TW201311457A - 熱塑物之層間靭化 - Google Patents
熱塑物之層間靭化 Download PDFInfo
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- TW201311457A TW201311457A TW101130298A TW101130298A TW201311457A TW 201311457 A TW201311457 A TW 201311457A TW 101130298 A TW101130298 A TW 101130298A TW 101130298 A TW101130298 A TW 101130298A TW 201311457 A TW201311457 A TW 201311457A
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- fibers
- particles
- toughened
- toughening
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- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
- Y10T442/184—Nonwoven scrim
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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Abstract
本文中之一些實施例係關於一種熱塑性複合結構，其具有至少一個纖維增強之熱塑性樹脂之結構層及至少一個毗鄰該結構層之表面之韌化層。該韌化層經組態以在複合壓層中產生層間區域且可採取以下形式：聚合物膜、織造或非織造纖維材料、自由顆粒、韌化顆粒分散於其中之聚合物層或非織造紗罩、金屬網或箔。
Description
本申請案主張2011年8月29日提出申請之美國臨時申請案第61/528,561號之優先權。
按照慣例，將熱塑性韌化劑添加至熱固性樹脂系統中以賦予韌性並減弱所存在不含熱塑性韌化劑之複合材料之脆性。舉例而言，將熱塑性韌化顆粒或熱塑性韌化劑與結構複合物一起使用以改良基於熱固性樹脂之系統之韌性。與熱固性樹脂系統相比，熱塑性樹脂系統通常並不使用其他韌化材料進行增強，此乃因普遍認為熱塑性系統已具有足夠韌性。然而，在航天工業及其他工業中，因需要改良之性能(例如，改良之熱塑性材料韌性)，從而影響了複合材料之進化發展。
熱塑性複合物之許多益處之一係聚合物會賦予高基質韌性。在使用當前技術狀態之熱塑性複合物預浸物之合併壓層中，層間區域通常極小或不存在。此組態可使得更容易地將衝擊事件傳遞至下一板層，此將擴大損壞區。
習用壓層需要進一步改良。賦予合併壓層改良之韌性或衝擊後壓縮(CAI)性能係業內之有益進步，且可較在所需環境中需要複合材料來實施之其他工業尤其為較大商業運輸及/或軍事航天工業所快速接受。
已發現，藉由增加層間區域大小及熱塑性壓層之含量，
衝擊後壓縮(CAI)性能得以改良。另外，為改良最終壓層之CAI韌性，進一步需要解決結構之板層間區域內之剩餘脆弱性。
為解決該等問題，本文中之一些實施例係關於一種合併或未合併熱塑性複合結構，其具有至少一個由經熱塑性樹脂基質浸漬之強化纖維構成之結構層及至少一個位於結構層之表面上之韌化層。韌化層經組態以在複合壓層中產生層間區域且可採取以下形式：聚合物膜、織造或非織造纖維材料、自由顆粒、韌化顆粒分散於其中之聚合物層或非織造紗罩、未浸漬或浸漬金屬網或箔。
以堆疊配置將複數個該結構層鋪層，從而將韌化層定位於兩個毗鄰結構層之間。由於此組態，複合壓層在合併後之CAI強度大於並無韌化層之相同壓層。
與含有使用可交聯之層間顆粒或層韌化之熱固性樹脂系統之習用複合材料相比，用於本文中之結構層之熱塑性樹脂基質並不依賴於與韌化材料進行交聯以形成韌化層。在一些態樣中，韌化層在處理溫度下並不熔化或具有高熔化黏度，且由此韌化材料不會廣泛地遷移或摻和至纖維增強之結構層中之熱塑性基質樹脂中。因此，纖維增強之結構層之熱塑性基質樹脂形成層間區域之確定邊界，此繼而得到在毗鄰結構層之間提供離散間隔之中間層(或中間板層)。與之相比，一些基於熱固性樹脂之複合物具有較不確定之層間區域，此乃因韌化層可能因因樹脂與韌化材料
之間之交聯而形成較小離散層。基於熱固性樹脂且並無韌化劑之早期複合物具有較小層間區。然而，韌化劑已用於一些基於熱固性樹脂之複合物中以產生板層間區域。然而，可適用於熱固性樹脂系統中之韌化材料可能與熱塑性樹脂系統不相容。具體而言，基於熱塑性樹脂之複合物通常在大於基於熱固性樹脂之複合物之溫度下合併，且在一些情形下合併溫度幾乎為典型熱固性樹脂固化溫度之兩倍。因此，熱固性複合物中所使用之在熱塑物處理溫度之前熔化並可能熱降解之韌化材料將不相容。
處理溫度係指在層壓熱塑性結構層期間之操作溫度，其通常在高於示差掃描熱量測定(DSC)掃描中之峰值熔點20℃-40℃(對於半結晶聚合物而言)及高於玻璃轉變溫度(Tg)(對於非晶型聚合物而言)80℃-150℃之範圍內。
此背景中之熱塑性複合物或壓層包含複數個呈堆疊配置之結構層，每一結構層皆由經熱塑性樹脂基質浸漬之強化纖維構成。樹脂基質包含一或多種熱塑性樹脂作為主要組份。因此，樹脂基質具有熱塑性；然而，樹脂基質可含有少量添加劑，例如增塑劑、流變改良劑、無機填充劑等。舉例而言，可將無機填充劑微粒(例如雲母、二氧化矽、碳化矽、氮化鋁、氮化硼、氧化鋁)與熱塑性樹脂混合。適宜熱塑性樹脂包含：聚醚亞醯胺(PEI)、聚芳基醚酮(PAEK)、聚苯硫醚(PPS)、聚醯胺(耐綸(Nylon))及其組合。聚芳基醚酮(PAEK)係結晶聚合物且可包含但不限於聚醚酮(PEK)、聚醚醚酮((PEEK)、聚醚酮酮(PEKK)及聚醚
酮醚酮酮(PEKEKK)。該等熱塑性樹脂具有固有韌性，且由此典型熱塑性樹脂通常並不視為需要韌化之材料。此韌性賦予最終壓層良好衝擊性能。然而，已發現，可將韌化層添加至熱塑性複合物中以進一步改良韌性特性。可使用測試方法ASTM D7136以衝擊後壓縮(CAI)性能形式來量測複合物韌性。在一些情形下，可獲得超過50 KSI之CAI性能。更具體而言，CAI性能可超過55 KSI、60 KSI、65 KSI或70 KSI。舉例而言，由半結晶CYPEK®-DS-E單向膠帶及韌化層形成之壓層可提供55 KSI之CAI。「單向膠帶」係指經樹脂浸漬之纖維層，其中纖維沿一個方向對準。
市售PAEK聚合物包含APC-2® PEEK、CYPEK®-DSM或DSE或FC及CYPEK®-THE，其皆購自Cytec Engineered Materials/Cytec Industries公司。CypekTM DSE、DSM、FC、THE係來自Cytec Industries公司之PEKK聚合物等級。DS代表聲明規範，M代表模製。THE代表高溫擠出，且FC代表「快速結晶」。
韌化層可採取以下形式：連續或多孔聚合物膜、織造或非織造纖維材料、自由顆粒、含有分散於其中之顆粒之聚合物層、含有分散於其中之韌化顆粒之隨機配置聚合纖維之非織造紗罩、未浸漬或浸漬金屬網或箔。適用於韌化層之材料包含：高熔點及高分子量熱塑性聚合物；增塑熱塑性聚合物；高流量聚合物；半結晶或快速結晶熱塑性聚合物；基質樹脂之聚合物混合物；多聚合物合金；熱固性聚
合物，例如聚醯亞胺；陶瓷，例如氧化鋁及矽酸鹽；金屬，例如銅、銀、鈦、鋁及其合金；及任一上述材料之組合。
用於韌化層之材料或材料組合之選擇取決於韌化層之組態及纖維增強之結構層之熱塑性樹脂基質。對於含有韌化顆粒之聚合物膜或紗罩而言，選擇材料以在聚合物膜或紗罩與層間區域中之韌化顆粒之間產生協同效應。
「高熔點熱塑性聚合物」係指熔化溫度(Tm)大於或等於280℃(如藉由DSC所量測)且處理溫度(T處理)大於或等於300℃之任一熱塑性聚合物。
「高分子量熱塑性聚合物」係指數量平均分子量(MW)大於10,000之聚合物。
「高流量聚合物」係指在10 s-1之視剪切速率及熔化處理溫度下熔化黏度小於600 Pa．s之聚合物，例如340℃下之CypekTM DS-M。
「半結晶聚合物」係指顯示熔化放熱(如藉由DSC所量測)之任一熱塑性聚合物，例如PEEK。
「快速結晶聚合物」係指在以10℃/min或更高值冷卻時可達到大於或等於15%之結晶含量之半結晶熱塑性聚合物，例如PEEK。
「基質樹脂之聚合物混合物」係指基礎基質聚合物之共聚物或接枝聚合物。
「多聚合物合金」係指兩種不同聚合物之相容或不相容聚合物摻合物。
增塑之熱塑性聚合物係指其中摻和有增塑劑之熱塑性聚合物。實例係摻和至PEEK中之二苯基碸。
對於含有韌化顆粒之熱塑性層及紗罩而言，該等顆粒包含微球體，例如玻璃微珠或陶瓷微球體(例如厚壁空心微珠(Zeosphere))。另一選擇為，韌化顆粒可由與分散有顆粒之熱塑性層或熱塑性紗罩不同之熱塑性聚合物形成。
在某些實施例中，可擠出兩種或更多種韌化材料，且然後研磨以形成顆粒。然後將該等顆粒置於結構層上。可使用具有不同粒徑之不同類型顆粒之摻合物作為韌化材料。可將顆粒及其混合物噴灑於結構層之表面上並熔化以形成韌化層。根據一實例，可將PEEK顆粒與矽酸鋁或其他類型之無機顆粒混合且然後藉由噴灑施加於結構層上，隨後熔化層壓，視情況施加熱。在另一實施例中，將兩種具有不同熔點及/或熔化黏度之不同熱塑性聚合物顆粒在兩種聚合物之較低熔化處理溫度下層壓。根據一實例，將CypekTM DSM(峰值熔點=300℃)顆粒及CypekTM HTE(峰值熔點=355-360℃)顆粒之顆粒混合物置於結構層上且然後在340℃下實施熔化層壓。
在增加韌性及產生板層間區域之另一實施例中，可將金屬顆粒沈積於結構層(例如經熱塑性聚合物浸漬之單向碳纖維之單向膠帶)之一個或兩個表面。金屬材料可為不規則形狀、絲狀或球形顆粒，且具有改良複合物之導電性之額外益處。
在使用顆粒之實施例中，顆粒可具有微尺寸。較佳地，
顆粒之粒徑大於3微米。
在另一實施例中，韌化層係金屬網或箔或金屬網及金屬箔之呈多層壓層形式之組合。在多個纖維增強之結構層之疊層中，在層間區域中存在複數個該金屬韌化層。
在另一實施例中，韌化層係玻璃纖維布。另外，可對玻璃纖維布實施化學氣相沈積(CVD)以將極薄金屬(例如鋁)層沈積於玻璃纖維上。金屬塗層可各自向板層間區域提供導電性。另外，此金屬塗層可賦予平面內導電性以有助於減小複合物部分中之邊緣發光(諸如機翼油箱等較大複合結構中之電容性放電)。
在另一實施例中，熱塑性基質樹脂及韌化層係由相同熱塑性樹脂(例如PAEK)製得。
在一些實施例中，可使用韌化聚合物及一或多種韌化顆粒之組合。舉例而言，可在擠出機中將顆粒與韌化聚合物複合以產生用於層間韌化之材料。舉例而言，將玻璃顆粒或纖維複合至PEEK或PEKK聚合物中以形成沈澱物或膜。隨後，可經由層壓或其他製程將沈澱物或膜施加至結構層上。根據另一實例，可組合CypekTM DS-M(峰值熔點=300℃)顆粒及PEEK(峰值熔點=340℃)樹脂，擠出，且施加為膜並層壓於結構層上。類似地，可組合PEEK顆粒及CypekTM DS-M樹脂，擠出，且施加為膜並層壓於結構層上，藉此PEEK顆粒僅部分地熔化於完全熔化之CypekTM DS-M中。可使用較高熔點聚合物顆粒與較低熔點聚合物基質之組合，例如存於CypekTM DS-M樹脂中之CypekTM FC
(峰值熔點=338℃)或CypekTM HT-E(峰值熔點=355℃-360℃)顆粒。
在一些實施例中，韌化層在整個層中至少係半結晶-此意指層在整個層中係半結晶，或含有均勻分散於層中之結晶部分。因此，毗鄰結晶層之非晶型層並不視為在各處至少係半結晶，此乃因材料層之部分主要係非晶型。具體而言，非晶型部分並不視為在該部分中至少係半結晶且由此並不視為在整個層中至少係半結晶。在一些實施例中，結構層係含有半結晶聚合物之單向膠帶且韌化層係由半結晶聚合物製得。通常，非晶型樹脂更易受溶劑侵襲，此並非係期望效應。兩種半結晶聚合物基於其化學配方可具有不同熔點及不同結晶速率，從而對於給定冷卻速率而言，每一半結晶聚合物將彼此在層中得到不同結晶含量，其中較低結晶含量之聚合物(較慢結晶速率)層提供韌化層。可使用協同較高或較低熔點之聚合物來韌化材料。
韌化層亦可呈織造纖維(例如織造織物)或非織造纖維(例如隨機配置纖維之紗罩或氈)之形式。若存在纖維，則通常較佳地其直徑至少為結構層中之結構強化纖維之一半。在一些情形下，韌化纖維及結構纖維大約具有相同直徑。舉例而言，強化或結構纖維(例如碳纖維)之長絲直徑可為約7 μm，而擬用作韌化材料之玻璃纖維之長絲直徑可為約5-9 μm。與同結構纖維具有大約相同直徑之韌化纖維相比，具有相對較小直徑之韌化纖維之製備較為昂貴。因此，亞微直徑纖維通常並非較佳。
通常，更具結晶性之熱塑物(亦即具有較高結晶度)產生較高壓縮強度及較低衝擊強度。與之相比，非晶型熱塑物產生較低壓縮強度及較高衝擊強度。在本文中之態樣中，使用結晶度來提供對於溶劑降解之抗性。較高結晶度值(高達35%)會改良抵抗此溶劑侵襲之聚合物性能。藉由DSC量測結晶度。此類熱塑物適用於結構層及韌化層二者之樹脂基質。
眾所周知，可藉由調節對苯二醯(「T」)與間苯二醯(「I」)之比率(「T：I比率」)來改變一些PAEK聚合物(例如PEKK及PEKEKK)之熔點及結晶速率。在PEKK之當前合成中，藉由對苯二醯氯及間苯二醯氯之相對量來控制「T」及「I」以製備嵌段共聚物。不期望受限於理論，據信，增加「I」區段之量會在聚合物主鏈中產生較多「扭折」，由此減緩鏈旋轉之速率及活化能以達成用於結晶形成之最小能量組態。此得到較低熔化溫度及較慢結晶速率。
對於上文所論述之大部分實施例而言，基於壓層中之基質樹脂之總重量，韌化材料之含量至多為20重量%。韌化材料之量足以在樹脂浸漬之強化纖維毗鄰層之間產生不同層間區域。
在結構層之熱塑性樹脂基質係基於PAEK聚合物(例如PEEK或PEKK)時，尤其適宜之韌化材料包含(i)由PEKK、PEEK、PEK或聚醯亞胺製得之聚合物膜；(ii)呈短切纖維形式之玻璃纖維、碳纖維或聚芳醯胺(aramid)纖維，非織
造氈或織造織物(例如面積重量為0.55 oz/yd2之玻璃纖維布)；(iii)由聚醯亞胺、PEEK、PEKK、PEK或玻璃製得之顆粒及其顆粒摻合物；(iv)由鋁、銅、鈦、鎳或其組合製得之金屬箔、網、薄片、纖維或顆粒。
在結構層之熱塑性樹脂基質係基於聚苯硫醚(PPS)聚合物時，尤其適宜之韌化材料包含(i)由PPS、PEEK、PEK、PEKK、PEKEKK、聚醯亞胺或聚醯胺(耐綸)製得之聚合物膜；(ii)呈短切纖維形式之玻璃纖維、碳纖維或聚芳醯胺纖維，非織造氈或織造織物；(iii)由PEEK、PEKK、PEK、PEKEKK或玻璃製得之顆粒及其顆粒摻合物；(iv)由鋁或不銹鋼製得之金屬箔、網、薄片、纖維或顆粒。
在韌化材料包含金屬箔或網時，可將金屬箔或網嵌入諸如PEEK或PEKK等韌化聚合物中。
在一實施例中，結構層係由經熱塑性基質樹脂浸漬之強化纖維構成，且韌化層係其中分散有熱塑性顆粒之隨機配置之熱塑性纖維之紗罩，其中熱塑性基質樹脂、紗罩及顆粒係由不同熱塑性材料製得。根據一實例，結構層係由經PPS浸漬之強化纖維構成，紗罩係由PEKK纖維構成且顆粒係由PEEK製得，或另一選擇為，紗罩係由PEEK纖維構成且顆粒係由PEKK製得。
可經由在產生單向膠帶之後使用各種方式施加(例如熱層壓、表面施加方法(包含靜電施加))韌化材料來將韌化材料添加至纖維強化複合物層(例如單向纖維增強之複合物
膠帶，亦即，具有樹脂及纖維之產物)中。此過程將韌化材料維持於其最為有效之材料外周邊處。進一步增加韌化材料之重量百分比可需要額外的樹脂膜以防止缺膠現象(starvation)，亦即壓層中之不足的樹脂將因局部較高纖維體積而具有空隙之情形。此努力展示壓層內低孔隙率有利，但藉由自單向膠帶中汲取樹脂來達成此情形。
在某些實施例中，藉由將韌化層線上層壓至產物上來增加藉由水性漿液及熔化浸漬方法製得之熱塑性單向膠帶之韌性。
本文所用之術語「纖維」具有彼等熟習此項技術者已知之其普通含義且可包含一或多種適於強化複合物之纖維材料。纖維可採取顆粒、薄片、晶鬚、短纖維、連續纖維、片、板層及其組合中之任一者的形式。連續纖維可進一步採用單向、多維(例如，二維或三維)、非織造、織造、針織、縫合、捲繞及編結組態以及卷曲纖維氈、毛氈及短切氈結構中之任一者。織造纖維結構可包括具有小於約1000條單絲、小於約3000條單絲、小於約6000條單絲、小於約12000條單絲、小於約24000條單絲、小於約48000條單絲、小於約56000條單絲、小於約125000條單絲及大於約125000條單絲之複數個織造纖維束。在其他實施例中，纖維束可藉由跨纖維束縫線、緯編插入針織縫線或少量樹脂(例如上膠)保持在適當位置。結構層中之強化纖維較佳地具有大於3500 MPa之拉伸強度。基於結構層之總重量，結構層中之強化纖維之含量較佳地至少為55重量%。
在一些態樣中，結構組份中所使用之纖維通常具有均勻直徑且通常具有習用直徑，例如約數微米至大約毫米範圍。因此，在一些態樣中，小直徑纖維可較為昂貴且可難以在層間區域中辨別，且由此並不提供用於本文所揭示壓層之離散層間區域。
纖維之組合物可視需要而變。纖維組合物之實施例可包含但不限於玻璃、碳、聚芳醯胺、石英、玄武岩、聚乙烯、聚酯、聚-對伸苯基-苯并雙噁唑(PBO)、硼、碳化矽、聚醯胺及石墨及其組合。在一實施例中，纖維係碳、纖維玻璃、聚芳醯胺或其他熱塑性材料。強化纖維可為有機或無機纖維。另外，纖維可包含紡織構造，包含彼等呈連續或非連續形式者。
結構纖維可包含單向膠帶或網片、纖維、預浸絲束或織物及非織造材料(例如氈或紗罩)。纖維增強之複合材料通常分類為膠帶、織造布、非織造布、紙張及其混合物。
「膠帶」通常係指沿條帶材料之單一軸延伸之單軸增強纖維。術語「布」通常係指沿條帶材料內之至少兩個不同軸放置之增強纖維。布係以雙軸、三軸及四軸形式購得，此表明纖維分別在兩個、三個或四個不同軸中延伸。纖維可視情況彼此為織造物，或可製成非織造布。大量複合增強纖維係以(例如)碳纖維、Kevlar®纖維、玻璃纖維及聚芳醯胺纖維形式購得。
本文所用之術語「基質」、「樹脂」及「基質樹脂」係指結構層中之樹脂組合物，且可包含少量可選添加劑(例
如無機填充劑)。
本文所用之術語「預浸物」包含經至少一部分纖維體積內之基質材料浸漬之纖維片或層。通常，預浸物呈備用於模製成微粒形狀並固化成最終複合物部分之可延展形式。該等複合物部分常用於製造承載結構部分及尤其航天複合物部分，例如機翼、機身、艙壁、控制表面、機動艇及施加韌性及衝擊性較為重要之其他應用。
本文所用之術語「中間層」具有彼等熟習此項技術者已知之其普通含義且包含置於其他層之間之層。在一實施例中，中間層可定位於複合物平面之中央。舉例而言，通常發現中間層位於結構纖維層之間。
「層間」係指兩個毗鄰層之間之區域。
壓層可由纖維增強之樹脂或預浸物之多個結構層構成。
本文所用之術語「疊層」具有彼等熟習此項技術者已知之其普通含義且可包含彼此毗鄰放置之一或多種預浸物。在某些實施例中，疊層內之預浸物可相對於彼此以所選定向進行定位。在又一實施例中，可視情況使用穿絲材料將預浸物疊層縫合在一起以抑制其相對運動偏離所選定向。在其他實施例中，「疊層」可包括本文所述完全浸漬預浸物、部分浸漬預浸物及多孔預浸物之任一組合。疊層可藉由包含但不限於手動疊層、自動膠帶疊層(ATL)、高級纖維佈置(AFP)及長絲捲繞在內之技術來製造。然後可(例如)藉由高壓滅菌將疊層固化以形成複合物件，其中韌化顆粒侷限於中間層中並向複合物件提供增加之韌性及損壞抗
性，此乃因顆粒即使在固化製程之後亦保持離散顆粒形式。
本文所用之術語「合併」及「未合併」具有彼等熟習熱塑物技術者已知之其普通含義。熔化可熔熱塑物之合併通常包含充分加熱以使熱塑性樹脂變形，使樹脂合併，並冷卻。熱層壓係典型合併製程。
在一些情形下，熱塑性樹脂在室溫下係固體。
在一些態樣中，製造方法包含將韌化劑熱層壓至單向膠帶外側，此係業內所使用之典型方法。
本文所用之術語「大約」、「約」及「實質上」代表接近仍能實施期望功能或達成期望結果所述量之量。舉例而言，術語「大約」、「約」及「實質上」可係指在小於10%、小於5%、小於1%、小於0.1%及小於0.01%所述量範圍內之量。
本文所用之術語「至少一部分」代表佔總體之量，其包括可包含該總體在內之佔總體的量。舉例而言，術語「一部分」可係指大於總體之0.01%、大於總體之0.1%、大於總體之1%、大於總體之10%、大於總體之20%、大於總體之30%、大於總體之40%、大於總體之50%、大於總體之60%、大於總體之70%、大於總體之80%、大於總體之90%、大於總體之95%、大於總體之99%及總體的100%之量。
藉由將兩個BGF 104 I617最終玻璃織物(玻璃增強物為0.55 oz/yd2)板層置於含有CypekTM-DSE樹脂及Hexcel AS4碳纖維(其係通常用於7 μm標稱直徑之12K纖維(12,000根長絲)之未定大小的碳纖維)之單向膠帶板層之間來形成測試壓層。不使用額外的樹脂膜。亦形成對照壓層，其與上述測試壓層相同，但並未使用玻璃織物韌化。使用ASTM D7136量測CAI性能。表1及2展示基於4份測試樣品之測試結果。
在與對照壓層相比時，發現玻璃織物會改良CAI性能。玻璃板層間韌化材料將CAI增加至57 KSI(正規化至固化板層厚度)，此較對照產物改良了2 ksi。玻璃韌化壓層之未正規化CAI強度為55.1 ksi，而未正規化對照為53.6 ksi。
圖1展示由基於CypekTM DSE基質之纖維增強之單向膠帶形成之對照壓層的DSC曲線，且圖2展示具有玻璃韌化層之壓層之DSC。
圖3係展示由基於CypekTM DSE基質之碳纖維增強之單向膠帶形成之對照壓層中層間區域的纖維照片。圖4係展示由基於CypekTM DSE基質之碳纖維增強之單向膠帶及玻璃韌化層形成之壓層中層間區域的纖維照片。
使用相同方法形成如上文在實例1中所論述之測試壓層，只是使用0.25 mil CypekTM-DSE膜作為用於韌化之中
間層來代替玻璃織物。使用ASTM D7136量測CAI性能。表3展示基於4份測試樣品之測試結果。
發現CypekTM DSE膜會改良衝擊後壓縮性能。達成55.1 ksi(未正規化)對53.6 ksi(未正規化，對照)。
圖5係展示根據此實例所形成壓層之層間區域之纖維照片。
藉由層疊經CypekTM DSE樹脂浸漬之AS4碳纖維之單向膠帶並在毗鄰單向膠帶之間插入兩個玻璃纖維布(0.72 oz/yd2)板層及兩個0.24 mil CypekTM DSE膜板層來製造測試壓層。使用710℉/100 psi之標準固化製程條件橫靠對照壓層來處理該等測試壓層。使用ASTM D7136量測CAI強度。表4及5展示基於4份測試樣品之測試結果。
對於基於對照CypekTM-DSE基質之碳纖維增強之壓層而
言，在1500 in-lb/in衝擊能量測試之後，CAI強度為49.8 ksi。對於使用玻璃織物及CypekTM DSE膜韌化之壓層而言，獲得平均為55.0 ksi之CAI強度。
儘管已在本揭示內容內闡述具體實施例，但應理解，該說明並不意欲具有限制意義，此乃因彼等熟習此項技術者可明瞭或可聯想到其他修改及變化。本申請案意欲涵蓋屬於隨附申請專利範圍之範圍內之所有該等修改及變化。
圖1展示由基於CypekTM DSE基質之纖維增強之單向膠帶形成之對照壓層的DSC曲線。
圖2展示由基於CypekTM DSE基質之碳纖維增強之單向膠帶及玻璃韌化層形成之改良壓層的DSC。
圖3係由基於APCTM-CypekTM DSE基質之碳纖維增強之單向膠帶形成之對照壓層中層間區域的顯微照片。
圖4係由基於CypekTM DSE基質之碳纖維增強之單向膠帶及玻璃韌化層形成之壓層中層間區域的顯微照片。
圖5係由基於CypekTM DSE基質之碳纖維增強之單向膠帶及CypekTM DSE韌化膜形成之壓層中層間區域的顯微照片。
Claims (20)
- 一種熱塑性複合壓層，其包括：複數個呈堆疊配置之結構層，每一結構層皆包括經熱塑性基質樹脂浸漬之強化纖維；及複數個層間區域，每一層間區域皆形成於兩個毗鄰結構層之間，其中每一層間區域皆包括選自以下之韌化材料：(a)非織造氈或織造織物，其包括玻璃纖維、碳纖維或聚芳醯胺(aramid)纖維；(b)具有分散於其中之韌化顆粒之熱塑性聚合物膜，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(c)非織造紗罩，該紗罩包括隨機配置之熱塑性纖維及分散於該紗罩中之韌化顆粒，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(d)韌化顆粒，其包括選自以下之材料：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(e)金屬箔、網、薄片、纖維或顆粒，其由選自以下之金屬材料製得：鋁、銅、鈦、鎳、不銹鋼及其組合。
- 如請求項1之熱塑性複合壓層，其中該結構層中之該熱塑性基質樹脂包括PPS、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)。
- 如請求項1之熱塑性複合壓層，其中該等強化纖維係由選自由碳、石墨、聚芳醯胺及玻璃組成之群之材料製得。
- 如請求項1之熱塑性複合壓層，其中該等結構層中之該等強化纖維係單向對準之纖維。
- 如請求項1之熱塑性複合壓層，其中該等PAEK聚合物係選自：聚醚酮(PEK)、聚醚醚酮(PEEK)、聚醚酮酮(PEKK)及聚醚酮醚酮酮(PEKEKK)。
- 如請求項1之熱塑性複合壓層，其中該韌化材料係包括由不同PAEK聚合物製得之韌化顆粒或由玻璃及PAEK聚合物之摻合物製得之韌化顆粒的熱塑性聚合物膜(b)或非織造紗罩(c)。
- 如請求項1之熱塑性複合壓層，其中該韌化材料係含有分散於其中之PAEK顆粒之PAEK聚合物膜，其中該聚合物膜及該等顆粒係由不同PAEK聚合物製得。
- 如請求項1之熱塑性複合壓層，其中基於該壓層中該基質樹脂之總重量，該韌化材料之含量至多為20重量%。
- 如請求項1之熱塑性複合壓層，其中該韌化材料係玻璃纖維布。
- 一種複合結構，其係藉由合併如請求項1之熱塑性複合壓層產生，其中該複合結構在合併後之衝擊後壓縮(CAI)強度大於53 ksi。
- 一種複合結構，其包括：結構層，其包括經熱塑性基質樹脂浸漬之強化纖維；及 兩個韌化層，其位於該結構層之相對表面上，該等韌化層中之每一者皆包括選自以下之韌化材料：(a)非織造氈或織造織物，其包括玻璃纖維、碳纖維或聚芳醯胺纖維；(b)具有分散於其中之韌化顆粒之熱塑性聚合物膜，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(c)非織造紗罩，該紗罩包括隨機配置之熱塑性纖維及分散於該紗罩中之韌化顆粒，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(d)韌化顆粒，其包括選自以下之材料：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合。
- 如請求項11之複合結構，其中該結構層中之該熱塑性基質樹脂包括PPS、PEEK或PEKK。
- 如請求項11之複合結構，其中該韌化材料係含有分散於其中之韌化顆粒之熱塑性聚合物膜或非織造紗罩，其中該等顆粒係由不同PAEK聚合物或玻璃及PAEK聚合物之混合物製得。
- 如請求項11之複合結構，其中該韌化材料係玻璃纖維布。
- 如請求項11之複合結構，其中該結構層中之該等強化纖維具有大於3500 MPa之拉伸強度。
- 如請求項11之複合結構，其中基於該結構層之總重量， 該結構層中之該等強化纖維之含量為至少55重量%。
- 如請求項11之複合結構，其中該等強化纖維係單向對準之纖維。
- 一種複合壓層，其係藉由層疊複數個如請求項11之複合結構來產生，以便在兩個毗鄰結構層之間形成層間區域，且該層間區域包括該韌化材料。
- 一種形成複合壓層之方法，其包括：形成複數個結構層，每一結構層皆包括經熱塑性基質樹脂浸漬之強化纖維；將韌化材料施加於每一結構層之至少一個表面上，該韌化材料係選自：(a)非織造氈或織造織物，其包括玻璃纖維、碳纖維或聚芳醯胺纖維；(b)含有分散於其中之韌化顆粒之熱塑性聚合物膜，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(c)非織造紗罩，該紗罩包括隨機配置之熱塑性纖維及分散於該紗罩中之韌化顆粒，其中該等顆粒係由選自以下之材料製得：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；(d)韌化顆粒，其包括選自以下之材料：PAEK聚合物、聚醯亞胺、玻璃、陶瓷及其組合；及層疊該等結構層以便使該韌化材料位於毗鄰結構層之間形成之層間區域中， 其中該等結構層中之該等強化纖維具有大於3500 MPa之拉伸強度。
- 如請求項19之方法，其中基於該結構層之總重量，該結構層中之該等強化纖維之含量為至少55重量%。
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Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8796164B2 (en) * | 2010-12-28 | 2014-08-05 | Cytec Technology Corp. | Multilayer and composition gradient structures with improved damping properties |
| CN104736328B (zh) * | 2012-10-18 | 2017-06-13 | 塞特工业公司 | 热塑性材料和工具的表面工程 |
| PL3024644T3 (pl) | 2013-07-24 | 2018-11-30 | Integrated Composite Products Inc. | Kompozytowy konstrukcyjny wyrób |
| CN103625040A (zh) * | 2013-11-04 | 2014-03-12 | 孙直 | 具有纤维界面增韧的复合材料-金属材料层合结构及方法 |
| US20150174872A1 (en) * | 2013-12-23 | 2015-06-25 | Cytec Engineered Materials Inc. | Toughened composite materials and methods of manufacturing thereof |
| EP3088448B1 (en) * | 2013-12-26 | 2021-02-24 | Katholieke Universiteit Leuven | Preform, sheet material, and integrated sheet material |
| FR3023746B1 (fr) | 2014-07-21 | 2016-07-29 | Univ Paul Sabatier - Toulouse Iii | Procede de preparation d'une structure composite stratifiee electriquement conductrice |
| US10046539B2 (en) * | 2014-07-22 | 2018-08-14 | United Technologies Corporation | Secondary reinforcement at interface of laminate structure |
| WO2016025564A2 (en) | 2014-08-13 | 2016-02-18 | Integrated Composite Products, Inc. | Reinforcing article |
| US10026522B1 (en) * | 2014-08-19 | 2018-07-17 | Superior Essex International LP | Flame retardant insulation material for use in a plenum cable |
| ES2905454T3 (es) * | 2014-09-22 | 2022-04-08 | Cytec Ind Inc | Materiales compuestos con alta conductividad eléctrica en la dirección Z |
| US10632718B2 (en) * | 2014-09-30 | 2020-04-28 | The Boeing Company | Filament network for a composite structure |
| US20200139642A1 (en) * | 2014-12-17 | 2020-05-07 | E.I. Dupont De Nemours And Company | Glass and carbon fiber composites and uses thereof |
| WO2016130784A1 (en) | 2015-02-12 | 2016-08-18 | Integrated Composite Products, Inc. | Pre-stressed fiber reinforcing member and method for its manufacture |
| EP3056337A1 (en) * | 2015-02-13 | 2016-08-17 | Advanced Materials Technology Innovation Company | Composite laminate with reinforcement of metal mesh |
| CN107428034B (zh) | 2015-03-10 | 2020-07-31 | 加固纤维热塑性塑料私人有限公司 | 制备单向纤维增强带的方法 |
| NL2014630B1 (en) * | 2015-04-14 | 2016-12-16 | Advanced Mat Tech Innovation Company | Composite Laminate with Reinforcement of Metal Mesh. |
| CN104842619B (zh) * | 2015-05-06 | 2017-09-12 | 江苏恒神股份有限公司 | 高韧性多层结构预浸料制造工艺 |
| CN104985180B (zh) * | 2015-07-31 | 2017-08-18 | 中国航空工业集团公司北京航空制造工程研究所 | 一种金属间化合物及其制备方法及设备 |
| CN113427841B (zh) * | 2015-11-12 | 2023-07-11 | 塞特工业公司 | 作为复合材料中的夹层的混合面纱 |
| ES2954423T3 (es) * | 2015-11-30 | 2023-11-22 | Cytec Ind Inc | Materiales de revestimiento para estructuras de material compuesto |
| US10370530B2 (en) | 2016-02-26 | 2019-08-06 | Ricoh Company, Ltd. | Methods for solid freeform fabrication |
| EP3251827B1 (en) * | 2016-05-30 | 2021-07-28 | Covestro Deutschland AG | Combined carbon- and glass-fiber reinforced thermoplastic polyurethane and polyamide composites and its manufacturing |
| US11591451B2 (en) | 2016-08-02 | 2023-02-28 | Solvay Specialty Polymers, Llc | Poly(aryl ether ketone) (PAEK) compositions including a low molecular weight aromatic compound |
| WO2018024744A1 (en) * | 2016-08-02 | 2018-02-08 | Solvay Specialty Polymers Usa, Llc | Poly(aryl ether ketone) (paek) compositions including a low molecular weight aromatic compound |
| US11014337B2 (en) | 2016-12-14 | 2021-05-25 | The Boeing Company | Laminate structures comprising fiber-reinforced thermoplastic prepreg plies |
| US11077644B2 (en) | 2016-12-14 | 2021-08-03 | The Boeing Company | Material systems and methods of manufacturing material systems |
| US11273622B2 (en) | 2016-12-14 | 2022-03-15 | The Boeing Company | Stiffening elements that comprise integral current flowpaths |
| KR102253106B1 (ko) * | 2017-05-30 | 2021-05-14 | (주)엘지하우시스 | 연속섬유 복합재 및 그 제조 방법 |
| US10710348B2 (en) | 2017-07-26 | 2020-07-14 | The Boeing Company | Methods and apparatus to increase fire resistance and fracture toughness of a composite structure |
| GB201803802D0 (en) * | 2018-03-09 | 2018-04-25 | Rolls Royce Plc | Composite fan blade and manufacturing method thereof |
| CN108975765B (zh) * | 2018-07-16 | 2021-04-06 | 江苏省苏安能节能建材科技有限公司 | 一种真空绝热板及其制备和应用 |
| JP7196464B2 (ja) * | 2018-08-24 | 2022-12-27 | 東レ株式会社 | 繊維強化熱可塑性樹脂基材およびそれを用いた成形品 |
| CN109467726A (zh) * | 2018-10-16 | 2019-03-15 | 厦门大学 | 采用玻璃微珠增强纤维/树脂基复合材料层合板层间强度的增强方法 |
| RU209510U1 (ru) * | 2019-08-22 | 2022-03-16 | РусКомПолимер | Композитный материал |
| EP3889208B1 (en) * | 2020-04-03 | 2022-11-30 | SHPP Global Technologies B.V. | Method of making a high filled fiber-mesh reinforced ceramic-thermoplastic polymer composites with outstanding mechanical performance |
| WO2022043387A1 (en) * | 2020-08-28 | 2022-03-03 | Toray Advanced Composites | Ud tape with improved processing characteristics and roughened surface and method for production thereof |
| CN112721230B (zh) * | 2020-11-16 | 2022-03-25 | 浙江大学 | 制造三维增强碳纤维复合材料的微细纤维高能植入装备 |
| CN114425891B (zh) * | 2022-02-25 | 2023-06-30 | 中国船舶重工集团公司第十二研究所 | 高渗透性插层增韧材料及其制备方法 |
| CN114773844A (zh) * | 2022-06-21 | 2022-07-22 | 北京玻钢院复合材料有限公司 | 一种聚酰亚胺增韧邻苯二甲腈树脂组合物、复合材料以及其制备方法 |
Family Cites Families (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1570000A (en) * | 1976-06-10 | 1980-06-25 | Nat Res Dev | Thermoplastics materials |
| US4604319B1 (en) * | 1984-06-01 | 1995-07-04 | American Cyanamid Co | Thermoplastic interleafed resin matrix composites with improved impact strength and toughness |
| US5141804A (en) * | 1988-11-01 | 1992-08-25 | American Cyanamid Company | Interleaf layer in fiber reinforced resin laminate composites |
| CA2026113C (en) * | 1989-01-25 | 1998-12-01 | Tsunoe Igarashi | Prepreg, composite molded body, and method of manufacture of the composite molded body |
| JP2892061B2 (ja) * | 1989-11-24 | 1999-05-17 | 旭化成工業株式会社 | 積層体 |
| US4957801A (en) * | 1989-05-17 | 1990-09-18 | American Cyanamid Company | Advance composites with thermoplastic particles at the interface between layers |
| CA2056034C (en) * | 1990-11-29 | 2001-04-17 | Toshihiro Hattori | Prepregs, process for producing the same and laminates produced with the same |
| JPH07238174A (ja) * | 1991-03-01 | 1995-09-12 | E I Du Pont De Nemours & Co | 繊維強化複合材料 |
| US5660901A (en) * | 1991-04-30 | 1997-08-26 | Dexter Corporation | Oriented expanded molded products |
| JPH05269909A (ja) * | 1992-03-30 | 1993-10-19 | Aisin Seiki Co Ltd | 繊維強化樹脂成形品 |
| JPH0797465A (ja) * | 1993-08-05 | 1995-04-11 | Mitsui Toatsu Chem Inc | プリプレグ及び積層構造体 |
| JP3089984B2 (ja) * | 1994-03-07 | 2000-09-18 | 東レ株式会社 | 補強織物とその製造方法および製造装置 |
| JP3440615B2 (ja) * | 1995-03-22 | 2003-08-25 | 東レ株式会社 | プリプレグおよび繊維強化複合材料 |
| US6265333B1 (en) * | 1998-06-02 | 2001-07-24 | Board Of Regents, University Of Nebraska-Lincoln | Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces |
| JP3877996B2 (ja) * | 2001-10-31 | 2007-02-07 | 敏夫 谷本 | 繊維強化プラスチック複合材料およびその製造方法 |
| US7087296B2 (en) * | 2001-11-29 | 2006-08-08 | Saint-Gobain Technical Fabrics Canada, Ltd. | Energy absorbent laminate |
| US6977247B2 (en) * | 2002-02-21 | 2005-12-20 | Supergen, Inc. | Sequential therapy comprising a 20(S)-camptothecin and a pyrimidine base analog |
| FR2859943B1 (fr) * | 2003-09-23 | 2007-07-13 | Rhodia Industrial Yarns Ag | Structure composite |
| TWI353303B (en) * | 2004-09-07 | 2011-12-01 | Toray Industries | Sandwich structure and integrated molding using th |
| EP1937774A2 (en) * | 2005-09-16 | 2008-07-02 | General Electric Company | Blends of poly aryl ether ketones and polyetherimide sulfones |
| GB0522960D0 (en) * | 2005-11-10 | 2005-12-21 | B I Group Plc | Composite material |
| US7759267B2 (en) * | 2006-04-05 | 2010-07-20 | Azdel, Inc. | Lightweight composite thermoplastic sheets including reinforcing skins |
| CN1923506B (zh) * | 2006-07-19 | 2010-08-04 | 中国航空工业第一集团公司北京航空材料研究院 | 一种增韧的复合材料层合板及其制备方法 |
| GB0619401D0 (en) * | 2006-10-02 | 2006-11-08 | Hexcel Composites Ltd | Composite materials with improved performance |
| GB0717507D0 (en) * | 2007-09-07 | 2007-10-17 | Cytec Tech Corp | Composite materials and their use |
| GB0805640D0 (en) * | 2008-03-28 | 2008-04-30 | Hexcel Composites Ltd | Improved composite materials |
| CN102271905B (zh) * | 2009-01-06 | 2015-02-18 | 塞特克技术公司 | 具有改进的声学和震动阻尼性能的结构复合材料 |
| DE102009006130B4 (de) * | 2009-01-26 | 2011-09-15 | Daimler Ag | Verbundbauteil mit Deckschicht |
| ES2733682T3 (es) * | 2009-02-05 | 2019-12-02 | Arkema Inc | Ensamblajes que contienen capas ligantes de polietercetonacetona |
| US8158245B2 (en) * | 2009-09-24 | 2012-04-17 | Cytec Technology Corp. | Thermoplastic composites and methods of making and using same |
| TWI496820B (zh) * | 2009-12-17 | 2015-08-21 | Cytec Tech Corp | 用於層間靭化之工程化交聯熱塑性顆粒 |
| ES2773041T3 (es) * | 2009-12-18 | 2020-07-09 | Cytec Tech Corp | Métodos para impartir conductividad a materiales usados en la fabricación de artículos compuestos y materiales del mismo |
| JP5920690B2 (ja) * | 2011-05-30 | 2016-05-18 | 福井県 | プリプレグシート材及びその製造方法 |
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| US20130052897A1 (en) | 2013-02-28 |
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| WO2013032620A1 (en) | 2013-03-07 |
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| RU2014111809A (ru) | 2015-10-10 |
| AU2012301482B2 (en) | 2014-11-13 |
| KR20140066201A (ko) | 2014-05-30 |
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