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標題: Mg2(Si, Sn)熱電合金氧化性質及氮化硼噴塗層對其氧化防護之研究
Oxidation Properties of Mg2(Si, Sn) Thermoelectric Alloy and its Oxidation Protection by Boron Nitride Spray Coating
作者: 彭康年
Kang- Nian Peng
關鍵字: Mg2(Si, Sn)熱電材料;氧化性質;錫鬚晶;氮化硼;Mg2(Si, Sn) thermoelectric material;Oxidation property;Tin whiskers;Boron Nitride
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鎂錫矽熱電材料Mg2(Si, Sn)材料為一具有發展潛力的中溫型熱電材料。由於鎂金屬具有高活性,易在高溫環境產生氧化行為,造成Mg2(Si, Sn)熱電合金會因氧化造成結構變化,進而影響熱電性能。鎂錫矽熱電材料最佳應用溫度約在400oC左右,文獻提鎂錫矽熱電材料會在430oC~500oC因為鎂元素氧化消耗,造成相分離,產生純錫球,且伴隨著大量氧化物的產生,持續性的裂紋擴展,破壞了試片原有結構。本研究首次發現在400oC加熱20hr後,發現了純錫球的產生,且鎂錫矽熱電材料在以空冷的方式冷卻,發現表面有較多團簇的氧化鎂,且有錫鬚晶產生。根據文獻,錫鬚晶生長點易始於基材與氧化物或是缺陷之界面處;在較多團簇的氧化鎂之鎂錫矽熱電合金試片表面,因提供較多的「界面」使錫鬚晶生長。此現象同時也代表成分配比的流失,故本研究將探討鎂錫矽熱電材料之氧化行為以及其防護措施。本實驗利用噴塗氮化硼(Boron Nitride)之方式,能防止鎂錫矽熱電材料結構崩解。以TEM解析,發現在氮化硼膜中,片狀氮化硼層間有網狀分布的黏結劑相互堆疊,使氮化硼膜更為緻密,防止氧氣持續進入熱電材料內部,且在介面形成一層約200nm之氧化鎂層,此兩種效果隔絕氧大量進入試片,防止鎂錫矽熱電材料形成更嚴重的氧化反應使材料產生崩解。

Mg2(Si, Sn) thermoelectric material is a medium-temperature thermoelectric material with development potential. Mg has high activity; it is easy to generate oxidation behavior in high temperature, which causes the structure change of Mg2(Si, Sn) thermoelectric alloy and affecting the thermoelectric performance. The optimum application temperature of Mg2(Si, Sn) thermoelectric materials is about 400oC. The literature mentions that Mg2(Si, Sn) thermoelectric materials will have an oxidation reaction in 430oC~500oC, causing phase separation, producing pure tin balls, a large number of oxides. The continuous crack propagation destroys the original structure. In this study, we found for the first time that after the heating at 400oC for 20hr, the production of pure tin balls was found, and the Mg2(Si, Sn) thermoelectric materials were cooled in an air-cooled manner, and it was found that there were many clusters of MgO on the surface, and tin whiskers were produced. According to the literature, the tin whisker growth point tends to start at the interface between the substrate and the oxide or defect; with more clusters, MgO on the surface and we can find the tin whisker on the surface. Clusters MgO provides more 'interface' for Sn whisker growth. This phenomenon also represents the loss of the distribution ratio, so this study will explore the oxidation behavior of Mg2(Si, Sn) thermoelectric materials and their protective measures. In this experiment, the method of spraying boron nitride (Boron Nitride) can prevent the disintegration of the structure of the Mg2(Si, Sn) thermoelectric material. By TEM analysis, it was found that in the boron nitride film, the network-formed binders between the lamellar boron nitride layers were stacked on each other to make the boron nitride film denser, preventing oxygen from continuously entering the inside of the thermoelectric material, and forming a layer on the interface. MgO layer is about 200 nm, which insulates a large amount of oxygen into the test piece, prevents the Mg2(Si, Sn) thermoelectric material from forming a more severe oxidation reaction to cause the material to disintegrate.
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