濡れ性が悪化し、低抵抗の配向性を得
ることが難しくなり、高性能の熱電材料を得ることがで
きない。従って、冷却ロ−ルの表面温度は（ＴＬ−１０
０）／１００乃至（ＴＬ＋２９００）／５０とすること
が好ましい。When the surface temperature of the cooling roll is (TL-100)
If it is less than / 100, the molten metal will be excessively strained during quenching, and the crystallinity will be lost, so that the orientation cannot be aligned with the low resistance direction, the resistance will increase, the figure of merit will decrease, and the high performance thermoelectric I can't get the material. On the other hand, when the surface temperature of the cooling roll exceeds (TL + 2900) / 50, the wettability between the molten metal and the cooling roll deteriorates, it becomes difficult to obtain a low-resistance orientation, and a high-performance thermoelectric material is used. Can not get. Therefore, the surface temperature of the cooling roll is (TL-10)
0) / 100 to (TL + 2900) / 50.
【００３２】溶湯射出ノズルと冷却ロールとの間隔：
０．３乃至２０ｍｍ
溶湯射出ノズルと冷却ロールとの間隔が０．３ｍｍ未満
では、冷却ロ−ル上の溶湯にノズルが埋没する射出形態
となり、均質な急冷箔を得ることができない。一方、溶
湯射出ノズルと冷却ロールとの間隔が２０ｍｍを超える
と、溶湯がロ−ルに接触するまでの時間が長くなり、冷
却速度が遅くなるため、結晶の配向性が乱れ高性能の熱
電材料を得ることができない。従って、溶湯射出ノズル
と冷却ロールとの間隔は０．３乃至２０ｍｍとすること
が好ましい。[0032]Spacing between melt injection nozzle and cooling roll:
0.3-20mm
The gap between the molten metal injection nozzle and the cooling roll is less than 0.3 mm
In the injection mode, the nozzle is buried in the molten metal on the cooling roll
And a homogeneous quenched foil cannot be obtained. On the other hand,
The distance between the hot water injection nozzle and the cooling roll exceeds 20 mm
And the time required for the molten metal to come into contact with the rolls increases,
The crystal orientation is disturbed due to the low
Electric material cannot be obtained. Therefore, the molten metal injection nozzle
The distance between the roller and the cooling roll should be 0.3 to 20 mm
Is preferred.
【００３３】冷却ロールの回転速度：（８ｄ＋３７）／
１９．７乃至（３０ｄ＋９７６）／１９．７
図４は縦軸に冷却ロールの回転速度、横軸に溶湯射出ノ
ズルと冷却ロールとの間隔をとり、急冷箔の製造条件を
示すグラフ図である。図４に示すように、下記数式６及
び７に示す直線により表すことができる。 Rotation speed of cooling roll: (8d + 37) /
19.7 to (30d + 976) /19.7 FIG. 4 is a graph showing the production conditions of the quenched foil, with the vertical axis representing the rotation speed of the cooling roll and the horizontal axis representing the distance between the molten metal injection nozzle and the cooling roll. As shown in FIG. 4, it can be represented by a straight line represented by the following formulas 6 and 7.
【００３４】[0034]
【数６】１９．７Ｒ＝８ｄ＋３７## EQU6 ## 19.7R = 8d + 37
【００３５】[0035]
【数７】１９．７Ｒ＝３０ｄ＋９７６## EQU7 ## 19.7R = 30d + 976
【００３６】冷却ロールの回転速度が（８ｄ＋３７）／
１９．７未満では、急冷速度が十分に得ることができ
ず、低抵抗方位に配向した超急冷箔を得ることができな
い。冷却ロールの回転速度が（３０ｄ＋９７６）／１
９．７を超えると、溶湯と冷却ロ−ルとの濡れ性が悪化
すると共に、箔が粉末状になるため、急冷速度が十分に
得ることができない。このため、低抵抗方位に配向した
超急冷箔を得ることができないと共に、箔の形状が一定
化せず、安定した性能を得ることができない。従って、
冷却ロールの回転速度は（８ｄ＋３７）／１９．７乃至
（３０ｄ＋９７６）／１９．７とすることが好ましい。The rotation speed of the cooling roll is (8d + 37) /
If it is less than 19.7, a rapid cooling rate cannot be sufficiently obtained, and a super-quenched foil oriented in a low resistance direction cannot be obtained. The rotation speed of the cooling roll is (30d + 976) / 1
If it exceeds 9.7, the wettability between the molten metal and the cooling roll deteriorates, and the foil becomes powdery, so that a sufficient rapid cooling rate cannot be obtained. For this reason, a super-quenched foil oriented in a low-resistance direction cannot be obtained, and the shape of the foil is not constant, so that stable performance cannot be obtained. Therefore,
The rotation speed of the cooling roll is preferably (8d + 37) /19.7 to (30d + 976) /19.7.
【００３７】溶湯射出圧力：０．１乃至７ｋｇｆ／ｃｍ
2
溶湯射出圧力が０．１ｋｇｆ／ｃｍ2未満では、圧力が
不足して溶湯を射出することができない。一方、溶湯射
出圧力が７ｋｇｆ／ｃｍ2を超えると、溶湯量、即ち、
溶湯の熱容量が大きくなりすぎて急冷速度が低下し、配
向性のよい箔を得ることができず、高性能の熱電材料を
得ることができない。従って、溶湯射出圧力は０．１乃
至７ｋｇｆ／ｃｍ2とすることが好ましい。 Molten injection pressure: 0.1 to 7 kgf / cm
(2) If the molten metal injection pressure is less than 0.1 kgf / cm 2 , the pressure is insufficient and the molten metal cannot be injected. On the other hand, when the molten metal injection pressure exceeds 7 kgf / cm 2 , the molten metal amount, that is,
The heat capacity of the molten metal becomes too large and the quenching rate is reduced, so that a foil with good orientation cannot be obtained, and a high-performance thermoelectric material cannot be obtained. Therefore, the injection pressure of the molten metal is preferably set to 0.1 to 7 kgf / cm 2 .
【００３８】冷却ロールの回転速度：（Ｐ＋４．５）／
２．３乃至（２５Ｐ＋３７７）／６．９
図５は縦軸に冷却ロールの回転速度、横軸に溶湯射出圧
力をとり、急冷箔の製造条件を示すグラフ図である。図
５に示すように、下記数式８及び９に示す直線により表
すことができる。 Rotation speed of cooling roll: (P + 4.5) /
2.3 to (25P + 377) /6.9 FIG. 5 is a graph showing the quenching foil production conditions with the vertical axis representing the rotation speed of the cooling roll and the horizontal axis representing the molten metal injection pressure. As shown in FIG. 5, it can be represented by a straight line represented by the following Expressions 8 and 9.
【００３９】[0039]
【数８】２．３Ｒ＝Ｐ＋４．５## EQU8 ## 2.3R = P + 4.5
【００４０】[0040]
【数９】６．９Ｒ＝２５Ｐ＋３７７6.9R = 25P + 377
【００４１】冷却ロールの回転速度が（Ｐ＋４．５）／
２．３未満では、冷却速度が低下し、必要な冷却速度を
得ることができない。このため、配向性の良い箔を得る
ことができず、高性能の熱電材料を得ることができな
い。一方、冷却ロールの回転速度が（２５Ｐ＋３７７）
／６．９を超えると、急冷箔が薄くなりすぎ粉末状にな
り箔の形状が一定化せず、配向性も崩れるため安定した
熱電材料を得ることができない。従って、冷却ロールの
回転速度は（Ｐ＋４．５）／２．３乃至（２５Ｐ＋３７
７）／６．９とすることが好ましい。The rotation speed of the cooling roll is (P + 4.5) /
If it is less than 2.3, the cooling rate decreases, and the required cooling rate cannot be obtained. Therefore, a foil having good orientation cannot be obtained, and a high-performance thermoelectric material cannot be obtained. On the other hand, the rotation speed of the cooling roll is (25P + 377)
If the ratio exceeds /6.9, the quenched foil becomes too thin and powdery, the shape of the foil is not constant, and the orientation is lost, so that a stable thermoelectric material cannot be obtained. Therefore, the rotation speed of the cooling roll is (P + 4.5) /2.3 to (25P + 37).
7) /6.9 is preferred.
【００４２】溶湯射出ノズルの口径：０．１乃至１０ｍ
ｍ
溶湯射出ノズルの口径が０．１ｍｍ未満では口径が小さ
すぎて溶湯を射出することができない。一方、溶湯射出
ノズルの口径が１０ｍｍを超えると、射出される溶湯の
熱容量が大きすぎて急冷が効かず、低抵抗方位に揃った
箔を形成することができない。このため、高性能の熱電
材料を形成することができない。従って、溶湯射出ノズ
ルの口径は０．１乃至１０ｍｍとすることが好ましい。 Diameter of molten metal injection nozzle: 0.1 to 10 m
If the diameter of the m injection nozzle is less than 0.1 mm, the diameter is too small to allow injection of the molten metal. On the other hand, when the diameter of the molten metal injection nozzle exceeds 10 mm, the heat capacity of the molten metal to be injected is too large to perform rapid cooling, and a foil having a low resistance orientation cannot be formed. Therefore, a high-performance thermoelectric material cannot be formed. Therefore, the diameter of the molten metal injection nozzle is preferably set to 0.1 to 10 mm.
【００４３】溶湯射出圧力：（−０．４φ＋４．９９）
／９．９乃至（−２φ＋６９．５）／９．９
図６は縦軸に溶湯射出圧力、横軸にノズルの口径をと
り、急冷箔の製造条件を示すグラフ図である。図６に示
すように、下記数式１０及び１１に示す直線により表す
ことができる。 Molten metal injection pressure: (-0.4φ + 4.99)
/9.9 to (-2φ + 69.5) /9.9 FIG. 6 is a graph showing the production conditions of the quenched foil, with the vertical axis representing the molten metal injection pressure and the horizontal axis representing the nozzle diameter. As shown in FIG. 6, it can be represented by a straight line represented by the following mathematical expressions 10 and 11.
【００４４】[0044]
【数１０】９.９Ｒ＝−０．４φ＋４．９９9.9R = −0.4φ + 4.99
【００４５】[0045]
【数１１】９.９Ｒ＝−２φ＋６９．５9.9R = −2φ + 69.5
【００４６】溶湯射出圧力は（−０．４φ＋４．９９）
／９．９未満では溶湯の粘性及び溶湯とノズルとの間の
摩擦力のため、射出することができない。一方、溶湯射
出圧力が（−２φ＋６９．５）／９．９を超えると、射
出される溶湯の量が多すぎて急冷が効かず、低抵抗方位
に配向の揃った箔を形成することができない。このた
め、高性能の熱電材料を得ることができない。従って、
溶湯射出圧力は（−０．４φ＋４．９９）／９．９乃至
（−２φ＋６９．５）／９．９とすることが好ましい。The injection pressure of the molten metal is (−0.4φ + 4.99)
If it is less than /9.9, it cannot be injected due to the viscosity of the molten metal and the frictional force between the molten metal and the nozzle. On the other hand, if the molten metal injection pressure exceeds (−2φ + 69.5) /9.9, the amount of the molten metal to be injected is too large to perform rapid cooling, and a foil having a uniform orientation in a low resistance direction cannot be formed. . Therefore, a high-performance thermoelectric material cannot be obtained. Therefore,
The molten metal injection pressure is preferably (−0.4φ + 4.99) /9.9 to (−2φ + 69.5) /9.9.
【００４７】[0047]
【実施例】以下、本発明の範囲に入る熱電材料の製造方
法の実施例について、その特性を比較例と比較して具体
的に説明する。EXAMPLES Examples of the method for producing a thermoelectric material falling within the scope of the present invention will be specifically described in comparison with comparative examples.
【００４８】第１実施例
Ｂｉ0.5Ｓｂ1.5Ｔｅ3＋２重量％Ｔｅ及びＢｉ1.8Ｓｂ
0.2Ｔｅ2.85Ｓｅ0.15＋０．１５重量％Ｓｂの原料を使
用し、溶湯射出温度及び冷却ロ−ルの回転速度を表１に
示す条件で急冷箔を作製し、この急冷箔を使用して熱電
材料を作製した。この得られた熱電材料の熱起電力、熱
伝導率及び比抵抗を測定し、性能指数Ｚを上記数式１に
より算出した。これらの結果を表１に示す。 First Embodiment Bi 0.5 Sb 1.5 Te 3 +2 wt% Te and Bi 1.8 Sb
Using a raw material of 0.2 Te 2.85 Se 0.15 + 0.15 % by weight of Sb, a quenched foil is produced under the conditions shown in Table 1 for the molten metal injection temperature and the rotation speed of the cooling roll. Was prepared. The thermoelectromotive force, the thermal conductivity, and the specific resistance of the obtained thermoelectric material were measured, and the figure of merit Z was calculated by the above formula 1. Table 1 shows the results.
【００４９】なお、表１の実施例No.１乃至３及び比較
例No.４６乃至４８はＢｉ0.5Ｓｂ1.5Ｔｅ3＋２重量％Ｔ
ｅの組成の熱電材料である。表１の実施例No.４乃至６
及び比較例No.５０乃至５６はＢｉ1.8Ｓｂ0.2Ｔｅ2.85
Ｓｅ0.15＋０．１５重量％Ｓｂの組成の熱電材料であ
る。In Examples 1 to 3 and Comparative Examples 46 to 48 in Table 1, Bi 0.5 Sb 1.5 Te 3 + 2% by weight T
e is a thermoelectric material having a composition of e. Example Nos. 4 to 6 in Table 1
And Comparative Examples No.50 to 56 Bi 1.8 Sb 0.2 Te 2.85
It is a thermoelectric material having a composition of Se 0.15 + 0.15 % by weight Sb.
【００５０】[0050]
【表１】 [Table 1]
【００５１】上記表１に示すように、本発明の範囲に入
る実施例No.１乃至６は比抵抗値が低いため、性能指数
が４．２１×１０-3１／Ｋを超える高い値となった。As shown in Table 1 above, Examples Nos. 1 to 6 which fall within the scope of the present invention have low specific resistance values, and have a high figure of merit exceeding 4.21 × 10 −3 1 / K. became.
【００５２】一方、比較例No.４６乃至５６は良好な性
能指数を得ることができなかった。比較例No.４６は冷
却ロ−ルの回転速度が本発明の範囲未満であるため、低
抵抗方位に配向した急冷箔を得ることができず、性能指
数が低くなった。On the other hand, in Comparative Examples Nos. 46 to 56, a good figure of merit could not be obtained. In Comparative Example No. 46, since the rotation speed of the cooling roll was less than the range of the present invention, a quenched foil oriented in a low resistance direction could not be obtained, and the figure of merit was low.
【００５３】比較例No.４７は冷却ロ−ルの回転速度が
本発明の範囲を超えているため、低抵抗方位に配向した
急冷箔を得ることができず、性能指数が低くなった。In Comparative Example No. 47, since the rotation speed of the cooling roll exceeded the range of the present invention, a quenched foil oriented in a low resistance direction could not be obtained, and the figure of merit was low.
【００５４】比較例No.４８は溶湯射出温度の値が（１
００Ｒ＋７７８００）／７８の値よりも大きいため、低
抵抗方位に配向した急冷箔を得ることができず、性能指
数が低くなった。In Comparative Example No. 48, the value of the molten metal injection temperature was (1).
(00R + 77800) / 78, a quenched foil oriented in a low resistance orientation could not be obtained, and the figure of merit was low.
【００５５】比較例No.４９は溶湯射出温度の値が（２
０Ｒ＋４６７６０）／７８の値よりも小さいため、低抵
抗方位に配向した急冷箔を得ることができず、性能指数
が低くなった。In Comparative Example No. 49, the value of the molten metal injection temperature was (2
0R + 46760) / 78, it was not possible to obtain a quenched foil oriented in a low resistance orientation, and the figure of merit was low.
【００５６】比較例No.５０は溶湯射出温度の値が（２
０Ｒ＋４６７６０）／７８の値よりも小さいため、低抵
抗方位に配向した急冷箔を得ることができず、性能指数
が低くなった。In Comparative Example No. 50, the value of the molten metal injection temperature was (2
0R + 46760) / 78, it was not possible to obtain a quenched foil oriented in a low resistance orientation, and the figure of merit was low.
【００５７】比較例No.５１は溶湯射出温度の値が（２
０Ｒ＋４６７６０）／７８の値よりも小さいため、低抵
抗方位に配向した急冷箔を得ることができず、性能指数
が低くなった。In Comparative Example No. 51, the value of the molten metal injection temperature was (2
0R + 46760) / 78, it was not possible to obtain a quenched foil oriented in a low resistance orientation, and the figure of merit was low.
【００５８】比較例No.５２は溶湯射出温度の値が（１
００Ｒ＋７７８００）／７８の値よりも大きいため、低
抵抗方位に配向した急冷箔を得ることができず、性能指
数が低くなった。In Comparative Example No. 52, the value of the molten metal injection temperature was (1).
(00R + 77800) / 78, a quenched foil oriented in a low resistance orientation could not be obtained, and the figure of merit was low.
【００５９】比較例No.５３は冷却ロ−ルの回転速度が
本発明の範囲を超えているため、低抵抗方位に配向した
急冷箔を得ることができず、性能指数が低くなった。In Comparative Example No. 53, since the rotation speed of the cooling roll exceeded the range of the present invention, a quenched foil oriented in a low resistance direction could not be obtained, and the figure of merit was low.
【００６０】比較例No.５４は冷却ロ−ルの回転速度が
本発明の範囲未満であるため、急冷速度を十分に得るこ
とができず、性能指数が低くなった。In Comparative Example No. 54, since the rotation speed of the cooling roll was less than the range of the present invention, a sufficient quenching speed could not be obtained, and the figure of merit was low.
【００６１】比較例No.５５は溶湯射出温度が本発明の
範囲未満であるため、溶湯を射出することできなかっ
た。In Comparative Example No. 55, the molten metal could not be injected because the molten metal injection temperature was lower than the range of the present invention.
【００６２】比較例No.５６は溶湯射出温度が本発明の
範囲を超えているため、組成が変化してしまい低抵抗方
位に配向した急冷箔を得ることができず、性能指数が低
くなった。In Comparative Example No. 56, since the molten metal injection temperature exceeded the range of the present invention, the composition was changed and a rapidly cooled foil oriented in a low resistance direction could not be obtained, and the figure of merit was low. .
【００６３】第２実施例
Ｂｉ0.4Ｓｂ0.1Ｔｅ3＋４重量％Ｔｅの原料を使用し、
冷却用のロ−ル表面温度及び溶湯射出温度を表２に示す
条件で急冷箔を作製し、この急冷箔を使用して熱電材料
を作製した。この得られた熱電材料の熱起電力、熱伝導
率及び比抵抗を測定し、性能指数Ｚを上記数式１により
算出した。これらの結果を表２に示す。 Second Example Using a raw material of Bi 0.4 Sb 0.1 Te 3 +4 wt% Te,
A quenched foil was produced under the conditions shown in Table 2 for the cooling roll surface temperature and the molten metal injection temperature, and a thermoelectric material was produced using the quenched foil. The thermoelectromotive force, the thermal conductivity, and the specific resistance of the obtained thermoelectric material were measured, and the figure of merit Z was calculated by the above formula 1. Table 2 shows the results.
【００６４】[0064]
【表２】 [Table 2]
【００６５】上記表２に示すように、本発明の範囲に入
る実施例No.８乃至１７は比抵抗値が低いため、性能指
数が４．２２×１０-3１／Ｋを超える高い値となった。As shown in Table 2 above, Examples Nos. 8 to 17 which fall within the range of the present invention have low specific resistance values, and therefore have a high figure of merit exceeding 4.22 × 10 -3 1 / K. became.
【００６６】一方、比較例No.５７乃至６２は良好な性
能指数を得ることができなかった。比較例No.５７は溶
湯射出温度が本発明の範囲を超えているため、組成が変
化してしまい低抵抗方位に配向した急冷箔を得ることが
できず、性能指数が低くなった。On the other hand, in Comparative Examples Nos. 57 to 62, a good figure of merit could not be obtained. In Comparative Example No. 57, since the molten metal injection temperature was beyond the range of the present invention, the composition changed, and it was not possible to obtain a quenched foil oriented in a low resistance direction, and the figure of merit was low.
【００６７】比較例No.５８は請求項１は満足するもの
のロ−ル表面温度の値が（ＴＬ−１００）／１００の値
よりも小さいため、急冷時に歪が過度に入り結晶性が崩
れ、低抵抗の方位に配向を揃えることができないため、
性能指数が若干低かった。Comparative Example No. 58 satisfies claim 1, but the roll surface temperature value is smaller than the value of (TL-100) / 100. Because it is not possible to align the orientation to the direction of low resistance,
The figure of merit was slightly lower.
【００６８】比較例No.５９は請求項１は満足するもの
のロ−ル表面温度の値が（ＴＬ−１００）／１００の値
よりも小さいため、急冷時に歪が過度に入り結晶性が崩
れ、低抵抗の方位に配向を揃えることができないため、
性能指数が若干低かった。Comparative Example No. 59 satisfies claim 1, but the value of the roll surface temperature is smaller than the value of (TL-100) / 100. Because it is not possible to align the orientation to the direction of low resistance,
The figure of merit was slightly lower.
【００６９】比較例No.６０は請求項１は満足するもの
のロ−ル表面温度の値が（ＴＬ＋２９００）／５０の値
よりも大きいため、溶湯と冷却ロ−ルとの濡れ性が悪化
し、低抵抗の方位に配向を揃えることができないため、
性能指数が若干低かった。Comparative Example No. 60 satisfies claim 1, but the roll surface temperature value is larger than (TL + 2900) / 50, so that the wettability between the molten metal and the cooling roll deteriorates. Because it is not possible to align the orientation to the direction of low resistance,
The figure of merit was slightly lower.
【００７０】比較例No.６１は請求項１は満足するもの
のロ−ル表面温度の値が（ＴＬ＋２９００）／５０の値
よりも大きいため、溶湯と冷却ロ−ルとの濡れ性が悪化
し、低抵抗の方位に配向を揃えることができないため、
性能指数が若干低かった。Comparative Example No. 61 satisfies claim 1, but the roll surface temperature value is larger than (TL + 2900) / 50, so that the wettability between the molten metal and the cooling roll deteriorates. Because it is not possible to align the orientation to the direction of low resistance,
The figure of merit was slightly lower.
【００７１】比較例No.６２は溶湯射出温度が本発明の
範囲未満であるため、溶湯を射出することができなかっ
た。In Comparative Example No. 62, the molten metal could not be injected because the molten metal injection temperature was lower than the range of the present invention.
【００７２】第３実施例
Ｂｉ0.4Ｓｂ1.6Ｔｅ2.95Ｓｅ0.05＋５重量％Ｔｅの原料
を使用し、冷却用のロ−ルの回転速度及びノズル口径を
表３に示す条件で急冷箔を作製し、この急冷箔を使用し
て熱電材料を作製した。この得られた熱電材料の熱起電
力、熱伝導率及び比抵抗を測定し、性能指数Ｚを上記数
式１により算出した。これらの結果を表３に示す。 Third Example Using a raw material of Bi 0.4 Sb 1.6 Te 2.95 Se 0.05 +5 wt% Te, a quenched foil was produced under the conditions shown in Table 3 with the rotation speed of the cooling roll and the nozzle diameter. A thermoelectric material was produced using this quenched foil. The thermoelectromotive force, the thermal conductivity, and the specific resistance of the obtained thermoelectric material were measured, and the figure of merit Z was calculated by the above formula 1. Table 3 shows the results.
【００７３】[0073]
【表３】 [Table 3]
【００７４】上記表３に示すように、本発明の請求項４
の範囲に入る実施例No.１８乃至２４は比抵抗値が低い
ため、性能指数が４．２１×１０-3１／Ｋを超える高い
値となった。As shown in Table 3 above, claim 4 of the present invention
In Examples Nos. 18 to 24 which fall within the range, the specific resistance was low, and the figure of merit was a high value exceeding 4.21 × 10 −3 1 / K.
【００７５】一方、比較例No.６３乃至６９良好な性能
指数を得ることができなかった。比較例No.６３は請求
項１は満足するもののノズル口径が本発明の範囲未満で
あるため、均質な急冷箔を得ることができない。このた
め、性能指数が低かった。On the other hand, in Comparative Examples Nos. 63 to 69, a good figure of merit could not be obtained. Comparative Example No. 63 satisfies Claim 1, but cannot obtain a homogeneous quenched foil because the nozzle diameter is less than the range of the present invention. Therefore, the figure of merit was low.
【００７６】比較例No.６４は請求項１は満足するもの
のノズル口径が本発明の範囲を超えるため、溶湯の熱容
量が大きく急冷箔を得ることができない。このため、性
能指数が低かった。Comparative Example No. 64 satisfies claim 1, but the nozzle diameter exceeds the range of the present invention, so that the heat capacity of the molten metal is large and a quenched foil cannot be obtained. Therefore, the figure of merit was low.
【００７７】比較例No.６５は請求項１は満足するもの
のロ−ル回転速度の値が（３０ｄ＋９７６）／１９．７
の値よりも大きいため、原料と冷却ロ−ルとの濡れ性が
悪化すると共に、箔が粉末状になる。このため、結晶の
配向が乱れ、性能指数が低かった。Comparative Example No. 65 satisfies claim 1, but the value of the roll rotation speed is (30d + 976) /19.7.
, The wettability between the raw material and the cooling roll deteriorates, and the foil becomes powdery. For this reason, the orientation of the crystal was disturbed, and the figure of merit was low.
【００７８】比較例No.６６は請求項１は満足するもの
のロ−ル回転速度の値が（８ｄ＋３７）／１９．７の値
よりも小さいため、急冷速度が十分に得ることができな
い。このため、性能指数が低かった。Although Comparative Example No. 66 satisfies claim 1, the rapid cooling rate cannot be sufficiently obtained because the value of the roll rotation speed is smaller than the value of (8d + 37) /19.7. Therefore, the figure of merit was low.
【００７９】比較例No.６７は請求項１は満足するもの
のロ−ル回転速度の値が（３０ｄ＋９７６）／１９．７
の値よりも大きいため、原料と冷却ロ−ルとの濡れ性が
悪化すると共に、箔が粉末状になる。このため、結晶の
配向が乱れ、性能指数が低かった。Although the comparative example No. 67 satisfies claim 1, the value of the roll rotation speed is (30d + 976) /19.7.
, The wettability between the raw material and the cooling roll deteriorates, and the foil becomes powdery. For this reason, the orientation of the crystal was disturbed, and the figure of merit was low.
【００８０】比較例No.６８は冷却ロ−ルの回転速度が
本発明の範囲未満であるため、急冷速度を十分に得るこ
とができず、性能指数が低くなった。In Comparative Example No. 68, since the rotation speed of the cooling roll was less than the range of the present invention, a sufficient quenching speed could not be obtained, and the figure of merit was low.
【００８１】比較例No.６９は冷却ロ−ルの回転速度が
本発明の範囲を超えているため、低抵抗方位に配向した
急冷箔を得ることができず、性能指数が低くなった。In Comparative Example No. 69, since the rotation speed of the cooling roll exceeded the range of the present invention, a quenched foil oriented in a low resistance direction could not be obtained, and the figure of merit was low.
【００８２】第４実施例
Ｂｉ1.9Ｓｂ0.1Ｔｅ3 。 65Ｓｅ0.35＋０．１５重量％Ｈｇ
Ｂｒ2の原料を使用し、冷却用のロ−ルの回転速度及び
溶湯射出圧力を表４に示す条件で急冷箔を作製し、この
急冷箔を使用して熱電材料を作製した。この得られた熱
電材料の熱起電力、熱伝導率及び比抵抗を測定し、性能
指数Ｚを上記数式１により算出した。これらの結果を表
４に示す。 Fourth Embodiment Bi 1.9 Sb 0.1 Te 3 . 65 Se 0.35 + 0.15% by weight Hg
Using a raw material of Br 2 , a quenched foil was produced under the conditions shown in Table 4 with the rotation speed of the roll for cooling and the injection pressure of the molten metal, and a thermoelectric material was produced using the quenched foil. The thermoelectromotive force, the thermal conductivity, and the specific resistance of the obtained thermoelectric material were measured, and the figure of merit Z was calculated by the above formula 1. Table 4 shows the results.
【００８３】[0083]
【表４】 [Table 4]
【００８４】上記表４に示すように、本発明の請求項５
の範囲に入る実施例No.２５乃至３４は比抵抗値が低い
ため、性能指数が４．２１×１０-3１／Ｋを超える高い
値となった。特に、実施例No.３３及び３４は比抵抗値
が低いために起電力が同じ値のものに比べて高い性能指
数を得ることができる。As shown in Table 4, claim 5 of the present invention
In Examples Nos. 25 to 34 in the range, the specific resistance was low, and the figure of merit was a high value exceeding 4.21 × 10 −3 1 / K. In particular, in Examples 33 and 34, since the specific resistance value is low, a higher figure of merit can be obtained as compared with those having the same electromotive force.
【００８５】一方、比較例No.７０乃至７５は良好な性
能指数を得ることができなかった。比較例No.７０は溶
湯射出圧力が本発明の範囲未満であるため、溶湯を射出
することができなかった。On the other hand, in Comparative Examples Nos. 70 to 75, a good figure of merit could not be obtained. In Comparative Example No. 70, the molten metal could not be injected because the molten metal injection pressure was less than the range of the present invention.
【００８６】比較例No.７１は請求項１は満足するもの
の溶湯射出圧力が本発明の範囲を超えているため、溶湯
量即ち、溶湯の熱容量が大きくなりすぎて急冷速度が低
下し、配向性の良い箔を得ることができない。このた
め、性能指数が低かった。Comparative Example No. 71 satisfies claim 1, but since the molten metal injection pressure exceeds the range of the present invention, the amount of molten metal, that is, the heat capacity of the molten metal becomes too large, so that the quenching speed is reduced, and Can not get a good foil. Therefore, the figure of merit was low.
【００８７】比較例No.７２は請求項１は満足するもの
のロ−ル回転速度の値が（Ｐ＋４．５）／２．３の値よ
りも小さいため、原料の冷却速度が低下し、必要な冷却
速度を得ることができない。このため、性能指数が低か
った。Comparative Example No. 72 satisfies claim 1, but the value of the roll rotation speed is smaller than the value of (P + 4.5) /2.3. No cooling rate can be obtained. Therefore, the figure of merit was low.
【００８８】比較例No.７３は請求項１は満足するもの
のロ−ル回転速度の値が（２５Ｐ＋３７７）／６．９の
値よりも大きいため、急冷箔が薄くなりすぎ粉末状にな
り、箔の形状が一定化せず配向性も崩れる。このため、
性能指数が低かった。Comparative Example No. 73 satisfies claim 1, but since the value of the roll rotation speed is larger than the value of (25P + 377) /6.9, the quenched foil becomes too thin and powdery. Is not fixed and the orientation is lost. For this reason,
The figure of merit was low.
【００８９】比較例No.７４は冷却ロ−ルの回転速度が
本発明の範囲を超えているため、低抵抗方位に配向した
急冷箔を得ることができず、性能指数が低くなった。In Comparative Example No. 74, since the rotation speed of the cooling roll exceeded the range of the present invention, a quenched foil oriented in a low resistance direction could not be obtained, and the figure of merit was low.
【００９０】比較例No.７５は冷却ロ−ルの回転速度が
本発明の範囲未満であるため、急冷速度を十分に得るこ
とができず、性能指数が低くなった。In Comparative Example No. 75, since the rotation speed of the cooling roll was less than the range of the present invention, a sufficient quenching speed could not be obtained, and the figure of merit was low.
【００９１】第５実施例
Ｂｉ1.9Ｓｂ0.1Ｔｅ3 。 75Ｓｅ0.25＋０．０６重量％Ａｇ
ｌの原料を使用し、ノズルの口径及び溶湯射出圧力を表
５に示す条件で急冷箔を作製し、この急冷箔を使用して
熱電材料を作製した。この得られた熱電材料の熱起電
力、熱伝導率及び比抵抗を測定し、性能指数Ｚを上記数
式１により算出した。これらの結果を表５に示す。 Fifth Embodiment Bi 1.9 Sb 0.1 Te 3 . 75 Se 0.25 +0.06 wt% Ag
A quenched foil was prepared using the raw material 1 under the conditions shown in Table 5 with the nozzle diameter and molten metal injection pressure, and a thermoelectric material was prepared using the quenched foil. The thermoelectromotive force, the thermal conductivity, and the specific resistance of the obtained thermoelectric material were measured, and the figure of merit Z was calculated by the above formula 1. Table 5 shows the results.
【００９２】[0092]
【表５】 [Table 5]
【００９３】上記表５に示すように、本発明の請求項６
の範囲に入る実施例No.３５乃至４５は比抵抗値が低い
ため、性能指数が４．２７×１０-3１／Ｋを超える高い
値となった。As shown in Table 5, claim 6 of the present invention
In Examples Nos. 35 to 45 falling within the range, the specific resistance was low, so that the figure of merit was a high value exceeding 4.27 × 10 −3 1 / K.
【００９４】一方、比較例No.７６乃至８１は良好な性
能指数を得ることができなかった。On the other hand, in Comparative Examples Nos. 76 to 81, a good figure of merit could not be obtained.
【００９５】比較例No.７６は溶湯射出圧力及び溶湯射
出圧力の値が（−２φ＋６９．５）／９．９の値より大
きいため、射出される溶湯の熱容量が大きすぎて急冷す
ることができず、低抵抗方位に配向の揃った箔を形成す
ることができない。このため、性能定数が低くくなっ
た。In Comparative Example No. 76, since the value of the molten metal injection pressure and the value of the molten metal injection pressure were larger than the value of (−2φ + 69.5) /9.9, the heat capacity of the injected molten metal was too large to be rapidly cooled. Therefore, it is impossible to form a foil having a uniform orientation in a low resistance direction. For this reason, the performance constant became low.
【００９６】比較例No.７７はノズル口径の値が（−
０．４φ＋４．９９）／９．９の値よりも小さいため、
溶湯の粘性及び溶湯とノズルとの間の摩擦力のため、射
出することができない。このため、性能指数が低くなっ
た。In Comparative Example No. 77, the value of the nozzle diameter was (−).
0.4φ + 4.99) /9.9.
Injection is not possible due to the viscosity of the melt and the frictional force between the melt and the nozzle. For this reason, the figure of merit was low.
【００９７】比較例No.７８はノズル口径の値が（−
０．４φ＋４．９９）／９．９の値よりも小さいため、
溶湯の粘性及び溶湯とノズルとの間の摩擦力のため、射
出することができない。このため、性能指数が低くくな
った。In Comparative Example No. 78, the value of the nozzle diameter was (−
0.4φ + 4.99) /9.9.
Injection is not possible due to the viscosity of the melt and the frictional force between the melt and the nozzle. Therefore, the figure of merit decreased.
【００９８】比較例No.７９は溶湯射出圧力の値が（−
２φ＋６９．５）／９．９の値より大きいため、射出さ
れる溶湯の熱容量が大きすぎて急冷することができず、
低抵抗方位に配向の揃った箔を形成することができな
い。このため、性能定数が低くくなった。In Comparative Example No. 79, the value of the molten metal injection pressure was (−
2φ + 69.5) /9.9, the molten metal to be injected has too large a heat capacity and cannot be rapidly cooled.
It is not possible to form a foil having a uniform orientation in a low resistance direction. For this reason, the performance constant became low.
【００９９】比較例No.８０はノズル口径が本発明の範
囲を超えているため、射出される溶湯の熱容量が大きす
ぎて急冷することができず、低抵抗方位に配向の揃った
箔を形成することができない。このため、性能定数が低
くくなった。In Comparative Example No. 80, since the nozzle diameter exceeded the range of the present invention, the heat capacity of the molten metal to be injected was too large to be rapidly cooled, and a foil having a uniform orientation in a low resistance direction was formed. Can not do it. For this reason, the performance constant became low.
【０１００】比較例No.８１はノズル口径が本発明の範
囲未満であるため、口径が狭すぎて溶湯を射出すること
ができなかった。In Comparative Example No. 81, since the nozzle diameter was less than the range of the present invention, the diameter was too small to inject the molten metal.
【０１０１】[0101]
【発明の効果】以上詳述したように本発明においては、
溶湯射出の溶湯射出温度をＴＬとし、冷却ロ−ルの回転
速度をＲとするとき、ＴＬは６００乃至１１００℃であ
り、Ｒは２乃至８０ｍ／秒であり、ＴＬは（２０Ｒ＋４
６７６０）／７８乃至（１００Ｒ＋７７８００）／７８
である条件で急冷箔を製造することにより、低抵抗に配
向された結晶を有する急冷箔を製造することができる。
このため、性能指数が高い熱電材料を得ることができ
る。As described in detail above, in the present invention,
When the molten metal injection temperature of the molten metal injection is TL and the rotation speed of the cooling roll is R, TL is 600 to 1100 ° C., R is 2 to 80 m / sec, and TL is (20R + 4
6760) / 78 to (100R + 77800) / 78
By manufacturing the quenched foil under the condition, it is possible to manufacture a quenched foil having crystals oriented with low resistance.
Therefore, a thermoelectric material having a high figure of merit can be obtained.
【図１】 本発明の実施例に係る熱電材料の製造装置を
示す模式図である。FIG. 1 is a schematic diagram showing an apparatus for manufacturing a thermoelectric material according to an embodiment of the present invention.
【図２】 縦軸に溶湯射出温度、横軸に冷却ロールの回
転速度をとり、急冷箔の製造条件を示すグラフ図であ
る。FIG. 2 is a graph showing production conditions of a quenched foil, with the vertical axis representing molten metal injection temperature and the horizontal axis representing the rotation speed of a cooling roll.
【図３】 縦軸に冷却ロールの表面温度、横軸に溶湯射
出温度をとり、急冷箔の製造条件を示すグラフ図であ
る。FIG. 3 is a graph showing production conditions of a quenched foil, with the vertical axis representing the surface temperature of the cooling roll and the horizontal axis representing the molten metal injection temperature.
【図４】 縦軸に冷却ロールの回転速度、横軸に溶湯射
出ノズルと冷却ロールとの間隔をとり、急冷箔の製造条
件を示すグラフ図である。FIG. 4 is a graph showing the production conditions of the quenched foil, with the vertical axis representing the rotation speed of the cooling roll and the horizontal axis representing the distance between the molten metal injection nozzle and the cooling roll.
【図５】 縦軸に冷却ロールの回転速度、横軸に溶湯射
出圧力をとり、急冷箔の製造条件を示すグラフ図であ
る。FIG. 5 is a graph showing production conditions of a quenched foil, with the vertical axis representing the rotation speed of the cooling roll and the horizontal axis representing the molten metal injection pressure.
【図６】 縦軸に溶湯射出圧力、横軸にノズルの口径を
とり、急冷箔の製造条件を示すグラフ図である。FIG. 6 is a graph showing production conditions of a quenched foil, with the vertical axis representing molten metal injection pressure and the horizontal axis representing the nozzle diameter.
【図７】 （ａ）乃至（ｄ）は従来の熱電材料の製造方
法を示す模式図である。FIGS. 7A to 7D are schematic diagrams illustrating a conventional method for manufacturing a thermoelectric material.
１；冷却ロール、 ２；ノズル、 ３；溶湯、 ４；開
口部、 ５；急冷箔、１００；石英管、 １０１；原
料、 １０２；管状炉、 １０３；凝固材DESCRIPTION OF SYMBOLS 1; Cooling roll, 2; Nozzle, 3; Molten, 4; Opening, 5; Quenched foil, 100; Quartz tube, 101; Raw material, 102; Tubular furnace, 103;
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−36583（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 35/34 H01L 35/16 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-36583 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 35/34 H01L 35/16
Claims (7)
ルから冷却ロ−ルに溶湯射出する液体急冷方法により急
冷箔を作製し、この急冷箔をそのまま又は粉砕した後、
固化成形して熱電材料を作製する熱電材料の製造方法に
おいて、 前記原料はＢｉ及びＳｂからなる群から選択された少な
くとも１種の元素と、Ｔｅ及びＳｅからなる群から選択
された少なくとも１種の元素と、を含有する組成を有
し、前記溶湯射出の溶湯射出温度をＴＬとし、前記冷却
ロ−ルの回転速度をＲとするとき、前記ＴＬは６００乃
至１１００℃であり、前記Ｒは２乃至８０ｍ／秒であ
り、前記ＴＬは（２０Ｒ＋４６７６０）／７８乃至（１
００Ｒ＋７７８００）／７８である条件で急冷箔を製造
する工程を有することを特徴とする熱電材料の製造方
法。1. A quenched foil is produced by a liquid quenching method in which a raw material is melted, and the raw material is injected from a molten metal injection nozzle to a cooling roll, and the quenched foil is directly or pulverized.
In the method for producing a thermoelectric material by solidifying and forming a thermoelectric material, the raw material is at least one element selected from the group consisting of Bi and Sb, and at least one element selected from the group consisting of Te and Se. TL is 600 to 1100 ° C., where R is the rotation speed of the cooling roll, and TL is 600 to 1100 ° C. To 80 m / sec, and the TL is (20R + 46760) / 78 to (1
(00R + 77800) / 78. A method for producing a thermoelectric material, comprising a step of producing a quenched foil under the condition of (00R + 77800) / 78.
Ａｇ及びＣｕからなる群から選択された少なくとも１種
の元素を含有することを特徴とする請求項１に記載の熱
電材料の製造方法。2. The raw material further comprises I, Cl, Hg, Br,
The method for producing a thermoelectric material according to claim 1, comprising at least one element selected from the group consisting of Ag and Cu.
とき、前記ＴＲは５乃至８０℃であり、前記ＴＲは（Ｔ
Ｌ−１００）／１００乃至（ＴＬ＋２９００）／５０で
ある条件で急冷箔を製造する工程を有することを特徴と
する請求項１又は２に記載の熱電材料の製造方法。3. When the surface temperature of the cooling roll is TR, the TR is 5 to 80 ° C., and the TR is (T
The method for producing a thermoelectric material according to claim 1, further comprising a step of producing a quenched foil under a condition of (L−100) / 100 to (TL + 2900) / 50.
の間隔をｄとするとき、前記ｄは０．３乃至２０ｍｍで
あり、前記Ｒは（８ｄ＋３７）／１９．７乃至（３０ｄ
＋９７６）／１９．７である条件で急冷箔を製造する工
程を有することを特徴とする請求項１乃至３のいずれか
１項に記載の熱電材料の製造方法。4. When the distance between the molten metal injection nozzle and the cooling roll is d, d is 0.3 to 20 mm, and R is (8d + 37) /19.7 to (30d).
The method for producing a thermoelectric material according to any one of claims 1 to 3, further comprising a step of producing a quenched foil under the condition of (+976) /19.7.
記Ｐは０．１乃至７ｋｇｆ／ｃｍ2であり、前記Ｒは
（Ｐ＋４．５）／２．３乃至（２５Ｐ＋３７７）／６．
９である条件で急冷箔を製造する工程を有することを特
徴とする請求項１乃至４のいずれか１項に記載の熱電材
料の製造方法。5. When the pressure of the molten metal injection is P, the P is 0.1 to 7 kgf / cm 2 , and the R is (P + 4.5) /2.3 to (25P + 377) / 6.
The method for producing a thermoelectric material according to any one of claims 1 to 4, further comprising a step of producing a quenched foil under the condition of (9).
き、前記φは０．１乃至１０ｍｍであり、前記Ｐは（−
０．４φ＋４．９９）／９．９乃至（−２φ＋６９．
５）／９．９である条件で急冷箔を製造する工程を有す
ることを特徴とする請求項１乃至５のいずれか１項に記
載の熱電材料の製造方法。6. When the diameter of the molten metal injection nozzle is φ, the φ is 0.1 to 10 mm, and the P is (−
0.4φ + 4.99) /9.9 to (−2φ + 69.
The method for producing a thermoelectric material according to any one of claims 1 to 5, further comprising a step of producing a quenched foil under the condition of (5) /9.9.
て、前記急冷箔を還元ガス雰囲気で熱処理し、固化成形
する工程を有することを特徴とする請求項１乃至６のい
ずれか１項に記載の熱電材料の製造方法。7. The method according to claim 1, further comprising a step of heat-treating the quenched foil in a reducing gas atmosphere and solidifying and forming the quenched foil as a post-step of the step of manufacturing the quenched foil. A method for producing the thermoelectric material according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09442399A JP3478162B2 (en) | 1999-03-31 | 1999-03-31 | Manufacturing method of thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09442399A JP3478162B2 (en) | 1999-03-31 | 1999-03-31 | Manufacturing method of thermoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000286471A JP2000286471A (en) | 2000-10-13 |
| JP3478162B2 true JP3478162B2 (en) | 2003-12-15 |
Family
ID=14109834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09442399A Expired - Lifetime JP3478162B2 (en) | 1999-03-31 | 1999-03-31 | Manufacturing method of thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3478162B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3594008B2 (en) * | 2000-11-30 | 2004-11-24 | ヤマハ株式会社 | Thermoelectric material, manufacturing method thereof and Peltier module |
| US7067733B2 (en) * | 2001-12-13 | 2006-06-27 | Yamaha Corporation | Thermoelectric material having crystal grains well oriented in certain direction and process for producing the same |
| JP4286053B2 (en) * | 2003-05-08 | 2009-06-24 | 株式会社Ｉｈｉ | THERMOELECTRIC SEMICONDUCTOR MATERIAL, THERMOELECTRIC SEMICONDUCTOR ELEMENT USING THE THERMOELECTRIC SEMICONDUCTOR MATERIAL, THERMOELECTRIC MODULE USING THE THERMOELECTRIC SEMICONDUCTOR ELEMENT, AND METHOD FOR PRODUCING THEM |
| CN100453216C (en) * | 2006-07-11 | 2009-01-21 | 武汉理工大学 | Method for preparing high performance bismuth telluride thermoelectric material |
-
1999
- 1999-03-31 JP JP09442399A patent/JP3478162B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000286471A (en) | 2000-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5108515A (en) | Thermoelectric material and process for production thereof | |
| KR100500493B1 (en) | Silicon based conductive material and process for production thereof | |
| US20060118161A1 (en) | Thermoelectric material having crystal grains well oriented in certain direction and process for producing the same | |
| US5246504A (en) | Thermoelectric material | |
| KR20160125132A (en) | Method for Bi-Te-based thermoelectric materials using Resistance Heat | |
| EP0235702B1 (en) | Thermoelectric material for low temperature use and method of manufacturing the same | |
| JP3478162B2 (en) | Manufacturing method of thermoelectric material | |
| EP0996174B1 (en) | Thermoelectric materials and thermoelectric conversion element | |
| JP3572939B2 (en) | Thermoelectric material and method for manufacturing the same | |
| JP3604308B2 (en) | Raw material alloy for nanocomposite magnet, powder and manufacturing method thereof, and nanocomposite magnet powder and magnet manufacturing method | |
| JPH1051037A (en) | Thermoelectric material and thermoelectric conversion element | |
| JPH0832588B2 (en) | Thermoelectric semiconductor material and manufacturing method thereof | |
| JP2000036627A (en) | Thermoelectric material and thermoelectric transfer element | |
| JP3603698B2 (en) | Thermoelectric material and thermoelectric conversion element | |
| JP4553521B2 (en) | Powder thermoelectric material manufacturing apparatus and powder thermoelectric material manufacturing method using the same | |
| JP4303924B2 (en) | Method for manufacturing thermoelectric semiconductor member | |
| JP2879152B2 (en) | Manufacturing method of thermoelectric material | |
| JP3572877B2 (en) | Method for producing thermoelectric material and thermoelectric conversion element | |
| JP3861804B2 (en) | Thermoelectric material and manufacturing method thereof | |
| JP3575332B2 (en) | Thermoelectric material and method for manufacturing the same | |
| JPH0462981A (en) | Manufacture of amorphous fesi2 thermoelectric conversion semiconductor | |
| JP3572814B2 (en) | Manufacturing method of thermoelectric cooling material | |
| JP2002164584A (en) | Manufacturing method of peltier element material | |
| JP2003037302A (en) | Method for manufacturing thermoelectric material | |
| JP2000277817A (en) | Ingot for thermoelectric module, the thermoelectric module, and manufacture of the module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071003 Year of fee payment: 4 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071003 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081003 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091003 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101003 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101003 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111003 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111003 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121003 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121003 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131003 Year of fee payment: 10 |
|
| EXPY | Cancellation because of completion of term |