JP5606986B2 - 改良型複合材料 - Google Patents
改良型複合材料 Download PDFInfo
- Publication number
- JP5606986B2 JP5606986B2 JP2011088803A JP2011088803A JP5606986B2 JP 5606986 B2 JP5606986 B2 JP 5606986B2 JP 2011088803 A JP2011088803 A JP 2011088803A JP 2011088803 A JP2011088803 A JP 2011088803A JP 5606986 B2 JP5606986 B2 JP 5606986B2
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- JP
- Japan
- Prior art keywords
- resin
- composite material
- particles
- composite
- resistivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2041—Two or more non-extruded coatings or impregnations
- Y10T442/2123—At least one coating or impregnation contains particulate material
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
- Y10T442/2426—Elemental carbon containing
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/67—Multiple nonwoven fabric layers composed of the same inorganic strand or fiber material
-
- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/659—Including an additional nonwoven fabric
- Y10T442/673—Including particulate material other than fiber
Description
但し、
ρは静的抵抗率(オームメーターで測定)であり、
Rは、材料からの均一な試験片の電気抵抗(オームで測定)であり、
lは試験片の長さ(メートルで測定)であり、
Aは、試験片の横断面積である(平方メートルで測定)。
すべての成分を均一にブレンドし、サーモスタットで制御された180℃の炉で2時間硬化することにより、M21の純エポキシ樹脂試料を製造した。実施例1の試料は導電性粒子を含まないので、これは本発明の範囲以内にはなく、比較の目的のために表記した。次いで、Monroe Electronicsからの抵抗率計モデル272を使用して、純樹脂試験片の表面に円板電極を置き、計器盤上に測定され表示された値を読み取ることにより、硬化樹脂シートの表面抵抗率を測定した。試験片とプローブ間の接触が良好であることが重要である。したがって、純樹脂試料は水平、平滑、及び均一であることが望ましい。結果を表1に示した。
銀被覆中実ガラス球体(大きさ20μm)を以下の水準で含む樹脂(M21)の試料:
2−1 1.0体積%(2.5重量%に相当)
2−2 2.0体積%(5.0重量%に相当)
2−3 3.0体積%(7.5重量%に相当)
2−4 4.0体積%(10.0重量%に相当)
を作製し、180℃の炉で2時間硬化した。次いで、実施例1に詳述したものと同じ抵抗率計及び手順を使用して表面抵抗率を測定した。結果を表1に示した。
銀被覆ポリメチルメタクリレート(PMMA)粒子(大きさ20μm)を以下の水準で含む樹脂(M21)の試料:
3−1 2.5体積%(2.5重量%に相当)
3−2 5.0体積%(5.0重量%に相当)
3−3 7.5体積%(7.5重量%に相当)
3−4 10.0体積%(10.0重量%に相当)
を作製し、180℃の炉で2時間硬化した。次いで、実施例1に詳述した抵抗率計及び手順を使用して表面抵抗率を測定した。結果を表1に示した。
銀被覆中空ガラス球体(大きさ20μm)を以下の水準で含む樹脂(M21)の試料:
4−1 2.5体積%(2.5重量%に相当)
4−2 5.0体積%(5.0重量%に相当)
4−3 7.5体積%(7.5重量%に相当)
4−4 10.0体積%(10.0重量%に相当)
を作製し、180℃の炉で2時間硬化した。次いで、実施例1に詳述した抵抗率計及び手順を使用して表面抵抗率を測定した。結果を表1に示した。
これらの結果は、10体積%以下の導電性銀粒子の添加が硬化した純エポキシ樹脂の表面抵抗率に影響し、一般に複合材料の導電率を改善することを実証するものである。
純エポキシ樹脂試料を製造した。これは、LY1556(50.0g)にElectrovac of Austria製のカーボンナノファイバー(直径150nm)を加えたものである。この繊維を、Flaktec Speedmixerを使用して、2500rpmで15分間この樹脂に分散した。この混合物に、銀被覆ビーズ(20μm)2.0体積%、カーボンナノファイバー(110nm)2.0重量%、及び4,4’−ジアミノジフェニルスルホンを加え、撹拌してブレンドした。この配合物を、サーモスタットで制御された180℃の炉で2時間硬化した。次いで、Monroe Electronicsからの抵抗率計モデル272を使用して、硬化シートの表面抵抗率を測定した。結果は表2に要約して示した。
これらの結果は、銀被覆中実ガラス球体のみを含むエポキシ樹脂と比較した場合、銀被覆ガラス球体とカーボンナノファイバーの組み合わせは、エポキシ樹脂の表面抵抗率をさらに低下させることを示す。
M21樹脂を、Z−ブレードミキサー(Winkworth Machinery Ltd,Reading,England)で構成成分をブレンドすることにより製造した。この樹脂をシリコーン離型紙上に薄膜として塗布した後、(Hexcel Composites,Duxford,UK)から市販されている中間弾性率の炭素繊維IM7にホットプレスを使用して樹脂重量35%で含浸させ、一方向プリプレグを作った。約10cm×10cmの5プライのプリプレグを一方向にレイアップし、圧力7バール、177℃で2時間、真空テーブル上で硬化した。接触抵抗が低いことを確かめるために、長方形の試料の両側の正方形に金をスパッタリングすることによって、この複合体のz方向の電気抵抗値をまず測定した。次いで、試験片の金スパッタリング領域にプローブを適用し、電圧又は電流のいずれかを変えることができる動力源(TTi EL302P Programmable 30V/2A Power Supply Unit,Thurlby Thandar Instruments,Cambridge,UK)の使用により抵抗率を測定した。
M21樹脂を、この樹脂の0.8〜2.4体積%の範囲の銀被覆ガラス球体(20μm)で変性し、これらの成分をWinkworthミキサーでブレンドした。この樹脂をシリコーン離型紙上に薄膜として塗布した後、中間弾性率の炭素繊維IM7にホットプレスを使用して樹脂重量35%で含浸させ、一方向プリプレグを作った。約10cm×10cmの5プライのプリプレグを一方向にレイアップし、圧力7バール、177℃で2時間、真空テーブル上で硬化した。実施例5の方法に従って、z方向の電気抵抗値を測定した。結果は表3に要約して示した。
表3の結果は、実施例6の純樹脂材料と比較した場合にz方向体積抵抗が減少すること、及び銀被覆ガラス球体の量が材料中で増加した場合に抵抗率が低下することを明白に示している。
M21樹脂を、この樹脂の2.5〜10.0体積%の範囲の銀被覆中空ガラス球体(20μm)で変性し、これらの構成成分をWinkworthミキサーでブレンドした。この樹脂をシリコーン離型紙上に薄膜として塗布した後、中間弾性率の炭素繊維IM7にホットプレスを使用して樹脂重量35%で含浸させ、一方向プリプレグを作った。約10cm×10cmの5プライのプリプレグを一方向にレイアップし、圧力7バール、177℃で2時間、真空テーブル上で硬化した。実施例6の方法に従って、z方向の電気抵抗値を測定した。結果は表4に要約して示した。
表4の結果は、材料中の銀被覆ガラス球体の量が増加した場合にz方向体積抵抗率が低下することを明白に示している。
M21樹脂を、この樹脂の2.5〜10.0体積%の範囲の銀被覆ポリメチルメタクリレート粒子(20μm)で変性した。この樹脂は、Winkworthミキサーでこれらの構成成分をブレンドすることにより製造した。この樹脂をシリコーン離型紙上に薄膜として塗布した後、中間弾性率の炭素繊維IM7にホットプレスを使用して樹脂重量35%で含浸させ、一方向プリプレグを作った。約10cm×10cmの5プライのプリプレグを一方向にレイアップし、圧力7バール、177℃で2時間、真空テーブル上で硬化した。実施例6の方法に従って、z方向の電気抵抗値を測定した。結果は表5に要約して示した。
表5の結果は、材料中の銀被覆ガラス球体の量が増加した場合にz方向体積抵抗率が低下することを明白に示している。
M21樹脂を、この樹脂の0.30体積%の添加量の樹枝状銀/銅(40μm)で変性した。この樹脂は、Winkworthミキサーでこれらの構成成分をブレンドすることにより製造した。この樹脂をシリコーン離型紙上に薄膜として塗布した後、中間弾性率の炭素繊維IM7にホットプレスを使用して樹脂重量35%で含浸させ、一方向プリプレグを作った。約10cm×10cmの5プライのプリプレグを一方向にレイアップし、圧力7バール、177℃で2時間、真空テーブル上で硬化した。実施例6の方法に従って、z方向の電気抵抗値を測定した。結果は表6に要約して示した。
M21樹脂を、この樹脂の1.0体積%の添加量の銀被覆ガラスビーズ(100μm)で変性した。プリプレグ及び複合体を実施例9に従って製造した。Z方向電気抵抗値を実施例6に従って測定した。結果は表6に要約して示した。
M21樹脂を、この樹脂の1.25重量%の添加量の銀被覆ガラス繊維(190μm)で変性した。プリプレグ及び複合体を実施例9に従って製造した。Z方向電気抵抗値を実施例6に従って測定した。結果は表6に要約して示した。
表6の結果は、一般に導電性粒子量の増加と共にz方向の体積抵抗率が低下することを示している。さらに、これらの結果では、高分子樹脂層の厚みと実質的に等しい大きさを有する銀被覆ガラス球体を使用した実施例11における低下が特に大きい。
実施例12に従ってM21プリプレグを製造した。大きさ約10cmx10cmの6プライ疑似等方性(QI)ラミネートを作製し、圧力7バール、177℃で2時間、真空テーブル上で硬化した。この複合体のガラス転移温度(Tg)は、貯蔵弾性率E’のトレースから動的熱分析によって194.5℃であることが分かった。硬化したパネルから正方形の試料を切り出し、以下のようにz方向の抵抗率を測定した。十分な電気的コンタクトを確保するために、複合体の適切な部分には、電源との接続が行われる近辺に金を真空めっきした。次いで、電源から1アンペアの電流を流し、得られた電圧を測定することにより抵抗率を求めた。
M21樹脂を20μmの銀被覆ガラスビーズ(2体積%、5重量%)で変性し、実施例13の方法に従ってプリプレグを製造した。大きさ約10cmx10cmの6プライ疑似等方性ラミネートを作製し、圧力7バール、177℃で2時間、真空テーブル上で硬化した。この複合体のガラス転移温度(Tg)は、比較例14と同様にして、196.0℃と測定された。したがって、銀被覆ビーズの添加はTgに有害な影響を与えない。硬化したパネルから正方形の試料を切り出し、実施例13と同様にして、z方向抵抗率を測定した。抵抗率は著しく改善されている。
M21樹脂を20μmの銀被覆ガラスビーズ(2体積%、5重量%)及び樹脂の2重量%のカーボンナノファイバー(直径150nm)で変性した。比較例13に従ってプリプレグを製造した。大きさ約10cmx10cmの12プライ疑似等方性ラミネートを作製し、圧力7バール、177℃で2時間、真空テーブル上で硬化した。この複合体のガラス転移温度(Tg)は、比較例14と同様にして、196.5℃と測定された。したがって、銀被覆ビーズの添加はTgに有害な影響を与えていない。硬化したパネルから正方形の試料を切り出し、実施例13と同様にしてz方向抵抗率を測定した。抵抗率は著しく改善されている。
Winkworthミキサーを使用してM21樹脂を製造した後、シリコーン離型紙上にその膜を形成した。次いで、この樹脂膜を、パイロットスケールのUDプリプレグ装置を使用して、単向性の中間弾性率炭素繊維に含浸させた。この装置で、樹脂35重量%で268g/m2の面積重量を有するプリプレグを製造した。約60cm×60cmの2つの6プライプリプレグを製造した(レイアップ0/90)。これらを、圧力7バール、177℃で2時間、真空テーブル上で硬化した。
M21樹脂を、銀被覆ガラス球体(樹脂の2体積%、5重量%)で変性し、Winkworthミキサーを使用してブレンドした後、シリコーン離型紙上にその膜を形成した。この樹脂膜を、単向性の中間弾性率炭素繊維に含浸させ、樹脂35重量%で268g/m2の面積重量を有するプリプレグを製造した。約60cm×60cmの2つの6プライプリプレグを製造した(レイアップ0/90)。これらを、圧力7バール、177℃で2時間、真空テーブル上で硬化した。次いで、比較例16の方法に従って落雷試験を行った。
M21樹脂を、銀被覆ガラス球体(樹脂の2体積%、5重量%)とカーボンナノファイバー(直径150nm、樹脂の2重量%)で変性し、Winkworthミキサーを使用してブレンドした後、シリコーン離型紙上にその膜を形成した。この樹脂膜を、単向性の中間弾性率炭素繊維に含浸させ、樹脂35重量%で268g/m2の面積重量を有するプリプレグを製造した。約60cm×60cmの2つの6プライプリプレグを製造した(レイアップ0/90)。これらを、圧力7バール、177℃で2時間、真空テーブル上で硬化した。次いで、実施例16の方法に従って落雷試験を行った。
Claims (9)
- 複合構造体を作製する際に使用される複合材料であって、前記複合材料は、
2の導電性繊維層、
前記導電性繊維層の間に配置された樹脂層であって、厚みを有し、かつ高分子樹脂を含む樹脂層、及び
前記樹脂層の端から端までにわたるような大きさで前記導電性繊維層同士を電気的に接続する導電性ブリッジであって、該導電性ブリッジの少なくとも一つが、前記樹脂層と等しい大きさを有する導電性粒子を含有する、上記導電性ブリッジ
を含む、前記複合材料。 - 前記高分子樹脂は、前記繊維層の片側又は両側に含浸されてプリプレグを形成する、請求項1に記載の複合材料。
- 前記導電性粒子が炭素粒子である、請求項1に記載の複合材料。
- 前記高分子樹脂が強化剤及び/又は強化粒子を含む、請求項1に記載の複合材料。
- 前記樹脂層がカーボンナノ材料を含む、請求項1に記載の複合材料。
- 前記高分子樹脂が、ポリエーテルスルホンを含む強化剤と、ポリアミド粒子を含む強化粒子とを含む、請求項3に記載の複合材料。
- 請求項1に記載の複合材料を含む複合構造体であって、前記高分子樹脂が硬化されている複合構造体。
- 飛行機の一部である、請求項7に記載の複合構造体。
- 前記導電性粒子が炭素粒子である、請求項7に記載の複合構造体。
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JP2015084674A Active JP6027643B2 (ja) | 2006-11-06 | 2015-04-17 | 改良型複合材料 |
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