TW201005012A - Carbon nanotube-reinforced nanocomposites - Google Patents

Carbon nanotube-reinforced nanocomposites Download PDF

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TW201005012A
TW201005012A TW097137566A TW97137566A TW201005012A TW 201005012 A TW201005012 A TW 201005012A TW 097137566 A TW097137566 A TW 097137566A TW 97137566 A TW97137566 A TW 97137566A TW 201005012 A TW201005012 A TW 201005012A
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composite material
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dong-sheng Mao
Zvi Yaniv
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Applied Nanotech Holdings Inc
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Description

201005012 九、發明說明 相關申請案之交互參照 此申請案係美國專_利申請案第1 1 /757,272號之連續 申請案’該申請案主張美國專利申請案第60/8 19，3 19和 6 0/8 1 0,3 94號之優先權，茲將前述申請案全數以引用方式 . 納入本文中。此申請案係美國專利申請案第1 1 /693,454 號之連續申請案，該申請案主張美國專利申請案第 φ 60/788,234和60/8 1 0,3 94號之優先權，茲將前述申請案全 數以引用方式納入本文中。此申請案係美國專利申請案第 1 1/69 5,8 77號之連續申請案，該申請案主張美國專利申請 案第60/789,300和60/8 1 0,394號之優先權，茲將前述申 請案全數以引用方式納入本文中。 【發明所屬之技術領域】 本發明係有關經奈米管補強之奈米複合物。 ❿ 【先前技術】 自從於1991年首次被觀察到，碳奈米管（CNT)曾爲許 多硏究的焦點（S.Iijima， “Helical microtubules of graphitic carbon,” Nature 354，56(1991))。許多硏究者已 報導此新形式的碳之卓越的物理和機械性質。基本上，單壁 CNT(SWNT)中的 CNT 直徑爲 0.5-1.5 奈米，雙壁 CNT(DWNT)直徑貝[J爲1-3奈米，多壁CNT(MWNT)直徑則 爲5奈米至100奈米。由於具有獨特的電子性質和高於鑽 -4- 201005012 石的導熱性及機械性質（其韌性、強度和回彈性超過目前 的任何材料），CNT在發展重要的新材料系統方面提供極 佳的機會。特別地，CNT之特別的槪械性質（E>1.0TPa和 拉伸強度爲50 GPa)以及低密度（1-2.0克/立方公分）使它 們在發展 CNT-強化的複合材料方面引人注意（Eric W. Wong, Paul E. Sheehan, Charles M.Lieber, “Nanobeam Mechanics ： Elasticity, Strength, and Toughness of Nanorods and NanotubesScience 277,1971(1997)) ° CNT 是世上已知的最強材料。相較於MWNT，由於SWNT和 DWNT具有較高的表面積和較高的縱橫比，所以更可能作 爲複合物的強化材料。表1列出SWNT、DWNT和MWNT 的表面積和縱橫比。 表1 SWNT DWNT MWNT 表面積(平方米/克） 300-600 300-400 40-300 縱橫比(長度/直徑） 〜10,000 -5,000 100-1000
CNT的一個問題在於在它們生長時，通常相當長（由 數微米至超過1〇〇微米），此使得它們難穿透纖維強化的 塑料（FRP)中的基質，此因最近的纖維之間的距離很小之 故。例如，對於單方向碳纖維或織物強化的環氧樹脂複合 物，碳纖維的含量約60體積％，使得最近的碳纖維之間 的距離爲約1微米（假設碳纖維直徑爲7-8微米且密度約 1.75-1.80克/立方公分且環氧樹脂基質的密度爲1.2克/ -5- 201005012 立方公分）。對於玻璃纖維和用以製造複合物的其他纖維 類型而言也是如此。CNT可強化聚合物樹脂以改良機械性 質（如，強度和模數），但它們因爲會在FRP製造期間內被 纖維所濾出而無法強化FRP。 【發明內容】 . 短至或短於2微米的CNT可穿透纖維之間’並因此 φ 明顯改良FRP的機械性質。 【實施方式】 本發明的一體系中，提供此體系的詳細實例以便更能 說明本發明。 環氧樹脂、SWNT、DWNT、MWNT和硬化劑 環氧樹脂（雙酣A)得自日本 Arisawalnc·,。硬化劑（ ® 雙氰胺）得自相同公司，其用以固化環氧樹脂奈米複合物 。SWNT、DWNT 和 MWNT 得自比利時 Nanocyl，Inc.。 此CNT可純化至>90%碳含量。但亦可使用原始的CNT或 '經官能基（如羧酸和胺基官能基）官能化者。CNT長度可以 約5-20微米。圖式2顯示MWNT的SEM數位影像。除了 環氧樹脂以外，也可以使用其他的熱固性材料（如聚醯亞 胺、酚系、氰酸酯和雙順丁烯二醯亞胺）或熱塑性材料（如 尼龍）。 圖式1顯示根據本發明體系之環氧樹脂/ CNT奈米複 201005012 合物之製造流程圖。所有的成份可於真空爐中於70 t：乾 燥16小時以去除濕氣。每一種樹脂的CNT載量可爲1.0 重量％。CNT置於丙酮1〇1，並在步驟1〇2中藉微射流機 (Microfluidics Co.，的市售品，型號Υΐΐ〇)分散。此微射流 機使用高壓流，此高壓流在精確定義的微米尺寸通道中以 超高速度碰撞。其合倂的切變和衝擊力作用在產物上而製 造均勻的分散液。此CNT /丙酮因此而形成凝膠103，使 得CNT良好地分散於丙酮溶劑中。但也可以使用其他方 法（如超音波震碎法或高切變混合法）。亦可使用界面活性 劑將CNT分散於溶液中。之後在步驟104中，將環氧樹 脂加至CNT /丙酮凝膠中以製造環氧樹脂/ CNT /丙酮溶 液105，其於之後藉超音波震碎法在70 °C的浸液中1小時 (步驟106)以製造環氧樹脂/ CNT/丙酮懸浮液107。在步 驟108中，此CNT可以使用攪拌器混合法，於70 °C和轉 速1,400轉/分鐘下進一步分散半小時，以製得環氧樹脂 / CNT /丙酮凝膠109。之後在步驟1 10中，硬化劑以 4.5重量％的比例加至環氧樹脂/CNT /丙酮凝膠109中 ，並於70°C攪拌1小時。所得凝膠111於步驟112中在 真空爐中於70 °C脫氣48小時。材料113可於之後於160 °C固化2小時。爲了測試材料1 1 3，可於之後將其倒入鐵 弗龍模具中’使得於拋光法115之後’測定出試樣的機械 性質（彎曲強度和彎曲模數）。 前述樹脂（環氧樹脂/CNT/硬化劑）於70°C脫氣48 小時之後，亦可使用熱熔法製造FRP。碳纖維（得自Toray 201005012
Industries, Inc·，型號T700- 1 2k)可用於預浸物製備。“ 預浸物”一詞係指此技術中已知之“經預先浸泡”的複合纖 維。這些可爲梭織或單方向形式。它們含有的基質材料量 用以使得它們和與其他組份於製造期間內結合在一起。此 預浸物因爲最常因熱而活化，因此可儲存在冷卻的區域中 。因此，預浸物的複合物結構建構大多須要爐或壓熱器使 其固化。 CNT強化的環氧樹脂先塗佈在脫模紙上。之後藉由以 CNT強化的環氧樹脂薄膜浸泡單方向性的碳纖維而得到此 預浸物。碳纖維的體積控制於60%。此預浸物的單位面積 重量是180克/平方米。 奈米複合物的機械性質 表2列出CNT強化的環氧樹脂及經單方向性碳纖維 強化的樹脂之機械性質（彎曲強度和彎曲模數）。由樹脂形 式可看出，相較於純環氧樹脂，機械性質獲大幅改良（每 一者的彎曲強度改良超過3 0%且彎曲模數改良至少1 〇%) 。但在碳纖維強化的聚合物（CFRP)形式中，CNT強化的 CFRP相較於純環氧樹脂CFRP，此二性質皆未獲改良。 201005012 表2 樣品 樹脂的機械性質 CFRP 的4 幾械性質 彎曲強度 (MPa) 彎曲模數 (GPa) 彎曲強度 (MPa) 彎曲模數 (GPa) 純環氧樹脂 116 3.18 1394 62.3 環氧樹脂/MWNT (1.0重量％) 149 3.54 1388 61.5 環氧樹脂/DWNT (1.0 ms%) 159 3.69 1354 61.7 環氧樹脂/SWNT (1.0重量％) 164 3.78 1408 62.8 之後，可以使用掃描式電子顯微鏡（SEM)檢測CNT於 樹脂和CFRP樣品中之分散。樹脂形式中，CNT強化的環 氧樹脂樣品顯示極佳的CNT分散（參考圖式3A-3C)。然而 ，CNT被單方向性碳纖維濾至預浸物的端層（參考圖式 4A-4B，DWNT強化的環氧樹脂CFPR)。這是因爲最近的 碳纖維的間隔僅約1微米，而且CNT很長，使得它們無 法穿透碳纖維之間之故。此即樹脂中的CNT強化無法轉 移至CFRP的原因。 CNT的縮短以及環氧樹脂和CFRP之強化 CNT因爲很長，使得它們在預浸物製法期間內無法穿 透碳纖維之間，因而必須將CNT縮短，以使其不會被碳 纖維濾出。MWNT、DWNT和 SWNT可以與濃酸混合物 (HN03:H2S04 = 3:1)混合，並於120°C攪拌4小時。使用濾 紙（具2微米開口的聚碳酸酯濾紙，用以濾除酸）過濾CNT 。之後，以去離子水清洗CNT4-5次，並在真空中於50°c 201005012 乾燥12小時。圖式5A-5C分別爲縮短的MWNT、DWNT 和SWNT(縮短至長度低於2微米）之S EM數位影像。 表3列出縮短之CNT強化的環氧樹脂及經單方向性 碳纖維強化的樹脂之機械性質（彎曲強度和彎曲模數）。由 樹脂形式可看出，相較於純環氧樹脂，機械性質獲大幅改 良（每一者的彎曲強度改良超過30%且彎曲模數改良至少 1 0%)，此與前述之經長 CNT強化的環氧樹脂類似。在 CFRP形式中，相較於純環氧樹脂CFRP，兩種性質皆獲得 改良。例如，相較於純環氧樹脂CFRP，SWNT強化的 CFRP之彎曲強度改良了 17%。 表3 樣品 樹脂的機械性質 CFRP 的 1 幾械性質 彎曲強度 (MPa) 彎曲模數 (GPa) 彎曲強度 (MPa) 彎曲模數 (GPa) 純環氧樹脂 116 3.18 1394 62.3 環氧樹脂/MWNT (1.0重量％) 150 3.60 1561 65.4 環氧樹脂/DWNT (1.0重量％) 160 3.65 1603 67.3 環氧樹脂/SWNT Π.0重量％) 162 3.70 1630 70.8 之後，可以使用掃描式電子顯微鏡（SEM)檢測CNT於 CFRP樣品中之分散。如圖 6A-6C中所示者，縮短的 MWNT、DWNT和SWNT穿透碳纖維，且良好地分散於碳 纖維之間。 -10- 201005012 【圖式簡單說明】 圖1爲根據本發明體系之製造奈米複合物的方法； 圖2爲MWNT的SEM數位影像； 一 圖3A-3C分別是MWNT強化的環氧樹脂、DWNT強 化的環氧樹脂和SWNT強化的環氧樹脂之SEM數位影像 » 圖4A爲DWNT強化的CFRP之斷面的SEM數位影像 ，顯示沒有DWNT穿透碳纖維之間； 圖4B圖爲DWNT強化的CFRP之斷面的SEM數位影 像，顯示DWNT被濾至預浸物的端層； 圖5A-5C分別爲縮短的MWNT、DWNT和SWNT之 SEM數位影像；而 圖6A-6C分別爲MWNT強化的CFRP、DWNT強化的 CFRP和SWNT強化的CFRP之SEM數位影像。

Claims (1)

  1. 201005012 十、申請專利範圍 1 . ~種複合材料，其 ’其中碳奈米管的平均長 2 .如申請專利範圍第 熱固性或熱塑性塑料。 ， 3 ·如申請專利範圍第 料選自由聚醯亞胺、酚系 Λ 組成之群。 ρ 4·如申請專利範圍第 未經官能化。 5. 如申請專利範圍第 經官能化成羧酸官能基或 6. 如申請專利範圍第 經官能化成胺官能基。 7. 如申請專利範圍第 議 單一方向性碳纖維。 包含碳奈米管、 聚合物和碳纖維 度低於2微米。 1項之複合材料 ，其中聚合物係 2項之複合材料 ，其中熱固性塑 、氰酸酯和雙||| τ烯二醯亞胺所 1項之複合材半斗 ’其中碳奈米管 1項之複合材料 ’其中碳奈米管 胺官能基。 1項之複合材半斗 ’其中碳奈米管 1項之複合材料 ’其中碳纖維爲 -12-
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110125412A1 (en) * 1998-12-17 2011-05-26 Hach Company Remote monitoring of carbon nanotube sensor
US9056783B2 (en) * 1998-12-17 2015-06-16 Hach Company System for monitoring discharges into a waste water collection system
US7454295B2 (en) 1998-12-17 2008-11-18 The Watereye Corporation Anti-terrorism water quality monitoring system
US8958917B2 (en) * 1998-12-17 2015-02-17 Hach Company Method and system for remote monitoring of fluid quality and treatment
US8920619B2 (en) 2003-03-19 2014-12-30 Hach Company Carbon nanotube sensor
US20110160346A1 (en) * 2006-03-31 2011-06-30 Applied Nanotech Holdings, Inc. Dispersion of carbon nanotubes by microfluidic process
US20110027603A1 (en) * 2008-12-03 2011-02-03 Applied Nanotech, Inc. Enhancing Thermal Properties of Carbon Aluminum Composites
US20110147647A1 (en) * 2009-06-05 2011-06-23 Applied Nanotech, Inc. Carbon-containing matrix with additive that is not a metal
US20100310447A1 (en) * 2009-06-05 2010-12-09 Applied Nanotech, Inc. Carbon-containing matrix with functionalized pores
DE102010040040A1 (de) * 2010-08-31 2012-03-01 Sgl Carbon Se Verstärktes Epoxidharz
CN102120882B (zh) * 2011-01-12 2012-07-25 同济大学 碳纳米管及功能化碳纤维增强双马来酰亚胺树脂复合材料的制备方法
US10023702B2 (en) 2011-09-02 2018-07-17 Bae Systems Plc Curable monomers
WO2013133941A1 (en) * 2012-03-06 2013-09-12 Applied Nanotech Holdings, Inc. Carbon nanotube reinforced nanocomposites
WO2013147257A1 (ja) * 2012-03-29 2013-10-03 三菱レイヨン株式会社 炭素繊維熱可塑性樹脂プリプレグ、炭素繊維複合材料、ならびに製造方法
DE102012212290A1 (de) * 2012-07-13 2014-01-16 Siemens Aktiengesellschaft Polymere Faserverbunde modifiziert mit einwandigen Kohlenstoffnanoröhren
US10758936B2 (en) 2015-12-08 2020-09-01 The Boeing Company Carbon nanomaterial composite sheet and method for making the same
US9972420B2 (en) 2015-12-08 2018-05-15 The Boeing Company Carbon nanotube shielding for transmission cables
US10093041B2 (en) 2016-04-11 2018-10-09 The Boeing Company Conductive pre-impregnated composite sheet and method for making the same
CN105778424B (zh) * 2016-04-22 2019-05-24 武汉理工大学 一种碳纳米管、碳纤维协同改性环氧树脂复合材料及其制备方法
AU2018202595B2 (en) * 2017-04-20 2020-01-30 Otis Elevator Company Fire-resistant synthetic tension members
US11244775B2 (en) * 2018-12-11 2022-02-08 Universities Space Research Association Physically unclonable all-printed carbon nanotube network
WO2020264090A1 (en) * 2019-06-25 2020-12-30 The Trustees Of Indiana University Fibers, prepreg materials, compositions composite articles, and methods of producing composite articles
CN111320841B (zh) * 2020-01-08 2022-08-26 浙江宝旌炭材料有限公司 一种芳纶纤维/碳纳米管复合增强碳纤维树脂预浸料
CN112980026A (zh) * 2021-03-09 2021-06-18 山东非金属材料研究所 一种碳纳米管改性纤维增强热固性树脂基预浸料的制备方法
MX2024007977A (es) 2021-12-22 2024-07-30 Nabors Energy Transition Solutions Llc Nanomaterial a base de carbono dopado con azufre y procedimientos de formacion del mismo.
WO2023168219A1 (en) 2022-03-04 2023-09-07 Nabors Energy Transition Solutions Llc Boron doped carbon-based nanomaterial and methods of forming the same
KR20240107210A (ko) * 2022-12-28 2024-07-09 재단법인 한국섬유기계융합연구원 유도가열 방식을 이용한 고분자 복합재의 성형방법
CN120757974A (zh) * 2025-06-25 2025-10-10 无锡嘉德复合材料有限公司 一种纤维复合材料及其制备方法

Family Cites Families (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5846245B2 (ja) 1980-06-25 1983-10-15 日本黒鉛工業株式会社 表面潤滑性に優れたプラスチツク成形品の製造方法
US5096556A (en) * 1990-06-25 1992-03-17 Ppg Industries, Inc. Cationic microgels and their use in electrodeposition
US5565505A (en) * 1993-06-30 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
WO1995018165A1 (en) * 1993-12-27 1995-07-06 Henkel Corporation Self-dispersing curable epoxy resins and coatings
US5604269A (en) * 1993-12-27 1997-02-18 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US5565506A (en) * 1994-03-01 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US5854313A (en) * 1994-09-28 1998-12-29 Takeda Chemical Industries, Ltd. Fine particles of high heat resistant polymer and epoxy esters
US5750595A (en) * 1994-12-29 1998-05-12 Henkel Corporation Self-dispersing curable epoxy resin dispersions and coating compositions made therefrom
EP0821726B1 (en) * 1995-03-10 2014-05-07 Meso Scale Technologies, LLC. Multi-array, multi-specific electrochemiluminescence testing
US6140045A (en) * 1995-03-10 2000-10-31 Meso Scale Technologies Multi-array, multi-specific electrochemiluminescence testing
US5719201A (en) * 1995-03-30 1998-02-17 Woodbridge Foam Corporation Superabsorbent hydrophilic isocyanate-based foam and process for production thereof
EP0755946A3 (en) * 1995-07-24 1997-10-01 Basf Corp Method for the preparation of hydrophobic emulsion polymers, the polymers thus obtained and the aqueous coating compositions containing these polymers
US5969030A (en) * 1995-07-24 1999-10-19 Basf Corporation Waterborne coating compositions containing hydrophobically modified emulsions
US5569715A (en) * 1995-07-24 1996-10-29 Basf Corporation Process for obtaining hydrophobically modified emulsion polymers and polymers obtained thereby
US5760108A (en) * 1996-10-22 1998-06-02 Henkel Corporation Self-dispersing curable epoxy resin esters, dispersions thereof and coating compositions made therefrom
US5719210A (en) 1996-11-26 1998-02-17 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
US6770583B2 (en) * 1997-03-14 2004-08-03 The United States Of America As Represented By The Secretary Of The Navy Transistion metal containing ceramic with metal nanoparticles
US6333016B1 (en) * 1999-06-02 2001-12-25 The Board Of Regents Of The University Of Oklahoma Method of producing carbon nanotubes
EP1818358A1 (en) * 1999-12-07 2007-08-15 William Marsh Rice University Oriented nanofibers embedded in polymer matrix
US7073201B2 (en) * 2001-09-21 2006-07-11 Denki Kagaku Kogyo Kabushiki Kaisha Aqueous Adhesive
JP3948217B2 (ja) * 2000-06-05 2007-07-25 昭和電工株式会社 導電性硬化性樹脂組成物、その硬化体、及びその成形体
CA2415929A1 (en) * 2000-07-14 2002-01-24 Board Of Control Of Michigan Technological University Wood-based composite board and method of manufacture
US20030151030A1 (en) * 2000-11-22 2003-08-14 Gurin Michael H. Enhanced conductivity nanocomposites and method of use thereof
TW583246B (en) * 2001-02-05 2004-04-11 Toray Industries Carbon fiber-enforced resin composition and shaped material
EP1385481A4 (en) * 2001-03-26 2006-06-07 Eikos Inc CARBON NANOTUBES IN STRUCTURES AND REPAIR COMPOSITIONS
US6689835B2 (en) * 2001-04-27 2004-02-10 General Electric Company Conductive plastic compositions and method of manufacture thereof
US6808939B2 (en) * 2001-06-29 2004-10-26 Igen International, Inc. ECL labels having improved non-specific binding properties, methods of using and kits containing the same
US6680016B2 (en) * 2001-08-17 2004-01-20 University Of Dayton Method of forming conductive polymeric nanocomposite materials
US20050127329A1 (en) * 2001-08-17 2005-06-16 Chyi-Shan Wang Method of forming nanocomposite materials
US6524777B1 (en) * 2001-08-30 2003-02-25 Eastman Kodak Company Method of activating a protective layer on a photographic element employing an organic solvent in the wash solution
US20030099798A1 (en) * 2001-11-29 2003-05-29 George Eric R. Nanocomposite reinforced polymer blend and method for blending thereof
US6846345B1 (en) * 2001-12-10 2005-01-25 The United States Of America As Represented By The Secretary Of The Navy Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds
JP2003201388A (ja) * 2002-01-08 2003-07-18 Toray Ind Inc エポキシ樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化複合材料
US7162302B2 (en) * 2002-03-04 2007-01-09 Nanoset Llc Magnetically shielded assembly
US6864418B2 (en) * 2002-12-18 2005-03-08 Nanoset, Llc Nanomagnetically shielded substrate
JP4241070B2 (ja) 2002-02-12 2009-03-18 東レ株式会社 樹脂組成物およびその製造方法
JP4196567B2 (ja) 2002-02-14 2008-12-17 東レ株式会社 炭素繊維強化樹脂組成物、成形材料およびその成形品
US20040038251A1 (en) * 2002-03-04 2004-02-26 Smalley Richard E. Single-wall carbon nanotubes of precisely defined type and use thereof
WO2003078315A2 (en) 2002-03-20 2003-09-25 Facultes Universitaires Notre-Dame De La Paix Nanocomposites: products, process for obtaining them and uses thereof
US7153903B1 (en) * 2002-06-19 2006-12-26 The Board Of Regents Of The University Of Oklahoma Carbon nanotube-filled composites prepared by in-situ polymerization
DE60321805D1 (de) * 2002-07-15 2008-08-07 Henkel Ag & Co Kgaa Selbstabscheidende mit ungesättigtem monomer modifizierte epoxy dispersion
US7094367B1 (en) * 2002-08-13 2006-08-22 University Of Florida Transparent polymer carbon nanotube composites and process for preparation
JP4480368B2 (ja) 2002-09-13 2010-06-16 大阪瓦斯株式会社 ナノスケールカーボンを含有する樹脂組成物、導電性ないし制電性樹脂成形体、導電性ないし制電性樹脂コーティング組成物及び帯電防止膜及びこれらの製造法
JP3735651B2 (ja) * 2002-10-08 2006-01-18 独立行政法人 宇宙航空研究開発機構 カーボンナノファイバー分散樹脂繊維強化複合材料
US6800946B2 (en) * 2002-12-23 2004-10-05 Motorola, Inc Selective underfill for flip chips and flip-chip assemblies
JP4342929B2 (ja) 2002-12-26 2009-10-14 昭和電工株式会社 導電性組成物用炭素質材料及びその用途
DE10312494A1 (de) * 2003-03-20 2004-10-07 Association pour la Recherche et le Développement des Méthodes et Processus Industriels (Armines) Kohlenstoff-Nanostrukturen und Verfahren zur Herstellung von Nanoröhren, Nanofasern und Nanostrukturen auf Kohlenstoff-Basis
WO2004091571A2 (en) * 2003-04-08 2004-10-28 New Jersey Institute Of Technology (Njit) Polymer coating/encapsulation of nanoparticles using a supercritical antisolvent process
DE102004025048A1 (de) * 2003-05-20 2004-12-23 Futaba Corp., Mobara Ultra-dispergierter Nano-Kohlenstoff und Verfahren zu seiner Herstellung
CA2532190C (en) 2003-06-16 2012-08-21 William Marsh Rice University Sidewall functionalization of carbon nanotubes with hydroxyl-terminated moieties
WO2005012171A2 (en) 2003-07-28 2005-02-10 William Marsh Rice University Sidewall functionalization of carbon nanotubes with organosilanes for polymer composites
CN1902716B (zh) 2003-08-21 2010-11-03 伦塞勒高聚技术研究所 具有受控电特性的纳米组合物
JP4403265B2 (ja) 2003-09-05 2010-01-27 国立大学法人信州大学 粉体の混合方法
US7262266B2 (en) * 2003-10-24 2007-08-28 William Marsh Rice University Copolymerization of polybenzazoles and other aromatic polymers with carbon nanotubes
US7005550B1 (en) * 2004-01-22 2006-02-28 The United States Of America As Represented By The Secretary Of The Air Force Arylcarbonylated vapor-grown carbon nanofibers
JP4546749B2 (ja) 2004-03-09 2010-09-15 帝人テクノプロダクツ株式会社 導電性芳香族ポリアミド樹脂組成物及びそれを用いてなる導電性芳香族ポリアミド樹脂成形体
US7862624B2 (en) * 2004-04-06 2011-01-04 Bao Tran Nano-particles on fabric or textile
US7296576B2 (en) * 2004-08-18 2007-11-20 Zyvex Performance Materials, Llc Polymers for enhanced solubility of nanomaterials, compositions and methods therefor
US7078683B2 (en) * 2004-10-22 2006-07-18 Agilent Technologies, Inc. Nanowire target support and method
JP4931168B2 (ja) 2005-01-06 2012-05-16 国立大学法人名古屋大学 高純度２層〜５層カーボンナノチューブの製造方法
US20060216508A1 (en) 2005-03-24 2006-09-28 3M Innovative Properties Company Polymer nanocomposite having surface modified nanoparticles and methods of preparing same
TWI267220B (en) * 2005-05-24 2006-11-21 Univ Tsinghua Manufacturing process of high gas permeability-resistance and heat-resistance conductive polymer composite bipolar plate for fuel cell
US20060270790A1 (en) * 2005-05-26 2006-11-30 Brian Comeau Carbon-nanotube-reinforced composites for golf ball layers
US20090039308A1 (en) * 2005-07-22 2009-02-12 Iouri Kuzmich Gounko Nanocomposite polymers
US20070023839A1 (en) * 2005-07-27 2007-02-01 International Business Machines Corporation Finfet gate formed of carbon nanotubes
JP2007126637A (ja) * 2005-10-03 2007-05-24 Toray Ind Inc 樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化複合材料
US20070276077A1 (en) * 2006-04-05 2007-11-29 Nano-Proprietary, Inc. Composites
US20080152913A1 (en) * 2006-12-22 2008-06-26 3M Innovative Properties Company Method of making compositions including particles
CN100487046C (zh) * 2007-02-07 2009-05-13 黄德欢 一种碳纳米管/聚丙烯复合材料的制备方法
US20100158193A1 (en) * 2008-12-22 2010-06-24 Bates Mark C Interventional Devices Formed Using Compositions Including Metal-Coated Nanotubes Dispersed In Polymers, And Methods Of Making And Using Same

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