405273 A7 _B7 五、發明説明（/ ) —- [發明領域] 本發明關於熱電轉換器元件用之燒結材料的製法，以 此方法製造之熱電轉換器元件用的燒結材料，以=用此燒 結材料製成的熱電轉換器元件。 兀 [先前技藝之描述] 熱電兀件具有將熱能轉換成電能的功能(Seebeck效應) ’以及將電能轉換成熱能(Pertier效應）的功能。因此，希 望應用此種熱電元件於能源轉換科技。特別而言，於利用 penier效應的領域裡’希望將它用做支持光電領域之光電 裝置中的溫度控制器用模組。關於溫度控制器用的模組， 已有人提供一種模組，其中Bi-Te-Sb型熱電轉換器元件( 此後稱爲p型熱電轉換器元件)和Bi-Te-Se型熱電轉換器元 件(此後稱爲η型熱電轉換器元件）彼此連接，並供應它們 DC電壓，如此引發熱產生和熱吸收。 至於上述P型熱電轉換器元件和η型熱電轉換器元件 的製法，已有人提供一種方法，其包含的步驟有：將材料 粉末熔解，並使用單向凝固法使單晶棒長得長些(如掲示於 曰本專利公開案特開平1-2〇2343);另一種方法包含的步驟 有：將材料粉末熔解，將所得之多晶柱塊磨碎，並使用熱 壓法將所得的合金粉末燒結成塊體(如揭示於日本專利公開 案特開平1-106748)。使用上述方法所得之單晶柱或塊狀燒 結材料，再切割形成所要的形狀’以製造熱電轉換器元件 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） „----1¾衣------，訂------^ (請先閲讀背面之注意事項再填寫本頁) . , 蛵濟部智慧財產局員工消費合作社印挺 經濟部智慧財產局S工消費合作社印製 ----405273_1Z_ 五、發明説明（>) 〜 然而’根據日本專利公開案特開平1-2〇2343所述的製 法’的確有可能得到熱電效能相對優良的熱電轉換器元件 ’但是所得元件的機械強度極差，因此容易於成形時受損 ’導致產率很差。此外，很多此種熱電轉換器元件的尺寸 正確度很差。另一方面，根據日本專利公開案特開平b 1〇6748所述的製法’有可能得到機械強度稍大於以前述培 解型方法所製造的熱電轉換器元件，但是由於粉末表面的 氧化或當多晶柱塊粉碎成粉末時的污染，所以很難得到I 有優良性質的熱電轉換器元件。 再者’·已有人提供一種方法，當熱電材料是以硏磨混 合材料粉末、成形、燒結而製備時，於硏磨混合、燒結或 退火的任何過程中採用還原處理(如揭示於日本專利公開案 特開平3-41780)。在此方法中，事實上是於還原氣氛中產 生燒結。因此’的確有可能得到熱電效能優良的熱電轉換 器元件’但是燒結過程需要長時間，導致生產力很差。另 外’由於燒結材料的晶粒長得粗大，所以得到之燒結材料 的機械強度很差，因此很難形成所要的尺寸和形式，導致 成形率很差。 [本發明所要解決的問題] 本發明的目的就是要提供一種熱電轉換器元件用之燒 結材料的製法，其能使燒結材料具有優良的生產力、較大 的機械強度以及優良的熱電效能。此目的也是要提供一種 以此方法製造之熱電轉換器元件用的燒結材料，以及一種 —本紙张尺度適财關家標準（CNS ) A4規格（21GX 2957公釐） ------.----1^------II------.^ C請先閱讀背面之注意事項再i/ir本頁〕 ‘ 經濟部智慧財產局員工消资合作社印製 羞 A7 --405 m __B7 五、發明説明（夕） ' ----- 用此燒結材料製成的熱電轉換器元件。 [解決問題的方式] 根ii本發刚钟5轉_第1帛，係提供—種熱電 讎器元件用之燒結材料的製法，其係要職Bi_Te_Sb型 熱電轉換器元件，此方法包酬步驟有：將至少含有秘 (Βι)的粉末、至少含有蹄(Te)的粉末和至少含有銻讲)的粉 末’放入一防止大氣之密封狀況下的罐中；使用有機溶劑 做爲分散介質，淫磨並混合之；於惰性氣體氣氛中乾燥之 ，接者使用熱壓法，於溫度i〇〇到25〇°c的真空中預熱混 合且硏磨過的粉末；然後於溫度42〇到5〇(rc的惰性氣體 氣氛中燒結之。此方法的特徵在於：至少含有Bi的粉末是 Bi基單元素粉末，至少含有Te的粉末是Te基單元素粉末 ，至少含有Sb的粉末是Sb基單元素粉末。 根據本發明的申請專利範圍第3項，係提供一種熱電 轉換器元件用之燒結材料的製法，其係要用於Bi_Te_Se型 熱電轉換器元件，此方法包括的步驟有：將至少含有鉍 (Bi)的粉末、至少含有碲(Te)的粉末和至少含有硒（se)的粉 末’放入一防止大氣之密封狀況下的罐中；使用有機溶劑 做爲分散介質，溼磨並混合之·，於惰性氣體氣氛中乾燥之 ;接著使用熱壓法，於溫度100到250°C的真空中預熱混 合且硏磨過的粉末；然後於溫度420到52〇°C的惰性氣體 氣氛中燒結之。此方法的特徵在於：至少含有Bi的粉末是 Bi基單元素粉末，至少含有Te的粉末是Te基單元素粉末 本紙張尺度遑用中國國家標隼（CNS ) A4規格（210X297公釐） .. ; I 訂 線 (請先閱讀背面之注意事項再>/寫本頁) - - A7 B7 五 發明説明G ) ’至少含有Se的粉末是Se基單元素粉末。此方法的進— 步特徵在於：Sbl3做爲摻雜物，添加於至少含有Bi的粉末 、至少含有Te的粉末和至少含有Se的粉末。此方法的更 進一步特徵在於：相對於至少含有Bi的粉末、至少含有 Te的粉末和至少含有Se的粉末之總量而言，添加大於〇 重量°/。而至多達0·2重量％的Sbl3。 根據本發明，係提供一種熱電轉換器元件用的燒結材 料’係要用於Bi-Te-Sb型熱電轉換器元件，其由以 (Bi2Te3)x(Sb2Te3)k表示之組成的金屬間化合物所組成，其 中X値的範圍從0·15到〇.25。同時，也提供—種熱電轉換 器元件用的燒結材料，係要用於Bi_Te_Se型熱電轉換器元 件’其由以(BhTeAWBijeA表示之組成的金屬間化合物 所組成’其中X値的範圍從〇到〇1。再者，用於Bi_Te_Sb 型熱電轉換器元件的燒結材料的特徵在於其晶粒大小爲1.0 至15//m，而用於Bi_Te_Se型熱電轉換器元件的燒結材料 的特徵在於其晶粒大小爲01至1〇/zm。此外，用於Bi_405273 A7 _B7 V. Description of the Invention (/) —- [Field of Invention] The present invention relates to a method for manufacturing a sintered material for a thermoelectric converter element, and a sintered material for a thermoelectric converter element manufactured by this method, in order to use the sintered material Made of thermoelectric converter elements. [Description of the prior art] The thermoelectric element has a function of converting thermal energy into electrical energy (Seebeck effect) and a function of converting electrical energy into thermal energy (Pertier effect). Therefore, it is desirable to apply such thermoelectric elements to energy conversion technology. In particular, in the field using the penier effect, it is desired to use it as a module for a temperature controller in a photovoltaic device supporting the photovoltaic field. Regarding the module for the temperature controller, a module has been provided in which a Bi-Te-Sb type thermoelectric converter element (hereinafter referred to as a p-type thermoelectric converter element) and a Bi-Te-Se type thermoelectric converter element (hereinafter (Referred to as n-type thermoelectric converter elements) are connected to each other and supply them with a DC voltage, thus causing heat generation and heat absorption. As for the manufacturing method of the above-mentioned P-type thermoelectric converter element and n-type thermoelectric converter element, a method has been provided, which includes the steps of melting the material powder and using a one-way solidification method to make the single crystal rod grow longer ( As shown in Japanese Patent Application Laid-Open No. Hei1-2102343); another method includes the steps of melting the material powder, grinding the obtained polycrystalline pillar block, and using the hot pressing method to obtain the alloy powder. Sintered into blocks (as disclosed in Japanese Patent Laid-Open No. 1-106748). Use the single crystal column or block sintered material obtained by the above method, and then cut to form the desired shape 'to manufacture the thermoelectric converter element. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) „---- 1¾ clothing ------, order ------ ^ (Please read the notes on the back before filling out this page)., Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the work of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative ---- 405273_1Z_ V. Description of the invention (>) ~ However, it is indeed possible to obtain a thermoelectric converter element with relatively good thermoelectric efficiency according to the "manufacturing method described in Japanese Patent Laid-Open No. Hei1-2102343" 'But the mechanical strength of the obtained element is extremely poor, and therefore it is easy to be damaged during molding.' This results in poor yield. In addition, many of these thermoelectric converter elements have poor dimensional accuracy. On the other hand, according to Japanese Patent Publication, The method described in Kaiping b 106748 has the possibility of obtaining a mechanical strength slightly higher than that of the thermoelectric converter element produced by the aforementioned digestion method, but due to the oxidation of the surface of the powder or when the polycrystalline pillar block is pulverized into powder, Contamination, so it is difficult to obtain thermoelectric converter elements with excellent properties. Furthermore, a method has been provided that when a thermoelectric material is prepared by honing a mixed material powder, forming, and sintering, it is mixed and sintered by honing. Reduction treatment is used in any process of annealing or annealing (as disclosed in Japanese Patent Laid-Open No. Hei 3-41780). In this method, sintering is actually generated in a reducing atmosphere. Therefore, it is indeed possible to obtain thermoelectricity with excellent thermoelectric efficiency. The converter element 'but the sintering process takes a long time, resulting in poor productivity. In addition,' Since the grains of the sintered material grow coarse, the mechanical strength of the sintered material obtained is very poor, so it is difficult to form the desired size and form, resulting in [The problem to be solved by the present invention] The object of the present invention is to provide a method for manufacturing a sintered material for a thermoelectric converter element, which can make the sintered material have excellent productivity, large mechanical strength, and excellent Thermoelectric efficiency. The purpose is also to provide a burner for thermoelectric converter elements manufactured by this method. Materials, and one—this paper standard is suitable for financial affairs (CNS) A4 specification (21GX 2957 mm) ------.---- 1 ^ ------ II ------ . ^ C Please read the notes on the back before i / ir this page] '' Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 --405 m __B7 V. Description of the Invention (Even) '' ----- Use The thermoelectric converter element made of this sintered material. [Method for solving the problem] Root ii 5 minutes of the clock _ 1st, is to provide a method of manufacturing a sintered material for thermoelectric element, which is a key Bi_Te_Sb type The thermoelectric converter element, the method includes the steps of: putting powder containing at least (Bι), powder containing at least hoof (Te) and powder containing at least antimony) into a tank in a sealed condition to prevent the atmosphere Medium; use organic solvent as dispersion medium, grind and mix; dry it in an inert gas atmosphere, then use hot pressing method, preheat mixing and honing in a vacuum at a temperature of 100 to 25 ° c Passed powder; then sintered in an inert gas atmosphere at a temperature of 42 ° C to 50 ° C. This method is characterized in that the powder containing at least Bi is a Bi-based single element powder, the powder containing at least Te is a Te-based single element powder, and the powder containing at least Sb is an Sb-based single element powder. According to item 3 of the scope of patent application of the present invention, a method for manufacturing a sintered material for a thermoelectric converter element is provided, which is to be used for a Bi_Te_Se type thermoelectric converter element. The method includes the steps of: containing at least bismuth (Bi ) Powder, powder containing at least tellurium (Te), and powder containing at least selenium (se) are put into a tank in a sealed state against the atmosphere; using an organic solvent as a dispersion medium, wet milling and mixing, Dry in an inert gas atmosphere; then use hot pressing to pre-heat the mixed and honed powder in a vacuum at a temperature of 100 to 250 ° C; then sinter it in an inert gas atmosphere at a temperature of 420 to 52 ° C . This method is characterized in that the powder containing at least Bi is a Bi-based single element powder, and the powder containing at least Te is a Te-based single element powder. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) .. ; I order (please read the precautions on the back and then write this page)--A7 B7 Five Inventions G) 'The powder containing at least Se is a Se-based single element powder. This method is further characterized in that Sbl3 is added as a dopant to a powder containing at least Bi, a powder containing at least Te, and a powder containing at least Se. This method is further characterized by adding more than 0% by weight relative to the total amount of the powder containing at least Bi, the powder containing at least Te, and the powder containing at least Se. And up to 0.2% by weight of Sbl3. According to the present invention, a sintered material for a thermoelectric converter element is to be used for a Bi-Te-Sb type thermoelectric converter element, which is composed of an intermetallic compound represented by (Bi2Te3) x (Sb2Te3) k Composition where X 値 ranges from 0.15 to 0.25. At the same time, a sintered material for thermoelectric converter elements is also provided, which is to be used for Bi_Te_Se type thermoelectric converter elements. It is composed of an intermetallic compound composed of (BhTeAWBijeA), where X 値 ranges from 0 to 〇 1. Furthermore, the sintered material for Bi_Te_Sb type thermoelectric converter element is characterized by its grain size of 1.0 to 15 // m, and the sintered material for Bi_Te_Se type thermoelectric converter element is characterized by its grain size 01 to 10 / zm. In addition, it is used for Bi_
Te-Sb型熱電轉換器元件的燒結材料的特徵在於含有〇 25 至ι·〇體積％的氧，而用於Bi_Te_Se型熱電轉換器元件的 燒結材料的特徵在於含有〇」至〇·6體積％的氧。另外，上 述的燒結材料的特徵在於其壓縮強度大於或等於 10kgf/mm2。 一本發明進一步的目的在於提供使用前述任何熱電轉換 器元件用之燒結材料所製成的熱電轉換器元件。 I ^ 裝 訂 n 線 (請先閱讀背面之注意事項再V寫本頁} 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 經濟部智慧財產局員工消费合作社印製 405273 " " 五、發明説明（<) [圖式簡述] 圖1爲顯示一冷卻模組和獲得冷卻模組之冷卻效能的 評估方式之示意圖。 圖2爲顯示冷卻模組之冷卻效能的圖形。 [較佳具體實施例的詳細描述] 下式表示一效率指數「z」，其代表熱電材料的效能： z = a1/ p n 其中α是Seebeck係數(當元件兩端之間引起丨它之跑 度差異時所產生的熱電動力），P是比電阻’ /C是導熱率。 從此方程式可明顯得知：爲了改善效率指數「z」，須要土f 加α而減少p和/C。這些α、p和/c大大地受到構成熱電财 料之元素的種類、數量和組成比例的影響，同時也受到g 製法的影響。 於本發明中，已經使用粉末冶金科技製出由細微晶粒 所組成之熱電材料做的燒結材料。已經做了多樣的探討， 來獲得熱電轉換器元件用之燒結材料，其機械強度優良， 切割和成形操作時不會受損與破裂，並且成形率優良。因 此，已經證明：當選擇適合的材料粉末，此材料粉末以能 達到所要熱電效能之合金組成的適當混合比例加以混合， 並於適當的保護氣氛下硏磨並混合此材料粉末達一段適當 的時間，然後於適當的氣氛下燒結經過硏磨混合的材料粉 末達一段適當的時間，則可以獲得由細微晶粒所組成之熱 電轉換器元件用的燒結材料，其已適當地氧化達一定程度 本紙浪尺度通用中國國豕標準（CNS ) A4規格（210x297公廣） 11 I —11-1 辦衣 I I . H.訂 I I — I I i (請先閱讀背面之注意事項再>寫本頁) ' , 經濟部智«-財產局員工消費合作社印製 _ 40_5273_ __ 五'發明説明（t) ’並具有所要的優良機械強度和優良的熱電效能。現在底 下要詳細描述本發明。 首先解釋Bi-Te-Sb型熱電轉換器元件(P型熱電轉換器 兀件）用之燒結材料的製法。關於材料粉末，可使用至少包 含Bi、Te和Sb其中至少一種元素的合金粉末。此種合金 粉末舉例而言可以將Bi、Te和Sb熔成合金錠塊，並把合 金錠塊粉碎成合金粉末而獲得。否則也可以使用Bi基單元 素粉末、Te基單元素粉末和sb基單元素粉末。這些材料 粉末的顆粒大小最好不超過200/zm。這些材料粉末根據化 學配比加以坪重’如此以(BisTesMSbsTeA—x表示之組成的 金屬間化合物中，「X」的値會在〇_15到0.25的範圍內。 於燒結這些材料粉末而獲得組成以表示 的燒結材料中’如果「X」的値低於0.15或高於0.25，則 效率指數「z」變低而不利。「X」的値更好地可以在0.18 到0.22的範圍內。 如此秤重的材料粉末加以硏磨並混合。此時可以採用 乾式硏磨或者淫式硏磨，但是須要硏磨並混合材料粉末達 到保持它們不比所需氧化多太多的程度。在溼式硏磨的情 況中’將材料粉末裝入罐裡之後，罐子進一步塡充以有機 溶劑直到其上緣。此時有機溶劑應該盡可能溫和地倒入罐 子’如此材料粉末才不會與有機溶劑一起浮流上來。裝了 預定量的材料粉末之後，罐子以一蓋子加以關閉，如此包 封住材料粉末和有機溶劑。此時罐子乃小心地關閉，而沒 有空氣保持於罐子上緣部份的周圍。關於有機溶劑，可以 本^尺度適财ϋ®家橾( CNS ) A4規格（21GX29^公釐) ~ -- ------„----1^------、玎------線 (請先閱讀背面之注意事項再填寫本頁〕 - A7 A7 經濟部智慧財產局員工消費合作社印製 __ 405273 五、發明説明（1 ) 使用例如乙醇或丁醇的醇類和其他各種的溶劑。然而，考 慮到操作環境以及丙酮的高蒸發率，最好可以使用丙酮。 如此包封於罐裡的材料粉末和有機溶劑’使用一混合 和硏磨同時的方式加以硏磨並混合，例如球^ °最好可以 使用衛星型球磨。硏磨和混合的時間最好可以是1至12小 時，雖然這要視罐子的旋轉速度而定。如此’材料粉末被 硏磨並混合成平均粒子大小〇.〇5至2·5#ηι的細微粉末， 同時粉末的表面乃適當地氧化到一定程度。在使用Bi基粉 末、Te基粉末和Sb基粉末做爲材料粉末的情況中，上述 的硏磨和皞合促進Bi、Te和Sb做機械式的融合，結果， 透過此種機械式的融合可以獲得超細微的合金’而於稍後 的燒結過程中做固相燒結，如此製造出由細微晶粒所組成 的緊密結構。 如此硏磨、混合並適當氧化的細微混合粉末，於氮氣 流動其中的密閉容器中加熱而乾燥’如此以避免進一步的 氧化。 如此乾燥的細微混合粉末放入指定大小的碳模中，並 使用熱壓法加以燒結。此燒結之進行’係於溫度100到 250。(：的真空中預熱細微的混合粉末’然後於溫度420到 500°C的惰性氣體氣氛中燒結停留15分鐘至2小時。粉末 於真空中預熱有助於移除當粉末放入模中時所吸附的氧氣 。因此，可以製造含有預定量之氧的燒結材料。如果預熱 溫度低於1〇〇。(3，則無法充分地移除吸附的氧，因而無法 獲得具有所要之效率指數「z」的燒結材料。另一方面，如 ___----- 本紙張尺度適用中國國家標準（CNS〉Α4規格（2丨0X297公瘦） -----—裝------訂------線 (請先閱讀背面之注意事項再填寫本頁) - A7 A7 經濟部智慧財產局員工消費合作社印製 40527S_b7__ 五、發明説明（J) 果預熱溫度超過250°C，則在施加壓力之前就過度加速金 屬的擴散，因而使得晶粒長得不利地粗大。預熱時間約5 至60分鐘即可能足夠。預熱之後，氣氛更換爲例如氬氣的 惰性氣體，如此以避免粉末的蒸發和揮發，然後有效加熱 至燒結的均熱溫度。加熱溫度達到燒結的均熱溫度以後， 以lOOkg/cm2至lt/cm2的熱加壓進行壓力的施加。如果壓 力低於100kg/cm2,則所得的燒結材料在其密度方面並未 完全改進，以致無法製出具有足夠機械強度的燒結材料。 另一方面’如果施加的壓力超過lt/cm2，則·燒結材料在其 密度方面尊未再改進，導致經濟上的損失。如果燒結的均 熱溫度低於420 C ’則未充分地促進金屬的擴散，因此需 要較長的燒結時間’不利地導致生產力變差。另一方面， 如果燒結的均熱溫度超過50(TC，則發生液相，並且不利 的是晶粒長得極粗大。燒結的均熱時間約15分鐘至2小時 即可能足夠，而製出具有足夠機械強度的燒結材料。如果 燒結的均熱時間短於b分鐘，則未完全發生金屬的擴散， 因此無法製出具有足夠機械強度的燒結材料。另一方面， 如果燒結的均熱時間超過2小時，則晶粒長得粗大，因 無法製出具有足夠機械強度的燒結材料。 經由上述的步驟’可獲得Bi-Te_Sb型熱電轉換器 (P型熱電轉換器元件）。 一接下來解釋Bi.Te-Se型熱霸換器元件(n型熱電轉換 器兀件)用之燒結材料的製法。關於材料粉末，可使用至小 包含Bi、Te和Se其中至少—種元素的合錄末。此種^ 本紙張尺度適用中國國家蘇（CNS ) A4^Ul()x心公缓} -------- ------.---^丨壯衣------II------線 (請先閱讀背面之注意事項再_寫本頁) - - 405273 五、發明説明（j) 金粉末舉例而言可以將Bi、Te和Se熔成合金錠塊，並把 合金錠塊粉碎成合金粉末而獲得。否則也可以使用Bi基單 元素粉末、Te基單元素粉末和Se基單元素粉末。這些材 料粉末的顆粒大小最好不超過200/zm。這些材料粉末根據 化學配比加以秤重，如此以(BisTesUBizSeA袠示之組成 的金屬間化合物中，「X」的値會在0到0·1的範圍內。於 燒結這些材料粉末而獲得組成以(BhTeOi.JBisSeJx表示的 燒結材料中，如果「X」的値超過0.1，則效率指數「z」變 低而不利。「X」的値更好地可以在0到〇.〇5的範圍內。 η型勢電轉換器元件比p型熱電轉換器元件更容易受 到載子密度的影響。因此，爲了改善效率指數「ζ」，增加 載子密度以減少比電阻ρ係有利的。所以，做爲〜種增加 載子密度的摻雜物，可以於硏磨包含Bi、Te和Se其中至 少一種元素的合金粉末之時加入Sbl3。相對於上述合金粉 末的總量而言，最好可以添加大於0重量％而至多達0.2重 量°/〇的Sbl3。當Sbl3的添加量超過0.2重量％時，雖然比電 阻P減少了、Seebeck係數α也減少了，但是導熱率/c增加 了，因此不利地導致較低的效率指數「ζ」。The sintered material of the Te-Sb type thermoelectric converter element is characterized by containing 0.25 to ι · 0% by volume of oxygen, and the sintered material for the Bi_Te_Se type thermoelectric converter element is characterized by containing 0% to 0.6% by volume Of oxygen. In addition, the sintered material described above is characterized in that its compressive strength is 10 kgf / mm2 or more. A further object of the present invention is to provide a thermoelectric converter element made of a sintered material for any of the foregoing thermoelectric converter elements. I ^ Binding n-line (please read the precautions on the back before writing this page) Printed by the Consumer Cooperative of the Ministry of Economic Affairs and the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by 405273 ) [Brief Description of the Drawings] Figure 1 is a schematic diagram showing a cooling module and an evaluation method for obtaining the cooling performance of the cooling module. Figure 2 is a graph showing the cooling performance of the cooling module. [Details of the preferred embodiment Description] The following formula represents an efficiency index "z", which represents the effectiveness of thermoelectric materials: z = a1 / pn where α is the Seebeck coefficient (thermoelectric force generated when the two ends of a component cause a difference in its running speed) , P is the specific resistance '/ C is the thermal conductivity. From this equation, it is obvious that in order to improve the efficiency index "z", it is necessary to add f to α to reduce p and / C. These α, p, and / c are greatly affected by the composition The influence of the type, quantity and composition ratio of the elements of thermoelectric materials is also affected by the g method. In the present invention, powder metallurgy technology has been used to produce sintered thermoelectric materials composed of fine grains. Various discussions have been made to obtain sintered materials for thermoelectric converter components, which have excellent mechanical strength, are not damaged and broken during cutting and forming operations, and have excellent forming rates. Therefore, it has been proven that: Material powder, the material powder is mixed at an appropriate mixing ratio of the alloy composition capable of achieving the desired thermoelectric efficiency, and the material powder is honed and mixed under an appropriate protective atmosphere for an appropriate time, and then sintered in an appropriate atmosphere After honing the mixed material powder for an appropriate period of time, a sintered material for thermoelectric converter elements composed of fine grains can be obtained, which has been properly oxidized to a certain degree. ) A4 size (210x297 public broadcasting) 11 I —11-1 Clothes II. H. Order II — II i (Please read the notes on the back before writing this page) ', Ministry of Economic Affairs «-Property Bureau staff Printed by Consumer Cooperatives _ 40_5273_ __ Five 'Invention (t)' and have the required excellent mechanical strength and excellent thermoelectric efficiency. Now detailed below The invention will be described. First, a method for manufacturing a sintered material for a Bi-Te-Sb type thermoelectric converter element (P-type thermoelectric converter element) will be explained. As a material powder, a material containing at least one of Bi, Te, and Sb can be used. Alloy powder. For example, this alloy powder can be obtained by melting Bi, Te, and Sb into alloy ingots, and pulverizing the alloy ingots into alloy powders. Otherwise, Bi-based single-element powders and Te-based single-element powders can also be used. And sb-based single element powders. The particle size of these material powders is preferably not more than 200 / zm. These material powders are weighted according to the chemical ratio so that in the intermetallic compound composed of (BisTesMSbsTeA-x, "X"値 will be in the range of 0-15 to 0.25. In the sintered material obtained by sintering these material powders to obtain a composition represented by "," if the 値 of "X" is lower than 0.15 or higher than 0.25, the efficiency index "z" becomes low and disadvantageous. The 値 of "X" can better be in the range of 0.18 to 0.22. The material powder thus weighed is honed and mixed. Dry or honing can be used at this time, but the material powders need to be honed and mixed to keep them not much more than the required oxidation. In the case of wet honing, after the material powder is filled into the jar, the jar is further filled with an organic solvent up to its upper edge. At this time, the organic solvent should be poured into the jar as gently as possible so that the material powder does not float up with the organic solvent. After the predetermined amount of the material powder is filled, the jar is closed with a lid, so that the material powder and the organic solvent are enclosed. The jar was carefully closed at this time, and no air remained around the upper edge of the jar. Regarding organic solvents, you can use this standard ϋϋ 家 ϋ (CNS) A4 specification (21GX29 ^ mm) ~------- „---- 1 ^ ------, 玎- ----- line (please read the notes on the back before filling this page)-A7 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs __ 405273 V. Description of the invention (1) Use alcohol such as ethanol or butanol And other various solvents. However, considering the operating environment and the high evaporation rate of acetone, it is best to use acetone. The material powder and organic solvent so encapsulated in the tank are mixed using a mixing and honing method Grind and mix, such as ball ^ ° It is best to use a satellite ball mill. The honing and mixing time is preferably 1 to 12 hours, although this depends on the rotation speed of the jar. So 'the material powder is honed and Mix into a fine powder with an average particle size of 0.05 to 2.5 # n, and the surface of the powder is properly oxidized to a certain degree. In the case of using Bi-based powder, Te-based powder, and Sb-based powder as the material powder In the above, the above honing and blending promote the mechanical fusion of Bi, Te and Sb. As a result, ultra-fine alloys can be obtained through this mechanical fusion, and solid phase sintering is performed in the later sintering process, so that a compact structure composed of fine grains is produced. Such honing, mixing and appropriate The oxidized finely mixed powder is heated and dried in a closed container in which nitrogen flows, so as to avoid further oxidation. The dryly mixed finely powder is placed in a carbon mold of a specified size, and sintered by hot pressing. This sintering It is carried out 'at a temperature of 100 to 250. (: Preheating the finely mixed powder in a vacuum') and then sintering in an inert gas atmosphere at a temperature of 420 to 500 ° C for 15 minutes to 2 hours. The powder is preheated in a vacuum. Helps remove the oxygen absorbed when the powder is placed in the mold. Therefore, a sintered material containing a predetermined amount of oxygen can be manufactured. If the preheating temperature is lower than 100. (3, the adsorbed cannot be removed sufficiently Oxygen, so it is impossible to obtain a sintered material with the desired efficiency index "z". On the other hand, such as ___----- This paper size applies the Chinese national standard (CNS> Α4 specifications) 2 丨 0X297 male thin) --------- install ------ order ------ line (please read the precautions on the back before filling in this page)-A7 A7 Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 40527S_b7__ 5. Description of the invention (J) If the preheating temperature exceeds 250 ° C, the diffusion of the metal is excessively accelerated before the pressure is applied, thus causing the grains to grow unfavorably coarse. The preheating time is about 5 to 60 minutes That may be enough. After preheating, the atmosphere is changed to an inert gas such as argon, so as to avoid evaporation and volatilization of the powder, and then effectively heat to the soaking temperature of the sintering. After the heating temperature reaches the soaking temperature of the sintering, 100kg / The application of pressure is performed by hot pressing from cm2 to lt / cm2. If the pressure is lower than 100 kg / cm2, the obtained sintered material is not completely improved in its density, so that a sintered material having sufficient mechanical strength cannot be produced. On the other hand, if the applied pressure exceeds lt / cm2, the density of the sintered material is not improved any more, resulting in economic loss. If the soaking temperature of the sintering is lower than 420 C ', the diffusion of the metal is not sufficiently promoted, so that a longer sintering time is required' disadvantageously leading to poor productivity. On the other hand, if the soaking temperature of the sintering exceeds 50 ° C., a liquid phase occurs, and disadvantageously, the crystal grains grow extremely coarse. The soaking time of sintering, which is about 15 minutes to 2 hours, may be sufficient, and the production has Sintered material with sufficient mechanical strength. If the soaking time for sintering is shorter than b minutes, metal diffusion does not completely occur, so a sintered material with sufficient mechanical strength cannot be produced. On the other hand, if the soaking time for sintering exceeds 2 When it is small, the crystal grains grow coarse, because a sintered material with sufficient mechanical strength cannot be produced. Through the above steps, a Bi-Te_Sb type thermoelectric converter (P type thermoelectric converter element) can be obtained. Next, explain Bi. Production method of sintered material for Te-Se type heat exchanger element (n-type thermoelectric converter element). Regarding the material powder, it can be used at the end of the list containing at least one of Bi, Te and Se. This Species ^ This paper size is applicable to the Chinese National Soviet (CNS) A4 ^ Ul () x heart bradycardia} -------- ------.--- ^ 丨 Zhuang Yi ------ II ------ Line (Please read the precautions on the back before writing this page)--405273 V. Invention (J) For example, gold powder can be obtained by melting Bi, Te, and Se into alloy ingots, and pulverizing the alloy ingots into alloy powders. Otherwise, Bi-based single-element powder, Te-based single-element powder, and Se can also be used. Single element powder. The particle size of these material powders is preferably not more than 200 / zm. These material powders are weighed according to the chemical ratio. Thus, among the intermetallic compounds composed of (BisTesUBizSeA), the "X" In the range of 0 to 0.1. In a sintered material obtained by sintering these material powders to obtain a composition represented by (BhTeOi. JBisSeJx), if the 値 of "X" exceeds 0.1, the efficiency index "z" becomes unfavorable. " X "can be better in the range of 0 to 0.05. Η-type potential converter elements are more susceptible to carrier density than p-type thermoelectric converter elements. Therefore, in order to improve the efficiency index" ζ It is advantageous to increase the carrier density to reduce the specific resistance ρ. Therefore, as a kind of dopant that increases the carrier density, it can be added when honing alloy powder containing at least one element of Bi, Te and Se Sbl3. Relative For the total amount of the above alloy powder, it is preferable to add Sbl3 in an amount of more than 0% by weight up to 0.2% by weight. When Sbl3 is added in an amount exceeding 0.2% by weight, although the specific resistance P is reduced, the Seebeck coefficient α is also reduced. It decreases, but the thermal conductivity / c increases, thus disadvantageously leading to a lower efficiency index "ζ".
要做成η型熱電轉換器元件用的燒結材料之如此秤重 的材料粉末，乃以相同於ρ型材料的方式，加以硏磨並混 合成細微的粉末，並適當地氧化到一定程度。然後以相同 於ρ型材料的方式，將細微的粉末於氮氣流動其中的密閉 容器中加熱而乾燥。接著，如此硏磨混合且乾燥的細微粉 末’除了加熱溫度(燒結的均熱溫度)的範圍從420到520°C 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公董） (請先閱讀背面之注意事項再"寫本頁) ί 經濟部智慧財產局員工涓费合作社印製 A7 B7The material powder so weighed to make the sintered material for the η-type thermoelectric converter element is honed and mixed into a fine powder in the same manner as the ρ-type material, and is appropriately oxidized to a certain degree. Then, in the same manner as the p-type material, the fine powder is heated and dried in a closed container in which nitrogen flows. Then, the fine powder mixed and dried in this way is' except for the heating temperature (soaking temperature for sintering) ranging from 420 to 520 ° C. This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 public directors) (Please (Please read the notes on the back before writing this page) ί Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Employees' Cooperative, printed A7 B7
AQ32Z 五、發明説明 以外’其献蝴於P簡购條件下加以燒結，如此製 出Ϊ1型熱電轉換器元件用的燒結材料。燒結之均熱溫度的 上下限係以相同於P型材料的原因而界定的。 如此製造之P型熱電轉換器元件用的燒結材料，係由 以(Bi2Te3)x(Sb2Te3)“x表示之組成的金屬間化合物所組成， 其中X値的範圍最好從0」5到〇.Μ，5里由如前所述。同時 ，如此製造之η型熱電轉換器元件用的燒結材料，係由以 (Bi2Te3)Nx(Bi2Se3)x表示之組成的金屬間化合物所組成，其 中X値的範圍最好從〇到（U，理由也如前所述。 〆、 再者，.如此製造之用於p型熱電轉換器元件的燒結材 料’其日日粒大小最好爲1.0至丨5_，而用於η型熱電轉 換器元件的燒結材料，其晶粒大小最好爲〇1至 此外，用於P型元件的燒結材料最好含有Ο·。至ι 〇體積 %的氧，而用於η型元件的燒結材料最好含有〇1至〇 f體 積％的氧。另外，這些燒結材料的壓縮強度最好各^ iOkgf/mm2。在本文中，要獲得晶粒大小小於〇 iym的燒 結材料係極困難的。類晶粒大小大於15鋒的燒結材料 則太脆，也就是說機械強度很差，以致容易於成形時受填 ’導致產率很差。在臓p麵件之燒結材料的情況中， 晶粒大小爲0.1 或更大的燒結材料可達到不錯的效率指 數「=。另—方面，在用於11型元件之燒結材料的情況中 ，晶粒大小爲10//m或更小的燒結材料可達到不錯的效率 指數「z」。再者，在用於p型元件之燒結材料的情況中 當燒結材料含有低於0.25體積％的氧時，以及當它含有） ----------^------.η------線 f請先閱讀背面之注意事項再取一^本頁} * . 經濟部智慧財產局員工消費合作社印製 ΜΛ張尺度適财國國家榇準（CNS )八4規格（21()>< 297公瘦） 經濟部智慧財產局員工消費合作社印製 五、發明説明（“ ) ''—~ --- 過1.0體積％的氧時，它達不到良好的效率指數「Z」。在 用於η型兀件之燒結材料的情況中，當燒結材料含有低於 ^體積％的氧時’以及當它含有超過〇,6體積％的氧時， 匕達不到良好的效率指數「ζ」。這些情況均非有利的。此 t，當燒結材料的壓縮強度低於1〇kgf/mm2時，此種燒結 材料在成形時的機械強度很差，因此容易於成形時受損， 此亦不利的。雖然其壓縮強度的上限並未特別加以界定， 但是要製造壓縮強度超過3〇kgf/mm2的燒結材料係極困難 的。 一 本發哥底下參照範例做更詳細的說明。 [範例1 :用於p型熱電轉換器元件之燒結材料的製造] 關於材料粉末，純度五個9的Bi粉末、純度五個9的 Sb粉末和純度四個9的Te粉末乃加以抨重，如此以具有 以(BizTeJJSl^TeA-x表示之組成的金屬間化合物中之化學 配比的「X」値，如表1所示。這些材料粉末放入氧化鋁做 的罐子，然後罐子以丙酮塡滿直到其上緣。此時有機溶劑 乃盡可能溫和地倒入罐子，如此材料粉末才不會與有機溶 劑一起浮流上來。然後罐子以完全沒有空氣留在罐子上緣 部份周圍的方式，以一蓋子加以關閉，如此材料粉末和有 機溶劑乃成爲防止大氣之狀況下密封。如此裝有材料粉末 和有機溶劑並關閉的罐子，則放在衛星型球磨機上，其以 250r.p.ni·的速度旋轉，時間則如表1所示，如此以混合並 硏磨材料粉末。完成混合硏磨的粉末漿體則從罐子取出， -__ _______14_________ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨〇乂297公釐） -I I I I I 壯衣— n II — -βτI I I —I n (請先閱讀背面之注意事項再填>?本頁) _ 經濟部智慧財產局員工消費合作社印製 __405273__β77 五、發明説明（\/) 然後於氮氣流動其中的密閉容器中，以6〇到9(rc的溫度 加熱而乾。接下來，乾燥的細微混合粉末裝入碳模中， 並使用熱壓法加以燒結。此燒結之進行，係於表i所示條 =下的真②中軸粉末，然後於表丨所示條件下的氬氣氣 氛中均熱燒結之。達到預熱溫度和達到燒結之均熱溫度的 溫度上升速率各爲10t:/min。加熱溫度上升到燒結的均熱 溫度^後，於表丨所示的條件下進行熱壓的壓力施加。表 1所示的燒結時間過了以後，則讓燒結的粉末逐漸冷卻。 如此獲得用於P型熱電轉換器元件的燒結材料。 [範例2 :用於η型熱電轉換器元件之燒結材料的製造] 關於材料粉末，純度五個9的Bi粉末、純度四個9的 Te粉末和純度兩個9的Se粉末乃加以秤重，如此以具有 以(BhTesVJB^Se3)、表不之組成的金屬間化合物中之化學 配比的「X」値，如表2所示。再者，某些樣品中加有sbl3 ，其量如表2所示。這些材料粉末於如表2所示的條件下 ，以相同於範例1的方式加以硏磨混合及乾燥。接下來， 乾燥的細微混合粉末於如表2所示的條件下，以相同於範 例1的方式加以燒結，如此製出用於η型熱電轉換器元件 的燒結材料。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ^ 1 訂 線 (请先閱讀背面之注意事項再續Α本頁) 4051,73 at B7 五、發明説明（\>/) 表1 用於P型熱電轉換器元件之燒結材料的製造條件 樣 品 No. 組 成 ⑷ 硏磨/ 混合（ 小時） 預熱 燒結的均熱 壓力 (kgf/mm2) 分組 溫度 (°C) 時間（ 分鐘） 溫度 (°〇 時間（ 小時） 1 0.1 2 200 15 450 1 300 比較性範例 2 0.15 2 200 15 450 1 300 範例 3 0.2 2 200 15 450 1 300 範例 4 0.25 2 200 15 450 1 300 範例 5 0.3 2 200 15 450 1 300 比較性範例 6 0.2 0.5 200 15 450 1 300 比較性範例 7 0.2 1 200 15 450 1 300 範例 8 0.2 10 200 15 450 1 300 範例 9 0.2 12 200 15 450 1 300 範例 10 0.2 14 200 15 450 1 300 比較性範例 11 0.2 2 90 15 450 1 300 比較性範例 12 0.2 2 100 15 450 1 300 範例 13 0.2 2 250 15 450 1 300 範例 14 0.2 2 270 15 450 1 300 比較性範例 15 0.2 2 200 5 450 1 300 範例 16 0.2 2 200 60 450 1 300 範例 17 0.2 2 200 15 400 1 300 比較性範例 18 0.2 2 200 15 420 1 300 範例 19 0.2 2 200 15 500 1 300 範例 20 0.2 2 200 15 520 1 300 比較性範例 21 0.2 2 200 15 450 0.2 300 比較性範例 22 0.2 2 200 15 450 0.25 300 範例 23 0.2 2 200 15 450 3 300 比較性範例 24 0.2 2 200 15 450 1 70 比較性範例 25 0.2 2 200 15 450 1 100 範例 26 0.2 2 200 15 450 1 1000 範例 ---------1批衣------1T------^ (請先閱讀背面之注意事項再填寫本頁) ‘ ’ 經濟部智慧財產局員工消費合作社印製 _Ιή 本紙張尺度適用中國國家標準（CNS ) Α4規格（2ΙΟΧ 297公釐） 經濟部智慧財產局員工消費合作社印製 A7 405273_b7 五、發明説明（\A) 表2 用於η型熱電轉換器元件之燒結材料的製造條件 樣 組 添加 Sbl3 硏磨/ 混合（ 預熱 燒結的均熱 壓力 (kgf/m m2) 品 成 溫度 時間（ 溫度 時間（ 分組 No. (X) (皇量％) 小時） (t) 分鐘） (°C) 小時） 27 0 0.05 8 200 15 480 1 300 範例 28 0.03 0.05 8 200 15 480 1 300 範例 29 0.05 0.05 8 200 15 480 1 300 範例 30 0.1 0.05 8 200 15 480 1 300 範例 31 0.12 0.05 8 200 15 480 1 300 比較性範例 32 0.05 0 8 200 15 480 1 300 比較性範例 33 0.05 0.1 8 200 15 480 1 300 範例 34 0.05 0.2 8 200 15 480 1 300 範例 35 0.05 0.23 8 200 15 480 1 300 比較性範例 36 0.05 0.05 0.5 200 15 480 1 300 比較性範例 37 0.05 0.05 1 200 15 480 1 300 範例 38 0.05 0.05 10 200 15 480 1 300 範例 39 0.05 0.05 12 200 15 480 1 300 比較性範例 40 0.05 0-.05 8 90 15 480 1 300 比較性範例 41 0.05 0.05 8 100 15 480 1 300 範例 42 0.05 0.05 8 250 15 480 1 300 範例 43 0.05 0.05 8 270 15 480 1 300 比較性範例 44 0.05 0.05 8 200 5 480 1 300 範例 45 0.05 0.05 8 200 60 480 1 300 範例 46 0.05 0.05 8 200 15 400 1 300 比較性範例 47 0.05 0.05 8 200 15 420 1 300 範例 48 0.05 0.05 8 200 15 520 1 300 範例 49 0.05 0.05 8 200 15 540 1 300 比較性範例 50 0.05 0.05 8 200 15 480 0.2 300 比較性範例 51 0.05 0.05 8 200 15 480 0.25 300 範例 52 0.05 0.05 8 200 15 480 2 300 比較性範例 53 0.05 0.05 8 200 15 480 1 70 比較性範例 54 0.05 0.05 8 200 15 480 1 100 範例 55 0.05 0.05 8 200 15 480 1 1000 範例 (請先閱讀背面之注意事項再本頁) .裝. 訂 線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 405〜 A7 _____B7 五、發明説明（ί ί) 從如此獲得及形成的燒結材料切下 2.5mmx2.5mmx20mm的試片，_式其各種性質。便用dc 四端點法測定比電阻P。由當試片兩端之間引起1〇t之溫 度差異時所產生的熱電動力計算得出Seebeck係數α。2 用雷射閃光法測定導熱率/ί。這些測定的數値分別代入下 式：z = a2/p /c ’藉此獲得效率指數「2；」。再者，使用 掃描式電子顯微鏡拍攝燒結材料的斷裂表面，以從五個角 度拍照’如此獲得平均的晶粒大小。此外，使用紅外線吸 收法測定每個試片的氧含量。另外測定每個試片的壓縮強 度。這些悻質的測定結果顯示於表3和4。同時，藉由比 較性範例’以熔解法製備之市售可得材料所做的p型熱電 轉換器兀件和η型熱電轉換器元件’其性質的測定結果也 顯示於表3和4。 ------.--1裝------訂------線 (請先閱讀背面之注意事項再壤"'本頁) 一 · 經濟部智慧財產局員工消资合作社印製 本紙張尺度適用中國國家榡準（CNS ) Λ4規格（2丨0Χ 297公釐） 405273 五、發明説明（\ b ) A7 B7AQ32Z V. Description of the invention Other than that, it was sintered under the condition of simple purchase, and thus a sintered material for a type 1 thermoelectric converter element was produced. The upper and lower limits of the sintering soaking temperature are defined for the same reasons as for P-type materials. The sintered material for the P-type thermoelectric converter element manufactured in this manner is composed of an intermetallic compound represented by (Bi2Te3) x (Sb2Te3) "x, where X 値 preferably ranges from 0" 5 to 0. M, 5 li as described above. At the same time, the sintered material for the η-type thermoelectric converter element manufactured in this way is composed of an intermetallic compound represented by (Bi2Te3) Nx (Bi2Se3) x, and the range of X 値 is preferably from 0 to (U, The reason is also as described above. 〆, Furthermore, the sintered material used for the p-type thermoelectric converter element thus manufactured has a daily grain size of preferably 1.0 to 5_, and is used for the η-type thermoelectric converter element. The sintered material preferably has a grain size of 0 to 1. In addition, the sintered material used for the P-type element preferably contains 0. to ι vol% oxygen, and the sintered material used for the η-type element preferably contains 〇1 to 0f% by volume of oxygen. In addition, the compressive strength of these sintered materials is preferably ^ 10kgf / mm2. In this article, it is extremely difficult to obtain sintered materials with a grain size of less than 0. Sintered materials larger than 15 fronts are too brittle, that is to say, the mechanical strength is so poor that it is easy to be filled during forming, resulting in poor yield. In the case of sintered materials of 臓 p surface parts, the grain size is 0.1 or Larger sintered materials can achieve good efficiency index "= On the other hand, in the case of a sintered material for an 11-type component, a sintered material with a grain size of 10 // m or less can achieve a good efficiency index "z". Furthermore, it is used in a p-type component. In the case of sintered materials of components, when the sintered material contains less than 0.25% by volume of oxygen, and when it contains) ---------- ^ ------. Η ------ Please read the precautions on the back of the line f and take another one ^ this page} *. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives, printed on the MΛ Zhang scale, suitable for the country of wealth (CNS), 8 specifications (21 () > < 297 thin) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (“”) — ~ --- When it exceeds 1.0% by volume of oxygen, it does not reach a good efficiency index “Z”. In the case of a sintered material for an n-type element, when the sintered material contains less than ^ vol% of oxygen 'and when it contains more than 0.6% by volume of oxygen, a good efficiency index cannot be achieved " ζ ". None of these situations are favorable. At this point, when the compressive strength of the sintered material is less than 10 kgf / mm2, the mechanical strength of the sintered material during molding is poor, so it is easily damaged during molding, which is also disadvantageous. Although the upper limit of its compressive strength is not specifically defined, it is extremely difficult to produce a sintered material having a compressive strength exceeding 30 kgf / mm2. A detailed explanation will be made with reference to the example below. [Example 1: Production of sintered materials for p-type thermoelectric converter elements] Regarding material powders, Bi powders with a purity of five 9, Sb powders with a purity of 5 9 and Te powders with a purity of 9 are criticized. In this way, "X" 値 having a chemical ratio in an intermetallic compound having a composition represented by (BizTeJJSl ^ TeA-x) is shown in Table 1. These material powders were put into a jar made of alumina, and then the jar was acetone 塡Fill it up to its upper edge. At this time, the organic solvent is poured into the jar as gently as possible so that the powder of the material will not float up with the organic solvent. Then the jar is left without air around the upper edge of the jar. A lid is closed so that the material powder and the organic solvent are sealed from the atmosphere. The closed jar containing the material powder and the organic solvent is placed on a satellite-type ball mill, which is 250r.p.ni · The speed is rotated, and the time is shown in Table 1. In this way, the material powder is mixed and honed. The powder slurry that has completed the mixing and honing is taken out of the jar. -__ _______14_________ This paper size is applicable to China Home Standard (CNS) A4 Specification (2 丨 〇 公 297mm) -IIIII Zhuang Yi — n II — -βτI II —I n (Please read the precautions on the back before filling >? This page) _ Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau __405273__β77 5. Description of the invention (\ /) Then in a closed container with nitrogen flowing therein, heat and dry at a temperature of 60 to 9 (rc.) Next, the dry finely mixed powder is charged into The carbon mold was sintered using the hot pressing method. The sintering was performed on the true ② bottom axis powder under the bar = shown in Table i, and then it was thermally sintered in an argon atmosphere under the conditions shown in Table 丨. The temperature increase rates of reaching the preheating temperature and the soaking temperature for sintering are each 10 t: / min. After the heating temperature rises to the soaking temperature for sintering ^, the pressure application of hot pressing is performed under the conditions shown in Table 丨. Table After the sintering time shown in 1, the sintered powder is gradually cooled. In this way, a sintered material for a P-type thermoelectric converter element is obtained. [Example 2: Manufacturing of a sintered material for an η-type thermoelectric converter element] About material powder, purity five 9 The Bi powder, the Te powder with a purity of 9 and the Se powder with a purity of 9 are weighed. In this way, the "X" with a chemical ratio of (BhTesVJB ^ Se3) and an intermetallic compound having a composition shown in the table is used.値, as shown in Table 2. Furthermore, some samples were added with sbl3, the amount of which is shown in Table 2. These material powders were honed in the same manner as in Example 1 under the conditions shown in Table 2. Mixing and drying. Next, the dried finely mixed powder was sintered in the same manner as in Example 1 under the conditions shown in Table 2. Thus, a sintered material for an n-type thermoelectric converter element was prepared. This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) ^ 1 Thread (please read the precautions on the back before continuing on this page) 4051,73 at B7 V. Description of the invention (\ > /) Table 1 Manufacturing conditions of sintered materials for P-type thermoelectric converter components Sample No. Composition ⑷ Honing / mixing (hours) Soaking pressure for preheating sintering (kgf / mm2) Grouping temperature (° C) Time (minutes) Temperature (° 〇 Time (hours) 1 0.1 2 200 15 450 1 300 Comparative Example 2 0.15 2 200 15 450 1 300 Example 3 0.2 2 200 15 450 1 300 Example 4 0.25 2 200 15 450 1 300 Example 5 0.3 2 200 15 450 1 300 Comparative Example 6 0.2 0.5 200 15 450 1 300 Comparative Example 7 0.2 1 200 15 450 1 300 Example 8 0.2 10 200 15 450 1 300 Example 9 0.2 12 200 15 450 1 300 Example 10 0.2 14 200 15 450 1 300 Comparative Example 11 0.2 2 90 15 450 1 300 Comparative Example 12 0.2 2 100 15 450 1 300 Example 13 0.2 2 250 15 450 1 300 Example 14 0.2 2 270 15 450 1 300 Comparative Example 15 0.2 2 200 5 450 1 300 Example 16 0.2 2 200 60 450 1 300 Example 17 0.2 2 200 15 400 1 300 Comparative Example 18 0.2 2 200 15 420 1 300 Example 19 0.2 2 200 15 500 1 300 Example 20 0.2 2 200 15 520 1 300 Comparative Example 21 0.2 2 200 15 450 0.2 300 Comparative example 22 0.2 2 200 15 450 0.25 300 Example 23 0.2 2 200 15 450 3 300 Comparative example 24 0.2 2 200 15 450 1 70 Comparative example 25 0.2 2 200 15 450 1 100 Example 26 0.2 2 200 15 450 1 1000 Example --------- 1 batch of clothes ------ 1T ------ ^ (Please read the precautions on the back before filling this page) '' '' Consumption by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative _Ιή This paper size applies the Chinese National Standard (CNS) A4 specification (2ΙΟχ 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 405273_b7 V. Description of the invention (\ A) Manufacturing condition of converter element sintered material Add Sbl3 honing / mixing (preheating sintering soaking pressure (kgf / m m2)) Product temperature time (Temperature time (Group No. (X) (Amount%)) Hours) (t) minutes) (° C) hours) 27 0 0.05 8 200 15 480 1 300 Example 28 0.03 0.05 8 200 15 480 1 300 Example 29 0.05 0.05 8 200 15 480 1 300 Example 30 0.1 0.05 8 200 15 480 1 300 Example 31 0.12 0.05 8 200 15 480 1 300 Comparative Example 32 0.05 0 8 200 15 480 1 300 Comparative example 33 0.05 0.1 8 200 15 480 1 300 Example 34 0.05 0.2 8 200 15 480 1 300 Example 35 0.05 0.23 8 200 15 480 1 300 Comparative example 36 0.05 0.05 0.5 200 15 480 1 300 Comparative example 37 0.05 0.05 1 200 15 480 1 300 Example 38 0.05 0.05 10 200 15 480 1 300 Example 39 0.05 0.05 12 200 15 480 1 300 Comparative example 40 0.05 0-.05 8 90 15 480 1 300 Comparative example 41 0.05 0.05 8 100 15 480 1 300 Example 42 0.05 0.05 8 250 15 480 1 300 Example 43 0.05 0.05 8 270 15 480 1 300 Comparative Example 44 0.05 0.05 8 200 5 480 1 300 Example 45 0.05 0.05 8 200 60 480 1 300 Example 46 0.05 0.05 8 200 15 400 1 300 Comparative Example 47 0.05 0.05 8 200 15 420 1 300 Example 48 0.05 0.05 8 200 15 520 1 300 Example 49 0.05 0.05 8 200 15 540 1 300 Comparative Example 50 0.05 0.05 8 200 15 480 0.2 300 Comparative example 51 0.05 0.05 8 200 15 480 0.25 300 Example 52 0.05 0.05 8 200 15 480 2 300 Comparative example 53 0.05 0.05 8 200 15 480 1 70 Comparative example 54 0.05 0.05 8 200 15 480 1 100 Example 55 0.05 0.05 8 200 15 480 1 1000 Example (please read the precautions on the back first and then this page). Binding. Thread size This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) 405 ~ A7 _____B7 5 2. Description of the invention (ί ί) From the sintered material thus obtained and formed, a test piece of 2.5mmx2.5mmx20mm is cut out, and its various properties are expressed. Then use the dc four-terminal method to measure the specific resistance P. The Seebeck coefficient α was calculated from the thermoelectric force generated when a temperature difference of 10 t was caused between the two ends of the test piece. 2 Determine the thermal conductivity / ί by laser flash method. These measured values are substituted into the following formulas: z = a2 / p / c 'to obtain the efficiency index "2;". Furthermore, the fracture surface of the sintered material was photographed using a scanning electron microscope to take pictures from five angles' so as to obtain an average grain size. Further, the oxygen content of each test piece was measured using an infrared absorption method. In addition, the compression strength of each test piece was measured. The measurement results of these substances are shown in Tables 3 and 4. At the same time, the results of measuring the properties of p-type thermoelectric converter elements and n-type thermoelectric converter elements using comparative examples' commercially available materials prepared by melting method are shown in Tables 3 and 4. ------.-- 1 Packing ------ Order ------ Line (Please read the precautions on the back first and then "quoting this page" I. Consumers of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the cooperative is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0 × 297 mm) 405273 V. Description of the invention (\ b) A7 B7
表3 經濟部智慧財產局員工消費合作社印製 値I晶粒大 ΙΟ'3 1/Κ)Table 3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (large grain size ΙΟ'3 1 / Κ)
範例 範例 範例 比較性範例 比較性範例 m¥\~~ 範例 範例 比較性範例 比較性範例 範例 範例 比較性範例 範例 範例 比較性範例 範例 範例 比較性範例 比較性範例 C 1 2.3 31 1 附註c :以熔解法製造之市售可得的材料· 比較性範例 比較性範例 範例 比較性範例 上匕較性範例 範例 範例 ,, ^ —裝 II 訂 I 線 (請先閱讀背面之注意事項再填為本頁) - · 19 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠） 經濟部智慧財產局員工消費合作社印製 405273 at B7 -- ----' —^ 五、發明説明（叫） 表4用於η型熱電轉換器兀件之燒結材料的性質評估結果 樣品 No. 有利z的數値 卜 10·3 1/K) 晶粒大 小（Aim) 氧含量(％) 壓縮強度 (kgf/mm2) 分組 27 3.0 0.7 0.35 21 範例 28 3.3 0.5 0.32 20 範例 29 3.1 0.4 0.29 23 範例 30 2.9 0.4 0.28 22 範例 31 2.8 0.6 0.30 21 比較性範例 32 2.8 0.3 0.37 25 比較性範例 33 3.0 1 0.35 21 範例 34 2.9 2 0.35 19 範例 35 2.7 3 0.37 20 比較性範例 36 2.6 21 0.10 7 比較性範例 37 3.1 9 0.10 11 範例 38 3.0 0.1 0.60 30 範例 39 2.8 0.1 0.80 31 比較性範例 40 2.7 0.3 0.70 21 比較性範例 41 2.9 0.4 0.50 19 範例 42 2.9 5 0.30 16 範例 43 2.8 10 0.30 9 比較性範例 44 2.9 0.5 0.30 19 範例 45 3.0 3 0.10 23 範例 46 2.5 0.4 0.40 19 比較性範例 47 2.9 0.5 0.40 21 範例 48 3.3 1 0.26 18 範例 49 3.0 3 0.10 15 比較性範例 50 2.8 0.3 0.40 21 比較性範例 51 2.9 0.5 0.40 18 範例 52 2.7 3 0.20 10 比較性範例 53 2.8 5 0.20 8 比較性範例 54 2.9 3 0.20 12 範例 55 3.1 0.3 0.30 30 範例 C 2.4 33 0.50 8 比較性範例 — II .. I n I 線 (請先閱讀背面之注意事項再填寫本頁) _ . ——______ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） A7 B7 --40^g73 五、發明説明（) 如表3和4所示，根據本發明的p型燒結材料和n型 燒結材料，與市售可得的熔解型材料相比，不僅在機械性 質方面比較優秀，而且效率指數「ζ」也比較優秀。 其次，從表3中樣品Νο·3的ρ型燒結材料切出形成截 面2mmx2mm、高2.5mm的樣品元件，以及從表4中樣品 Νο·28的η型燒結材料切出形成相同大小的另一個樣品元 件。然後如圖1所示，ρ型元件和η型元件的一端經由一 共同的銅板彼此連接，而其另一端各以一銅板所附著做爲 端子，如此製出一熱電冷卻模組。然後此冷卻模組置於真 空中並供以直流電，如此引起溫度落差。測定如此引起的 溫度落差’以評估熱電冷卻模組的冷卻效能。另一方面， 從熔解法獲得之市售可得的ρ型材料和η型材料，分別切 出形成具有如上述相同大小的ρ型樣品元件和η型樣品元 件’而以上述相同的方式評估其冷卻效能。評估的結果顯 示於圖2。如圖2所示，本發明的熱電轉換器元件比市售 可得的熱電轉換器元件展現更優良的冷卻效能。 [本發明的功效] 根據本發明的熱電轉換器元件用之燒結材料的製法， 其包括的步驟有：選擇適合的材料粉末，此材料粉末以能 達到所要熱電效能之合金組成的適當混合比例加以混合， 並於適當的保護氣氛下硏磨並混合此材料粉末達一段適當 的時間，然後於適當的氣氛下燒結達一段適當的時間。使 用本發明之製法所製造的熱電轉換器元件用之燒結材料， 本紙張尺度適用中國國家梯準（CNS ) Α4规格（210X297公釐） ------,--1裝------訂------線 (請先閱讀背面之注意事項再恭寫本頁) ' . 經濟部智慧財產局員工消費合作社印製 A7 --44)5273-B」__ 五、發明説明（（/ ) 係由適當氧化的細微晶粒所組成，並具有所要的優良機械 強度，也展現優良的效率指數。再者，使用本發明的熱電 轉換器元件用之燒結材料所做成的熱電轉換器元件，具有 優良的熱電效能。 . ,.Λ*衣 訂 線 (請先閲讀背面之注意事項再填寫本頁) . . 經濟部智慧財產局員工消费合作社印^ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨Ο X 297公釐）Example Example Comparative Example Comparative Example m ¥ \ ~~ Example Example Comparative Example Example Comparative Example Example Example Comparative Example Example Example Comparative Example Example Comparative Example Comparative Example C 1 2.3 31 1 Note c: Dissolve Commercially available materials manufactured by law · Comparative examples Comparative examples Examples Comparative examples Examples of dagger comparison examples, ^ — Install II and order I line (please read the precautions on the back before filling this page) -· 19 — This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297). Printed by the Intellectual Property Bureau Employees 'Cooperative of the Ministry of Economic Affairs 405273 at B7-----'-^ 5. Description of the invention (called) Table 4 Evaluation results of properties of sintered materials used for η-type thermoelectric converter components Sample No. Favorable z Number 10 · 3 1 / K) Grain size (Aim) Oxygen content (%) Compressive strength (kgf / mm2) Group 27 3.0 0.7 0.35 21 Example 28 3.3 0.5 0.32 20 Example 29 3.1 0.4 0.29 23 Example 30 2.9 0.4 0.28 22 Example 31 2.8 0.6 0.30 21 Comparative example 32 2.8 0.3 0.37 25 Comparative example 33 3.0 1 0.35 21 Example 34 2.9 2 0.35 19 Example 35 2.7 3 0.37 20 Comparative example 36 2.6 21 0.10 7 Comparative example 37 3.1 9 0.10 11 Example 38 3.0 0.1 0.60 30 Example 39 2.8 0.1 0.80 31 Comparative example 40 2.7 0.3 0.70 21 Comparative Example 41 2.9 0.4 0.50 19 Example 42 2.9 5 0.30 16 Example 43 2.8 10 0.30 9 Comparative Example 44 2.9 0.5 0.30 19 Example 45 3.0 3 0.10 23 Example 46 2.5 0.4 0.40 19 Comparative Example 47 2.9 0.5 0.40 21 Example 48 3.3 1 0.26 18 Example 49 3.0 3 0.10 15 Comparative example 50 2.8 0.3 0.40 21 Comparative example 51 2.9 0.5 0.40 18 Example 52 2.7 3 0.20 10 Comparative example 53 2.8 5 0.20 8 Comparative example 54 2.9 3 0.20 12 Example 55 3.1 0.3 0.30 30 Example C 2.4 33 0.50 8 Comparative Example — II .. I n I line (please read the precautions on the back before filling this page) _. ——______ This paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) A7 B7 --40 ^ g73 V. Description of the invention () As shown in Tables 3 and 4, the p-type sintered material and n-type sintered material according to the present invention Compared with melting materials are commercially available, not only in relatively good mechanical terms of quality and efficiency index "ζ" is relatively good. Secondly, cut out a sample element with a cross-section of 2mmx2mm and a height of 2.5mm from the ρ-type sintered material of sample No. · 3 in Table 3, and cut out another η-type sintered material of sample No. · 28 from Table 4 to form another of the same size. Sample components. Then, as shown in FIG. 1, one end of the p-type element and the n-type element are connected to each other through a common copper plate, and the other ends thereof each have a copper plate attached as a terminal, so as to produce a thermoelectric cooling module. The cooling module is then placed in the air and supplied with DC power, which causes a temperature drop. The temperature drop thus caused 'is measured to evaluate the cooling performance of the thermoelectric cooling module. On the other hand, commercially available ρ-type materials and η-type materials obtained from the melting method were cut out to form a ρ-type sample element and an η-type sample element having the same size as above, respectively, and evaluated in the same manner as described above. Cooling efficiency. The results of the evaluation are shown in Figure 2. As shown in Fig. 2, the thermoelectric converter element of the present invention exhibits better cooling efficiency than commercially available thermoelectric converter elements. [Efficacy of the present invention] The method for producing a sintered material for a thermoelectric converter element according to the present invention includes the steps of selecting a suitable material powder, and the material powder is added in an appropriate mixing ratio of an alloy composition capable of achieving the desired thermoelectric efficiency. Mix and hob and mix the powder of the material for a proper period of time under a suitable protective atmosphere, and then sinter for a proper period of time under a suitable atmosphere. The sintered material for the thermoelectric converter element manufactured by the manufacturing method of the present invention, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ------,-1 pack ---- --Order ------ line (please read the precautions on the back before writing this page) ''. Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 --44) 5273-B '' __ 5. Description of the invention ((/) Is composed of appropriately oxidized fine grains, has the required excellent mechanical strength, and also exhibits an excellent efficiency index. Furthermore, thermoelectrics made using the sintered material for the thermoelectric converter element of the present invention The converter element has excellent thermoelectric performance.. .. Λ * Thread (please read the precautions on the back before filling out this page).. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ This paper size applies to Chinese national standards (CNS) A4 size (2 丨 〇 X 297 mm)