JP4755902B2 - 金属被覆ナノファイバー - Google Patents
金属被覆ナノファイバー Download PDFInfo
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- JP4755902B2 JP4755902B2 JP2005508425A JP2005508425A JP4755902B2 JP 4755902 B2 JP4755902 B2 JP 4755902B2 JP 2005508425 A JP2005508425 A JP 2005508425A JP 2005508425 A JP2005508425 A JP 2005508425A JP 4755902 B2 JP4755902 B2 JP 4755902B2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D01F6/42—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
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- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/338—Organic hydrazines; Hydrazinium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2958—Metal or metal compound in coating
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- 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
- Y10T442/2033—Coating or impregnation formed in situ [e.g., by interfacial condensation, coagulation, precipitation, etc.]
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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
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
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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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- 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]
- Y10T442/654—Including a free metal or alloy constituent
- Y10T442/655—Metal or metal-coated strand or fiber material
Description
a)還元剤に対する結合能を備える官能基を有するポリマーナノファイバーを、周囲条件でエレクトロスピンさせることにより調製する工程;
b)工程a)で得られるエレクトロスピンされたポリマーナノファイバーを、還元剤と接触させ、それにより、ポリマーナノファイバー表面のエポキシ環を開き、前記還元剤で置き換える工程;
c)工程b)で得られる還元剤修飾ポリマーフィルムを、アルカリ媒体中の金属塩溶液と反応させる工程;
d)工程c)で得られるエレクトロスピンされたマットを水で処理し、構造物中のエポキシ環を開き、鎖を架橋させて、完全な状態とする工程。
図1は、ポリ(アクリロニトリル−コ−グリシジルメタクリレート)(PGMA)の1H NMRスペクトルである、
図2は、(a)P(AN−GMA)および(b)ヒドラジン処理したP(AN−GMA)のIRスペクトルである、
図3は、(a)P(AN−GMA)および(b)ヒドラジン処理したP(AN−GMA)の電子顕微鏡画像である、
図4は、P(AN−GMA)およびAg処理したヒドラジン修飾P(AN−GMA)の熱分析曲線である、
図5は、P(AN−GMA)ナノファイバー上のAg粒子のX線回折解析である、
図6は、Ag被覆P(AN−GMA)ナノファイバーの、3つの異なる倍率での電子顕微鏡画像である、
図7は、ポリ(スチレン−コ−グリシジルメタクリレート)の1H NMRスペクトルである、
図8は、2kV/cmで、溶液からエレクトロスピンされたポリ(スチレン−コ−グリシジルメタクリレート)ナノファイバーの光学顕微鏡画像である。
a)還元剤に対する結合能を備える官能基を有するポリマーナノファイバーを、周囲条件でエレクトロスピンさせることにより調製する工程;
b)工程a)で得られるエレクトロスピンされたポリマーナノファイバーを、還元剤と接触させ、それにより、ポリマーナノファイバー表面のエポキシ環を開き、前記還元剤で置き換える工程;
c)工程b)で得られる還元剤修飾ポリマーフィルムを、アルカリ媒体中の金属塩溶液と反応させる工程;
d)工程c)で得られるエレクトロスピンされたマットを水で処理し、構造物中のエポキシ環を開き、鎖を架橋させて、完全な状態とする工程。
使用したすべての化学物質は、分析等級化学物質であり、更に精製することなく使用した。グリシジルメタクリレートGMA(Fluka)、アクリロニトリル(AN);(Fluka)、および水酸化ヒドラジニウム(100%;E.Merck)、スチレン(STY)(Merck)である。
100mLのフラスコに、34.16mLのジメチルホルムアミド(DMF)、12.64gのアクリロニトリル(AN)、23.35gのグリシジルメタクリレート(GMA)モノマーおよび0.47gの過硫酸アンモニウム重合開始剤を加える。モノマー混合物中のANおよびGMAの量は、それぞれ、60mol%および40mol%であった。ラジカル重合のために、前記混合物を50℃に加熱し、24時間にわたって攪拌する。30重量%固形分含量を有するポリマー溶液75mLを得る。ポリ(アクリロニトリル−コ−グリシジルメタクリレート)コポリマーの組成を、図1に示すポリマーの1H NMRスペクトル(Varian 500MHz)を用いて決定した。
実施例1のポリマー溶液を、パスツールピペットに入れ、電位12.3kVに付した。接地したシートを、ポリマー溶液を充填したガラス管内の高圧プローブを横切るように配置した。電位差が表面張力に打ち勝つと、前記ガラスチップ上に保持された前記ポリマー液滴から細いジェットが噴出した。溶媒を蒸発除去すると、ナノスケールの繊維が接地したシートに残った。最後に、マット状の構造物が得られ、箔から容易に取り外すことができた。ポリマー溶液をガラスキャピラリーに保持した。キャピラリーおよびそのチップの直径は、それぞれ、5mmおよび1mmであった。
700mgのエレクトロスピンされたポリマー繊維(web)を、20mLの水酸化ヒドラジニウム(100%)と、250mLのフラスコ中で混合し、一晩攪拌した。ついで、500mLのメタノールで6回洗浄した。窒素ガスで流量0.5bar、20分間、蒸留水を脱気した。生成物を、真空、50℃で24時間乾燥させた。
700mgのヒドラジン修飾エレクトロスピンされたマットを、密閉ガラス瓶内の5mLの0.1M AgNO3溶液、0.5mLの1M KOH溶液および1mLの濃縮NH3溶液の混合液に導入した。ナノファイバー上への金属の即時析出が数分以内に生じた。
熱重量分析(TGA)
TGAは、酸化媒体下、Netzsch STA 449Cを用いて行い、H2OおよびCO2中で前記ポリマーを焼成した。加熱速度10℃で、700mgの試料を室温から1000℃まで加熱した。P(AN−GMA)およびAg処理したヒドラジン修飾P(AN−GMA)の熱分析曲線を、図4に示す。
図5は、Ag陽イオンのメタライゼーション処理後のP(AN−GMA)のX線回折(XRD)曲線を示す。30〜90°の間のX線スペクトルで5つのピークが検出された。主なピークは、Agの(111)ピークに対応する20=38.1°付近に現れた。そのほかの4つのピークは、44.3°、64.5°、77.4°、81.8°であった。前記スペクトルの横軸は、AgについてのJCPDS参考回折データファイルに基づく。Agを備えたマットのスペクトルは、Ag単体と一致する。
ナノファイバーの電子顕微鏡分析は、Jeol marka電子顕微鏡840A型を用いて、異なる倍率で行った。堆積したAg原子を、高分解能電子顕微鏡を用いて観察した。
30mLのテトラヒドロフラン(THF)、15gのスチレン(STY)、15gのグリシジルメタクリレート(GMA)モノマーおよび0.08gのアゾ−ビス−イソ−ブチロニトリル(AIBN)重合開始剤を、100mLフラスコに加える。前記モノマー混合物中のSTYおよびGMAの量は、それぞれ、42mol%および58mol%であった。ラジカル重合のために、前記混合物を80℃に加熱し、26時間にわたって攪拌する。50wt%固形分含量を有する75mLのポリマー溶液を得る。ポリ(スチレン−コ−グリシジルメタクリレート)コポリマーの組成を、図7に示すポリマーの1H NMRスペクトル(Varian 500 MHz)を用いて決定する。
50wt%のポリ(スチレン−コ−グリシジルメタクリレート)のTHF溶液を、DMFで25wt%濃度に希釈する。ポリマー溶液に、電場2kV/cmをかける。図8に示すエレクトロスピンされた繊維の直径は、おおよそ100nm程度である。
もろく、透明なエレクトロスピンされたマットを、Al箔から容易に除去し、水性ヒドラジン溶液に含浸させた。前記マットを48時間、還元媒体中で保持する。洗浄処理後、前記マットは金属被覆の準備ができている。
1gのヒドラジン修飾エレクトロスピンされたマットを、密閉ガラス瓶内の、5mLの0.1M AgNO3溶液、0.5mLの1M KOH溶液および1mLの濃縮NH3溶液の混合液に導入した。ナノファイバー上の金属即時析出が、数分以内に生じる。前記マットを、24時間還元媒体中に保持した。
被覆した試料を30°〜90°のXRDで分析する。図5に示すものと同一のスペクトルが得られる。
(1)Srinivasan G, Reneker DH. Polymer International 1995;36:195.
(2)Demir M.M.; Yilgor E.; Yilgor I.; Erman B.; Polymer 2002, 42, 3303.
(3)Bicak, N.; Sungur S; Tan N.; Bensebaa F.; Deslandes, Y. J. Poly.Sci. Part A Polymer Chemistry 2002, 40, 748.
(4)Butenko AN, Savenkov AS; Russ J Appl Chem+ 2000, 73 (11), 1942-1945.
(5)Monnier JR, Medlin JW, Barteau J Catalysis 2001, 203 (2) 362-368.
(6)WO-A- 01/51690 or Norris ID, Shaker MM, Frank KK, MacDiarmid AG. Synthetic Metals 2000;114:109.
Claims (7)
- 金属で被覆されたポリマーナノファイバーの調製方法であって、以下の工程を含むことを特徴とする方法。
a)ポリ(アクリロニトリル−コ−グリシジルメタクリレート)およびポリ(スチレン−コ−グリシジルメタクリレート)からなる群から選択されるポリマーナノファイバーを、周囲条件でエレクトロスピンさせることにより調製する工程;
b)工程a)で得られるエレクトロスピンされたポリマーナノファイバーを、ヒドラジン、水素化ホウ素アルカリ、CuCl、SnCl2からなる群から選択される還元剤と接触させ、それにより、ポリマーナノファイバー表面のエポキシ環を開き、前記還元剤に置き換える工程;
c)工程b)で得られる還元剤修飾ポリマーフィルムを、アルカリ媒体中の金属塩溶液と反応させ、エレクトロスピンされたマットを得る工程;
d)工程c)で得られるエレクトロスピンされたマットを水で処理し、構造物中のエポキシ環を開き、鎖を架橋して完全な状態とする工程。 - 工程b)における還元剤が、ヒドラジンであることを特徴とする請求項1記載の調製方法。
- 工程c)における金属溶液が、水中のAgNO3、水中のAgCl、水中のNiCl2およびDMF中のPdCl2を含む溶媒中の可溶性遷移金属塩を含むことを特徴とする請求項1又は2に記載の調製方法。
- 請求項1から3のいずれか一項に記載の方法により得られる金属被覆ポリマーナノファイバー。
- ナノチューブ、触媒、導線、太陽電池、センサー用電極、電気化学アクチュエーター、プロトン交換膜および電極、水素貯蔵膜、高密度パッキング構造体、薄膜トランジスタ、リフレクタ、コンパクトディスクおよび装飾用途からなる群から選択される用途における、請求項1から3のいずれか一項に記載の方法により得られる金属被覆ポリマーナノファイバーの使用。
- 請求項1から3のいずれか一項に記載の方法により得られる金属被覆ポリマーナノファイバーを含む触媒。
- 請求項1から3のいずれか一項に記載の方法により得られる金属被覆ポリマーナノファイバーを含む導線。
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US20070218281A1 (en) | 2007-09-20 |
US8986594B2 (en) | 2015-03-24 |
DK1658396T3 (da) | 2009-10-19 |
AU2003269796A1 (en) | 2005-03-16 |
DE60328050D1 (de) | 2009-07-30 |
WO2005021845A1 (en) | 2005-03-10 |
US20110201240A1 (en) | 2011-08-18 |
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US20130082425A1 (en) | 2013-04-04 |
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