TWI401160B - 複合材料、及包含該材料之產品和纖維-金屬複合材料 - Google Patents

複合材料、及包含該材料之產品和纖維-金屬複合材料 Download PDF

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TWI401160B
TWI401160B TW094132998A TW94132998A TWI401160B TW I401160 B TWI401160 B TW I401160B TW 094132998 A TW094132998 A TW 094132998A TW 94132998 A TW94132998 A TW 94132998A TW I401160 B TWI401160 B TW I401160B
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layer
layers
thickness
carbon fiber
thin
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TW094132998A
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TW200624260A (en
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Stephen W Tsai
Kazumasa Kawabe
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Itochu Corp
Ilt Corp
Mitsuya Co Ltd
Fukui Prefectural Government
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    • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
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    • B31F1/00—Mechanical deformation without removing material, e.g. in combination with laminating
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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Description

複合材料、及包含該材料之產品和纖維-金屬複合材料 發明背景 發明領域
本發明係大致有關於纖維複合材料，且特別是有關於使用薄層以達成較佳物理性質之複合材料及製造這些材料之方法。
 先前技術之說明
具有或沒有滲浸樹脂之習知複合層的厚度至少為0.12mm，且複合層之積層係利用將多數單向層堆疊在一起並接著利用某種固化與硬化製程而形成。具有不同方位之層必須在一個以上之方向提供機械性質，因此，最少需要兩層方位，例如，一層方位呈一參考0°角且另一層方位呈90°。在以下說明之層方位係使用例如[0/90]或[＋45/－45]之記號表示一層呈0°且另一層以90°積層在該第一層上或一層呈＋45°且另一層以－45°積層在另一層上，且以度表示相對一軸之相對方位。此外，積層必須對稱地堆疊以避免捲曲。因此，在先前技術中，由於各層至少有0.12mm，故不論是否需要這厚度，如[0/90/0]之最少3層或如[0/90/90/0]之最少4層將具有0.36或0.48之最小總(隔距)厚度。實務上通常是具有[0/90/45/－45]之4層方位，且使這對稱時，則需要8層且在使用至少0.12mm之習知層之情形下，最小總積層厚度大約是8x0.12mm，或大約1mm。
層間分離通常會發生在一積層之自由邊緣處、或在施加一集中負載之點處、或在一受到一橫向衝擊或在該積層硬化時形成一應力之點處。無論其來源為何，層間分離是一種通常會使一多方向積層無法完全具有重要平面內負載承接能力之失效形態。由於如同波音(Boeing)787與空中巴士(Airbus)350及380飛行器一般地不斷使用複合材料作為更多的主要結構，複合材料組件可能數百層厚。層間分離對於在許多應用中接受複合材料而言是一嚴重之威脅。
一般的解決方式是形成一作為一立體編織織物的積層，且這編織方法有許多種形態，而其至少有兩個缺點：成本高、且該平面內性質降低以產生平面外纖維用之空間。另一種方法是使用橫向車縫，這方法不僅成本高而且具有不可靠的價值。又，車縫會對複合積層產生另外的損害。
 發明概要
簡言之，本發明之一實施例包括一使用厚度等於或小於0.08mm之薄層構成的積層。另一實施例包括一厚度小於0.08mm之薄層與多數厚度至少0.12mm之較厚習知層的組合，且這些組合可提供對微破裂與層間分離之較佳抵抗性、積層之較薄最小隔距、厚與薄層可混用、補強結合接點、具有高於習知編織織物之效能的互相交錯產品、管路與容器之較佳線上固化、及切碎纖維，以形成較強之片狀模製成形化合物。多數層方位次積層(以下稱為“次積層模組”)可以形成為一供複合積層用之基本構成元件，因此可減少組裝成本並且維持對層間分離之高抵抗性。不論是否為自動化，來自薄層次積層與積層的產品對於由習知厚層積層構成者而言，在成本上是具有競爭力的。
使用一習知纖束散布法，可以散布碳、玻璃或克維拉(Kevlar)纖維之習知12k纖束以形成一厚度薄至0.02mm之帶。以這種薄層，本發明之3層方向對稱次積層可以具有與習知0.12mm層相同之0.12mm厚度，且最小隔距可減少至習知層厚度之六分之一(1/6)。在一對稱4層積層中，該最小隔距為0.16mm，且這種薄隔距模組可提供習知厚層無法提供之設計選擇性，並且對層間分離具有更高之抵抗性。事實上，習知複合結構之許多設計係取決於這層間分離準則。 因此，較高效能或較輕重量之結構可以使用薄層積層來有效地設計。
圖式簡單說明
第1圖顯示本發明之薄層積層；第2圖顯示先前技術之較厚層；第3圖是正向應力隨層厚度變化之圖；第4圖是剪應力隨層厚度變化之圖；第5圖是層間分離開始應力隨層厚度變化之圖；第6A圖顯示使用厚與薄層之情形；第6B圖顯示一次積層；第7A圖是使用次積層之複合材料的立體圖；第7B圖是使用次積層之複合材料以顯示接點的側視圖；第8A圖是剛性隨層厚度變化之圖；第8B圖是最大應力隨層厚度變化之圖；第9圖顯示乾薄層；第10圖顯示一樹脂浸滲薄層片；第11圖顯示三層積層；第12圖顯示及在一捲曲交換區域中之層編織與角度；第13A圖是一易碎黏著劑在各種溫度下，負載變形對層厚度之圖；第13B圖是一可延展黏著劑在各種溫度下，負載變形對層厚度之圖；第14圖顯示使用薄層來接合兩層；第15圖是一顯示第14圖之接點有效性的表；第16圖顯示在一積層一側上使用金屬箔；第17圖顯示在一積層兩側上之金屬箔；第18A圖顯示一在積層兩側與中心上之金屬箔；第18B圖是第18A圖之放大部份；及第19圖顯示在該積層中心無金屬箔之層構造。
 實施例之詳細說明
本發明之複合材料10係顯示於第1圖中，且該複合材料10具有多數包括以點表示並定向於第一方向之第一層12的層(薄層)。該等第一層12係被多數定向於與該第一方向不同之第二方向的第二層14分開，且該等第二層14係以無任何記號之方式表示以在第1圖中與該等第一層12做區別。依據本發明，該等薄層具有小於0.08mm，且最好是0.02mm至0.06mm之厚度“t”。第2圖僅用以顯示一習知/先前技術之積層係由如厚度大於本發明之厚度的交錯層16、18構成，且各層具有一等於或大於0.12mm之厚度“T”。
依據本發明，薄層積層提供較佳之抗層間分離性。它們不需要平面外纖維且因此可保持較佳之平面內性質，舉例來說，在一積層之自由緣處顯現之計算出的正向與剪應力係顯示在第3與4圖中，且隨著層厚度變化。該至少0.12MM之習知/先前技術之層厚度係顯示在各圖右方，且層厚度朝左方向下減少至0.02mm。這些測量顯示當層厚度減少至0.12mm之習知薄層積層之1/3與1/6時，該正向與剪應力大幅減少，而這對於先前技術而言是一未預期到的結果。如此，該薄層積層提供較佳之抗層間分離性。
薄層在層間分離開始時之效果的另一例子係顯示在第5圖中，且第5圖顯示層間分離所需應力隨有效層厚度變化。當層厚度減少時，該層間分離應力再次大幅增加。
另一實施例中，厚與薄層之混合組合可在效能與成本之間提供一平衡，且這組合係包含在本發明中。薄層不僅增加韌性，它們亦以降低層厚度來增加之撓性。這是利用一次積層模組來達成，且在該次積層模組中，一具有不同方位之有薄層模組或一具有不同方位之薄與厚層組合係預成形為供積層用之建構元件。在此非降低個別的層厚度，而是降低次積層模組之層厚度。
例1 ：本發明之一例包括厚度0.12mm之厚層與厚度0.02mm之薄層的組合，這顯示在具有薄層21與厚層23之第6A圖中。此外，在6B圖中之次積層25可以是一具有一厚[0]層27與一薄[90]層29之厚薄混合體，且這次積層模組之總厚度可為0.12mm＋0.02mm並且此時之[0]的百分比將是0.12/0.14＝86%。使用這次積層來建構一起重桿或吊桿可產生一具有以僅使用厚層之習知積層無法具有之韌性的高異向性結構。對後者之情形而言，厚層之重覆模組將必須是9層[0]與一層[90]，且總次積層厚度將是1.20mm並且[0]之百分等於90%。這結構具有堆疊在一起之9層[0]，而這由韌性之觀點來看是不良之設計。這實務使起重桿不穩定且容易因扣合而失效。
例2 ：如果需要更高百分比之[0]，則可使兩厚層[0]緊接在一薄層[90]後。此時，[0]之百分比將是0.24/0.26＝92%。一具有兩[0]與一[＋/－45]之三向次積層模組的[0]之百分比將是0.24/0.28＝86%。這兩個例子將給予該起重桿或吊桿更高韌性之積層，且這混合結構亦可用於驅動桿、板片彈簧及運動物品(如，撐竿跳桿、曲棍球桿、高爾夫球桿等)。
例3 ：一厚三層積層之例子是一具有一厚0.12mm層[0]與兩薄0.02mm、具角度層[＋/－30]或[＋/－45]之三向次積層，如一[＋30/0/－30]或[＋45/0/－45]模組。總次積層厚度是0.16mm，且這可以在一個步驟中以一次降低層厚度來達成。如此可產生任一厚與薄層之組合的三方向模組，而這設計彈性使產品具有明顯較佳之積層效能及在製造時明顯的節省成本效果。
例4 ：多方向次積層之相同觀念可以設計作為一複合結構之次結構之桁或肋架，在此例中，在網架中之剪切模數是最重要的，且一厚薄混合體可具有與薄[0]組合之厚[＋/－45]。在所有的這些應用中，次積層之積層過程可以是在單一方向上，如沿著該桁架之軸。若為機翼之表面，該積層過程可沿著機翼之軸進行。若為機身時，則該積層過程可在兩方向上，一方向沿著箍環方向而另一方向沿著軸方向，或沿著兩螺旋角度。如此可非常明顯地節省積層機能力與積層時間及人力。
本發明之複合材料可以多數次積層模組構成。第7A圖顯示一包括多數次積層模組33之複合材料31，且第7B圖是一類似於第7A圖並且顯示一具有多數次積層37之複合材料35的平面側視圖，以顯示多數次積層接點39。多數次積層片係在寬度上結合在一起並且該等片以不需在厚度方向上重覆該接點部份的方式堆疊。第7A、7B圖之次積層可以完全相同，或者它們可以是不同的。一次積層可具有所有薄層，或一薄與厚層之組合、及/或該次積層可具有多數互相交錯織物之層，如第12圖所示。利用薄層可使次積層厚度與一習知層厚度大致相同。利用這方法，可得到具有優異機械性質之大型複合模製成形品。
一形成多數薄層纖束之方法係利用散布習知纖束，且該等分散纖束之橫截面是矩形的，且厚度等於或小於0.04mm，而寬度為20mm。這些分散纖束可以輕易地互相交錯並形成一編織物，且互相交錯之纖束的橫截面係顯示在第12圖中。互相交錯織物提供可輕易配合複雜工具幾何形狀之高效能積層，且這種互相交錯織物之總厚度可為該薄層厚度之總厚度的兩倍，即，若使用0.02mm之薄層，則厚度為0.04mm。一具有厚與薄層之互相交錯織物的結構效能係顯示在第8A與8B圖中，其中顯示當層厚度由右至左減少時機械性質增加。當使用0.02mm層而不是0.12mm層時，剛性增加35%且最大應力減少20%。
薄層24可以是(a)一或多數纖維26(即，沒有樹脂浸滲)，如第9圖所示，且具有小於0.08mm並以小於0.06mm為佳之厚度，或是(b)多數在一樹脂浸滲(預浸)片28中之纖維26，且具有小於0.08mm並以小於0.06mm為佳之厚度(第10圖)。
舉例而言，積層28係顯示在第11圖，且三層30、32、34具有多數薄層36。薄層可位在靠近末端38處且沿著在40處之側並在此與層42接合，而在其間會有間隙。因為該層厚度非常小，所以這些間隙只會稍微影響該積層之機械性質。
第12圖是互相交錯層41之橫截面圖，且因為該捲曲互換區域42之尺寸及第12圖所示之所得角度在層厚度減少時會變小，故薄層積層具有較佳性質。當該等分散纖束接合垂直相交之纖束而上下編織時，該捲曲之受影響區域隨纖束變薄而變小。該等互換之纖束必須配合彼此的厚度，且該等纖束愈薄，在纖束互換處所需之配合度愈小。如此，互相交錯纖束與在互換處產生之應力會受到這厚度之影響。該等纖束愈薄，剛性將愈高且局部應力將愈低。
結合之接點提供接合兩複合組件之最佳方法，且結合接點易於產生且在接點處產生之應力集中最小。廣義來說，有兩種結合接點黏著劑：易脆且具延展性的黏著劑。第13A與13B圖分別顯示一易脆黏著劑與一延展性黏著劑在各種溫度下之負載－變形曲線。該最堅硬之黏著劑負載－變形曲線是室溫行為，而當溫度增加時，該黏著劑將會愈來愈像一可延展材料。在第13A圖中之易脆黏著劑是一玻璃粉末補強環氧樹脂；該延展性黏著劑是PMMA。
一新的結合接點43可使用薄層產生而作為一補強物，如第14圖所示。這種接點之有效性係顯示在第15圖之表中，其中顯示由一特定元件分析所得之預測值，請注意應力降低至未補強黏著劑之應力的56%與30%。此外，這接點設計在剝離與剪應力之間達成一平衡，沒有一者凌駕於另一者之情形，如同未補強黏著劑之情形一般。對薄層補強黏著劑，該[0]方位與施加於該結合接點之軸向力對齊。
片狀模製成形化合物與墊可以使用切碎薄層纖維，且因為由於捲曲互換所造成之剛性與強度損失減少，這些產品具有較高之效能。此外，薄層利用立方關係減少彎曲剛性；即，厚層厚度之1/6將具有原始剛性之1/216。如此，一由切碎薄層纖束製成之片狀模製成形化合物可更輕易地配合在一模製零件中之曲線與形狀的劇烈變化。除了這加工優點以外，還有較佳剛性與強度。
碳補強熱塑性帶之線上固化亦可在品質與加工速度方面由薄層得到好處，且當該帶厚度較小時，該等厚層帶之一般似板硬度(高剛性)可以明顯減少成更可撓曲或彎曲之帶。前述相同之立方關係亦同樣適用於帶撓曲硬度。在使用薄帶之線上加工時，不需要僅為了使該帶更具撓性而預熱。這製程可以用來利用單纖維彎曲並接著硬化來製造壓力容器。
第16－18圖示本發明之積層的另一實施例，且該積層包括金屬與薄層積層。第16圖顯示附加於薄層積層46一側上之金屬44，且第17圖顯示在薄層積層52兩側上之金屬48、50。第16與17圖顯示一金屬基材複合物結合於一薄層積層之一或兩側的產品，且該金屬層可以多種包括金屬箔、蒸鍍(CVD)、金屬埋入聚合物、電鍍等習知方式產生。該金屬可保護該積層，且在一沒有塗層之薄層積層中，該表面曾非常薄。當在該積層中之外側纖維受損時(例如因撞擊或刮傷)，在該表面層中會輕易發生纖維解體，而這會導致該積層失效。第16與17圖所示之產品有助於防止這種纖維解體與失效。第18B圖是第18A圖之一部份，並顯示在第18A圖之積層層中之纖維的方位(90°、45°)。當金屬基材複合物插入薄層積層中心時，如第18A與18B圖，可防止積層厚度成為兩倍。這有助於對稱積層，其中在該積層中心處厚度加倍會導致基材破裂與層間分離。第19圖顯示如果沒有設置金屬，則該中心層之厚度會成為兩倍，而這會產生該積層之破裂與層間分離可能性。
一組使用金屬與薄層複合物之新金屬基材複合物可以相當低的成本製造，例如，可形成使用薄碳纖維強化塑膠結合鈦(Tigr：鈦-石墨)或銅(Cugr：銅-石墨)之高溫複合材料(CFRP)。這種金屬基材複合物對包括化學管路與容器之許多應用均具有耐高溫性與獨特之耐腐蝕性。
對墊與交錯織物而言，包括樹脂轉移成型(RTM)法及真空輔助樹脂轉移成型(VARTM)法，使用薄層材料可使材料更容易流動，且增加複雜表面之配合性並保持優異物理性質。
前述實施例係作為本發明之例子，且發明所屬技術領域中具有通常知識者可了解這些例子之變化例。這些變化例係包含在本發明之精神中。
10．．．複合材料
12．．．第一層
14．．．第二層
16,18．．．交錯層
21．．．薄層
23．．．厚層
24．．．薄層
25．．．次積層
26．．．纖維
27．．．厚[0]層
28．．．樹脂浸滲(預浸)片；積層
29．．．薄[90]層
30,32,34．．．層
31．．．複合材料
33．．．次積層模組
35．．．複合材料
36．．．薄層
37．．．次積層
38．．．末端
39．．．次積層接點
40．．．側
41．．．互相交錯層
42．．．捲曲互換區域
43．．．結合接點
44．．．金屬
46．．．薄層積層
48,50．．．金屬
52．．．薄層積層
54,56．．．側
58．．．中心
60,62．．．薄層積層
T,t．．．厚度
第1圖顯示本發明之薄層積層；第2圖顯示先前技術之較厚層；第3圖是正向應力隨層厚度變化之圖；第4圖是剪應力隨層厚度變化之圖；第5圖是層間分離開始應力隨層厚度變化之圖；第6A圖顯示使用厚與薄層之情形；第6B圖顯示一次積層；第7A圖是使用次積層之複合材料的立體圖；第7B圖是使用次積層之複合材料以顯示接點的側視圖；第8A圖是剛性隨層厚度變化之圖；第8B圖是最大應力隨層厚度變化之圖；第9圖顯示乾薄層；第10圖顯示一樹脂浸滲薄層片；第11圖顯示三層積層；第12圖顯示及在一捲曲交換區域中之層編織與角度；第13A圖是一易碎黏著劑在各種溫度下，負載變形對層厚度之圖；第13B圖是一可延展黏著劑在各種溫度下，負載變形對層厚度之圖；第14圖顯示使用薄層來接合兩層；第15圖是一顯示第14圖之接點有效性的表；第16圖顯示在一積層一側上使用金屬箔；第17圖顯示在一積層兩側上之金屬箔；第18A圖顯示一在積層兩側與中心上之金屬箔；第18B圖是第18A圖之放大部份；及第19圖顯示在該積層中心無金屬箔之層構造。
10．．．複合材料
12．．．第一層
14．．．第二層
t．．．厚度

Claims (13)

  1. 一種複合材料，包含至少多數碳纖維薄層之一第一層以及多數碳纖維薄層之一鄰近的第二層，該等碳纖維薄層具有自0.02至0.06 mm之厚度，其中該第一層中之該等碳纖維薄層係被定向於一第一方向，以及該第二層中之該等碳纖維薄層係被定向於與該第一方向呈一角度之一第二方向，其中該材料包括具有一厚度為至少0.12mm之多數習知層及具有一厚度為自0.02至0.06mm之多數薄層的一組合。
  2. 如申請專利範圍第1項之材料，其中該材料包括多數碳纖維薄層之次積層模組的一組合。
  3. 如申請專利範圍第2項之材料，其中該材料包括多數碳纖維薄層之多數次積層模組及多數習知層之多數次積層模組。
  4. 如申請專利範圍第2項之材料，其中該材料包括具有多數碳纖維薄層及多數習知層之多數次積層模組。
  5. 如申請專利範圍第1、2、3或4項之材料，其中該等碳纖維薄層係互相交錯或編織。
  6. 如申請專利範圍第1、2、3或4項之材料，其中該材料係使用樹脂轉移成型法形成。
  7. 如申請專利範圍第1、2、3或4項之材料，其中該等碳纖維薄層係與一黏著劑結合，以提供一用以結合複合及/或金屬組件與多數結合接點之補強結合材料。
  8. 如申請專利範圍第1、2、3或4項之材料，其中該等碳纖維薄層係與一黏著劑結合，以提供一供複合組件用之補強結合材料。
  9. 一種包含複合材料之產品，該複合材料係如申請專利範圍第1、2、3或4項之該材料，且其中該等碳纖維薄層係被併入一熱固性或熱塑性帶，並且該產品係藉由一纖維捲繞法形成，且該帶係經硬化。
  10. 一種纖維-金屬複合材料，其係包含如申請專利範圍第1、2、3或4項之材料、及一金屬片。
  11. 如申請專利範圍第10項之複合材料，其中該金屬片係僅鋪設成一表面層。
  12. 如申請專利範圍第10項之複合材料，其中該金屬片係鋪設在具有相同纖維方向之多數碳纖維薄層之多數層之間。
  13. 如申請專利範圍第10項之複合材料，其中該金屬係選自於由鈦與銅構成之群組。
TW094132998A 2004-09-24 2005-09-23 複合材料、及包含該材料之產品和纖維-金屬複合材料 TWI401160B (zh)

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ATE553917T1 (de) 2012-05-15
RU2007115401A (ru) 2008-10-27
JP2008514458A (ja) 2008-05-08
EP1793989A2 (en) 2007-06-13
CN102514284B (zh) 2015-08-19
WO2006037083A3 (en) 2006-12-21
US20060093802A1 (en) 2006-05-04
RU2420407C2 (ru) 2011-06-10
EP1793989A4 (en) 2010-08-11
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TW200624260A (en) 2006-07-16
KR20070083765A (ko) 2007-08-24
CA2581042C (en) 2013-11-19
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SG155936A1 (en) 2009-10-29
CA2581042A1 (en) 2006-04-06
AU2005289392B2 (en) 2011-08-25
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WO2006037083A2 (en) 2006-04-06
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