TWI649196B - 具有導電及抗脫層性質之複合材料 - Google Patents
具有導電及抗脫層性質之複合材料 Download PDFInfo
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- TWI649196B TWI649196B TW103142649A TW103142649A TWI649196B TW I649196 B TWI649196 B TW I649196B TW 103142649 A TW103142649 A TW 103142649A TW 103142649 A TW103142649 A TW 103142649A TW I649196 B TWI649196 B TW I649196B
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Abstract
本文提供可用於需要高機械性能及高導電率二者之應用中之可固化複合材料。該可固化複合材料包括兩個或更多個已經可固化基質樹脂浸沒或浸漬之強化纖維層及含有碳奈米材料(例如碳奈米管)及不可溶聚合韌化粒子之層間區域。該等碳奈米材料之大小與該等聚合韌化粒子相比顯著較小。該等聚合韌化粒子在該複合材料固化時實質上不溶於該基質樹脂中,且在固化後以離散粒子形式保留在該層間區域處。在某些實施例中,該等聚合韌化粒子係可溶脹粒子。本文亦揭示用於製造可固化複合材料及固化複合結構之方法。
Description
在航空工業中,將纖維強化聚合物複合物用於飛機之一級及二級結構中變得愈發普遍。複合結構傳統上係藉由將經樹脂浸漬之纖維狀強化物(稱為預浸體)之複數個層(或夾層)鋪疊於模具表面上、然後壓實及/或固化來製得。纖維強化聚合物複合物之優點包括高強度對重量比率、極佳耐疲勞性、抗腐蝕性及撓性,從而容許組成部分顯著減少,且減少對緊固件及接頭之需要。然而,將該等材料應用於現代飛機之一級及二級結構因基質樹脂之介電性質所致而呈現特殊挑戰。儘管在複合材料中使用碳纖維作為強化纖維可因其石墨性質而沿其縱向方向遞送一定程度之導電率,但複合材料中基質樹脂之介電性質會減小複合材料之總導電率。
業內期望提高纖維強化聚合物複合物之導電率以滿足對飛機之雷擊保護的要求且避免稱為「邊緣輝光」之現象,此對複合翼總成尤其重要。邊緣輝光現象自身表現為在具有足以成為油汽之潛在點火源之能量的複合蒙皮/翼樑總成中之亮輝光或火花。
此邊緣輝光現象可在雷擊事件期間、尤其在具有低z-方向導電率之複合壓層上出現。在雷擊事件期間,具有高強度電流之暫態電荷行進穿過蒙皮,且然後因連接兩個複合部分之緊固件進入翼子結構(例如結構翼樑或翼肋)。因此通常,在複合蒙皮/翼樑總成中,電流部分
在蒙皮上行進且部分穿過代表油箱之一個壁的翼樑。
電流自緊固件橫向穿過翼樑之毗鄰複合夾層,且往往因與樹脂基質相比較高之導電率而沿纖維行進。此路徑可在翼樑/翼肋帽緣產生典型的亮輝光或火花,彼等熟習此項技術者將其稱為「邊緣輝光」現象。
圖1展示在雷擊事件期間複合翼盒上可能的關鍵電流路徑。邊緣輝光現象在纖維強化物之夾層之間的樹脂具有高度抗性時出現更為關鍵,且因此電流往往不會在毗鄰夾層之間流動。若z-方向導電率過低,則可能在雷擊期間在夾層之間產生顯著電壓降,從而增加邊緣輝光之風險。
如彼等熟習此項技術者已知,邊緣輝光現象與複合邊緣處之電子錶面彈射或電漿產生相關,且通常呈現為一類樹脂***。關於此現象之性質之不確定性已引起對雷擊事件期間油汽之點火能力的相當關注。
習用解決方案係在油箱處施加密封劑(參見圖2)。該油箱密封劑之實例係來自LE JOINT FRANCAIS之PR 1776 B類密封劑。然而,該方法會導致額外重量,且因缺乏標準化且難以用於密封劑應用中而並不始終有效。隨時間流逝,密封劑因老化而變得無效,或可被箱中之燃油完全洗滌掉。另外,雷擊可在切割邊緣處產生可能破壞邊緣密封之高壓氣體。業內仍需要可解決上文所論述之邊緣輝光問題、同時提供諸如抗衝擊及脫層等良好機械性質之多功能複合材料。
本文揭示具有導電性及抗衝擊性質之複合材料。該等複合材料在毗鄰強化物纖維層之間之層間區域含有聚合韌化粒子及基於碳之奈米級結構。聚合韌化粒子在複合材料固化期間實質上不溶於層間區域處之熱固性基質樹脂中,且以離散粒子形式保留在固化複合材料之層
間區域處。
20‧‧‧可固化複合材料
20a‧‧‧層間區域
20b‧‧‧層間區域
21‧‧‧強化纖維層
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24a‧‧‧層間樹脂
24b‧‧‧層間樹脂
25‧‧‧碳奈米材料
26‧‧‧聚合韌化粒子
31‧‧‧樹脂膜
32‧‧‧樹脂膜
33‧‧‧纖維層
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35‧‧‧膜
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40‧‧‧可固化複合材料
40a‧‧‧層間區域
40b‧‧‧層間區域
41‧‧‧強化纖維層
42‧‧‧強化纖維層
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45‧‧‧碳奈米材料
46‧‧‧聚合韌化粒子
51‧‧‧樹脂膜
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圖1展示在雷擊事件期間產生「邊緣輝光」現象之複合翼盒上之典型電流路徑。
圖2展示在複合翼之典型構築之翼樑帽緣處施加之密封劑。
圖3示意性圖解說明根據本發明實施例之具有含有韌化粒子及碳奈米材料之層間區域的可固化複合材料。
圖4示意性圖解說明根據本發明之另一實施例之具有含有均勻分散於基質中之韌化粒子及碳奈米材料之層間區域的可固化複合材料。
圖5及圖6圖解說明根據一實施例之製造複合材料之方法。
圖7及圖8圖解說明根據本發明之另一實施例之製造複合材料之方法。
圖9A及9B展示經碳奈米管(CNT)改質之複合壓層對未經改質之複合壓層之彼等的機械性質。
圖10A及10B展示不同聚合韌化粒子對經CNT改質之複合材料之機械性質的效應。
圖11展示含有CNT及聚鄰苯二甲醯胺粒子之固化壓層(4b)之橫截面的顯微照片影像。
圖12展示含有CNT及芳香族聚醯亞胺粒子之固化壓層(4a)之橫截面的顯微照片影像。
圖13展示不同聚合韌化粒子對經CNT改質之複合壓層之z-方向DC導電率及對未經CNT改質之彼等的效應。
在航空工業中公認,飛機複合結構之兩種主要的設計驅動劑係其對特定衝擊事件之抗性及其對衝擊後由損壞傳播引起之災難性故障的耐受性。
複合壓層之層間區域呈現一種最具挑戰的故障機制。該複合壓層之脫層係複合材料之重要故障模式。脫層出現在兩個彼此脫黏合之層壓層。重要設計限制要素包括起始脫層所需之能量及傳播其所需之能量。
改良複合結構、尤其飛機一級結構之抗衝擊性能之需要已觸發經層間粒子韌化之複合材料之新產生的研發。該技術解決方案提供針對碳纖維強化複合物之高抗衝擊性,且亦產生毗鄰夾層之間之電絕緣層間區域,從而顯著降低尤其z-方向上之複合結構之總導電率。「z-方向」係指與將強化纖維配置在複合結構中之平面或穿過複合結構厚度之軸正交之方向。
複合材料之導電率可藉由將不同的導電材料(例如導電粒子)納入纖維強化聚合物複合物之基質樹脂中或多層複合結構(例如預浸體積層)之層間區域中來改良。例如,可在高負載下添加金屬填充劑以提高樹脂導電率,但此引起顯著的重量增加及抗衝擊相關性質(例如衝擊後壓縮強度(CAI)以及模式I及II之斷裂韌度(GIc及GIIc))降低。因此,最新解決方案在於可改良複合物之z-方向導電率但並不同時改良其機械性能。具有經改良衝擊性能之固化複合物(例如預浸體積層)係具有經改良之CAI及斷裂韌度(GIc及GIIc)者。CAI量測複合材料耐受損壞之能力。在用於量測CAI之測試中,使固化複合物經歷給定能量之衝擊且然後在壓縮中負載。在衝擊後及壓縮測試之前量測損壞面積及凹痕深度。在此測試期間,認為複合材料確保不發生彈性不穩定性且記錄複合材料之強度。
斷裂韌度係闡述含有裂縫之材料抵抗斷裂之能力之性質,且係用於航空應用之材料之最重要性質之一。斷裂韌度係表示在存在裂縫時材料之抗脆性斷裂性之定量方式。
可將斷裂韌度量化為應變能釋放率(Gc),其係每單位新產生之斷
裂表面積在斷裂期間所耗散之能量。Gc包括GIc(模式1-開口模式)或GIIc(模式II-呈平面剪切形式)。下標「Ic」表示在垂直於裂縫之正常拉伸應力下形成之模式I裂縫開口,且下標「IIc」表示藉由平行於裂縫之平面且垂直於裂縫前端起作用之剪切應力產生之模式II裂縫。脫層之起始及生長通常係藉由檢查模式I及模式II斷裂韌度來確定。
已發現,在多層複合材料之層間區域處組合碳奈米材料與某些聚合粒子會產生包括改良z-方向導電率、且同時改良CAI及GIc的協同效應。該協同效應係藉由組合碳奈米材料之正效應與韌化粒子之正效應而發現,其中複合材料中之該等組份之相互作用產生大於其個別效應總和之效應。
本文揭示可固化多功能複合材料,其可成功地用於彼等需要高機械性能及高導電率之飛機應用中。在固化狀態下,複合材料經改良之導電率可發揮在自複合材料製造之複合結構之較大面積內擴散或耗散電流(例如由雷擊產生之彼等)之功能,由此降低災難性損壞複合結構之局部部分的可能性。因此,使用此多功能複合材料可係用於減輕雷擊之直接效應並防止上文所論述複合物之邊緣輝光現象之有效解決方案。另外,固化複合材料提供電磁屏蔽之其他益處。
本發明之一態樣係關於由兩個或更多個已經可固化基質樹脂、較佳熱固性樹脂浸沒或浸漬之強化纖維層構成之可固化複合材料。毗鄰強化纖維層之間之層間區域含有碳奈米材料分散於整個基質樹脂中且聚合韌化粒子包埋於相同基質樹脂中之可固化基質樹脂。碳奈米材料之大小與聚合韌化粒子相比顯著較小。聚合韌化粒子在複合材料固化時實質上不溶於基質樹脂中,且在固化後以離散粒子形式保留在層間區域處。在某些實施例中,聚合韌化粒子係可溶脹粒子。層間區域較佳不含在固化時溶解於基質樹脂中之任何可溶性熱塑性粒子。
層間區域處之樹脂(不含奈米材料及韌化粒子)可與浸漬強化纖維
之基質樹脂相同或不同。在一些實施例中,浸漬強化纖維之基質樹脂亦含有分散於其中之碳奈米材料。
圖3示意性圖解說明根據本發明實施例之可固化複合材料20。複合材料20含有在已經可固化基質樹脂浸沒或浸漬之強化纖維層21、22、23之間形成之層間區域20a及20b。層間區域20a及20b中之每一者皆含有碳奈米材料25分散於其中且聚合韌化粒子26包埋於相同基質樹脂中之可固化基質樹脂(分別為24a、24b)。層間樹脂24a及24b之樹脂組成(不含奈米材料及韌化粒子)可與浸漬纖維層21、22、23之基質樹脂組成相似或不同。當層間樹脂(24a、24b)與浸漬纖維層21、22、23之基質樹脂相似時,樹脂基質通常含有一或多種熱固性樹脂。聚合韌化粒子26可並排定位,且一起形成單粒子層。以此方式,藉由粒徑來確定層間區域之深度。較佳地,韌化粒子26之大小相似(例如,球形粒子具有大致相同之直徑),且層間區域之深度大致等於或稍大於韌化粒子26之平均直徑。
圖4示意性圖解說明根據本發明之另一實施例之可固化複合材料40。複合材料40含有在強化纖維層41、42、43之間形成之層間區域40a及40b,且該等層間區域含有聚合韌化粒子46。強化纖維(41、42、43)及聚合粒子46浸沒有含有分散於其中之碳奈米材料45之可固化基質樹脂或包埋於該可固化基質樹脂中。如在圖3所展示之實施例中,聚合粒子46可並排定位,且一起形成單粒子層。另外,層間區域之深度可藉由粒徑來確定。較佳地,韌化粒子46之大小相似(例如,球形粒子具有大致相同之直徑),且層間區域之深度大致大於或稍大於韌化粒子46之平均直徑。
固化時,根據本文所揭示實施例之固化複合材料具有以下性質:如在DC條件下根據4-探針測試方法所量測的z-方向導電率大於1S/m(西門子/米),如根據ASTM7136/37所量測的在30J衝擊後之CAI大
於250MPa,及如根據EN6033所量測的模式I層間斷裂韌度(GIc)大於300)/m2。
如本文所使用之術語「碳奈米材料」或基於碳之奈米級結構係指具有至少一個小於約0.1微米(<100奈米)之尺寸且全部或大部分由在分子級上以五邊形或六邊形或二者配置之碳原子構成的材料。
碳奈米級結構可具有50:1至5000:1之縱橫比。如本文所使用之術語「縱橫比」係指3維本體之最長尺寸對最短尺寸之比率。此術語適用於任何形狀及大小之結構。當此術語用於球形或大體球形粒子時,相關比率將係球形本體之最大橫截面直徑對最小橫截面直徑的比率。作為實例,完美球形粒子將具有1:1之縱橫比。
適用於本文預期目的之碳奈米級結構包括(但不限於)碳奈米管、碳奈米纖維、碳奈米索、碳奈米帶、碳奈米纖絲、碳奈米針、碳奈米薄片、碳奈米棒、碳奈米錐、碳奈米捲(捲狀形狀)及碳奈米歐姆、碳黑、石墨奈米微片或奈米點、石墨烯及其他類型之富勒烯(fullerene)材料。該等富勒烯材料中之任一者可具有部分或全部金屬塗層。奈米粒子可具有任何適宜的三維形狀,包括例如球形、橢圓形、球狀、盤狀、樹突狀、棒、圓盤、長方體或多面體。
較佳碳奈米材料係碳奈米管(CNT)。通常,CNT係具有介於0.4nm至約100nm範圍內之外徑之管狀鏈狀結構,較佳地,外徑小於50nm,且更佳小於25nm。
CNT可具有任何對掌性。涵蓋扶手椅型奈米管。另外,CNT可係半導體奈米管或顯示導電性之任何其他類型。適宜CNT可包括單壁碳奈米管(SWCNT)、雙壁碳奈米管(DWCNT)及多壁碳奈米管(MWCNT)。較佳碳奈米材料係MWCNT。
用於本文預期目的之碳奈米材料可以佔複合材料中總樹脂含量
之0.1wt.%至10wt.%之範圍、較佳介於0.5wt.%至2wt.%之間、且更佳1wt.%至1,5wt.%之範圍存在。如本文所使用,「wt.%」係指重量百分比。
適用於本文目的之聚合韌化粒子包括熱塑性或彈性粒子。如先前所論述,適宜韌化粒子係在複合材料固化期間實質上不溶於該等複合材料之熱固性基質樹脂中、且在固化後以離散粒子形式保留之固化基質樹脂中之粒子。在某些實施例中,聚合韌化粒子在固化期間亦係複合材料之熱固性基質樹脂中之可溶脹粒子。另外,聚合韌化粒子不具諸如金屬等非聚合塗層。
韌化粒子較佳以基於含於複合材料中之總基質樹脂之重量為2%至20%、較佳介於5%至15%範圍內、且更佳介於5%至12%範圍內之含量均勻分散於在毗鄰強化纖維層之間形成的層間區域中。
聚合韌化粒子可具有任何三維形狀,但其較佳為大體球形。韌化粒子亦較佳具有小於5:1之縱橫比,較佳地,縱橫比為約1:1。提及韌化粒子之術語「縱橫比」係指粒子之最大橫截面尺寸對粒子之最小橫截面尺寸的比率。
對於球形粒子(縱橫比為約1:1),平均粒徑係指其直徑。對於非球形粒子,平均粒徑係指粒子之最大橫截面尺寸。
出於本文所揭示之目的,聚合韌化粒子可具有小於100μm、較佳介於50μm-90μm、更佳10μm-40μm範圍內之平均粒徑(d50),如使用例如在0.002奈米至2000微米範圍內操作之Malvern Mastersizer 2000藉由雷射繞射技術所量測。
「d50」表示粒徑分佈之中值,或另一選擇為使得50%的粒子具有此值或更小之粒徑的分佈之值。
另外,聚合韌化粒子之大小與碳奈米結構相比較大。聚合韌化
粒子之平均粒徑(d50)較佳係碳奈米結構之最小尺寸的至少100倍。
作為實例,當碳奈米結構係碳奈米管時,韌化粒子之平均粒徑(d50)係碳奈米管直徑的至少100倍。
確定某些粒子不可溶抑或可溶係與粒子在其所駐留之具體樹脂系統中之溶解度相關。樹脂系統可包括一或多種熱固性樹脂、固化劑及/或觸媒以及最小量之用於改質未固化或固化基質樹脂之性質的可選添加劑。
可使用熱台顯微術來確定粒子在樹脂系統中為不可溶、部分可溶抑或可溶脹。首先,藉由顯微術來表徵乾燥聚合粒子(其未與樹脂合併)之樣品且使用來自國家健康研究院(National Institutes of Health,Bethesda,Maryland,USA)之ImageJ軟體分析影像以確定平均粒徑及體積。其次,經由機械混合使粒子之樣品分散於期望基質樹脂中。再次,將所得混合物之樣品置於顯微鏡載玻片上,然後將該載玻片置於顯微鏡下之熱台設置中。然後,以期望斜坡速率將樣品加熱至期望固化溫度,且在10幀/秒下連續記錄粒子之大小、體積或形狀之任何變化。對於球形粒子通常量測直徑,而在非球形粒子之情形下量測最長邊,以使用ImageJ軟體確定大小及體積之變化。所有熱台測試皆可在不含固化劑或觸媒之基質樹脂中10wt.%之粒子負載下實施。
當使韌化粒子經歷上述熱台顯微術分析且與初始「乾燥」粒子相比粒子直徑或體積之變化為0或小於5%時,則認為粒子不可溶且不可溶脹。當所韌化粒子經歷上述熱台顯微術分析且粒子直徑或體積增加5%以上時,則認為粒子「可溶脹」且不可溶。溶脹係由周圍樹脂浸沒於粒子之外表面中所引起。
在一些實施例中,不可溶粒子包括在熱台顯微術分析期間熔融、但與基質樹脂不相容、且因此在冷卻時再形成離散粒子之粒子。僅出於分析之目的,不可溶粒子可在熱台顯微術分析期間流動且亦可
改變結晶度。
在可能難以測定直徑或體積之情形下,可使用替代分析。可根據固化方案製造自單向預浸帶製得且含有基於富含樹脂之層間區域中總基質樹脂之重量為10%之粒子負載的16層準各向同性複合板,且然後沿橫截面切割固化板以藉由顯微術來評估。若粒子在固化後保留為可辨別之離散粒子,則認為粒子係不可溶粒子。若粒子完全溶解於層間區域及纖維床周圍之基質中且在冷卻時不可辨別為離散粒子,則認為粒子並非不可溶層間粒子。
對於基於環氧化物之基質樹脂,不可溶聚合粒子之組合物可含有至少一種選自以下各項之聚合物:聚醯胺醯亞胺(PAl)、脂肪族聚醯胺(PA)、聚鄰苯二甲醯胺(PPA)、聚芳基醚酮(PAEK)(例如聚醚醚酮(PEEK)及聚醚酮酮(PEKK))、聚苯硫(PPS)、液晶聚合物(LCP)、其共聚物及其衍生物。在一些實施例中,聚合粒子之組合物含有至少一種選自以下各項之彈性聚合物或材料:交聯聚丁二烯、聚丙烯酸、聚丙烯腈、聚苯乙烯、其共聚物及其衍生物(例如由Zeon Chemicals公司出售之DuoMod DP5045)。
在較佳實施例中,不可溶粒子係在固化製程期間不溶且保留在固化複合材料之層間區域內之不可溶熱塑性粒子。適宜不可溶熱塑性粒子之實例包括在其固化週期期間不溶於環氧樹脂系統中之聚醯胺醯亞胺(PAl)粒子及聚醯胺(PA)粒子(例如耐綸(nylon))或聚鄰苯二甲醯胺(PPA)粒子。
某些等級之聚醯亞胺粒子可能適宜作為不可溶韌化粒子。例如,自二苯甲酮四甲酸二酐(BTDA)、4,4'-亞甲基雙苯胺(MDA)及2,4-甲苯二胺(TDA)製備、及具有含有介於90%與92%之間之芳香族碳的非鄰苯二甲醯亞胺碳含量之聚醯亞胺。
已發現不可溶熱塑性粒子可有效地作為避免熱/潤濕性能損失之
層間韌化劑。由於該等熱塑性粒子即使在固化後仍不溶於基質樹脂中,故其賦予經改良之韌度、損壞耐受性、熱/潤濕性能、處理、抗微裂性及對固化樹脂降低的溶劑敏感性。
製造本文所述不可溶粒子之方法可包括呈任何順序之乳化、沈澱、乳液聚合、洗滌、乾燥、擠出、研磨、磨碎、冷凍磨碎、噴射研磨及/或篩分粒子。彼等熟習此項技術者應瞭解,該等步驟可藉由多種業內已知方法中之任一者來達成。
用於本文預期目的之不可溶粒子包括交聯熱塑性粒子。根據一實施例,交聯熱塑性粒子係由藉由使一或多種具有一或多個反應性基團之可交聯熱塑性聚合物與對反應性基團具有化學反應性之交聯劑反應產生之交聯網絡構成,其中該交聯劑使聚合物鏈經由反應性基團直接彼此交聯。反應性基團可係聚合物骨架上之端基或側基。此實施例之直接交聯反應可闡述為經由使用一或多個反應性基團直接交聯聚合物鏈來「綁住」聚合物分子。
上述交聯熱塑性粒子可藉由如於2010年12月2日公開之美國專利申請與公開案第2010/0304118號中所闡述之製程來製造,該公開案以引用方式併入本文中。此方法包括將具有反應性官能基之熱塑性聚合物、交聯劑及觸媒溶解於與水不可混溶之常見溶劑中。然後在水中藉由使用非離子表面活性劑產生乳液,藉此形成乳化粒子。隨後將乳化粒子乾燥且固化以使得聚合鏈可以化學方式交聯。反應條件及交聯劑類型將決定粒子之最終性質。反應條件(例如溫度)引起較強交聯。具有兩個或更多個反應性位點(即官能基)之交聯劑較佳。所得交聯熱塑性粒子係可添加至可固化樹脂中之自由移動之離散粒子。
帶有易於交聯之反應性基團之適宜熱塑性聚合物的實例包括(但不限於)以下各項中之一或多者:聚醚、聚碳酸酯、聚醚醯亞胺(PEl)、聚醯胺、聚醯亞胺、聚碸、聚醚碸(PES)、聚苯醚(PPO)、聚醚
酮、聚芳基醚酮(PAEK)(例如聚醚醚酮(PEEK)及聚醚酮酮(PEKK))、聚苯硫醚(PPS)、聚羥基醚、苯乙烯-丁二烯、聚丙烯酸酯、聚縮醛、聚對苯二甲酸丁二酯、聚醯胺-醯亞胺、聚醚醚碸(PEES)、其摻合物或其共聚物、PES均聚物(例如來自Sumitomo Chemical公司之SUMIKAEXCEL 5003P或來自Solvay之Radel® PES)或PEES均聚物。PES共聚物之特定實例包括具有不同重複單元比率之PES/PEES共聚物。上文所列示之熱塑性塑膠可作為單一組份用於形成粒子,或當使用一種以上之熱塑性聚合物時,形成雜合結構或雜合粒子。
在其他實施例中,交聯粒子係自熱塑性聚合物之摻合物形成。在其他實施例中,本文所述之交聯粒子可自其中使用兩種或更多種熱塑性聚合物之雜合結構形成。
可交聯熱塑性聚合物上之反應性基團可係以下各項中之一或多者:胺;羥基;酸酐;縮水甘油基;羧酸;馬來醯亞胺;異氰酸酯;酚;納迪克醯亞胺(nadimide);氰酸酯;乙炔;乙烯基;乙烯基酯;二烯;或其衍生物。在一些情形下,聚合物鏈上之不飽和可用作交聯點(用於丙烯酸及甲基丙烯酸家族以及一些不飽和橡膠、乙烯基酯或不飽和聚酯)。反應性基團之數量可係每條鏈上一種反應性基團之最小值,且在一些實施例中視為產生經連接聚合物骨架所需之最小分率;約等於或大於1之數值較佳以產生緊密交聯之聚合物或互穿網絡。官能基大於2之聚合物容易製造高度反應性凝膠。
端視熱塑性聚合物之端基/官能基之化學性質,可選擇具有多個反應性位點之適宜多功能交聯劑。該等交聯劑之實例係:烷基化三聚氰胺衍生物(例如CYMEL® 303)、醯氯(例如1,3,5苯三甲醯氯)、多官能基環氧化物(例如ARALDLTE® MY0500、MY721)、羧酸(例如苯四甲酸)。
在另一實施例中,交聯粒子係由與獨立交聯網絡纏結在一起之
熱塑性聚合物鏈構成之互穿聚合物網絡(IPN)構成。IPN係藉由在熱塑性聚合物存在下使一或多種具有一或多個反應性基團之化合物(例如可交聯單體或聚合物)與對反應性基團具有化學反應性之交聯劑反應來產生。該反應(其在某些交聯或固化條件下發生)使得化合物經由反應性基團交聯,由此形成獨立的交聯網絡。因此,將熱塑性聚合物鏈與獨立交聯網絡在分子層面上纏結在一起形成IPN。此方式可闡述為經由形成單獨且獨立的交聯網絡「綁住」熱塑性聚合物鏈,由此產生互穿網絡。因此,在此實施例中,熱塑性聚合物上無需具有反應性基團。此類型之交聯粒子可藉由於2010年12月2日公開之美國專利申請與公開案第2010/0305239號中所闡述之製程來製造,該公開案以引用方式併入本文中。所得交聯熱塑性粒子係可添加至可固化樹脂中之離散粒子。
作為實例,具有IPN之交聯粒子可藉由以下方式來製造:(i)形成含有熱塑性聚合物、多功能環氧樹脂及能夠交聯環氧樹脂之胺固化劑之乳液;(ii)自乳液移除溶劑且收集呈固體粒子形式之濃縮物;(iii)乾燥粒子、然後固化(例如藉由加熱),以使得環氧樹脂變得交聯。由於固化,交聯環氧化物在每一粒子中形成含有熱塑性聚合物之IPN。
某些可溶脹交聯熱塑性粒子尤其適宜作為層間韌化粒子。該等交聯熱塑性粒子在固化期間在基於環氧化物之樹脂系統中溶脹,但以離散粒子形式保留在為固化樹脂中。溶脹係由周圍樹脂浸沒於粒子之外表面中所引起。
該等可溶脹交聯熱塑性粒子亦與其在固化期間所駐留之周圍基質樹脂形成「梯度界面」。如本文所使用之術語「梯度界面」係指介於每一粒子與周圍基質樹脂之間之強過渡界面。梯度界面係藉由使用經改造在熱力學上與熱固性樹脂(例如環氧化物)相容之交聯熱塑性粒
子來達成。交聯熱塑性粒子核心中熱塑性聚合物之濃度在中心處最大且朝向粒子之外表面逐漸減小,此乃因基質樹脂自外表面進入粒子且朝向核心移動。此熱塑性粒子之自核心至外表面之熱塑性濃度逐漸減小在每一熱塑性粒子與周圍基質樹脂之間形成梯度界面。因此,在熱固性樹脂與熱塑性粒子之間不存在清晰描繪或轉化。若存在清晰描繪或轉化,在複合材料中介於熱塑性與熱固性樹脂之間之界面與含有梯度界面之複合材料相比弱得多。因此,認為該等交聯熱塑性粒子「可溶脹」,此乃因在加熱樹脂且其黏度降低時圍繞粒子之樹脂通過粒子之外表面擴散至粒子中,由此增加粒徑。然而,交聯粒子在樹脂固化後保留為離散及可辨別粒子。
本文所闡述之交聯熱塑性粒子係可添加至熱固性樹脂(例如基於環氧化物之樹脂)中之自由移動之離散粒子(即呈分開狀態),且其在化學上交聯以防止其在樹脂之固化週期期間完全溶解於樹脂中。另外,其經設計以在熱力學上與熱固性樹脂相容。
如本文所使用之「離散粒子」係指在基質樹脂中可辨別、且可藉由使用掃描電子顯微術(SEM)、光學顯微術或干涉相位差顯微術(DIC)檢測之粒子。
用於浸漬/浸沒強化纖維之可固化基質樹脂(或樹脂組合物)較佳係含有一或多種包括(但不限於)以下各項之未固化熱固性樹脂的可硬化或熱固性樹脂:環氧樹脂、醯亞胺(例如聚醯亞胺或雙馬來醯亞胺)、乙烯基酯樹脂、氰酸酯樹脂、經異氰酸酯改質之環氧樹脂、酚醛樹脂、呋喃樹脂、苯并噁、甲醛縮合樹脂(例如與脲、三聚氰胺或酚)、聚酯、丙烯酸、雜合物、摻合物及其組合。
適宜環氧樹脂包括芳香族二胺、芳香族單一級胺、胺基酚、多元酚、多元醇、多羧酸之聚縮水甘油基衍生物。適宜環氧樹脂之實例
包括雙酚(例如雙酚A、雙酚F、雙酚S及雙酚K)之聚縮水甘油醚;及基於甲酚及苯酚之聚縮水甘油醚之酚醛樹脂。
特定實例係4,4’-二胺基二苯基甲烷之四縮水甘油基衍生物(TGDDM)、間苯二酚二縮水甘油醚、三縮水甘油基-對-胺基酚、三縮水甘油基-間-胺基酚、溴雙酚F二縮水甘油醚、二胺基二苯基甲烷之四縮水甘油基衍生物、三羥基苯基甲烷三縮水甘油醚、苯酚-甲醛之聚縮水甘油醚酚醛樹脂、鄰-甲酚之聚縮水甘油基醚酚醛樹脂或四苯基乙烷之四縮水甘油醚。
適用於主體基質樹脂中之市售環氧樹脂包括N,N,N',N'-四縮水甘油基二胺基二苯基甲烷(例如來自Huntsman之MY 9663、MY 720及MY 721);N,N,N',N'-四縮水甘油基-雙(4-胺基苯基)-1,4-二異-丙苯(例如來自Momentive之EPON 1071);N,N,N',N'-四縮水甘油基-雙(4-胺基-3,5-二甲基苯基)-1,4-二異丙苯(例如來自Momentive之EPON 1072);對-胺基酚之三縮水甘油醚(例如來自Hunstman之MY 0510);間-胺基酚之三縮水甘油醚(例如來自Hunstman之MY 0610);基於雙酚A之二縮水甘油醚之材料,例如2,2-雙(4,4'-二羥基苯基)丙烷(例如來自Dow之DER 661或來自Momentive之EPON 828及較佳在25℃下黏度為8-20Pa.s之酚醛樹脂);苯酚之縮水甘油醚酚醛樹脂(例如來自Dow之DEN 431或DEN 438);基於二-環戊二烯之苯酚酚醛樹脂(例如來自Huntsman之Tactix 556);1,2-鄰苯二甲酸二縮水甘油酯(例如GLY CEL A-100);二羥基二苯基甲烷(雙酚F)之二縮水甘油基衍生物(例如來自Huntsman之PY 306)。其他環氧樹脂包括環脂肪族化合物,例如3',4'-環氧基環己基-3,4-環氧基環己烷甲酸酯(例如來自Huntsman之CY 179)。
通常,可固化基質樹脂含有一或多種熱固性樹脂與其他添加劑之組合,該等添加劑係(例如)固化劑、固化觸媒、共單體、流變控制劑、增黏劑、無機或有機填充劑、熱塑性或彈性聚合物作為韌化劑、
穩定劑、抑制劑、顏料、染料、阻燃劑、反應性稀釋劑及彼等熟習此項技術者熟知用於在固化之前或之後改質基質樹脂之性質的其他添加劑。
適用於可固化樹脂組合物之韌化劑包括(但不限於)單獨或以下各項之組合的均聚物或共聚物:聚醯胺、共聚醯胺、聚醯亞胺、聚芳醯胺、聚酮、聚醚醯亞胺(PEI)、聚醚酮(PEK)、聚醚酮酮(PEKK)、聚醚醚酮(PEEK)、聚醚碸(PES)、聚醚醚碸(PEES)、聚酯、聚胺基甲酸酯、聚碸、聚硫化物、聚苯醚(PPO)及經改質PPO、聚(環氧乙烷)(PEO)及聚環氧丙烷、聚苯乙烯、聚丁二烯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸、聚苯基碸、高性能烴聚合物、液晶聚合物、彈性物及分段彈性物。
在可固化基質樹脂中添加固化劑及/或觸媒係可選的,但若需要,可使用此提高固化速率及/或降低固化溫度。固化劑係適宜地選自已知固化劑,例如芳香族或脂肪族胺或胍衍生物。芳香族胺固化劑較佳,較佳每分子具有至少兩個胺基之芳香族胺,且尤佳者係例如其中胺基處於碸基團之間位或對位之二胺基二苯基碸。具體實例係3,3'-及4-,4'-二胺基二苯基碸(DDS);亞甲基雙苯胺;雙(4-胺基-3,5-二甲基苯基)-1,4-二異丙苯;雙(4-胺基苯基)-1,4-二異丙苯;4,4’亞甲基雙-(2,6-二乙基)-苯胺(來自Lonza之MDEA);4,4’亞甲基雙-(3-氯,2,6-二乙基)-苯胺(來自Lonza之MCDEA);4,4’亞甲基雙-(2,6-二異丙基)-苯胺(來自Lonza之M-DIPA);3,5-二乙基甲苯-2,4/2,6-二胺(來自Lonza之D-ETDA 80);4,4’亞甲基雙-(2-異丙基-6-甲基)-苯胺(來自Lonza之M-MIPA);4-氯苯基-N,N-二甲基-脲(例如Monuron);3,4-二氯苯基-N,N-二甲基-脲(例如DIURON TM)及二氰基二醯胺(例如來自Pacific Anchor Chemical之AMICURE TM CG 1200)。
適宜固化劑亦包括酸酐,尤其聚羧酸酐,例如納迪克酸酐、甲
基納迪克酸酐、鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、內亞甲基四氫鄰苯二甲酸酐及偏苯三甲酸酐。
層間區域處之可固化基質樹脂亦係含有一或多種上文所論述類型之未固化熱固性樹脂之可硬化或熱固性樹脂。在某些實施例中,層間區域處之可固化基質樹脂與含有強化纖維之區域中之基質樹脂相同。在其他實施例中,層間區域處之樹脂與含有強化纖維之區域中之基質樹脂不同。
為製造高性能複合材料及預浸體,適宜強化纖維係(但不限於)具有高拉伸強度、較佳大於500ksi(或3447MPa)之纖維。可用於此目的之纖維包括碳或石墨纖維、玻璃纖維及自碳化矽、氧化鋁、硼、石英及諸如此類形成之纖維以及自有機聚合物(例如聚烯烴、聚(苯并噻唑)、聚(苯并咪唑)、聚芳酯、聚(苯并噁唑)、芳香族聚醯胺、聚芳基醚及諸如此類)形成之纖維,且可包括具有兩種或更多種該等纖維之混合物。較佳地,纖維係選自玻璃纖維、碳纖維及芳香族聚醯胺纖維,例如由DuPont公司以商品名KEVLAR出售之纖維。強化纖維可以由多個長絲構成之不連續或連續絲束形式、以連續單向或多向帶或以織造、非褶皺或非織造織物來使用。織造形式可選自平坦、緞紋或斜紋織物式樣。非褶皺織物可具有多個夾層及纖維取向。
纖維可經定大小或未經定大小。纖維通常可以5重量%至35重量%、較佳至少20重量%之濃度添加。對於結構應用,例如玻璃或碳較佳尤其以30體積%至70體積%、更尤其50體積%至70體積%使用連續纖維。
根據一實施例,在浸漬強化纖維之前(即在預浸體製造之前)混合
特定量之碳奈米材料及聚合韌化粒子與可固化樹脂組合物。在此實施例中,樹脂膜係藉由以下方式來製造:首先將含有粒子之樹脂組合物塗覆於離型紙上。然後,藉助熱及壓力將該等樹脂膜中之一或兩者層壓至強化纖維層之一或兩側上以浸漬纖維,由此形成具有特定纖維面積重量及樹脂含量之纖維強化聚合物層(或預浸體夾層)。在層壓製程期間,韌化粒子被過濾出且因粒徑大於纖維長絲之間之間距的事實而保留在纖維層之外部。所得預浸體夾層含有毗鄰一或兩個其中包埋有聚合韌化粒子之基質樹脂層之結構性纖維強化層。隨後,當經由鋪疊製程將兩個或更多個其中含有韌化粒子之預浸體夾層彼此上下層壓時,韌化粒子位於兩個毗鄰纖維層之間之層間區域中。在此實施例中,層間區域處之基質樹脂(不含聚合韌化粒子)與含於結構性纖維強化層中之基質樹脂相同且含有均勻分散的碳奈米材料。
在第二實施例中,將不含碳奈米材料或聚合韌化粒子之可固化基質樹脂塗覆於離型紙上以形成樹脂膜。然後使此樹脂膜與纖維層之一側接觸。在施加壓力時,樹脂膜浸漬纖維且將極少或無樹脂留在纖維層之外表面上。隨後,將含有碳奈米材料及聚合韌化粒子之可固化樹脂之膜層壓至經樹脂浸漬之纖維層之所暴露外表面。攜載奈米材料及聚合韌化粒子之可固化樹脂可與浸漬強化纖維之基質樹脂相同或不同。因此,含有粒子之樹脂層保留在浸漬纖維層外部且並不進一步浸漬纖維。將複數個該等結構層壓在一起以形成碳奈米材料及聚合韌化粒子位於層間區域中之複合結構。
在第三實施例中,將含有碳奈米材料、但不含聚合韌化粒子之可固化基質樹脂塗覆於離型紙上以形成樹脂膜。然後使此樹脂膜與纖維層之一側接觸。在施加壓力時,樹脂膜浸漬纖維且將極少或無樹脂留在纖維層之外表面上。隨後,將含有碳奈米材料及聚合韌化粒子之可固化基質樹脂之膜層壓至經樹脂浸漬之纖維層之所暴露外表面。當
將複數個該等結構層壓在一起以形成複合結構時,使碳奈米材料均勻分散於含有強化纖維之層及含有韌化層間粒子之層間區域中。
在另一實施例中,如藉由圖5所圖解說明,將不含碳奈米材料或韌化層間粒子之可固化基質樹脂之兩個膜31、32層壓至纖維層33之兩個相對表面。樹脂膜31、32浸漬纖維且將極少或無樹脂留在纖維層之外表面上,從而產生經樹脂浸漬之纖維層34。隨後,使含有碳奈米材料及聚合韌化粒子之可固化基質樹脂之兩個膜35、36與經樹脂浸漬之纖維層34之相對表面接觸,如藉由圖6所圖解說明,以形成夾心結構。該方式往往在固化壓層中產生經明確界定且規則的層間區域。
在另一實施例中,如藉由圖7所圖解說明,將含有碳奈米材料、但不含聚合韌化粒子之可固化基質樹脂之兩個膜51、52層壓至纖維層53之兩個相對表面。樹脂膜51、52浸漬纖維且將極少或無樹脂留在纖維層之外表面上,從而產生經樹脂浸漬之纖維層54。隨後,使含有碳奈米材料及聚合韌化粒子之可固化基質樹脂之兩個膜55及56與經樹脂浸漬之纖維層54之相對表面接觸,如藉由圖8所圖解說明,以形成夾心結構。該方式往往提供井然有序之壓層及均勻分散於壓層中之碳奈米管。
如本文所使用之術語「預浸體」係指在至少一部分纖維體積內已經可固化樹脂組合物浸漬之纖維薄片或層。用於製造航空結構之預浸體通常係單向強化纖維(例如碳纖維)之經樹脂浸漬之薄片,其通常稱為「帶」或「單向帶」。預浸體可完全浸漬預浸體或部分浸漬預浸體。浸漬強化纖維之基質樹脂可呈部分固化或未固化狀態。
通常,預浸體係呈準備用於鋪疊且模製成三維構形、然後固化成最終複合部分/結構之柔韌或撓性形式。此類型之預浸體尤其適於製造帶有負載之結構性部分,例如飛機之翼、機身、隔框及控制表面。固化預浸體之重要性質在於高強度及勁度以及減小的重量。
為形成複合結構,可將複數個預浸體夾層以堆疊序列鋪疊於工具上以形成「預浸體積層」。積層內之預浸體夾層可位於針對彼此之所選取向上,例如0°、±45°、90°等。預浸體積層可藉由可包括(但不限於)以下各項之技術來製造:手工積層、自動化帶積層(ATL)、先進的纖維置放(AFP)及長絲纏繞。
本文所揭示複合材料或預浸體積層之固化通常係藉由以下方式來實施:在高達200℃、較佳介於170℃-190℃範圍內之升高溫度下及使用升高壓力以阻止逸出氣體之變形效應或阻止孔隙形成,適宜地在高達10巴(1MPa)、較佳介於3巴(0.3MPa)至7巴(0.7MPa)範圍內之壓力下。較佳地,固化溫度係藉由以至多5℃/min、例如2℃/min至3℃/min加熱來獲得且維持至多9h、較佳至多6h、例如2h至4h之所需時段。在基質樹脂中使用觸媒可容許甚至更低之固化溫度。自始至終釋放壓力,且藉由以至多5℃/min、例如至多3℃/min冷卻來降低溫度。可在介於190℃至350℃範圍內之溫度及常壓下採用適宜加熱速率實施後固化,以改良基質樹脂之玻璃轉化溫度。
本文所述組合物可用於製造鑄件或模製結構性材料,且尤其適於製造具有經改良體積導電率之帶有纖維強化負載或抗衝擊之複合結構。
本文所揭示之複合材料適於製造用於傳輸應用之組份,該等運輸應用包括航空、航天、航海及陸地運輸工具、汽車及鐵路。例如,複合材料可用於製造一級及二級飛機結構、空間及彈道結構。該等結構性組份包括複合翼結構。本文所揭示之複合材料亦發現在建造及建築應用以及其他商業應用中之效用。應注意,複合材料尤其適於製造帶有負載或抗衝擊之結構。
根據下文所闡述之方法來表徵所揭示組合物方法:
在橋接方法中藉助Burster-Resistomat 2316毫歐計量測與固化複合壓層表面正交之方向上之導電率,其將電阻值記錄為所施加電壓與電流之間之比率。使用克爾文測試探針來產生兩個樣品表面之間之接觸。所有量測皆係在室溫下在標準濕度條件下根據4線量測方法來實施。
對自根據EN 2565方法B製備之無缺陷準各向同性板提取的試樣實施量測。對約3mm厚之方形樣品進行表徵。
複合樣本表面係藉由以下方式來製備:移除富含樹脂之頂層以暴露下方之碳纖維,從而確保與電極直接接觸。然後使用商業銀膠來製造相對試樣表面上之兩個電極。
對每種材料測試最少5種樣品及積層。
根據以下等式計算DC導電率,以[S/m]表示:
其中:R係經量測之電阻[以歐姆表示];l係樣品厚度[以m表示];S係樣品表面積[以m2表示]
使用24層準各向同性壓層來測定30焦衝擊後之衝擊後壓縮(CAI)。在室溫下對自根據EN 2565方法B製備之無缺陷板提取之試樣實施量測,且在180℃下固化2小時。根據ASTM7136/37加工、衝擊並測試樣本。
使用經氟-乙烯聚合物(FEP)膜固化之16層單向壓層作為中間平面
處之裂縫起裂劑來測定模式I之層間斷裂韌度。在室溫下根據EN6033對自無缺陷板提取之試樣實施GIc量測。
根據表1中所展示之調配物來製備含有聚合韌化粒子(1a、1b、1c及1d)且不含聚合韌化粒子(對照1)之基質樹脂。所有量皆係以基於調配物重量之重量百分比(w/w%)來展示。
在表1中,Araldite® PY 306係自Huntsman購得之雙酚F二縮水甘油醚樹脂,Araldite® MY 0510係自Huntsman購得之對-胺基酚之三縮水甘油醚樹脂,且SUMIKAEXCEL 5003P係自Sumitomo Chemical公司購得之聚醚碸聚合物。粒子A係玻璃轉化溫度為約340℃且平均粒徑為40微米之芳香族聚醯亞胺,且係以商品名P84自Evonik出售。粒子B係熔點為約250℃且平均粒徑為35微米、以商品名Vestamid® TGP3551自Evonik出售之聚鄰苯二甲醯胺。粒子C係來自Cytec Industries公司之平均粒徑為25微米之可溶脹交聯PES-PEES粒子。粒
子D係由Evonik以商品名VESTOSINT® Z2649供應之平均粒徑為25微米之脂肪族耐綸粒子。
藉由將5003P分散於環氧化物成份中且在125℃下加熱約1小時以溶解5003P來製備基質。將所得混合物冷卻至80℃,且然後添加剩餘成份並充分混合。
然後使用樹脂組合物來製造不同的單向(UD)預浸體。使用表1中所揭示之每一可固化樹脂組合物藉由將樹脂組合物塗覆於離型紙上來製造樹脂膜。然後,藉助熱及壓力將該等樹脂膜中之兩者層壓至單向碳纖維(來自Toho Tenax,USA之IMS65E)之連續層之兩側上,以形成UD預浸體。每一所得預浸體皆具有197gsm之平均FAW(纖維面積重量)及基於總預浸體重量35% w/w之樹脂含量。根據上文所論述之EN2565方法自預浸體製備測試複合壓層。
使測試複合壓層經歷機械測試且結果展示於表2中。如表2中可見,與對照2(不含韌化粒子之基線)相比,在纖維層之間含有層間聚醯亞胺、聚鄰苯二甲醯胺、交聯PES-PEES或聚醯胺韌化粒子之固化複合壓層獲得損壞耐受性(30J下之CAI)及層間斷裂韌度(GIc)值之改良。
亦量測固化複合壓層之z-方向體積導電率且結果展示於表3中。
與表2之機械結果相反,若與不含經明確界定之層間區域之複合物(對照2)相比,在固化複合壓層中納入層間聚合韌化粒子獲得z-方向DC導電率之顯著減小。此減小主要歸因於聚合韌化粒子係介電性質。例如,與未經改質之基線(對照2)相比,將粒子C添加至基線系統中會使固化壓層2c之z-方向導電率減小幾乎一個數量級。
藉由分散1.35重量%與1.55重量%之間的碳純度>98%、平均直徑為15nm且平均長度為約1mm之多壁碳奈米管(MWCNT)來改質於實例1之表1中所揭示之相同可固化樹脂組合物。經MWCNT改質之樹脂組合物展示於表4中。所有量皆係以基於調配物重量之重量百分比(w/w%)來展示。
基於表4之調配物來製備可固化基質樹脂。然後根據實例1中所闡述之相同製造方法使用基質樹脂來製造UD碳纖維強化預浸體。每一預浸體皆具有197gsm之平均FAW及基於總預浸體重量35% w/w之樹脂含量。根據上文所論述之EN2565方法自預浸體製備測試複合壓層。
使測試複合壓層經歷機械測試且結果展示於表5中。表5中所報告之機械結果展示,與僅經MWCNT改質(對照4)或不具聚合韌化粒子(對照2)之原本相同之材料相比,在基質樹脂中引入聚合韌化粒子與MWCNT之組合可獲得CAI(在30J下)及GIc值之顯著改良。
人們認為兩種機械性質CAI[30J]及GIc之同時改良係MWCNT與聚合韌化粒子之間協同效應的結果。
圖9A及9B展示與未經改質之壓層(對照2)相比,將MWCNT添加至不含聚合韌化粒子之壓層(對照4)中不會獲得CAI及GIc性能之任何顯著改良。
圖10A及10B展示與不含MWCNT之相同壓層(壓層2a、2b、2c及2d)相比,在含有聚合韌化粒子之壓層(壓層4a、4b、4c及4d)中添加MWCNT產生較高之CAI及GIc值。
圖11係含有MWCNT及聚鄰苯二甲醯胺粒子(粒子B)之固化壓層4b之橫截面之顯微照片影像。如自圖11可見,將聚合粒子分散於富含樹脂之層中,以在纖維層之間產生經明確界定之延展性層間區域。
表6報告含有層間聚合粒子之經MWCNT改質之壓層(壓層4a、4b、4c及4d)及不含層間聚合粒子之壓層(對照4)的平均z方向導電率值。
觀察到添加在固化時可溶於基質樹脂(3a)之粒子A對z-方向導電率值具有中性效應。圖12係含有MWCNT及芳香族聚醯亞胺粒子(粒子A)之固化壓層4a之橫截面的顯微照片。
令人驚奇地,添加不可溶粒子(粒子B及D)及可溶脹粒子(粒子C)獲得優於僅經MWCNT改質之壓層(對照4)的電性能之電性能。此結果令人驚奇之原因在於,傳統上預期將絕緣元件添加至層間區域中實質上與不含MWCNT之相應壓層之情形一樣減小固化複合物之體積導電率(參見實例1、表3、壓層2a、2b、2c及2d)。該改良明顯係藉由將樹脂系統中之總MWCNT含量自1.55% w/w(對照3)降低至1.35% w/w(基質樹脂3b、3c及3d)來達成。
圖13展示壓層對照2、2b、2c、2d、對照4、4b、4c及4d之z-方向導電率。如圖13中所展示,添加不可溶及可溶脹交聯粒子會減小未經改質壓層之z-方向導電率,而在包括MWCNT之壓層中添加聚合韌化粒子可改良z-方向導電率值。
根據表7中所展示之調配物製備含有不可溶彈性粒子之基質樹脂
(對照5)。藉由分散1.35重量%之具有碳純度>98%、平均直徑為15nm且平均長度為約1mm之多壁碳奈米管(MWCNT)來改質相同的可固化樹脂組合物。經MWCNT改質之樹脂組合物(5a)展示於表7中。所有量皆係以基於調配物重量之重量百分比(w/w%)來展示。
在表7中,Araldite® PY 306係自Huntsman購得之雙酚F二縮水甘油醚樹脂,Araldite® MY 0510係自Huntsman購得之對-胺基酚之三縮水甘油醚樹脂,且SUMIKAEXCEL 5003P係自Sumitomo Chemical公司購得之聚醚碸聚合物。粒子E係玻璃轉化溫度為約-5℃且平均粒徑為50微米的呈粉末形式之羧基官能基彈性物,且以商品名DuoMod® DP5045自Zeon Chemicals L.P出售。
樹脂基質係藉由將5003P熱塑性分散於環氧化物成份中且在125℃下加熱約1小時以溶解5003P熱塑性塑膠來製備。將所得混合物冷卻至80℃,且然後添加剩餘成份並充分混合。
然後使用樹脂組合物來製造不同的單向(UD)預浸體。使用表7中所揭示之每一可固化樹脂組合物藉由將樹脂組合物塗覆於離型紙上來製造樹脂膜。然後,藉助熱及壓力將該等樹脂膜中之兩者層壓至單向碳纖維(來自Toho Tenax,USA之IMS65E)之連續層上,以形成UD預浸
體。每一所得預浸體皆具有197gsm之平均FAW(纖維面積重量)及基於總預浸體重量35% w/w之樹脂含量。根據上文所論述之EN2565方法自預浸體製備測試複合壓層。
使具有粒子E及MWCNT之測試複合壓層經歷機械測試且結果展示於表8中。表8中所報告之機械結果展示與僅經MWCNT改質之原本相同之材料(如實例2、表5中所揭示之對照4)或不含MWCNT或聚合韌化粒子的材料(如比較實例1、表2中所揭示之對照2)相比,在基質樹脂中引入不可溶彈性粒子與MWCNT之組合可獲得CAI(在30J下)及GIc值之顯著改良。
人們認為兩種機械性質CAI[30J]及GIc之同時改良係MWCNT與聚合韌化粒子之間協同效應之結果。
表9報告自樹脂組合物對照5及5a之包含粒子E之預浸體製備之測試複合壓層的平均z方向導電率值。
含有不可溶彈性粒子(粒子E)、但不含MWCNT之測試複合壓層之Z-方向DC導電率等於0.56S/m(對照6)。僅含有MWCNT且不含層間聚合粒子之測試複合壓層之Z-方向DC導電率等於6.00S/m(對照4)。令人驚奇地,添加不可溶粒子(粒子E)獲得優於僅經MWCNT改質之壓層的電性能(6.00S/m)之電性能(8.25S/m)。此結果令人驚奇之原因在於,傳統上預期將絕緣元件添加至層間區域中實質上與不含MWCNT之相應壓層之情形一樣減小固化複合物之體積導電率(表9、對照2及對照6)。該改良明顯係藉由將樹脂系統中之總MWCNT含量自1.55% w/w(對照4)降低至1.35% w/w(壓層6a)來達成。
Claims (24)
- 一種可固化複合材料,其包含:至少兩個經可固化基質樹脂浸漬之強化纖維層;及至少一個在毗鄰強化纖維層之間形成之層間區域,該層間區域包含(i)分散於可固化基質樹脂中之基於碳之奈米級結構,及(ii)包埋於同一可固化基質樹脂中之不可溶聚合韌化粒子,其中該等基於碳之奈米級結構具有至少一個小於100nm(0.1μm)之尺寸且係於該層間區域中僅有的導電組份,該等聚合韌化粒子之平均粒徑(d50)係該等基於碳之奈米級結構之最小尺寸的至少100倍,且該平均粒徑介於10μm至100μm範圍內,該等聚合韌化粒子在該複合材料固化期間不溶於該層間區域處之該基質樹脂中,且在固化後保留為離散粒子,且固化時,該複合材料展現大於1S/m之z-方向導電率、根據ASTM7136/37所量測的在30J衝擊後大於250MPa之衝擊後壓縮強度(CAI)及根據EN6033所量測的大於300J/m2之模式I層間斷裂韌度(GIc)。
- 如請求項1之可固化複合材料,其中該等聚合韌化粒子係以基於該複合材料中總基質樹脂含量之為重量2重量%至20重量%的含量分散於該層間區域中。
- 如請求項1之可固化複合材料,其中該等基於碳之奈米級結構係以基於該複合材料中總基質樹脂含量之重量介於0.1重量%至10重量%範圍內之量存在。
- 如請求項1之可固化複合材料,其中該等聚合韌化粒子係包含至 少一種選自由以下組成之群之熱塑性塑膠的不可溶熱塑性粒子:聚醯亞胺、聚醯胺醯亞胺、聚醯胺、聚醚酮、聚苯硫、液晶聚合物、其共聚物及其衍生物。
- 如請求項1之可固化複合材料,其中該等不可溶聚合韌化粒子係包含至少一種選自由以下組成之群之聚合物或聚合材料的不可溶彈性粒子:交聯聚丁二烯、聚丙烯酸、聚丙烯腈、聚苯乙烯、其共聚物及其衍生物。
- 如請求項1之可固化複合材料,其中該等不可溶聚合韌化粒子係交聯粒子,每一粒子皆包含以下各項中之一者:(a)交聯網絡,其係藉由交聯具有一或多個反應性基團之可交聯熱塑性聚合物與對該等反應性基團具有化學反應性之交聯劑產生,及(b)互穿聚合物網絡(IPN),其包含與獨立交聯網絡纏結之熱塑性聚合物鏈,其中該IPN係藉由使至少一種具有一或多個反應性基團之化合物、對該等反應性基團具有化學反應性之交聯劑與熱塑性聚合物反應來產生。
- 如請求項6之可固化複合材料,其中該等交聯粒子係交聯聚醚碸-聚醚醚碸(PES-PEES)粒子。
- 如請求項1之可固化複合材料,其中該等基於碳之奈米級結構係選自由以下組成之群:碳奈米管(CNT)、碳奈米纖維、碳奈米索、碳奈米帶、碳奈米針、碳奈米薄片、碳奈米棒、碳奈米錐、碳奈米歐姆、碳黑、石墨奈米微片或奈米點、石墨烯及其組合。
- 如請求項1之可固化複合材料,其中該等基於碳之奈米級結構係碳奈米管(CNT)。
- 如請求項1至9中任一項之可固化複合材料,其中該等基於碳之 奈米級結構係多壁碳奈米管(MWCNT)。
- 如請求項9之可固化複合材料,其中該等碳奈米管(CNT)具有50:1至5000:1之縱橫比。
- 如請求項1之可固化複合材料,其中該等不可溶聚合韌化粒子具有介於5:1至1:1範圍內之縱橫比。
- 如請求項1之可固化複合材料,其中該層間區域不含在固化時溶解於該基質樹脂中之任何可溶性熱塑性粒子。
- 如請求項1之可固化複合材料,其中該等韌化粒子為大體球形且在該層間區域中形成單粒子層,使得該層間區域具有由該等韌化粒子之直徑界定之深度。
- 如請求項1之可固化複合材料,其中浸漬該等強化纖維之該可固化基質樹脂及該層間區域中之該可固化基質樹脂包含一或多種為兩種基質共用之熱固性樹脂。
- 如請求項1之可固化複合材料,其中浸漬該等強化纖維之該可固化基質樹脂實質上與該層間區域中不含該等奈米級結構及韌化粒子之該可固化基質樹脂相同。
- 如請求項1之可固化複合材料,其中浸漬該等強化纖維之該可固化基質樹脂及該層間區域中之該可固化基質樹脂包含均勻分散的基於碳之奈米級結構。
- 如請求項1之可固化複合材料,其中該等強化纖維係碳纖維。
- 如請求項1之可固化複合材料,其中該等聚合韌化粒子之形狀為大體球形且該等基於碳之奈米級結構係碳奈米管,其中該等聚合韌化粒子之平均粒徑(d50)係該等碳奈米管直徑的至少100倍。
- 如請求項1之可固化複合材料,其中該基質樹脂係包含環氧化物 或雙馬來醯亞胺作為主要組份之熱固性樹脂。
- 一種製造可固化複合材料之方法,其包含:(a)將基於碳之奈米級結構及聚合韌化粒子分散於第一種可固化基質樹脂中以形成可固化導電基質樹脂;(b)自該可固化導電基質樹脂形成至少一個樹脂膜;(c)形成包含強化纖維層之結構層,該等強化纖維經不含聚合韌化粒子之第二種可固化基質樹脂浸漬;及(d)將該至少一個樹脂膜置於該結構層之外表面上,其中該等基於碳之奈米級結構具有至少一個小於100nm(0.1μm)之尺寸且係於該層間區域中僅有的導電組份,該等聚合韌化粒子之平均粒徑(d50)係該等基於碳之奈米級結構之最小尺寸的至少100倍,且該平均粒徑介於10μm至100μm範圍內,且該等聚合韌化粒子在該複合材料固化期間不溶於該層間區域處之該基質樹脂中,且在固化後保留為離散粒子。
- 如請求項21之方法,其中該第二種可固化基質樹脂進一步包含基於碳之奈米級結構。
- 一種製造可固化複合材料之方法,其包含:(a)將基於碳之奈米級結構及聚合韌化粒子分散於可固化基質樹脂中以形成可固化基質樹脂;(b)藉由使用該可固化基質樹脂浸漬強化纖維層形成複合材料,使得該等聚合韌化粒子存在於該強化纖維層之至少一側上,其中該等基於碳之奈米級結構具有至少一個小於100nm(0.1μm)之 尺寸且係於該層間區域中僅有的導電組份,該等聚合韌化粒子之平均粒徑(d50)係該等基於碳之奈米級結構之最小尺寸的至少100倍,且該平均粒徑介於10μm至100μm範圍內,且該等聚合韌化粒子在該複合材料固化期間不溶於該層間區域處之該基質樹脂中,且在固化後保留為離散粒子。
- 一種製造複合結構之方法,其包含:(a)以堆疊配置鋪疊至少兩種自如請求項21至23中任一項之方法製造之可固化複合材料,以形成積層;及(b)固化該積層,其中在固化後,該固化複合結構展現大於1S/m之z-方向導電率、根據ASTM7136/37所量測的在30J衝擊後大於250MPa之衝擊後壓縮強度(CAI)及根據EN6033所量測的大於300J/m2之模式I層間斷裂韌度(GIc)。
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BR112016013450A2 (pt) | 2017-08-08 |
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US9908298B2 (en) | 2018-03-06 |
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