TW202212292A - 透明陶瓷之製造方法 - Google Patents

透明陶瓷之製造方法 Download PDF

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Publication number
TW202212292A
TW202212292A TW110125810A TW110125810A TW202212292A TW 202212292 A TW202212292 A TW 202212292A TW 110125810 A TW110125810 A TW 110125810A TW 110125810 A TW110125810 A TW 110125810A TW 202212292 A TW202212292 A TW 202212292A
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Taiwan
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organic additive
aforementioned
additive composition
glass transition
composition
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TW110125810A
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English (en)
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田中恵多
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日商信越化學工業股份有限公司
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Publication of TW202212292A publication Critical patent/TW202212292A/zh

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Abstract

本發明係具有高透過率且面內全面具有均一插入損失而無氣泡缺陷之透明陶瓷之製造方法。 本發明之透明陶瓷之製造方法包含下述步驟： 獲得包含黏合劑、任意選擇之分散劑與可塑劑之候補組成物之步驟， 將前述候補組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下，測定玻璃轉移點之步驟， 選定該玻璃轉移點為25℃以上且60℃以下之候補組成物作為有機添加劑組成物之步驟， 以前述選定之步驟中所得之組成，調製包含前述黏合劑、任意選擇之分散劑與可塑劑之有機添加劑組成物之步驟， 將自金屬氧化物粉末形成之燒結用原料與前述有機添加劑組成物予以粉碎獲得粉碎混合物之步驟， 將前述粉碎混合物顆粒化之步驟， 將前述經顆粒化之混合物予以燒結而獲得燒結體之步驟，及 將前述燒結體加壓之步驟。

Description

透明陶瓷之製造方法
本發明係有關於可見光及紅外區域具有透光性之透明陶瓷，尤其製造光學用途之螢光體、光學透鏡、磁光學元件所利用之透明陶瓷時，用以製造氣泡系光學缺陷不存在之透明陶瓷之方法，及於該方法中作為中間體而製造，且可作為透明陶瓷之原料使用之顆粒體。
陶瓷過去係製造磁磚及陶瓷器，於近年廣泛製造成如壓電元件及超電導元件、透明陶瓷體之精密陶瓷，係各種產業、實際生活中重要的材料。
於有各種之陶瓷中，透明陶瓷於1990年代雷射共振被報導以來，被加速開發。透明陶瓷之主要用途為雷射材料、光學透鏡、螢光體、磁光學元件等。對透明陶瓷要求之特性，係具有高透過率、不存在肉眼可見之氣泡等之光學缺陷。尤其若後者之光學缺陷存在，則例如會成為使雷射品質降低之要因，故被要求完全無光學缺陷。
而且，不僅於透明陶瓷，一般陶瓷之製造方法亦大致分為乾式法及濕式法。乾式法係於原料粉中與分散介質一起混合黏合劑及各種添加劑作成漿料狀，藉由噴霧乾燥等方法將其形成乾燥顆粒並填充至模具中，藉由施加外壓而成型之方法。另一方面，濕式法係於原料粉中與分散介質一起混合黏合劑及各種添加劑作成漿料狀，將該漿料移至石膏等之鑄模並去除分散介質而成型之方法。一般濕式法對少量多品種之生產較優，乾式法對大量生產較優。從工業生產性之觀點，陶瓷一般大多以乾式法製作。
作為乾式法之問題點，因將顆粒填充於模具而成型，故於顆粒與顆粒間容易有間隙，容易發生氣泡缺陷生。成型中發生氣泡於成型‧燒結後仍殘存，於所得之透明陶瓷，會作為肉眼可見之光學缺陷殘留。因此，如何於成型階段消除氣泡缺陷至為重要。
解決上述乾式法之問題的一手段係檢討將粉末漿料化時混合之有機添加劑。例如有機黏合劑具有藉由提高顆粒之壓碎性而壓潰顆粒間之間隙之同時提高成型體保形性之效果。又，分散劑可提高漿料之安定性。該等有機添加劑雖係為了安定製造陶瓷所必要者，但相反的錯誤選定時會成為劣質製品。亦即作為決定陶瓷品質之要因，有機添加劑顯示出較大比例，只能進行試錯慢慢決定使用何種有機添加劑。
藉由於顆粒以特定比率範圍混合二種黏合劑，而提供具有特定物性之陶瓷顆粒之技術為已知(例如參照專利文獻1)。又，使用由具有聚乙烯醇系聚合物嵌段與源自具有離子性基之乙烯性不飽和單體之聚合物嵌段的嵌段共聚物所成之陶瓷形成用黏合劑之技術為已知(例如參照專利文獻2)。
已知根據顆粒之硬度使透明陶瓷之透光性變化(例如參照專利文獻3)。具體而言，專利文獻3揭示若顆粒之壓壞強度為0.3MPa以上6.0MPa以下，則較適於製造透明性優異之陶瓷。因此其原因係壓壞強度未滿0.3MPa時顆粒內部之空壁較多，容易殘留氣泡，相對地若壓壞強度大於6.0MPa則無法壓壞而無法壓碎顆粒間空壁之故。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2011-207673號公報 [專利文獻2]日本特開2001-233678號公報 [專利文獻3]國際公開WO2016/021346號
[發明欲解決之課題]
記載於專利文獻1之技術必須使用二種特定之黏合劑，有使製造步驟繁雜之虞。記載於專利文獻2之技術必須使用特定之嵌段共聚物，但預測此等嵌段共聚物使製造成本提高。因此，基於抑制有機添加劑之成本之觀點欠佳，而謀求以單純之聚合物構造獲得目的物性。於專利文獻3係改變球磨機混合時間而抑制顆粒壓壞強度，並未考慮有機添加劑之影響。
本發明鑒於上述，提供具備選定有機添加劑之組成之步驟，用以製造具有高透過率且面內全面具有均一插入損失而無氣泡缺陷之透明陶瓷之方法。又提供於該方法作為中間體而製造之可作為透明陶瓷之原料使用之顆粒體。 [用以解決課題的手段]
亦即，本發明中，依據一實施形態係一種透明陶瓷之製造方法，其包含下述步驟： 獲得包含黏合劑、任意選擇之分散劑與可塑劑之候補組成物之步驟， 將前述候補組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下，測定玻璃轉移點之步驟， 選定該玻璃轉移點為25℃以上且60℃以下之候補組成物作為有機添加劑組成物之步驟， 以前述選定之步驟中所得之組成，調製包含前述黏合劑、任意選擇之分散劑與可塑劑之有機添加劑組成物之步驟， 將自金屬氧化物粉末形成之燒結用原料與前述有機添加劑組成物予以粉碎獲得粉碎混合物之步驟， 將前述粉碎混合物顆粒化之步驟， 將前述經顆粒化之混合物予以燒結而獲得燒結體之步驟，及 將前述燒結體加壓之步驟。
本發明，依據其他態樣，係一種顆粒體，其包含 (i)有機添加劑組成物，及 (ii)自金屬氧化物粉末形成之燒結用原料， 前述有機添加劑組成物包含黏合劑、任意選擇之分散劑與可塑劑，將該有機添加劑組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下測定時之玻璃轉移點為25℃以上且60℃以下。
以下，說明本發明之實施形態。但本發明並非限定於以下說明之實施形態者。
[第1實施形態：透明陶瓷之製造方法] 本發明中依據第1實施形態，係一種透明陶瓷之製造方法，其包含以下步驟(1)~(8)。 (1)獲得包含黏合劑、任意選擇之分散劑與可塑劑之候補組成物之步驟 (2)將前述候補組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下，測定玻璃轉移點之步驟 (3)選定該玻璃轉移點為25℃以上且60℃以下之候補組成物作為有機添加劑組成物之步驟 (4)以前述選定之步驟中所得之組成，調製包含前述黏合劑、任意選擇之分散劑與可塑劑之有機添加劑組成物之步驟 (5)將自金屬氧化物粉末形成之燒結用原料與前述有機添加劑組成物予以粉碎獲得粉碎混合物之步驟 (6)將前述粉碎混合物顆粒化之步驟 (7)將前述經顆粒化之混合物予以燒結而獲得燒結體之步驟 (8)將前述燒結體加壓之步驟 於步驟(8)之後，並可任意選擇實施步驟(9)光學研磨步驟。
藉由本發明之第1實施形態之製造方法製造之透明陶瓷，係指於可見光及紅外線區域具有透光性之陶瓷，係指於可見光及紅外線區域，較佳具有75%以上，更佳80%以上之透過性之陶瓷。該等透明陶瓷較佳為用於光學用途者，但亦可作為螢光體、光學透鏡、磁光學元件等使用，但不限定於此。用於光學用途之透明陶瓷，較佳為不具有約30μm至1000μm之氣泡缺陷，且具備光學面之平面度為λ/8以下，較佳為λ/10以下之特性者。又，藉由本實施形態之製造方法的步驟(1)~(3)選定，藉由步驟(4)調製之有機添加劑組成物，係使用於透明陶瓷之製造且包含1或2種以上有機添加劑之組成物。1或2種以上之有機添加劑包含黏合劑、可塑劑、分散劑。有機添加劑使用於透明陶瓷之製造，詳細而言，係指藉由乾式法之透明陶瓷之製造中，添加於作為原料之金屬氧化物，於形成漿料時使用。
(1)獲得有機添加劑組成物之候補組成物之步驟 首先，於獲得有機添加劑組成物之候補組成物之步驟，決定有機添加劑組成物之候補組成。有機添加劑組成物係以黏合劑為必要成分，亦可含有任意選擇之分散劑及可塑劑。
黏合劑可為高分子化合物，較佳為主鏈具有芳香環及不含碳-碳雙鍵的單鍵碳鏈之構造。其原因係若為不飽和度高的聚合物構造，則於脫脂時有機物不燃燒而殘存，結果有對陶瓷之透明性造成影響之虞。又構成高分子化合物之元素，以碳、氫、氧、氮作為主成分，較佳由碳、氫、氧、氮所成。期望不含硫等之難燃燒性物質。高分子化合物之聚合度雖未特別限定，但基於處理容易性之觀點，較佳為200以上10000以下，更佳為200以上2000以下。作為該等黏合劑，可使用一般作為黏合劑市售之高分子化合物。
較佳之黏合劑之例，舉例為乙烯系樹脂、纖維素衍生物、丙烯酸系樹脂、聚乙烯系樹脂、聚丙烯系樹脂。作為乙烯系樹脂，較佳為包含選自乙酸乙烯酯、乙烯醇、乙烯縮丁醛之一種類以上的重複單位之共聚物。更具體而言，較佳之黏合劑可為乙酸乙烯酯-乙烯醇共聚物、以聚乙烯縮丁醛為主成分之乙烯縮丁醛-乙酸乙烯酯-乙烯醇共聚物、羥丙基甲基纖維素、乙烯-乙酸乙烯酯共聚物，但不限定於此。
有機添加劑組成物所含之黏合劑，根據情況，可為1種，亦可為2種以上。基於簡便性之觀點，黏合劑較佳僅由1種所成。
可塑劑係可使構成黏合劑之高分子化合物之玻璃轉移點降低之添加劑。可塑劑亦較佳為主鏈具備芳香環或不含碳-碳雙鍵之單鍵碳鏈之構造之高分子化合物。又，構成高分子化合物之元素以碳、氫、氧、氮為主成分，較佳為由碳、氫、氧、氮所成。期望不含硫等之難燃燒性物質。作為此等可塑劑可使用一般作為可塑劑而市售之高分子化合物。可塑劑可為聚氧乙烯系化合物，亦可為例如聚乙二醇、三乙二醇、甘油、聚氧乙烯烷基醚系化合物。又，可為具有鄰苯二甲酸酯鍵、磷酸酯鍵、檸檬酸酯鍵之高分子，亦可為分子內具有C-O-C鍵之高分子。有機添加劑組成物所含之可塑劑，根據情況，可為1種，亦可為2種以上。
分散劑係為了保持漿料中之粒子分散性、防止凝集而使用之添加劑。分散劑若為具有分散性保持、凝集防止機能之化合物，則可為高分子化合物亦可為低分子化合物。作為由高分子化合物所成之分散劑，較佳為具備主鏈具有芳香環、或不含碳-碳雙鍵之單鍵碳鏈之構造之高分子化合物。又，構成高分子化合物之元素以碳、氫、氧、氮為主成分，較佳為由碳、氫、氧、氮所成。期望不含硫等之難燃燒性物質。該等分散劑可使用一般作為分散劑而市售之高分子化合物。作為高分子化合物之較佳分散劑，舉例為例如聚氧乙烯烷基醚系化合物，亦可為包含OH基、磺基、磷酸基之高分子材料，但不限定於此。作為低分子化合物之較佳分散劑，舉例為例如磺酸鹽系分散劑、磷酸鹽系分散劑，更具體而言，舉例為十二烷基苯磺酸鈉鹽、焦磷酸鈉。有機添加劑組成物所含之分散劑，根據情況，可為1種，亦可為2種以上。
於本實施形態中，於本步驟決定有機添加劑組成物之候補組成後，於後續步驟，選定具有特定範圍之玻璃轉移點之組成。因此，選定候補組成時，以使有機添加劑組成物具有特定玻璃轉移點之方式，決定相對於黏合劑之可塑劑及/或分散劑之種類及量。黏合劑之玻璃轉移點係由黏合劑之主鏈構造及側鏈之官能基間之相互作用決定。例如，具有伸乙基骨架之主鏈構造之黏合劑分子，因不阻礙碳-碳鍵之旋轉運動，故玻璃轉移點變低。另一方面，具有苯及環己烷骨架之黏合劑分子，由於主鏈之移動受限制，玻璃轉移點變高。又於黏合劑分子之側鏈之官能基例如若存在羥基，則與其他之羥基於聚合物內或聚合物間形成氫鍵，限制了聚合物之移動故玻璃轉移點變高。即玻璃轉移點係由黏合劑本身之分子構造決定。有機添加劑組成物包含黏合劑以外之成分之情況，有機添加劑組成物之玻璃轉移點亦受其他成分影響。例如藉由於由聚乙烯醇所成之黏合劑中添加可塑劑甘油，而降低玻璃轉移點。可塑劑具有分斷聚合物側鏈之相互連接之作用，因解除了側鏈之自由度，使組成物之玻璃轉移點降低。且，有機添加劑組成物所含之各有機添加劑之效果，對於一個添加劑並非僅一個效果，亦有具有複數效果之情況。例如，聚氧乙烯系之添加劑，具有作為保持漿料安定性之分散劑之效果及作為使黏合劑柔軟化之可塑劑之效果。
於本步驟，適當決定以黏合劑為必須，且含有任意選擇之分散劑、可塑劑之有機添加劑組成物的候補組成後，混合各成分調製候補組成物。且，有機添加劑組成物中亦可包含溶劑，該溶劑可與下一步驟(2)所用之溶劑相同。
(2)測定玻璃轉移點之步驟 於本步驟，將候補組成物溶解於溶劑後，使含溶劑量降低，測定玻璃轉移點。溶劑若為係溶解黏合劑及若存在之情況下之可塑劑及分散劑，且可加熱除去之溶劑，則未特別限定。例如可使用乙醇、甲醇、丙醇、丙酮、純水及該等之混合溶劑，但不限定於特定溶劑。有機添加劑組成物所含之溶劑，依據情況，可為1種，亦可為2種以上。
含溶劑量之降低係藉由加熱‧乾燥溶解於溶劑之候補組成物而實施。加熱條件可依據使用之溶劑的揮發溫度適當決定。又，根據需要，可使用防爆型乾燥機，但加熱‧乾燥之條件及裝置不特別限定。例如，可藉由將溶解於溶劑之候補組成物放入至約70℃左右之乾燥機約24小時而加熱乾燥，但不限定於特定條件。藉由本步驟，可獲得膜狀物質或糊狀物質。尤其較佳乾燥至乾燥後之膜狀物質或糊狀物質全體之含溶劑量為0.1質量%以下。係因為殘留溶劑對玻璃轉移點之測定造成影響之故。含溶劑量可藉由溶解時之溶劑質量與將膜狀物質或糊狀物質加熱‧乾燥後之質量測定，例如放入70℃之乾燥機24小時後之質量測定而獲得。
接著，測定含溶劑量降低至上述所定量以下之候補組成物之玻璃轉移點。玻璃轉移點之測定，可使用市售之TG/DTA裝置或DSC裝置實施。以DTA或DSC曲線所見之吸熱反應之最大傾斜溫度作為玻璃轉移點。
(3)選定為有機添加劑組成物之步驟 本步驟係選定該玻璃轉移溫度為25℃以上60℃以下之候補組成物作為透明陶瓷之製造步驟所用之有機添加劑組成物。另一方面，於玻璃轉移點未滿25℃之情況及超過60℃之情況，基於本發明之觀點，可判斷該候補組成物不適於有機添加劑組成物。更佳選定玻璃轉移點為35℃以上55℃以下之候補組成物。藉由使用具有該範圍之玻璃轉移點之有機添加劑組成物，可獲得面內均一性高的透明陶瓷。
不欲受理論拘束，推測其理由如下。亦即，有利於一般乾式加壓成型之顆粒體，較佳具有於加壓時不輕易壓碎之硬度，但於最終成型階段為壓碎狀態。由於於加壓初期藉由施加壓力，粉愈接近細密填充構造排列者，顆粒體間的空隙變小，故必須具有某程度之硬度。另一方面，即使細密填充構造顆粒體間之空隙仍存在，但只要最終不壓碎則其間隙可不被埋填。亦即較佳為不過硬不過軟之顆粒體，作為達成該顆粒體之較佳硬度之方法，認為具有上述範圍之玻璃轉移點的有機添加劑之組成為必要。
(4)調製有機添加劑組成物之步驟 本步驟係以步驟(3)選定之組成，調製包含黏合劑、任意選擇之分散劑及可塑劑之有機添加劑組成物。有機添加劑組成物之調製可藉由混合選定之成分而實施。
經過步驟(1)~(4)所得之有機添加劑組成物，溶解於溶劑後，使含溶劑量降低至所定量時之玻璃轉移點落於特定範圍，藉由使用該等有機添加劑，可製造無氣泡及缺陷、面內均一性高的透明陶瓷。
以上步驟(1)~(4)係透明陶瓷之製造方法之一部份，亦可說是有機添加劑組成物之製造方法。同樣，步驟(1)~(3)亦可說是選定有機添加劑組成物組成之方法。因此，本發明亦提供有機添加劑組成物之製造方法及選定有機添加劑組成物組成之方法。
所得之有機添加劑組成物係使用於製造透明陶瓷之有機添加劑組成物，包含黏合劑、任意選擇之分散劑及可塑劑，且於將含溶劑量降低至0.1質量%以下測定時具有25℃以上60℃以下之玻璃轉移點。
(5)獲得粉碎混合物之步驟 本步驟係將由金屬氧化物粉末形成之燒結用原料與前述有機添加劑組成物予以粉碎。金屬氧化物粉末較佳為藉由燒結成為立方晶之金屬氧化物(立方晶組成氧化物)者。例如可例示包含1種或複數種之稀土類氧化物之粉末、包含稀土類氧化物及其他金屬氧化物之粉末，但不限定於此。作為成為立方晶構造且顯示透明性之代表性金屬氧化物，舉例為石榴石型氧化物、C型氧化物、燒綠石型氧化物等。正方晶系的氧化鋁等雖亦根據條件而可透明化，但正方晶因結晶方位所致之折射率差，會發生光散射，故無法使用於光學用途。
石榴石型氧化物係以A 3B 5O 12(A為選自由Y、Tb、Lu、Gd、La、Ce、Yb、Tm、Eu、Pr、Dy、Ho及Nd所成之群之至少1種元素，B為選自由Al、Ga及Sc所成之群之至少1種元素)表示之複合氧化物，例如舉例Y 3Al 5O 12(YAG)。C型(方鐵錳礦型)氧化物係由選自由Y、Tb、Lu、Yb、Tm、Ho、Dy、Ce、Gd、Eu、Pr及Nd所成之群之至少1種元素所成之氧化物，例如舉例Y 2O 3。燒綠石型氧化物係以A’ 2B’ 2O 7-Z(A’為選自由Y、Tb、Lu、Gd、La、Ce、Yb、Tm、Eu、Pr、Dy、Ho及Nd所成之群之至少1種元素，B’為選自由Zr、Hf、Ti、Sn、Ge及Si所成之群之至少1種元素，Z為0以上1以下之數)表示之複合氧化物，例如舉例La 2Z 2O 7。
所用之金屬氧化物粉末之規格並未特別限定，但較佳使用能獲得透明化容易的100nm以下之一次粒徑者。作為獲得100nm以下之一次粒徑之方法，有自離子狀態漸漸成長結晶之由下而上方式與自1μm以上之大粒子進行粉碎處理之自上而下方式，任一方式皆可使用。
粉碎混合物可藉由以一般方法混合金屬氧化物粉末、於步驟(1)~(4)選定‧調製之有機添加劑組成物及任意選擇的溶劑並粉碎而獲得。溶劑只要於後續步驟(6)、(7)中可藉加熱及/或燃燒去除之溶劑即可，可為與步驟(2)使用之溶劑相同。相對於金屬氧化物粉末的有機添加劑組成物之混合量，於將金屬氧化物粉末之質量設為100質量份時，有機添加劑組成物中之黏合劑之質量可為0.5~2質量份。又，混合溶劑時，溶劑之混合量，於將金屬氧化物粉末之質量設為100質量份時，為0~0.5質量份。黏合劑之混合‧粉碎，較佳為以如濕式球磨及濕式珠磨之濕式進行。混合‧粉碎較佳進行至漿料容易通過孔徑約20μm之尼龍過濾器為止。藉此，可獲得漿料狀之粉碎混合物。
(6)顆粒化之步驟 本步驟係對於步驟(5)所得之粉碎體混合物，進行噴霧乾燥處理並顆粒化成特定大小，調製顆粒體。噴霧乾燥處理可為以往習知之方法，可將粉碎混合物藉由噴霧器方式等之噴霧乾燥器，邊加熱至溶劑(水或有機溶劑)之沸點以上邊以一定處理速度噴霧乾燥而獲得顆粒體。顆粒體之平均粒徑宜為100~500μm左右，但未特別限定。顆粒體之平均粒徑係指藉由以光學顯微鏡測量100個以上之顆粒體之最長直徑與最短直徑之平均值之方法而測定之平均粒徑。顆粒體包含金屬氧化物粉末及有機添加劑組成物。溶劑係藉由噴霧乾燥加熱除去，顆粒體中實質上不含溶劑，但亦可一部分殘存。
(7)獲得燒結體之步驟 本步驟係將步驟(6)所得之顆粒體成型、脫脂、燒結，獲得燒結體。顆粒體之成型可藉由將顆粒體填充至鑄模並自一定方向加壓之加壓步驟及密閉收納於可變形之防水容器並以等水壓加壓之CIP(Cold Isostatic Pressing，冷等壓)實施。較佳成型為成型後所得之成型體之相對密度為50%以上60%以下。
成型體之脫脂可於可除去構成有機添加劑組成物之各有機添加劑之條件實施。例如，於大氣下，可藉由於可燃燒除去有機添加劑組成物之構成成分的400℃以上之溫度，歷時15~30小時加熱，進行成型體之脫脂。接著，使經脫脂之成型體燒結。燒結較佳於真空、氧或氫環境下於1200℃以上，且1800℃以下左右之溫度，歷時1~3小時而實施。燒結之更詳細溫度、時間條件，可決定為於燒結後所得之燒結體之相對密度成為95%以上。
(8)加壓燒結體之步驟 本步驟係加壓步驟(7)所得之燒結體，獲得透明陶瓷。燒結體之加壓，可藉由熱等壓加壓(HIP(Hot Isostatic Pressing))處理而實施。作為加壓氣體介質，可使用氬、氮等之惰性氣體，或Ar-O 2、Ar-CO 2。加壓之壓力可為50~ 300MPa，較佳為100~300MPa。施加壓力若為市售之HIP裝置可處理之196MPa以下則為簡便而較佳。藉由本步驟，可獲得透明陶磁(透明立方晶組成氧化物燒結體)。
(9)光學研磨步驟 於加壓燒結體之步驟之後，亦可任意選擇地包含進行光學研磨之步驟。本步驟較佳係針對步驟(8)所得之透明陶瓷，光學研磨位於其光學上利用之軸上的兩端面。此時之光學面之平面度較佳為λ/8以下，特佳為λ/10以下(λ=633nm)。且藉由於經光學研磨之面成膜適當抗反射膜可更減低光學損失。光學平面度若為λ/8以上則光束品質等惡化，無法使用於光學用途。光學平面度可藉透過波面及反射波面測定。
藉由步驟(1)至(8)，或藉由步驟(1)至(9)所得之透明陶瓷之品質，可藉由氣泡等缺陷之有無而評價。透明陶瓷內部之氣泡等缺陷之有無較佳以偏光顯微鏡確認。具體而言，使用倍率5倍之物鏡，藉由光學面觀察透明陶瓷全區域之內部。與本發明關連之源自成為問題之顆粒間空壁之氣泡，於透明陶瓷內部大小即使小仍達30μm以上。因此，即使倍率低之物鏡仍可充分觀測。藉由本實施形態製造之透明陶瓷，不存在30μm以上之1000μm之氣泡，確保遍及透明陶瓷全體之透明性，作為光學用途之構件為有用。
[第2實施形態：顆粒體] 本發明中根據第2實施形態係關於一種顆粒體，其包含 (i)有機添加劑組成物，及 (ii)自金屬氧化物粉末形成之燒結用原料， 前述有機添加劑組成物包含黏合劑、任意選擇之分散劑與可塑劑，將該有機添加劑組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下測定時之玻璃轉移點為25℃以上且60℃以下。
本實施形態之顆粒體係於透明陶瓷之製造中作為中間體而製造，經過加壓、燒結則成為透明陶瓷。然而，該顆粒體亦可稱為透明陶之材料。本實施形態之顆粒體可藉由實施於先前之透明陶瓷之製造方法之步驟(1)~(6)而獲得。 [實施例]
以下，舉例本發明之實施例具體說明，但本發明不限定於該等。
＜實施例1~6，比較例1~6＞ ＜玻璃轉移點測定＞ 將作為黏合劑之乙酸乙烯酯-乙烯醇共聚物(JMR-10L，Japan VAM&POVAL股份有限公司製)溶解於乙醇作成10質量%濃度。於所得之聚合物溶液，以相對於黏合劑為0質量%至200質量%之範圍添加可塑劑的聚乙二醇(PEG200，關東化學股份有限公司製)或甘油(關東化學公司製)。充分攪拌混合後，使用80℃之防爆型乾燥機去除乙醇溶劑。所得之膜狀聚合物或糊狀物質20.0mg填充至直徑4mm、深2mm之鉑盤中，使用TG/DTA分析裝置測定玻璃轉移點。此時，作為參考物質使用氧化鋁20.0mg，且測定溫度係自室溫至500℃，升溫速度為15℃/分，於大氣環境測定。可於DTA曲線確認之吸熱反應中，具有不具有波峰之一階段DTA數值下降之部分，將該部分之最大傾斜溫度設為玻璃轉移點。又明確之玻璃轉移點不明時設為室溫以下(25℃以下)。
＜透明陶瓷之製造＞ 將C型稀土類構造的秤量Y 2O 3粉末(粒徑1μm，純度99.9%，信越化學工業股份有限公司製)50g與乙醇(關東化學公司製)120g、2mm氧化鋯珠粒(NIKKATO股份有限公司製)600g秤量至500mL鍋中，進行20小時球磨粉碎處理。確認可粉碎至約100nm之一次粒徑後，放入相對於粉末100質量份為1質量份之黏合劑及相對於黏合劑指定量之可塑劑，進一步以球磨機混合4小時。使用噴霧方式之乾燥噴霧裝置將所得漿料顆粒化，獲得平均顆粒徑200μm之顆粒體。藉由單軸加壓成型所得之顆粒體，成型為Φ6mm×L15mm之圓筒形。成型體藉由於大氣環境下40℃20小時之熱處理而脫脂，隨後進行1600℃2小時(升溫速度100℃/h)之真空燒結處理，緻密化至相對密度96%。所得之燒結體實施Ar壓介質、198MPa、1720℃、2小時之HIP處理，獲得透明燒結體。隨後實施研削加工成Φ4mm×L11mm，並對兩端面實施λ/8之光學研磨處理。
＜氣泡之確認方法＞ 所得透明塑膠之氣泡確認係使用偏光顯微鏡。使用倍率5倍之物鏡，計算於透明陶磁Φ4mm之全範圍內部觀測之氣泡數。又，此處表現之氣泡係指大為1000μm、即使小仍約30μm者。存在於構成透明陶瓷之結晶粒間之1μm以下之小氣泡作為對象外。即僅計算可藉倍率5倍之物鏡觀測之氣泡。又氣泡量係以氣泡個數除以透明燒結體體積之值表示。
Figure 02_image001
表1顯示各種有機添加劑組成物之玻璃轉移點及透明陶瓷內部之氣泡量。與實施例1比較，可確認於添加可塑劑之全部有機添加劑組成物，其玻璃轉移點降低。但若黏合劑與可塑劑之比例超過100:50，則玻璃轉移點成為室溫以下，可知失去作為黏合劑之功能。另一方面，關於氣泡量，於使用玻璃轉移點為室溫以下之有機添加劑組成物時，於透明陶瓷內部產生氣泡，於使用具有30℃以上玻璃轉移點之有機添加劑組成物時，於透明陶瓷內部未觀測到氣泡。
＜實施例7~9，比較例7~9＞ 除了黏合劑係以聚乙烯縮丁醛為主成分之乙烯縮丁醛-乙酸乙烯酯-乙烯醇共聚物(SLEC BL-5，積水化學股份有限公司製)，可塑劑為三乙二醇(TEG，東京化成工業股份有限公司製)以外，與實施例1~6同樣測定有機添加劑組成物之玻璃轉移點，並使用其製造透明陶瓷。黏合劑之添加量與實施例1相同，相對於粉末為1質量%。
Figure 02_image003
結果示於表2。於實施例7~9，玻璃轉移點為60℃以下時，未觀測到氣泡。另一方面，無可塑劑或極小量，亦即若玻璃轉移點超過60℃，則成為零散看見氣泡之結果。比較例7之不透明意指部分透明但顆粒與顆粒之間不透明，無法獲得全體透光性。亦即認為因顆粒較硬，故於細密填充後顆粒未壓碎而直接殘留。另一方面於比較例9，可塑劑之量過多，玻璃轉移點過於降低，成為零散看見氣泡之結果。
＜實施例10~12、比較例10~11＞ 除了添加作為分散劑之聚氧乙烯烷基醚系分散劑(POE)(N1204，日本乳化劑股份有限公司製)以外，與實施例1同樣測定玻璃轉移點，且製造透明陶瓷。又分散劑為了維持分散性必須比可塑劑饋入更多。
Figure 02_image005
結果示於表3。於實施例10~12，分散劑之量雖較可塑劑多，但因玻璃轉移點為30℃以上故未觀測到氣泡。另一方面，分散劑之量較多之組成物，玻璃轉移點成為室溫以下，失去作為黏合劑之功能，成為觀測到氣泡之結果。
＜實施例13~15，比較例12~14＞ 除了加入作為分散劑之POE、作為可塑劑之PEG200兩者以外，進行與實施例1同樣操作，測定玻璃轉移點，製造透明陶瓷。
Figure 02_image007
結果示於表4。根據實施例13~15，於黏合劑添加可塑劑及分散劑兩者時，若玻璃轉移點成為室溫以上，則完全未觀測到氣泡。另一方面，根據比較例12~ 14，加入過量的分散劑或可塑劑任一者，且玻璃轉移點成為室溫以下時，成為零散看見氣泡之結果。

Claims (7)

  1. 一種透明陶瓷之製造方法，其包含下述步驟： 獲得包含黏合劑、任意選擇之分散劑與可塑劑之候補組成物之步驟， 將前述候補組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下，測定玻璃轉移點之步驟， 選定該玻璃轉移點為25℃以上且60℃以下之候補組成物作為有機添加劑組成物之步驟， 以前述選定之步驟中所得之組成，調製包含前述黏合劑、任意選擇之分散劑與可塑劑之有機添加劑組成物之步驟， 將自金屬氧化物粉末形成之燒結用原料與前述有機添加劑組成物予以粉碎獲得粉碎混合物之步驟， 將前述粉碎混合物顆粒化之步驟， 將前述經顆粒化之混合物予以燒結而獲得燒結體之步驟，及 將前述燒結體加壓之步驟。
  2. 如請求項1之方法，其中前述選定步驟中，玻璃轉移點為30℃以上55℃以下。
  3. 如請求項1之方法，其中前述黏合劑包含含有選自乙酸乙烯酯、乙烯醇、乙烯縮丁醛之一種以上的重複單位之共聚物。
  4. 如請求項1至3中任一項之方法，其中前述分散劑係選自聚氧乙烯烷基醚系分散劑。
  5. 如請求項1至3中任一項之方法，其中前述可塑劑係選自甘油、聚乙二醇、三乙二醇之一種以上。
  6. 如請求項1至3中任一項之方法，其中前述透明陶瓷係光學用途。
  7. 一種顆粒體，其包含 (i)有機添加劑組成物，及 (ii)自金屬氧化物粉末形成之燒結用原料， 前述有機添加劑組成物包含黏合劑、任意選擇之分散劑與可塑劑，將該有機添加劑組成物溶解於溶劑後，使含溶劑量降低至0.1質量%以下測定時之玻璃轉移點為25℃以上且60℃以下。
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