TWI430975B - 陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法 - Google Patents

陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法 Download PDF

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TWI430975B
TWI430975B TW098125893A TW98125893A TWI430975B TW I430975 B TWI430975 B TW I430975B TW 098125893 A TW098125893 A TW 098125893A TW 98125893 A TW98125893 A TW 98125893A TW I430975 B TWI430975 B TW I430975B
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Shingo Niinobe
Kazuhisa Hayakawa
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Shinetsu Chemical Co
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Description

陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法
本發明係有關陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法。
陶瓷材料中將有機黏合劑、界面活性劑、潤滑劑、可塑劑等之成形助劑進行混合，混煉得到之陶瓷坏土，藉由通過所期待形狀噴嘴，進行作成薄片狀、棒狀、中空管狀、角柱狀、中空角柱狀、蜂巢構造狀之陶瓷擠壓成形。陶瓷蜂巢之擠壓成形體特別適用於汽車及產業用之廢氣淨化觸媒載體、濾器、熱交換體等。而近年來以對應廢氣規制之強化為目的，為提昇淨化性能、壓力損失之降低、熱交換效率促使蜂巢構造體之壁面的薄壁化。
先行技術中，陶瓷擠壓成形體用組成物，由其具良好之可塑性與保水性及熱凝膠化特性，而專使用作為有機黏合劑之纖維素醚等。
惟，此等纖維素醚於擠壓成形時，與塑模部之磨擦力變強，因其電阻導致擠壓溫度之提昇，擠壓成形用組成物中之纖維素醚被熱可逆凝膠化，致使可塑劑之流動性變差，而提高成形壓力，使得陶瓷之擠壓成形體由擠壓成形塑模無法快速擠壓之缺點存在。因此，添加無法顯示熱凝膠化性之有機黏合劑進行擠壓成形時，提昇吐出溫度後有機黏合劑出現黏性下滑，雖可加速成形速度，而以熱可逆凝膠化性之纖維素醚作為有機黏合劑之陶瓷擠壓成形體時，不易提高成形速度之問題存在。
為克服此缺點，以改善擠壓成形性之目的下，使用特開平11-58335號公報(專利文獻1)、特開2002-293645號公報(專利文獻2)各種類似之有機添加劑進行研討，惟，尚無法滿足所期待。
[專利文獻1]特開平11-58335號公報
[專利文獻2]特開2002-293645號公報
本發明係鑑於上述情況，而以提供一種無損擠壓成形性，成形速度快，且無出現乾燥龜裂之陶瓷擠壓成形體之陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法者為其目的。
本發明者為解決上述先行技術之課題，進行精密研討後結果發現，藉由使用含有陶瓷材料、水溶性纖維素醚、苯乙烯磺酸鹽之陶瓷擠壓成形體用組成物，可於高溫下進行擠壓成形，可提昇擠壓成形速度，進而完成本發明。因此，本發明係提供以下之陶瓷擠壓成形體用組成物及陶瓷擠壓成形體之製造方法。
申請項1：其特徵係含有陶瓷材料、水溶性纖維素醚、苯乙烯磺酸鹽及水之陶瓷擠壓成形體用組成物。
申請項2：該陶瓷材料係選自謹青石陶瓷、碳化矽、鈦酸鋇、鈦酸鋯酸鉛、鈦酸鋁之申請項1所載之陶瓷擠壓成形體用組成物。
申請項3：該水溶性纖維素醚係選自烷基纖維素、羥烷基纖維素、羥烷基烷基纖維素之申請項1或2所載之陶瓷擠壓成形體用組成物。
申請項4：對於100質量份之陶瓷材料而言，含有1～15質量份之水溶性纖維素醚、1～15質量份之苯乙烯磺酸鹽、10～50質量份之水之申請項1～3中任一項之陶瓷擠壓成形體用組成物。
申請項5：使申請項1至4中任一項之陶瓷擠壓成形體用組成物進行混煉，擠壓成形後，乾燥及燒成者為其特徵之陶瓷擠壓成形體之製造方法。
本發明之陶瓷擠壓成形體用組成物係可提昇擠壓成形時可成形之上限溫度，亦可提昇每單位時間之生產性。
 [發明實施之最佳形態]
作為用於本發明陶瓷擠壓成形體用組成物之陶瓷材料者如：鋁陶瓷、謹青石陶瓷、碳化矽、氮化矽、金屬矽、鈦酸鋇、鈦酸鋯酸鉛、鈦酸鋁等例，較佳者為謹青石陶瓷、碳化矽、鈦酸鋇、鈦酸鋯酸鉛、鈦酸鋁。
作為水溶性纖維素醚者為熱可逆凝膠化性之水溶性纖維素醚之烷基纖維素、羥烷基纖維素、羥烷基烷基纖維素者宜，具體而言係使用甲基纖維素、羥乙基纖維素、羥丙基甲基纖維素、羥乙基甲基纖維素、羥乙基乙基纖維素等。
水溶性纖維素醚之黏度係於20℃之2質量%水溶液黏度下，為100～300000mPa‧s者宜，特別為40000～100000mPa‧s最佳。
作為取代度者，甲基纖維素時，為甲氧基25～35質量%者宜。
羥乙基纖維素時，為羥基乙氧基25～65質量%者宜。
羥丙基甲基纖維素時，為甲氧基20～35質量%，羥基丙氧基1～20質量%者宜。
羥乙基甲基纖維素時，為甲氧基20～35質量%，羥基乙氧基1～20質量%者宜。
羥乙基乙基纖維素時，為乙氧基10～50質量%，羥基乙氧基1～50質量%者宜。
水溶性纖維素醚之添加量，為進一步於陶瓷成形後之乾燥下不使成形體產生龜裂，之後之燒結步驟之脫黏合劑量不會變多，燒成時之收縮不致出現割裂之理想情況，故對於100質量份之陶瓷材料而言，為1～15質量份者宜，特別為3～7質量份最佳。
接著，苯乙烯磺酸鹽之例如：對苯乙烯磺酸鉀、對苯乙烯磺酸鈉、鄰苯乙烯磺酸鉀、鄰苯乙烯磺酸鈉、間苯乙烯磺酸鉀、間苯乙烯磺酸鈉之例，而特別是對苯乙烯磺酸鉀為可提昇水溶性纖維素醚水溶液之熱凝膠化之溫度較為理想者。另外，作為對苯乙烯磺酸鉀之製作方法者，並未特別限定，一般使用溴乙基苯磺酸之脫溴化氫化反應所製造者。
對於100質量份之陶瓷材料而言，苯乙烯磺酸鹽之添加量為1~15質量份者宜，特別為1~5質量份者最佳。
另外，對於100質量份之陶瓷材料而言，水的添加量為10~50質量份者宜，特別為15~35質量份最佳。
本發明之陶瓷擠壓成形體用組成物除上述成份之外，可於必要時添加可塑劑、有機系之造孔劑。作為可塑劑之例者如：甘油、甘油之衍生物、山梨聚糖脂肪酸酯類、聚丙烯與聚乙烯或與聚丁二烯之共聚物及其衍生物類之例。又，亦可添加使陶瓷本身於輕量化或多孔體所有添加之有機系造孔劑等。對於100質量份之陶瓷材料而言，造孔劑之添加量為0.1~20質量份者宜，特別為1~10質量份時可發揮必要程度的造孔效果最為理想。
另外，亦可添加先行技術之併用於水溶性纖維素醚之波帕爾、聚乙二醇、聚丙烯醯胺等之合成水溶性高分子、古柯豆膠等之天然水溶性高分子、維勒膠等之微生物發酵多糖類等。
本發明陶瓷擠壓成形體之製造方法係最初使陶瓷材料與水溶性纖維素醚進行乾式混合，更加入水及其他成份，進行濕式混合。以混煉機混煉如此所調製之陶瓷擠壓成形體用組成物，得到陶瓷擠壓成形體用混煉物。此時，混煉物的溫度為0~30℃者宜，特別佳者為15~25℃。之後，以真空擠壓機擠壓該陶瓷擠壓成形體用混煉物成所期待之形狀，可得到成形體。此時成形體之溫度為0~95℃者宜 ，特別佳者為20~80℃。將所得之成形體於均勻乾燥(經由微波爐等之誘導加熱乾燥)及不均勻乾燥(通風乾燥)下進行乾燥，判定是否出現龜裂。均勻乾燥時，將擠壓成形體切成長度20~30mm，以微波爐，100W，處理擠壓成形體1分鐘，上下重覆作業進行6次，可判定是否出現龜裂。另外，不均勻乾燥時，將擠壓成形體切成長度20~30mm，由單方向經由熱風之乾燥機內(如：80℃)使擠壓成形體乾燥1小時後，判定是否產生龜裂。
[實施例]
以下顯示實施例，進行本發明之具體的說明，惟本發明並未受限於下述實施例。
[實施例1~10]
將表1所示之水以外之材料以密閃式混合器進行混合3分鐘，加入所定量之水後，於4×3/4inch之小型3根滾輥混煉器(井上製作所(股份)製)經由放冷作成混煉物溫度15~25℃，通過5次滾輥，混煉，於螺旋徑20mm之小型真空擠壓成形機，測定使外徑20.5mm，間距2.5mm，壁厚0.5mm之蜂巢擠壓成形於擠出壓力5~10MPa，較佳者為7MPa下進行之各擠壓成形壓力下之成形體溫度。
成形物切成長度50mm，以微波爐、100W、每處理1分鐘後，使擠壓成形體進行6次上下重覆作業後，經由熱 風之80℃之乾燥機內，使擠壓成形體進行乾燥1小時後，判定是否出現龜裂。
觀察乾燥後是否產生龜裂，記載於表1。將乾燥品置入燒結爐，於500℃下維持3小時，實施脫黏合劑之後，使氧化鋁於1650℃下維持3小時，使碳化矽於氬等不活性氛圍下，2100℃維持3小時，使其他材料於氧化鎂之耐火盒中置入乾燥品，於1400℃下維持3小時，進行燒結。以「有」、「無」評定燒結品中之龜裂狀態，記載於表1。
(1)陶瓷材料
鋁陶瓷：AL-160，昭和輕金屬(股份)製
謹青石陶瓷：AF-2，丸Su釉藥(資)製
碳化矽：GP-1000，信濃電氣精鍊(股份)製
鈦酸鋇：YT-51，共立窰業原料(股份)製
鈦酸鋯酸鉛：PE-60A，富士鈦工業(股份)製
鈦酸鋁：Rekodit A、Orcella(股份)製
(2)水溶性纖維素醚 [1]羥丙基甲基纖維素
(甲氧基=29質量%，羥基丙氧基=9質量%，20℃，2質量%水溶液黏度：4000mPa．s，BL型黏度計No.3滾輥，12rpm下進行測定)
[2]羥丙基甲基纖維素
(甲氧基=28質量%，羥基丙氧基=6質量%，20℃，2質量%水溶液黏度：4000mPa．s，BL型黏度計No.3滾輥，12rpm下進行測定)
[3]羥丙基甲基纖維素
(甲氧基=29質量%，羥基丙氧基=9質量%，20℃，2質量%水溶液黏度：10000mPa．s，BL型黏度計No.4滾輥，30rpm下進行測定)
[4]羥丙基甲基纖維素
(甲氧基=28質量%，羥基丙氧基=6質量%，20℃，2質量%水溶液黏度：15000mPa．s，BL型黏度計No.4滾輥，30rpm下進行測定)
[5]羥丙基甲基纖維素
(甲氧基=29質量%，羥基丙氧基=9質量%，20℃，2質量%水溶液黏度：30000mPa．s，BL型黏度計No.4滾輥，12rpm下進行測定)
[6]羥丙基甲基纖維素
(甲氧基=28質量%，羥基丙氧基=6質量%，20℃，2質量%水溶液黏度：75000mPa．s，BL型黏度計No.4滾輥，6rpm下進行測定)
[7]羥丙基甲基纖維素
(甲氧基=23質量%，羥基丙氧基=7質量%，20℃，1質量%水溶液黏度：100000mPa‧s，BL型黏度計No.4滾輥，3rpm下進行測定)
[8]甲基纖維素
(甲氧基=30.5質量%，20℃，2質量%水溶液黏度：8000mPa‧s，BL型黏度計No.4滾輥，30rpm下進行測定)
[9]羥乙基纖維素
(羥基乙氧基=54質量%，20℃，2質量%水溶液黏度：10000mPa‧s，BL型黏度計No.4滾輥，30rpm下進行測定)
(3)苯乙烯磺酸鹽
對苯乙烯磺酸鉀、和光純藥(股份)試藥一級
對苯乙烯磺酸鈉、和光純藥(股份)試藥一級

Claims (4)

  1. 一種陶瓷擠壓成形體用組成物，其特徵係含有陶瓷材料100質量份、黏度為4000~100000mPa．s之水溶性纖維素醚1~15質量份、選自對苯乙烯磺酸鉀、對苯乙烯磺酸鈉、鄰苯乙烯磺酸鉀、鄰苯乙烯磺酸鈉、間苯乙烯磺酸鉀、間苯乙烯磺酸鈉之苯乙烯磺酸鹽1~15質量份及水10~50質量份。
  2. 如申請專利範圍第1項之陶瓷擠壓成形體用組成物，其中該陶瓷材料係選自謹青石陶瓷、碳化矽、鈦酸鋇、鈦酸鋯酸鉛、鈦酸鋁。
  3. 如申請專利範圍第1項或第2項之陶瓷擠壓成形體用組成物，其中該水溶性纖維素醚係選自烷基纖維素、羥烷基纖維素、羥烷基烷基纖維素。
  4. 一種陶瓷擠壓成形體之製造方法，其特徵係使申請專利範圍第1項或第2項之陶瓷擠壓成形體用組成物進行混煉，擠壓成形後，乾燥及燒成。
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