TWI701131B - 混合紗面及其應用以及用於製造經改質預浸體及複合結構之方法 - Google Patents
混合紗面及其應用以及用於製造經改質預浸體及複合結構之方法 Download PDFInfo
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- TWI701131B TWI701131B TW105136855A TW105136855A TWI701131B TW I701131 B TWI701131 B TW I701131B TW 105136855 A TW105136855 A TW 105136855A TW 105136855 A TW105136855 A TW 105136855A TW I701131 B TWI701131 B TW I701131B
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Abstract
本發明提供一種對液體樹脂可透之可撓性、自撐式混合紗面。該混合紗面包括:(a)呈非編織結構之形式的交纏、無規排列纖維;(b)分散在整個該非編織結構中之粒子,其中大部分該等粒子貫穿該非編織結構之厚度;及(c)在整個該紗面中存在之聚合黏合劑。此類混合紗面可併入至可用液體樹脂浸漬之複合層合物、預浸體、織物及預成型物中。
Description
本發明提供一種對液體樹脂可透之可撓性、自撐式混合紗面。此類混合紗面可併入至可用液體樹脂浸漬之複合層合物、預浸體、織物及預成型物中。
纖維加強聚合物複合物在主要航空結構(例如飛機機身)中、以及在高效能體育用品、船舶及風能結構中之使用變得愈加普遍。纖維加強聚合物複合物之優點包括高強度-重量比、極佳疲乏耐久性、耐腐蝕性及可撓性,從而允許組件部件顯著減少,且降低固定件及接合件之需求。
用於製造纖維加強複合材料之習知方法包括用可固化基質樹脂浸漬加強纖維,以形成預浸體。此方法通常稱作「預浸」法。可藉由使預浸體之多個層鋪疊在模具表面上,隨後固結並固化製得結構複合部件。
近年來,經由液體樹脂浸漬方法製得纖維加強聚合物複合部件,該等方法包括樹脂轉注成形(RTM)及真空輔助樹脂轉注成形(VARTM)。在典型樹脂浸漬方法中,將乾纖維材料之預成形預成型物置於模具中,隨後通常在高壓下將液體樹脂注入模具中,以便在原位直接浸漬預成型物。預成型物由加強纖維或編織織物之多個無樹脂層組成,其以與鋪疊經樹脂浸漬之預浸體類似之方式鋪疊。在樹脂浸漬之後,根據固化循環固化經樹脂
浸漬之預成型物以提供成品複合製品。在樹脂浸漬中,待用樹脂浸漬之預成型物為關鍵要素-預成型物本質上為待用樹脂處理之結構部件。液體樹脂浸漬技術尤其適用於製造複雜形狀結構,否則該等結構使用習知預浸體鋪疊技術難以製造。
習知纖維/樹脂多層複合物(或複合層合物)之主要弱點為其低層間斷裂韌性,從而造成在高能量力衝擊時複合層分層。當兩個層彼此去黏合時發生分層。對分層具有改良抗性之固化複合物為具有改良衝擊後抗壓強度(CSAI)及斷裂韌性之固化複合物。CAI量度複合材料耐受破壞之能力。在量測CAI之測試中,使複合材料經受給定能量之衝擊,隨後進行壓縮負載。斷裂韌性為表示當裂痕存在時材料抵抗脆性斷裂之定量方式,且可用應變能釋放率(Gc)定量,應變能釋放率為在斷裂期間每單位新形成斷裂表面積所消耗之能量。Gc包括GIc(模式I-開口模式)或GIIc(模式II-平面內剪切)。下標「Ic」表示模式I裂痕開口,其在垂直於裂痕之正常張應力下形成,且下標「IIc」表示藉由平行於裂痕平面且垂直於裂痕正面作用之剪切應力產生之模式II裂痕。分層之起始及增長通常藉由檢查模式I及模式II斷裂韌性判定。
由於在多層複合物或複合層合物之穿過厚度方向上之較弱特性,層間裂痕或分層為多層複合物所擔憂之主要失效模式,尤其因為此類失效模式通常為非外部可見的。層間斷裂韌性為分析在諸如疲乏、壓縮或衝擊後壓縮之條件下複合物效能之關鍵參數。在此等條件下,歸因於模式I及模式II負載之分層為材料失效之主要原因。導致分層之裂痕及瑕疵可由製造期間發生之材料特性之局部可變性、空隙或其他瑕疵或經由持續工作之破壞產生。
此外,根據習知預浸體鋪疊方法製造之具有諸如L、U或Z形部分之
彎曲部分的複雜複合部件通常展示在彎曲區域處之厚度降低。此類現象導致需要再分析結構以檢驗該等較薄部件是否仍能滿足負載抗性要求而不具有諸如分層或裂痕之任何機械失效。當厚度-半徑比增加時,厚度變化亦增加,因此,複合層合物中之各預浸體層具有臨界比率,高於該臨界比率時各預浸體層不能使用。儘管在固結複合層合物期間可施加額外壓力以使變薄現象降至最低,但纖維加強之架構及樹脂組合物仍為製造愈來愈複雜幾何結構及組件中之限制因素。
可經由諸如RTM與VaRTM之液體樹脂浸漬方法製造具有更複雜幾何結構之複合結構。在樹脂浸漬方法中,將預成型物置於模具中,注入可固化液體樹脂以使纖維層濕潤。用於RTM與VaRTM系統之基質樹脂必須具有極低注射黏度以允許預成型物之完全潤濕及浸漬。改良複合材料韌性之先前嘗試已包括在樹脂注入至模具之前向樹脂添加可溶熱塑性韌化劑。然而,樹脂中熱塑性韌化劑之添加導致黏度升高,因此,可添加之韌化劑的量受到液體樹脂注射必需之低黏度的限制。此限制使得通常添加至預浸體之韌化劑的添加不適於液體樹脂浸漬應用。
一種替代解決方案為使不溶熱塑性或橡膠韌化粒子在樹脂浸漬前分散至樹脂中。然而,除非粒子極小(例如亞微米尺寸),否則粒子將經預成型物中之加強纖維過濾,導致粒子之不均勻分佈且最終產物中粒子之不適宜局部濃度。此外,此過濾作用可導致完全阻礙預成型物進一步進行樹脂注入或浸漬。可添加至用於樹脂浸漬之液體樹脂中的粒子的類型及數量再次受到限制。
仍需要適用於多種複合產品形式之多功能層間韌化解決方案,複合產品形式包括適用於自動沈積法(例如自動纖維放置(AFP)及自動鋪帶
(ATL))之預浸體、用於樹脂浸漬之預成型物、織物及乾紡織物。需要具有可同時改良固化層合物之斷裂韌性及抗壓強度特性同時維持或改良體電導率,且亦可解決與具有彎曲部分之複合部件變薄問題相關之當前材料侷限性的多功能層間材料。
本發明提供一種對液體樹脂可透之可撓性、自撐式混合紗面。混合紗面包括:(a)呈非編織結構之形式的交纏、無規排列纖維;(b)分散在整個非編織結構中之粒子,其中大部分粒子貫穿非編織結構之厚度;及(c)在整個紗面中存在之聚合黏合劑。該混合紗面可併入至可用液體樹脂浸漬之複合層合物、預浸體、織物及預成型物中。
10:預浸體
11:上部壓力夾持輥/輥
12:下部壓力夾持輥/輥
13:連續加強纖維/纖維層/連續纖維層
14:上部樹脂膜/樹脂膜
15:下部樹脂膜
20:樹脂浸漬紗面
V:紗面/混合紗面
圖1為根據本發明之一實施例的混合紗面的示意性說明。
圖2為由利用濕式佈層法形成之實際混合紗面的電腦斷層掃描得到的3D重建影像。
圖3示意性說明相較於含有韌化粒子分散在紗面表面上的非編織紗面的類似固化複合層合物,在層間區域含有混合紗面之固化複合層合物。
圖4示意性說明作用於複合層合物凹模製表面(A)及凸模製表面(B)上的力。
圖5A至圖5D展示用於製造其中整合有混合紗面之經改質預浸體的各種實施例。
圖6示意性說明根據本發明之一實施例的編織織物。
圖7展示經由掃描電子顯微法(SEM)採集之例示性混合紗面的俯視影像。
圖8A及圖8B展示與不同混合紗面交織之兩種固化複合板之截面視圖,其顯示在經受GIc測試之後裂痕路徑擴展。
本文描述多功能紗面,亦稱作「混合紗面」,以及其中併有此類紗面之複合層合物、預浸體、織物及纖維預成型物。
本文揭示之混合紗面為可用作纖維加強聚合物複合物中之層間材料的低面重量多功能紗面。混合紗面為一種可撓性、自撐式、非編織結構,其由交纏、無規排列之纖維及分散在整個非編織結構中之粒子(其中大部分粒子貫穿非編織結構之厚度)組成。在一個實施例中,粒子均勻地分散在整個非編織結構中。紗面亦含有足以使纖維與粒子固持在一起且維持紗面完整性之量的少量聚合黏合劑。因此,紗面為自撐式的-意指其為不需要另一種支撐載體之各別結構。粒子與纖維共混且聚合物粒子中之至少一些存在於非編織結構之纖維之間。歸因於黏合劑與由交纏纖維產生之機械互鎖機構之組合,粒子保持在整個非編織結構之位置中。圖1為例示性混合紗面之示意性說明,其顯示截面視圖。圖2為由濕式佈層方法形成且由電腦斷層掃描掃描之實際紗面的3D(三維)重建影像。圖2中所示之紗面由非編織碳纖維及聚醯亞胺粒子組成。在325nm之解析度下掃描量測尺寸為5×5×25mm之非編織樣品。捕捉1600張個別2D X射線放射照片且重建成3D體積。隨後將碳纖維及粒子分段以允許非編織架構之繪製及辨識。
混合紗面之面重量可小於或等於12gsm,例如,4gsm至12gsm。紗面中纖維比粒子之重量比可為5:1至1:1.5。
構成混合紗面之非編織纖維可為碳纖維或熱塑性纖維,或不同纖維
之組合。碳纖維可經金屬塗佈。金屬塗層可具有任何適合之金屬,其包括(但不限於)銀、金、鉑、鈀、鎳、銅、鉛、錫、鋁、鈦、其合金及混合物。
熱塑性纖維包括由聚醯胺製成之纖維,聚醯胺諸如脂族聚醯胺(PA)、環脂族聚醯胺、芳族聚醯胺、聚鄰苯二甲醯胺(PAA)、醚或酯嵌段聚醯胺(PEBAX、PEBA)、聚伸苯基硫醚(PPS)、聚醚醯亞胺(PEI)、聚醯亞胺(PI)、具有苯基三甲基茚滿結構之聚醯亞胺、聚醯胺基醯胺(PAI)、聚碸、諸如聚醚碸(PES)之聚芳基碸、聚醚碸-醚醚碸(PES:PEES)、聚醚醚碸(PEES)、諸如聚醚酮(PEK)之聚芳醚酮(PAEK)、聚醚醚酮(PEEK)、聚胺甲酸酯、熱塑性聚胺甲酸酯、聚碳酸酯、聚縮醛、聚苯醚(PPO)、聚酯、聚醚、聚醚腈、聚苯并咪唑、熱塑性彈性體、液晶聚合物(LCP)、其組合及共聚物。
當混合紗面併入至纖維加強聚合物複合物中時,粒子充當層間韌化材料。適合於本文揭示之目的之粒子包括熱塑性及彈性粒子、自不同材料之混合物形成之複合粒子、及核殼粒子。核殼粒子係指具有經一或多個殼包圍之核的粒子。
更特定言之,粒子可為由選自以下之聚合物形成之顆粒形式:脂族聚醯胺(PA)、環脂族聚醯胺、芳族聚醯胺、聚鄰苯二甲醯胺(PPA)、醚或酯嵌段聚醯胺(PEBAX、PEBA)、聚芳基醚酮(PAEK)(諸如聚醚醚酮(PEEK)及聚醚酮酮(PEKK))、聚苯硫醚(PPS)、聚醯胺醯亞胺(PAI)、聚苯
醚(PPO)、聚酯、聚胺甲酸酯、熱塑性聚胺甲酸酯、聚醚、聚醚腈、聚苯并咪唑、熱塑性彈性體、液晶聚合物(LCP)、其共聚物及其衍生物。聚醯胺之粒子尤其適合,諸如PA-10,10或微晶PA-12。
在一些實施例中,聚合物粒子之組合物含有至少一種選自以下物質之彈性聚合物或材料:交聯聚丁二烯、丁基橡膠、聚丙烯酸、聚丙烯腈、聚苯乙烯、甲基丙烯酸甲酯、其共聚物及其衍生物。
某些等級之聚醯亞胺粒子亦可為適合的。舉例而言,由二苯甲酮四甲酸二酐(BTDA)、4,4'-亞甲基二苯胺(MDA)及2,4-甲苯二胺(TDA)製備且具有非鄰苯二甲醯亞胺碳成分(其含有介於90%與92%之間之芳族碳)的聚醯亞胺。
適合市售粒子之實例包括由Zeon Chemicals Inc.出售之DuoMod DP5045、來自HP Polymer Inc.之P84TM聚醯亞胺、來自Evonik之Vestamid® Terra生物基聚醯胺及Trogamid® CX級聚醯胺、來自Kuraray,Japan之PA9T(脂族芳族混合聚醯胺)。
適合之聚合物粒子亦包括交聯熱塑性聚合物之粒子,諸如美國專利第8,846,818號及美國專利申請公開案第2010/0304118號(其均以引用之方式併入本文中)中描述之粒子。
亦可使用樹脂可溶性熱塑性粒子。實例包括選自以下物質之顆粒熱塑性聚合物:聚芳基碸,例如聚醚碸(PES)、聚醚醚碸(PEES)、PES-PEES共聚物;聚醚醯亞胺(PEI)及聚醯亞胺(PI)。此等樹脂可溶性熱塑性粒子在環境溫度(20℃至25℃)下為固體粒子(例如粉末),但當加熱其混合物時或在熱固性樹脂之固化循環期間將溶解於熱固性樹脂。因此,此等粒子在固化樹脂基質中並不保持離散粒子形式。
如本文所使用,「溶解」於樹脂中意謂與樹脂形成均勻相或連續相。如本文所使用之「離散粒子」係指在基質樹脂中可辨別之粒子,且其可藉由使用掃描電子顯微法(SEM)、光學顯微法或差分干涉對比顯微法(Differential Interference Contrast microscopy;DIC)偵測。
在其他實施例中,粒子係由聚合物及導電材料之混合物形成。聚合物如上文對於聚合物粒子所描述。導電材料可選自金屬、非金屬導電材料、金屬塗層材料及其組合,其電導率大於約1×103S/m。適合之金屬包括任何已知金屬,包括(但不限於)銀、金、鉑、鈀、鎳、銅、鉛、錫、鋁、鈦、其合金及混合物。適合之非金屬導電材料包括(但不限於)碳及石墨。前述導電材料之電導率可利用四點法或利用根據DIN EN 2004-1及ASTM E 1004之渦流法測定。此類型粒子之特定實例為描述於國際公開案第WO 2014/011293號(其以引用之方式併入本文中)中之複合粒子。
亦涵蓋具有核殼結構之粒子,亦即經一或多個殼包圍之核。實例包括金屬塗層聚合物核、碳塗層聚合物核、金屬塗層陶瓷核、碳塗層陶瓷核、金屬塗層玻璃球、金屬塗層空心玻璃球。
上文所述之粒子可具有任意三維形狀,包括球狀或棒狀。粒子之縱橫比可低於5:1,較佳地,縱橫比為約1:1。關於粒子,術語「縱橫比」係指粒子之最大截面尺寸與最小截面尺寸之比率。
對於球形粒子(具有約1:1之縱橫比),平均粒度係指其直徑。對於非球形粒子,平均粒度係指粒子之最大截面尺寸。
出於本文揭示之目的,粒子之粒度分佈(d50)可低於100μm,尤其在10μm至50μm之範圍內、或在15μm至35μm之範圍內,如藉由雷射繞射技術所量測,例如利用Malvern Mastersizer 2000儀器(其在0.002奈米至
2000微米範圍內運作)。「d50」表示粒度分佈之中值,或者為50%粒子之粒度為此值或小於此值的分佈值。
混合紗面具有足量聚合黏合劑以使纖維與聚合物粒子固持在一起,但黏合劑量為足夠小以保持所得紗面多孔且對流體(液體及氣體)可透。可根據恆定體積流速下之飽和流實驗量測紗面之穿過厚度之氣體滲透率。此方法涉及記錄穿過測試樣品之壓降。所記錄壓降隨後用於利用以下壓降公式求出樣品之滲透率:
其中:K3=滲透率
Q=體積流速
h=樣品之厚度
△P=穿過樣品之壓降
A=圓柱形流動通道之截面積。
安放在樣品任一面上之壓力轉換器記錄測試流體(其與用於平面內實驗之流體相同)之壓降。
可使用National Instruments LabVIEWTM程式獲取及估計實驗資料以產生關於此穿過厚度資料之滲透率值。
紗面中黏合劑的量以紗面之總重量計可為約2重量%至約30重量%,在一些實施例中,約5重量%至約25重量%或約10重量%至約20重量%。黏合劑可為熱塑性、熱固性或彈性黏合劑。適合之聚合物黏合劑包括乙烯基類,諸如聚乙烯醇(PVA)、聚乙烯乙烯醇(PEVOH)、聚乙酸乙烯酯、聚乙
烯醚、聚氯乙烯(PVC)及聚乙烯酯;丁二烯,諸如聚苯乙烯丁二烯及聚丁二烯丙烯腈;聚矽氧;聚酯;共聚酯;聚醯胺;共聚醯胺;交聯聚酯;丙烯酸類,諸如苯乙烯丙烯酸及丙烯腈丙烯酸;環氧樹脂;苯氧基類;酚樹脂;聚胺甲酸酯;酚醛樹脂或脲醛樹脂;其組合及共聚物。市售黏合劑之實例包括來自BASF之Acronal® 888及Acrodur® 950丙烯酸黏合劑、來自Bayer之Baybond® PU330及XP2569、來自Celanese Corp.之Vinamul® 8828、來自COIM之Filco® 309。
作為一實例,本文所述之混合紗面可藉由習知濕式佈層方法製造。在濕式佈層方法中,將短切纖維及聚合物粒子分散於水性漿液中,該水性漿液可含有黏合劑及視情況選用之添加劑,諸如界面活性劑、黏度改質劑、消泡劑、排水助劑及/或其他化學試劑。選擇特定添加劑以獲得纖維於水中之穩定分散液而用於濕式佈層製造方法之持續時間中。當短切纖維經引入至漿液中時,強烈攪拌漿液使得纖維變得分散。隨後使含有纖維及粒子之漿液沈積至活動篩網上(在此處移除大部分水)以形成片材。隨後,可藉由真空及/或熱空氣乾燥自片材移除液體。當使用兩種液體移除方法時,較佳於稍後施加熱空氣乾燥,因為其可用於使黏合劑熔融或固化。當需要纖維及/或重量之均勻分佈時,通常使用此類濕式佈層方法。
如使用靜重測微計所量測,於經受1巴(bar)壓力後混合紗面厚度的中值較佳為80μm。在一些實施例中,經受1巴壓力後紗面的厚度(以微米為單位)與紗面面重量(A/W)(以gsm為單位)之間的比率小於10。
如本文所論述之紗面的中值厚度可藉由在正方形圖案上量測25個樣品來測定:在300mm×300mm之紗面樣品上,縱向五個且橫向五個。
上文所述之混合紗面可用作複合層合物中之夾層或中間層。在一個實施例中,複合層合物為以堆疊排列方式排列之預浸體的疊層且至少一個混合紗面***或交織在兩個相鄰預浸體層之間。在一較佳實施例中,存在複數個混合紗面與預浸體疊層交織,其中各紗面***於相鄰預浸體層之間。
如本文所使用之術語「預浸體」係指纖維體積之至少一部分中已用可固化基質樹脂預浸漬之加強纖維層。浸漬加強纖維之基質樹脂可呈部分固化或未固化狀態。預浸體為準備鋪疊且成形為三維構形,隨後固化成最終複合部件之可彎曲或可撓性材料。可在固化前經由施加壓力(在加熱或不加熱下)進行固結以防止疊層內空隙之形成。此類型之預浸體尤其適合於製造載荷結構部件,諸如飛行器之機翼、機身、艙壁及控制表面。經固化預浸體之重要特性為高強度及硬度且重量降低。
如本文所使用之術語「浸漬」係指將可固化基質樹脂材料引入至加強纖維以便用樹脂部分或完全封裝纖維。用於製造預浸體之基質樹脂可呈樹脂膜或液體之形式。另外,在黏合之前基質樹脂呈可固化或未固化狀態。可藉由施加熱及/或壓力促進浸漬。
預浸體中加強纖維之層可呈連續、單向對準(或「單向」)纖維或絲束、編織織物或非編織多軸向織物(例如非捲曲織物或NCF)之形式。連續絲束由多個纖維長絲,例如3000至24,000個長纖維組成。
加強纖維可由選自(但不限於)玻璃(包括電玻璃或E玻璃)、碳(包括石墨)、芳族聚醯胺、聚醯胺、高模數聚乙烯(PE)、聚酯、聚對伸苯基-苯并噁唑(PBO)、硼、石英、玄武岩、陶瓷及其組合之材料製成。為了製造高強度複合材料,例如,用於航空及汽車應用之材料,如根據ASTM
C1557-14所量測,較佳地加強纖維具有大於500ksi(或3447MPa)之抗張強度。
舉例而言,用於製備預浸體之浸漬方法可包括:(1)使連續、單向纖維或織物網不斷移動穿過熔融浸漬基質樹脂組合物之(經加熱)浴以使纖維完全或實質上完全濕潤;或(2)熱熔方法,其包括抵著連續、單向纖維或織物網之至少一側按壓樹脂膜,且施加熱以使樹脂膜熔融。
在一較佳實施例中,預浸體中之加強纖維為處於相同平面之連續單向碳纖維或石墨纖維。可將疊層內之預浸體相對於彼此置於所選方向上。舉例而言,預浸體疊層可包括具有相對於疊層之長度以所選角度θ(諸如0°、45°或90°)定向之單向纖維的預浸體。
當固結及固化預浸體疊層時,預浸體中之基質樹脂穿過交織、多孔紗面中之空隙或間隙,產生整合複合結構。固結係指在加熱、真空抽吸及施加壓力中之一或多者之作用下進行,從而基質樹脂流動以便取代空隙空間之方法。舉例而言,固結可使(但不限於)樹脂流至預浸體中之纖維之間的空隙空間、預浸體之間的空隙空間及其類似空間。固結與固化可在單一階段或分別進行。
在固化方法期間,紗面架構防止韌化粒子滲入加強纖維之結構層中。以此方式,高濃度之韌化粒子在結構層之間的層間區域產生,且對於固化複合結構在擴展裂痕正面實現恆定及受控塑性變形區域。混合紗面之架構將塑性變形區域限制在層間邊界,因此裂痕不會出現在夾層與加強纖維之間的介面中。因此,可實現更高的模式I及模式II層間斷裂韌性及CSAI值。
此外,由於粒子以化學及機械方法限制於非編織紗面中,無法使粒子擠壓至加強纖維絲束中,因此可避免波狀區域之產生。此類波狀區域通常造成複合物抗壓強度特性之降低。
在一些實施例中,由預浸體疊層形成之固化複合結構中之混合紗面所形成的層間區域的中值厚度低於60μm。藉由在不同部位獲取量測值且計算平均值求出中值厚度。
圖3示意性說明相較於含有韌化粒子分散在紗面表面上的非編織紗面的類似固化複合層合物,在層間區域含有混合紗面之固化複合層合物。複合層合物3B(右側)含有具有粒子缺乏部分之不可控、波狀層間區域。相比之下,歸因於紗面中粒子之限制,複合層合物3A(左側)含有充分受控之層間區域。
另外,當紗面由導電纖維(例如碳纖維)組成且聚合物韌化粒子均勻地分佈在整個紗面之非編織結構中時,固化複合層合物之體電導率可保持或改良。
已發現混合紗面併入複合結構中為拐角變薄問題(通常在具有L、U或Z形部分之複合部件中觀測到)之有效解決方案。圖4示意性說明在高壓釜或高壓釜外真空袋式裝置中在複合物之固化循環期間作用於複合層合物凹模製表面(A)及凸模製表面(B)上的力。
參看圖4,在凹拐角(A)中,工具表面(ST)大於袋表面(SP)。在凸拐角(B)中,工具表面(ST)小於袋表面(SP)。袋表面始終暴露於1atm之壓力(P)下。為滿足力之平衡,凹拐角中來自工具之反應壓力低於1atm(P-△P),而凸拐角中來自工具之反應壓力高於1atm(P+△P)。「T」係指拉伸縱向應力且<P係指較低壓縮壓力。因此,凹拐角通常經受拐角變厚,且凸拐角
通常呈現拐角變薄。
在複合層合物之層間區域中的混合紗面中之韌化粒子的實質上均勻分佈可實質上減小或消除變薄現象之產生而不降低曲樑強度,曲樑強度為每單位寬度引起分層形成之動量的量度。
在另一實施例中,本文揭示之混合紗面中的一或多者用作經組態以用於藉由樹脂浸漬方法(諸如RTM與VaRTM)接受液體樹脂之預成型物中的夾層/中間層。預成型物由多個乾加強纖維層構成,其中一或多個混合紗面***於乾加強纖維之相鄰層之間。
藉由使用混合紗面,可避免與添加韌化劑至液體樹脂系統用於RTM及VaRTM應用相關之前述問題。
預成型物中之加強纖維層可為先前技術中已知用於製造複合材料的任何類型紡織物。適合織物類型或構形之實例包括(但不限於):所有編織織物,實例為平紋織物、斜紋織物、棉緞織物、螺旋織物及單向織物;所有多軸向織物,其實例包括翹曲針織織物及非捲曲織物(NCF);針織織物;編結織物;所有非編織織物,其實例包括(但不限於)由短切及/或連續纖維長絲組成之墊織物、氈、及前述織物類型之組合。預成型物中之加強纖維由上文參照預浸體所揭示之材料製成。在較佳實施例中,預成型物中之至少一些纖維層由碳纖維或石墨纖維組成。
用於液體樹脂浸漬之模具可為兩組件、封閉式模具或真空袋密封、單側模具。雙組件、封閉式模具之使用為熟知的且描述於例如美國專利第4,891,176號中。真空袋密封、單側模具之使用亦為已知的,參看例如美國專利第4,942,013號、第4,902,215號、第6,257,858號及第8,652,371
號。
在樹脂浸漬之前,可藉由在預成型物之相鄰層之間分散少量聚合黏合劑使乾纖維預成型物穩定,隨後成形為所需構形。用於穩定之適合黏合劑為美國專利第8,927,662號(其內容以全文引用之方式併入本文中)中所揭示之熱塑性環氧樹脂黏合劑。
本文揭示之混合紗面可附著於織物層以形成改質織物,其可用於形成可使用液體樹脂浸漬經由諸如RTM與VaRTM之樹脂浸漬方法浸漬的預成型物。可藉由縫合或針織紗線或藉由紗面與織物之間黏合劑之純融熔及固結進行紗面與織物之附著。在一個實施例中,將一或多個混合紗面併入至多軸向、非捲曲織物(NCF)中。NCF由藉由縫合紗線連接之非捲曲纖維層構成。NCF中之各纖維層由以不同於另一纖維層中纖維之方向定向的連續單向纖維構成。一或多個混合紗面可交織在相鄰纖維層之間以形成經改質NCF,其可用於形成用於樹脂浸漬應用之預成型物。
在另一實施例中,將混合紗面切割成窄帶,其用單向纖維絲束以形成如圖6中所說明之編織織物之編織圖案編織。此織物可由液體透過且可用於形成可經由諸如RTM與VaRTM之樹脂浸漬方法使用液體樹脂浸漬的預成型物。
在一些實施例中,由樹脂浸漬之預成型物形成的固化複合結構中的混合紗面所產生之層間區域的中值厚度低於80μm,或低於60μm。藉由在不同部位獲取量測值且計算平均值求出中值厚度。
在一個實施例中,藉由施加熱及壓力使混合紗面直接層合至現有預浸體之一或兩個表面上,以形成其中整合有紗面之經改質預浸體。圖5A
說明此實施例之一實例。藉助於上部壓力夾持輥11與下部壓力夾持輥12之對使混合紗面V抵著活動、連續預浸體10按壓。亦可經由壓力夾持輥11及12向預浸體及紗面施加熱。初始預浸體10由已用可固化樹脂預浸漬或浸漬之加強纖維(例如單向碳纖維)之層組成。
在另一實施例中,在製造預浸體期間將混合紗面整合於預浸體中。首先,將樹脂塗佈於剝離型紙上以獲得薄樹脂膜。隨後藉由將紗面包夾在加強纖維層與樹脂膜之間隨後向組合層施加熱及壓力使混合紗面與樹脂膜及加強纖維層組合。圖5B說明此實施例之一實例。將連續加強纖維13層(下文稱作「纖維層」)包夾於上部樹脂膜14與下部樹脂膜15之間,且將混合紗面V***上部樹脂膜14與纖維層13之間。樹脂膜14及樹脂膜15各可藉由剝離型紙支撐,剝離型紙作為圖5B中所示之排列中之最外層安置。藉由輥11及輥12向組合層施加熱及壓力以形成其中包埋有混合紗面之經樹脂浸漬之預浸體。視情況,可將第二混合紗面***於纖維層13與下部樹脂膜15之間,隨後施加熱及壓力。
圖5C展示與圖5B中所示類似之另一實施例,但混合紗面V與上部樹脂膜14之外表面接觸,使得樹脂膜14在紗面V與纖維層13之間。在此排列中,移除支撐上部樹脂膜14之剝離型紙,隨後樹脂膜14與紗面V接觸。
在又一實施例中,用可固化樹脂組合物浸漬混合紗面以產生經樹脂浸漬之混合紗面。隨後,利用熱及壓力將預浸漬紗面與纖維層組合以形成其中整合有紗面之預浸體。圖5D說明此實施例之一實例。將連續纖維層13包夾於預浸漬紗面20與下部樹脂膜15之間。藉由輥11及輥12向組合層施加熱及壓力以使層固結。或者,下部樹脂膜15用第二預浸漬紗面替換。
本文揭示之混合紗面可併入至適用於自動鋪帶(ATL)或自動纖維放置(AFP)方法之連續預浸帶中。在一個實施例中,如上文所述形成其中併有一或多個混合紗面之預浸體,隨後切割成具有適合ATL寬度(例如6吋至12吋或152mm至305mm)或AFP寬度(例如0.125吋至1.5吋或3.17mm至38.1mm,包括0.25吋至0.50吋或6.35mm至12.77mm)之窄帶。此等帶可具有為其寬度至少十倍的連續長度。
ATL及AFP為使用電腦引導機器人技術將預浸帶之連續層鋪設至模具表面(例如心軸)上以產生複合結構之方法。例示性應用包括飛機機翼外皮及機身。ATL/AFP方法涉及將一或多個帶並排分配至心軸表面上以產生具有所需寬度及長度之層,隨後在先前層上建構額外層以提供具有所需厚度之疊層。ATL/AFP系統可配備有將預浸帶直接分配及壓縮至心軸表面上之構件。
AFP將多個個別預浸漬絲束或窄切割帶(例如0.125吋至1.5吋)自動置放在心軸上以構成給定總預浸帶寬。在置放期間在高速下利用數值控制置放頭分配、鉗夾、切割及重新起動各絲束進行材料置放。ATL機器鋪設織物之預浸體單向帶或連續帶,其寬於用於AFP中之單一絲束或切割帶。通常,在兩種方法中,藉由含有材料置放所需之機構的機器人控制頭施用材料。AFP傳統地用於極複雜表面上。
在另一實施例中,將混合紗面與單向加強纖維組合以形成適用於ATL及AFP方法之乾纖維帶。在此情況下,藉由ATL或AFP鋪設乾纖維帶以形成預成型物,其經組態用於諸如RTM及VaRTM之液體樹脂浸漬方法。
為形成乾纖維帶,藉助於黏合劑(其可呈粉末形式或液體形式)使混合
紗面層合至連續、單向加強纖維(例如碳纖維)層。視情況,使層壓結構進一步暴露於液體形式之第二黏合劑以便改良在切割期間經黏合劑處理纖維材料之跳紗抗性。經黏合劑處理材料隨後切割成適合於ATL或AFP方法之窄寬度帶。
根據一個實施例,用於製造乾帶之方法包括:向連續、單向加強纖維(例如碳纖維)之乾纖維網施用呈粉末形式或液體形式之第一黏合劑;使混合紗面黏合至纖維網之至少一側以形成纖維層合物;例如藉由浸塗向纖維層合物施用呈液體組成物形式之第二黏合劑;及例如在烘箱中乾燥經黏合劑處理之層合物。或者,向紗面施用第一黏合劑,隨後使紗面黏合至單向纖維。經乾燥、黏合劑處理之層合物隨後切割成適合於ATL/AFP之窄寬度帶,且視情況,使切割帶捲繞在線軸上。
除第一黏合劑外第二液體黏合劑之存在可防止在切割期間此等帶跳紗以及產生低體積帶。此類「低體積」特性為合乎需要的,因為如藉由自動置放方法之加熱及成形製程、及藉由樹脂浸漬及固化後之複合結構的固化厚度所測定,在加熱時由乾纖維帶形成之預成型物呈現低體積特性。因此,在固化前預成型物之體積減少為最小(或完全無必要的),因為在ATL/AFP方法期間當鋪設經黏合劑處理之帶以形成預成型物時發生體積減小。
用於形成乾纖維帶之適合黏合劑材料可選自:i.在高達50℃之溫度下為固體之黏合劑,如藉由DSC所量測其軟化點在75℃至125℃範圍內之溫度下,且由環氧樹脂與熱塑性聚合物之摻合物形成,但不含在75℃以上為活性之任何催化劑或交聯劑;ii.如下組合物,其包含至少一種多官能環氧樹脂;至少一種熱塑性
聚合物;及至少一種選自陰離子界面活性劑及非離子界面活性劑之界面活性劑;iii.聚羥基醚與聚胺甲酸酯之部分或完全交聯共聚物;iv.聚胺甲酸酯,其為非交聯、部分或完全交聯、或經改質之聚胺甲酸酯聚合物;v.環氧樹脂,其為非交聯、部分或完全交聯、或經改質之環氧樹脂;及vi.聚(羥基醚)樹脂,其為非交聯、部分或完全交聯的。
尤其適合之黏合劑為美國專利第8,927,662號(其讓與至Cytec Technology Corp.,其內容以全文引用之方式併入本文中)中所描述之熱塑性環氧樹脂黏合劑。此熱塑性環氧樹脂黏合劑可以粉末形式施用。另一種尤其適合之黏合劑為美國公開案第2014/0179187號(其內容以全文引用之方式併入本文中)中所描述之液體黏合劑組合物。此等黏合劑中之任一者可作為唯一黏合劑或作為兩種不同黏合劑中之第一種施用至紗面或單向加強纖維中。
可用於製造乾纖維帶之液體黏合劑為美國公開案第2014/0370237號(其內容以全文引用之方式併入本文中)中所描述之含有聚羥基醚-聚胺甲酸酯共聚物的液體黏合劑組合物。其他適合之液體黏合劑可選自含有以下各者中之一者的水性分散劑:聚胺甲酸酯、經改質聚胺甲酸酯聚合物、環氧樹脂及聚(羥基醚)樹脂。視情況,交聯劑包括於此等水性分散劑中。適合之液體黏合劑可為2015年6月25日申請之美國專利申請案第14/750,327號中所揭示之彼等黏合劑。
乾纖維帶中黏合劑材料之總量(包括紗面中之黏合劑)以乾帶之總重量
計為約15重量%或低於15重量%,例如約0.1重量%至約15重量%。黏合劑之總量足夠小以便經黏合劑處理纖維帶保持多孔且對用於樹脂浸漬方法中之液體樹脂可透。
用於浸漬如上文所述之加強纖維及預成型物的可固化基質樹脂較佳為含有一或多種未固化熱固性樹脂之可硬化或熱固性樹脂,其包括(但不限於)環氧樹脂、醯亞胺(諸如聚醯亞胺或雙馬來醯亞胺)、乙烯酯樹脂、氰酸酯樹脂、經異氰酸酯改質之環氧樹脂、酚樹脂、呋喃樹脂、苯并噁嗪、甲醛縮合物樹脂(諸如與尿素、三聚氰胺或苯酚縮合)、聚酯、丙烯酸類、其混合物、摻合物及組合。
適合之環氧樹脂包括芳族二胺、芳族單一級胺、胺基酚、多元酚、多元醇、聚羧酸之聚縮水甘油基衍生物。適合之環氧樹脂的實例包括諸如雙酚A、雙酚F、雙酚S及雙酚K之雙酚之聚縮水甘油醚;及甲酚基及酚基酚醛清漆之聚縮水甘油醚。
特定實例為4,4'-二胺基二苯基甲烷(TGDDM)之四縮水甘油基衍生物、間苯二酚二縮水甘油醚、三縮水甘油基對胺苯酚、三縮水甘油基間胺苯酚、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、酚甲醛酚醛清漆之聚縮水甘油醚、鄰甲酚酚醛清漆之聚縮水甘油醚或四苯基乙烷之四縮水甘油醚。
適用於主體基質樹脂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)-1,4-二異丙基苯(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)-1,4-二異丙基苯(例如來自Momentive之EPON 1072);對胺基苯酚之三縮水甘油醚(例如來自Hunstman之MY 0510);間胺基苯酚之三縮水甘油醚(例如來自Hunstman之MY 0610);基於雙酚A之二縮水甘油醚的材料,諸如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、及較佳地在25℃下具有8至20Pa.s黏度之酚醛清漆樹脂);苯酚酚醛清漆樹脂之縮水甘油醚(例如來自Dow之DEN 431或DEN 438);基於二-環戊二烯之酚系酚醛清漆(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族物,諸如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)。
一般而言,可固化基質樹脂含有一或多種熱固性樹脂以及其他添加劑,諸如固化劑、固化催化劑、共聚單體、流變控制劑、增黏劑、無機或有機填充劑、作為韌化劑之熱塑性及/或彈性聚合物、穩定劑、抑制劑、顏料、染料、阻燃劑、反應性稀釋劑及熟習此項技術者熟知之用於在固化之前及/或之後調節基質樹脂特性的其他添加劑。然而,可添加至用於液體樹脂浸漬之樹脂中的視情況存在之添加劑由如上文所述之低黏度要求及過濾作用限制。
若存在,用於可固化基質樹脂之韌化劑可包括(但不限於)單獨或與以下各物組合之均聚物或共聚物:聚醯胺、共聚醯胺、聚醯亞胺、芳香族聚醯胺、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、聚胺甲酸酯、聚碸、聚硫醚、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、聚苯碸、高效烴聚合物、液晶聚合物、彈性體及嵌段彈性體。
固化劑及/或催化劑之添加至可固化基質樹脂中為可選的,但若需要,使用此類物質可提高固化速率及/或降低固化溫度。固化劑宜選自已知固化劑,例如芳族胺或脂族胺或胍衍生物。較佳為芳族胺固化劑,較佳地每分子具有至少兩個胺基之芳族胺,且尤佳為二胺基二苯基碸,例如其中胺基相對於碸基呈間位或對位。特定實例為3,3'-二胺基二苯基碸及4,4'-二胺基二苯基碸(DDS);亞甲基二苯胺;雙(4-胺基-3,5-二甲基苯基)-1,4-二異丙基苯;雙(4-胺基苯基)-1,4-二異丙基苯;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-2,4-二胺/3,5-二乙基甲苯-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)及雙氰胺(例如來自Pacific Anchor Chemical之AMICURE TM CG 1200)。
適合之固化劑亦包括酸酐,尤其聚羧酸酐,諸如耐地酸酐、甲基耐地酸酐、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酸酐。
本發明中之「固化(Curing)」或「固化(Cure)」係指經由聚合物鏈之化學交聯進行的聚合材料硬化。提及組合物之術語「可固化」意指組合物能夠經受住將使組合物顯現經硬化或熱固狀態之條件。
如本發明使用之術語「約」表示接近規定量的量,其仍能夠執行所
需功能或實現所需結果。舉例而言,術語「約」可指在低於規定量1%內的量。
PY306係指Araldite® PY 306,來自Huntsman之雙酚F二縮水甘油醚樹脂。MY0510係指Araldite® MY 0510,來自Huntsman之對胺基苯酚樹脂的三縮水甘油醚,且SUMIKAEXCEL 5003P係指來自Sumitomo Chemical Co.之聚醚碸聚合物。4,4' DDS係指4,4'-二胺基二苯碸。
PA-10,10(聚醯胺)粒子由Evonik以商標Vestamid® Terra 9161供應,其為1,10-癸二胺(D)與1,10-癸烷二甲酸(癸二酸,S)之縮聚產物,具有37℃之Tg、206℃下之熔融峰。平均粒度(d50)為約26μm。
P84G為聚醯亞胺(P84 325目)與經P84聚醯亞胺塗佈之石墨的70:30摻合物(70重量%石墨:30重量% P84),由HP Polymer Inc.供應;平均粒度(d50)為22μm。
PILT係指交聯PES-PEES共聚物之可膨脹粒子,其根據美國專利第8,846,818號中所描述之方法製得,平均粒度(d50)為34μm。
PA9T為購自Kuraray,Japan之熱塑性聚醯胺,由對苯二甲酸、1,9壬二胺及2-甲基-1,8-辛二胺之固相縮聚合成,具有120℃至130℃之Tg、260℃及271℃下之兩個熔點及高於200℃之結晶溫度。使聚合物紡絲成纖維且使所得產物短切成具有所需長度之纖維。
CX7323係指來自Evonik之Trogamid® CX7323,其為由環脂族二胺與十二烷二酸縮聚合成之半芳族/脂族非晶形聚醯胺,具有140℃之Tg、260℃之熔融溫度及13μm之平均粒度(d50)。
實例中所揭示之所有粒度分佈藉由Malvern Mastersizer 2000量測。
根據表1中所揭示之配方製備五種不同樹脂組合物。所有量以重量與重量(weight by weight;w/w)百分比為單位。
R1為不具有層間粒子之均勻韌化基線樹脂系統,且R1之其他四種改質型式含有5w/w%及10w/w%之P84G或PA10,10粒子。
隨後利用熱熔性浸漬方法使用樹脂組合物產生不同單向(UD)預浸體。藉由將樹脂組合物塗佈至剝離型紙上製備樹脂膜。隨後,藉助於熱及壓力使兩種此類樹脂膜層合至單向碳纖維(來自Toho Tenax,Germany之TENAX®-E IMS65 E23 24K 830tex)之連續層的相對側以形成預浸體。所製造預浸體之以gsm(或g/m2)為單位的纖維面重量(FAW)及以重量百分比為單位的樹脂含量展示於表2中。
使用濕式佈層或紙張製備方法製造具有不同面重量之混合紗面。使用直徑為約5.2μm之短切、中等模數(IM)碳纖維(來自Hexcel之IM7G 12K)及所選擇熱塑性粒子形成混合紗面。表3提供紗面組成、熱塑性粒子含量、碳纖維含量及紗面面重量之概括。在表3中,IM7係指IM7G碳纖維。
為形成各紗面,首先將短切纖維與熱塑性粒子之混合物懸浮於水中,隨後使漿液沈積至多孔篩網上以移除水,形成非編織網,隨後藉由施用液體苯乙烯丙烯酸黏合劑(來自Basf之Acronal® 888)且在烘箱中乾燥非編織產物以蒸發任何殘餘水且使黏合劑交聯來使非編織網穩定。將特徵為在縱向(MD)與橫維方向(CD)上結構完整之所得產物捲繞成捲筒。
圖7展示經由掃描電子顯微鏡(SEM)採集之V1混合紗面(P84G/IM7)
的俯視圖影像。經展示粒子與碳纖維交纏且實質上均勻分佈在整個紗面結構中。熱塑性粒子貫穿紗面之厚度存在。許多粒子彙集於紗面結構內之多個纖維的交叉點處,滯留於黏合劑「池」中且藉由紗面架構簡單地保持在原位。
藉由鋪疊表2中所揭示之預浸體(P1、P2、P3)製得複合板。各板包含根據表4中報導之鋪疊構形定向之特定數量的預浸體層。P1預浸體疊層亦與表3中所揭示之不同混合紗面交織,隨後在高壓釜中在180℃及85psi之壓力下固結且固化2小時。出於對比目的,相同P1預浸體疊層與4gsm IM7G碳紗面交織。量測多種機械特性以評估紗面架構及組合物對層合物效能之作用。根據表4中報導之測試方法進行測試。
RT係指室溫(25℃)。DCB係指雙懸臂樑(Double Cantilever Beam)且ENF係指端部開口之撓曲(End Notched Flexure)。
CAI、GIc及GIIc結果報導於表5至表7中。σ表示標準差。
如表5中所示,與產生自基線預浸體(P1)之層合物相比,在30J衝擊之後,混合紗面用作單向預浸體之中間層可產生高達50%之抗壓強度改良。
值得注意的是,紗面V2(PA10,10/IM7)中少量(1.83gsm)PA-10,10粒子之均勻分佈相較於基線預浸體板P1產生40% CAI改良。更有趣的是,包含碳纖維及PA-10,10粒子之混合紗面架構展示出人意料之協同作用-使CAI改良高於且超過對於分別經碳紗面或韌化粒子韌化之預浸體板所量測的值。當紗面V2用作預浸體板之中間層時,相對於具有4gsm IM7碳紗面作為中間層之預浸體板及用PA-10,10粒子改質之預浸體板(P2、P3)發現CAI改良12%、25%及22%。
與無交織之基線預浸體P1板相比,含有紗面V1(P84G/IM7)及紗面V4(PILT/IM7/PA9T)作為中間層之預浸體板產生45%至50%之CAI改良,而相較於相同無交織之預浸體P1板,紗面V2、V3及V5使CAI效能提高33%至37%。另外,所揭示之混合紗面架構經證明比純碳紗面更有效地增強固化複合板之破壞耐受性及抗性效能。與具有4gsm IM7碳紗面作為中間層之板相比,表3中所揭示之所有混合紗面均得到高10%至20%之CAI值,但所有混合紗面均含有大致相同量(以重量計)之碳纖維。相對於基線預浸體P1板(約-50%)及相對於具有4gsm碳紗面作為中間層之相同預浸體板(減少10%與50%之間),在30J衝擊之後所揭示之混合紗面架構亦使固化層合物破壞面積大大減少。
如表6中所示,使用混合紗面作為單向預浸體之中間層相較於未改質
基線預浸體P1板(無粒子,無紗面)可產生高達70%之模式I中分層強度抗性改良。
更特定言之,包括含有PA-10,10、P84G、PILT及CX7323粒子之碳紗面相較於無交織之預浸體板P1分別產生33%、50%、33%及67%之改良。更有趣的是,與具有4gsm IM7碳紗面作為中間層之板相比,相同混合紗面產生15%與40%之間之改良。
另外,新穎紗面架構經證明與層間粒子同樣有效地以粒子含量之分率韌化預浸體。舉例而言,結構中僅包含1.8gsm PA10,10粒子之紗面V2產生的GIc值大大高於對於樹脂中含有5% PA-10,10粒子的預浸體P2板所量測之值,且與樹脂中含有10% PA-10,10粒子之預浸體P3板類似。
表7中之機械結果展示相比於基線預浸體P1板,混合紗面結構可產生
高達4倍之模式II層間斷裂抗性效能改良。
值得注意的是,相較於含有相同層間粒子分散於樹脂中之預浸體板(P2、P3),紗面V2中極低含量PA-10,10粒子(1.83w/w%)之均勻分佈分別產生25%及40%之GIIc改良。
另外,與含有4gsm IM7碳紗面作為中間層之板相比,紗面V1(含有極小濃度(1.8gsm)P84G粒子之均勻分佈)及紗面V5(含有極小濃度(0.5gsm)CX7323粒子)分別產生12%與36%之GIIc改良。
在經受GIc測試之後,圖8A展示具有CX7323/IM7(V5)混合紗面作為中間層之固化複合板的截面視圖且圖8B展示具有P84G/IM7(V1)混合紗面作為中間層之固化複合板。自圖8A及圖8B可見,歸因於新穎紗面架構,在層間區域產生相對高濃度之韌化粒子,從而在擴展裂痕正面產生恆定及受控之塑性變形區域。
自實例2中產生之複合板獲取測試試片,且根據4探針測試法在DC條件下量測其z向電導率。固化複合物之Z向電導率結果展示於表8中。
相比於產生自基線預浸體板(P1)之基線複合板,用5%(P2)或10%(P3)PA-10,10粒子改質之複合板產生超過一個數量級之z向電導率的大大降低。此類穿過厚度之電導率之降低將可能判定飛機複合機翼結構中之邊緣輝光現象。
相反地,含有混合紗面作為中間層之複合板產生大大高於韌化基線板之z電導率值(P1→0.7S/m)。
已發現混合紗面中介電韌化粒子之添加相比於與碳紗面交織之層合物不會使z向電導率發生任何大量損失。更有趣的是,含有用CX7323及P84粒子改質之紗面的板的Z向電導率勝過具有4gsm碳紗面之板。相比於具有碳紗面之板,包含均勻分佈之PILT及PA-10,10粒子之紗面產生略低複合物Z向電導率值。儘管如此,咸信所得電導率位準足以限制飛機複合機翼中之邊緣輝光現象。實際上結果仍比對於基線板P1所量測高5至10倍,再次表明所揭示之紗面架構為通用解決方案,其可解決當介電韌化成分併入複合結構中時與穿過厚度之電導率降低相關聯之問題。
根據ASTM D6415測定不同複合板之曲樑強度。藉由根據[+,0,-,90]3s構形鋪疊24個預浸體層形成各板,隨後在高壓釜中在180℃及85psi之壓力下固化2小時。實例1中所揭示之預浸體(P1、P2及P3)用以形成預浸體疊層。兩個預浸體疊層與4gsm IM7G碳紗面交織,且一個預浸體疊層與PA10,10/IM7混合紗面(V2)交織。表9中揭示板組分以及固化複合板之曲樑強度(CBS)結果。90°曲樑測試樣品用於所有測試。曲樑強度表示每單位寬度引起分層形成之力矩。
表9中報導之結果顯示相比於基線板P1,預浸體P2及P3中包括聚醯胺層間粒子使固化複合板之曲樑剪切強度(CBS)效能大大降低。對於用10% PA-10,10粒子改質之預浸體板(P3)量測之CBS值降低25%。低面重量IM7碳紗面(4gsm)不影響CBS效能,其與未改質之基線P1板一致。
與由基線預浸體P1組成之層合物相比,包括混合紗面V2(PA10,10/IM7)使CBS值降低達極小,而與基線板P1相比,4gsm IM7G碳紗面與經粒子改質之預浸體(P3)之組合展示大大降低之CBS值(-20%)。在此情況下,實驗強度為對於兩種不同改質劑(碳紗面及PA-10,10粒子)之量測值的數值平均數。
相比於對於用熱塑性粒子韌化之預浸體板所觀測,混合紗面架構能夠維持高CBS值且特定韌化粒子之存在同時改良固化複合物之機械及電性能。
對於由複合層合物形成之通道及角組件,將藉由角度之變化可見形狀之變形。此現象通常稱為回彈(spring-in)且為層合物之平面內及穿過厚度之方向上不同膨脹的結果。若層合物均勻地正交穿過厚度,則拐角半徑不會影響回彈角度。然而,當藉由高壓釜製造拐角(其中工具僅一半為剛
性的)時,預期在處理期間會發生局部拐角變薄/變厚。在傳統預浸體製造期間,熟知拐角變厚可在凹形工具拐角處發生且拐角變薄可在凸形拐角處發生。厚度之變化意謂纖維體積分率之變化,其影響回彈。
在具有凸半徑之工具上製造複合板以研究對厚度及回彈之影響。在工具上使用預浸體P1、P2、P3,隨後在高壓釜中在180℃及85psi之壓力下固化2小時形成[0]24預浸體疊層。P1預浸體疊層亦與4gsm IM7G碳紗面及混合IM7/PA10,10紗面V2交織,而P3與4gsm碳紗面交織,如表10中所指示。
由具有R8之凸半徑的碳纖維複合物製造工具。此意謂在凸拐角上製造之板將分別具有8mm及12mm之內徑與外徑。半徑變薄以平均凸緣厚度與半徑厚度之間的差值計算。體積因數以與標稱板厚度相比之百分位變化計算。
半徑變薄分析之結果展示於表10中。
已發現在高壓釜中凸工具上固化之基線預浸體板(P1)與凸緣部分相比展示半徑處5%體積減小及12%之厚度差。PA-10,10層間粒子之存在可部分減少此類現象。在用混合紗面V2改質之板中量測到半徑與凸緣部分之間的最低體積因數及最小厚度差。在所有其他情況下,即使對於半徑部分計算到更低體積因數,尤其對於基線板P1及經粒子改質之板(P2、P3)在凸緣處亦觀測到大量變厚現象。
表11展示根據上文所述之相同方法製造但疊層構形為準各向同性,更尤其[+,0,-,90]3s之預浸體板的結果。參看表11,對於準各向同性板發現類似結果。對於用混合紗面V2作為中間層之板量測到最低體積因數。類似於對於UD板所觀測,相比於基線預浸體P1板,未改質之材料展示半徑之5%變薄及凸緣厚度之2.5%變厚。對於經粒子改質板(P2、P3)之凸緣亦觀測到高體積因數。
利用液體樹脂浸漬,使用由Saertex(UK)供應之196gsm
IMS65E24K單向非捲曲織物(UD-NCF)製造複合層合物。織物含有4gsm聚酯縫合線以使碳絲束保持在一起。將5gsm細聚酯線鋪設在織物中以向織物提供側向完整性及穩定性。
織物塗佈有5gsm熱塑性改質環氧基黏合劑(來自Cytec Engineered Materials之Cycom® 7720)。使用粉末分散法使約5gsm黏合劑組合物沈積於各織物之兩個面上。使具有分散粉末之織物穿過雙重帶壓機以進一步驅使黏合劑穿過纖維網且保證UD纖維網之良好黏結。此稱作穩定步驟。隨後將經穩定織物切割成具有低於+/- 1.0mm寬度變化之50mm寬帶。切割帶之邊緣品質為足夠潔淨的,其具有有限橋接纖維、起毛及其他觀測到之瑕疵。
將無捲曲織物切割成較小層,且將層以{+,0,-,90]3s堆疊順序鋪設以形成疊層。利用V1、V4及4gsm IM7碳紗面將UD-NCF疊層交織。隨後藉由在烘箱中在130℃下預成形疊層30分鐘使經紗面交織之UD-NCF疊層固結,且用Prism® EP2400(購自Cytec Industries Inc.之韌化環氧樹脂系統)浸漬。在180℃下使經浸漬預成型物固化2小時後產生Vf(纖維體積分率)在54%至55%範圍內之板。
出於對比之目的,使用相同潔淨單向非捲曲織物製備其他方面相同的測試板。
量測多種機械特性以評估紗面架構及組成對固化複合物效能之作用。根據表12中報導之測試方法進行測試。
RT係指室溫(25℃)。DCB係指雙懸臂樑且ENF係指端部開口之撓曲。
CAI、GIc及GIIc結果報導於表13及表14中。 σ 表示標準差。
如表13中所示,與形成自未改質之非捲曲織物的相同板相比,在30J衝擊之後,混合紗面用作非捲曲織物之中間層可產生高達30%之抗壓強度改良。更特定言之,紗面V4中少量(1.83gsm)PILT粒子之均勻分佈相較於基線預浸體板P1產生40% CAI改良。此外,含有碳纖維、PA9T纖維及PILT粒子之混合紗面V4架構產生出人意料之協同作用-使CAI改良高於對於與4gsm碳紗面交織之NCF所量測的值。與無交織之基線織物相比,與紗面V1交織之NCF產生約25%之CAI改良。
如表14中所示,相較於與4gsm碳交織之非捲曲織物,使用混合紗面作為單向非捲曲織物之中間層可產生高達35%之模式I中分層強度抗性改良。
更特定言之,相對於與碳紗面交織之非捲曲織物,包括含有均勻分散粒子(P84G及PILT)之非編織碳紗面分別產生35%及10%改良。此外,相比於與碳紗面交織之非捲曲織物,紗面V4(PA9T及碳纖維以及PILT粒子)使GIc效能改良約15%。
表14中之機械結果展示相比於與碳紗面交織之非捲曲織物,所揭示之紗面架構可提供高達40%之模式II層間斷裂抗性效能改良。
值得注意的是,相較於與碳紗面交織之非捲曲織物,紗面V1(含有極低含量(1.9w/w%)P84G粒子)及紗面V3(含有低含量(2.4%)PILT粒子)分別產生30%及40%之GIIc改良。而相比於與碳紗面交織之非捲曲織物,紗面V4中PA9T纖維、IM7碳纖維及PILT粒子之組合產生約45%之GIIc增加。
Claims (36)
- 一種混合紗面,其為可撓性、自撐式的且對液體樹脂可透,其包含:(a)交纏、無規排列之纖維,其呈非編織結構之形式;(b)分散在整個該非編織結構中之粒子,其中大部分該等粒子貫穿該非編織結構之厚度;及(c)在整個該紗面中存在之聚合黏合劑;其中以該紗面之總重量計,該聚合黏合劑係以5重量%至25重量%之量存在;且其中當藉由雷射繞射量測,該等粒子之粒度分佈d50在約10μm至約50μm之範圍內。
- 如請求項1之混合紗面,其中該非編織結構之該等纖維為碳纖維、熱塑性纖維或其組合。
- 如請求項1或2之混合紗面,其中該混合紗面之面重量小於或等於12gsm。
- 如請求項3之混合紗面,其中該混合紗面之面重量為5gsm至12gsm。
- 如請求項1之混合紗面,其中該紗面中纖維與粒子之重量比在5:1至 1:1之範圍內。
- 如請求項1之混合紗面,其中以該紗面之總重量計,該聚合黏合劑係以10重量%至20重量%之量存在。
- 如請求項1之混合紗面,其中該非編織結構之該等纖維為具有在約3mm至約18mm範圍內之長度的短切纖維。
- 如請求項1之混合紗面,其中該非編織結構之該等纖維的截面直徑在約3.0μm至約15μm之範圍內。
- 如請求項1之混合紗面,其中該等粒子係選自聚合物粒子、核殼粒子及由不同材料之混合物形成之複合粒子。
- 如請求項1之混合紗面,其中該等粒子為包含一或多種選自以下之聚合物的聚合物粒子:熱塑性聚合物、彈性聚合物及交聯熱塑性聚合物。
- 如請求項1之混合紗面,其中該等粒子為聚醯胺粒子。
- 如請求項1之混合紗面,其中該等粒子為聚醯亞胺粒子。
- 如請求項1之混合紗面,其中該等粒子為由包含至少一種聚合物與至少一種導電材料之混合物形成之複合粒子。
- 如請求項13之混合紗面,其中該導電材料係選自金屬、金屬合金及碳。
- 如請求項1之混合紗面,其中當藉由雷射繞射量測,該等粒子之粒度分佈d50在約15μm至約35μm之範圍內。
- 如請求項1之混合紗面,其中該非編織結構包含碳纖維。
- 一種複合層合物,其包含:以堆疊排列方式排列之預浸體層之疊層,各預浸體層包含已用可固化基質樹脂浸漬之加強纖維之層,及交織在兩個相鄰預浸體層之間的至少一個如請求項1之混合紗面。
- 一種經組態以用於液體樹脂浸漬之纖維預成型物,其包含:複數個對液體樹脂可透之纖維層;交織在兩個相鄰纖維層之間的至少一個如請求項1之混合紗面。
- 如請求項18之纖維預成型物,其中該等纖維層係選自:編織及非編織織物及多軸向織物。
- 一種預浸體,其包含:用可固化樹脂浸漬之加強纖維;及 包埋在該可固化樹脂中之如請求項1之混合紗面。
- 如請求項20之預浸體,其中該等加強纖維為單向碳纖維。
- 一種適用於自動鋪帶(ATL)或自動纖維放置(AFP)方法之預浸帶,其包含:用可固化樹脂浸漬之加強纖維,及包埋在該可固化樹脂中之如請求項1之混合紗面,其中該預浸帶之窄寬為約0.125吋至約12吋且連續長度為其寬度之至少十倍。
- 一種適用於自動鋪帶(ATL)或自動纖維放置(AFP)方法之纖維帶,其包含:層合至如請求項1之混合紗面的單向加強纖維之層;其中該纖維帶具有約0.125吋至約12吋之窄寬及ATL,且其中該纖維帶對液體樹脂可透。
- 一種可用液體樹脂浸漬之織物,其包含:至少一個包含單向纖維之織物層;及附著至該織物層之如請求項1之混合紗面,其中該至少一個織物層對液體樹脂可透。
- 如請求項24之織物,其中該至少一個織物層實質上無樹脂。
- 一種對液體可透之編織織物,其包含:彼此平行排列之單向纖維絲束;及與該等單向纖維絲束以編織圖案交纏之混合紗面帶,其中各單向纖維絲束包含複數個連續纖維長絲,且其中該混合紗面係如請求項1中所述。
- 一種纖維加強聚合物複合結構,其包含:複數個纖維層,各纖維層包含彼此平行排列之單向纖維絲束及使該等絲束固持在一起之縫合線;交織在相鄰纖維層之間的至少一個如請求項1之混合紗面;及基質樹脂,其中包埋有該等纖維層及該至少一個混合紗面。
- 一種纖維加強聚合物複合結構,其包含:複數個包含加強纖維之纖維層;交織在相鄰纖維層之間的至少一個如請求項1之混合紗面;及基質樹脂,其中包埋有該等纖維層及該至少一個混合紗面。
- 一種用於製造經改質預浸體之方法,其包含:使如請求項1之混合紗面與包含已用可固化樹脂浸漬之加強纖維之層的預浸漬預浸體之表面接觸;向該紗面及預浸體施加熱及壓力,使得該紗面包埋在該可固化樹脂中。
- 一種用於製造經改質預浸體之方法,其包含:使如請求項1之混合紗面與加強纖維之層及第一樹脂膜接觸,使得該混合紗面夾於該加強纖維之層與該第一樹脂膜之間,從而形成層合物;向該層合物施加熱及壓力。
- 如請求項30之方法,其進一步包含:使第二樹脂膜與該加強纖維之層接觸,隨後施加熱及壓力,使得該加強纖維之層位在該第一樹脂膜與該第二樹脂膜之間。
- 如請求項30之方法,其進一步包含:***另一如請求項1之混合紗面以與該加強纖維之層接觸,隨後施加熱及壓力,使得該另一混合紗面位在該加強纖維之層與該第二樹脂膜之間。
- 一種用於製造經改質預浸體之方法,其包含:使如請求項1之混合紗面與加強纖維之層及第一樹脂膜接觸,使得該樹脂膜夾於該混合紗面與該加強纖維之層之間,從而形成層合物;向該層合物施加熱及壓力。
- 一種用於製造經改質預浸體之方法,其包含: 用可固化樹脂浸漬如請求項1之混合紗面;使該樹脂浸漬紗面與加強纖維之層接觸,從而形成層合物;向該層合物施加熱及壓力。
- 一種用於製造複合結構之方法,其包含:以堆疊排列方式鋪疊複數個經樹脂浸漬之預浸體,各預浸體包含可固化基質樹脂及包埋在該基質樹脂中之加強纖維;在相鄰預浸體之間交織至少一個如請求項1之混合紗面;固結並固化該預浸體疊層,其中,在固結及固化之後,該至少一個混合紗面形成厚度小於60μm之層間區域。
- 一種用於製造複合結構之方法,其包含:形成對液體樹脂可透之纖維預成型物,該纖維預成型物包含複數個纖維層及交織在相鄰纖維層之間之至少一個如請求項1之混合紗面;用包含一或多種熱固性樹脂之液體樹脂浸漬該纖維預成型物;及固化該樹脂浸漬預成型物,其中,在固化之後,該至少一個混合紗面形成厚度小於80μm之層間區域。
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