JP6067573B2 - 単結晶ナノ銀粒子の安定な分散系 - Google Patents
単結晶ナノ銀粒子の安定な分散系 Download PDFInfo
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- JP6067573B2 JP6067573B2 JP2013542253A JP2013542253A JP6067573B2 JP 6067573 B2 JP6067573 B2 JP 6067573B2 JP 2013542253 A JP2013542253 A JP 2013542253A JP 2013542253 A JP2013542253 A JP 2013542253A JP 6067573 B2 JP6067573 B2 JP 6067573B2
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- Prior art keywords
- silver
- particles
- dispersion
- particle size
- nanosilver
- Prior art date
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B22—CASTING; POWDER METALLURGY
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Description
1.平均粒径
2.微細粒分(d10)
3.分散系中の銀粒子の濃度
4.銀粒子中の単結晶の重量%。
本発明の濃縮分散系において、30〜300nmの範囲内の平均二次粒径(d50)を有するナノ銀粒子。これらの分散系は、単結晶銀粒子を概ねまたは主に含有する。
本発明の分散系における銀粒子は、少量の微細銀粒子をさらに特徴とすることができる。Brookhaven90Plus粒径分析器を用いると、本発明の分散系は、少なくとも25nm、より典型的には少なくとも30nm、少なくとも35nm、いくつかの場合においては少なくとも40nmのd10を示した。Brookhaven粒径分析器からのデータは、高分解走査電子顕微鏡(HRSEM)画像に基づく測定によって続いて確認した。
本発明の濃縮分散系中のナノ銀粒子の濃度は、典型的には30重量%〜75重量%の範囲内である。ナノ粒子の生成が典型的には実施され、比較的希釈された分散系が得られる。希釈分散系の構築は、洗浄、溶媒添加および/または置換などを含み得、銀ナノ粒子の凝集に主に寄与し得る。以下に記載のように、本発明プロセスにおいて、銀ナノ粒子の凝集が大きく回避される。
本発明の濃縮分散系において、ナノ銀粒子は、重量基準で概ねまたは主に単結晶銀粒子であってよい。単結晶の存在を電子後方散乱回折(EBSD)によって量的に実証した。以下により詳細に記載するように、結果の定量化を、ランダムに選択した点において複数の走査を実施することによって達成した。本発明者らは、本発明分散系において、ナノ銀粒子の少なくとも50%または少なくとも70%が単結晶であり、より典型的には、少なくとも80%または少なくとも90%が単結晶であることを見出した。
工程1:第1分散剤の存在下、水性媒体において少なくとも1種の可溶性銀化合物をアルカリ金属水酸化物と反応させて、1200nm未満の平均二次粒径を有する酸化銀固体を生成する工程;
工程2:第2分散剤の存在下、水性媒体において酸化銀固体を少なくとも1種の還元剤と反応させて、500nm未満、より典型的には、300nm未満の平均二次粒径を有する銀粒子を生成する工程;
工程3:工程2の銀粒子を水による洗浄によって生成する工程において;水性媒体を粒子から部分的に除去して、銀粒子の大部分を含有する濃縮物を形成していてもよい工程;
工程4:精製された銀粒子に、少なくとも1種の揮発性有機溶媒を導入し、これによって、水性媒体の大部分を置換する工程;
工程5:揮発性有機溶媒の大部分を、少なくとも1種の、典型的には不揮発性の有機溶媒によって置換する工程。
工程1
工程2
工程3
工程4
第2有機溶媒は、その同一性および特性が市場の要件によって決定されてよく、工程4で得られた分散系の揮発性有機溶媒の大部分、典型的には少なくとも80%、または少なくとも90%もしくは95%を置換するのに用いられ得る。溶媒の置換または置き換え方法は、工程3および/または工程4で利用した方法と同様であってよく、精製システムは、同様であっても同一であってもよい。
実施例
AgNO3−Aldrich
AgNO3(63.6%のAgを含有)−Saxonia(Germany)
KOH−Aldrich
過酸化水素(33%水溶液)−Makhteshim(Israel)
ポリビニルピロリドン(PVP)、MW=55,000−Aldrich
ポリビニルピロリドン(PVP)、MW=8,000−Aldrich
消泡剤Contraspum1012−Zschimmer&Schwarz(Germany)
無水エタノール−Aldrich
イソプロピルアルコール(IPA)−Aldrich
トリプロピレングリコールメチルエーテル(TPM)−Aldrich
酢酸ブチルカルビトール(BCA)−Aldrich
カプリル酸−Aldrich
Epoxy XY8000−Japan Epoxy Resins Co.,Ltd(日本)。Epoxy XY8000は、CASNo.30583−72−3によって特定され得、化学名がシクロヘキサノール、4,4−(1−メチルエチリデン)ビス−、(クロロメチル)オキシランとのポリマーである。
Brookhaven90Plus粒径分析器(Brookhaven Instruments Corporation、Holtsville、New York)を用いて粒径分析(d50)を実施した。
Malvern Master Sizer2000を用いて、実施例3における粒径分析(d50)を実施した。
HRSEM Ultra Plus Zeiss Gemini(lnlens Detector)を用いて、高分解走査電子顕微鏡(HRSEM)画像を一般的に得た。
E−SEM Quanta(商標)200(FEI、Hillsboro、Oregon)を用いて電子後方散乱回折(EBSD)パターンを得た。機器に、方位像顕微鏡(OIM)Channel5(Oxford Instruments、England)の取り付け具を備え付けた。
加熱浴(BUCHI Labortechnik AG、Flawil、Switzerland)を備え付けたR−215Rotavapor(登録商標)を用いて蒸発を実施した。
セラミック膜(JM Separations BV、The Netherlands)を含む膜システムを用いることにより、分散系の濾過を行った。
実施例1
実施例2
実施例3
実施例4
実施例5
実施例6
実施例7:分散系の濃縮
1.大部分が単結晶銀粒子である(EBSD補正により求め、典型的には、少なくとも70%、少なくとも80%、または少なくとも90%);
2.単結晶粒子は、三角形面、四角形面、六角形面、および七角形面を有する粒子を含む;
3.三角形面を有する単結晶粒子は、粒子数(SEM領域中の粒子の手動計数によって求めた)を基準にして少なくとも2%、少なくとも5%、典型的には、2%〜15%の銀粒子を提示する。
実施例8:揮発性有機溶媒による水の置換
(水−エタノール溶媒交換)
実施例9:揮発性有機溶媒(IPA)による水の置換
実施例10:有機非揮発性溶媒による揮発性有機溶媒の置換(エタノール−TPM溶媒交換)
実施例12:エポキシ樹脂による揮発性有機溶媒(IPA)の置換
(IPA−エポキシ樹脂交換)
実施例13
1.サンプルを、典型的には18mmの作動距離、20eVで走査電子顕微鏡(SEM)Quanta(商標)200を用いて走査し、回折パターンまたは画像を得る。スポットサイズは4.5であり;プローブ電流が約0.5nAであり;EBSDパターンで収集:300msec;積分:50。
2.回折画像の回折を機器のソフトウェアを用いて実施する(基本的な、銀の結晶学的データを比較);
3.回折の「解」と一致させ、結晶の方位を描写し、菊池線を格子内の適合する結晶学的平面と相関させた。菊池線と結晶学的平面(理論データによる)との間で完全一致であるとき、回折が単結晶の方位を決定する。
実施例14
実施例15
実施例16
分散系を、約3cm×3cmの寸法を有するガラス基材上に、ピペットを用いて、基材が完全に被覆されるまで滴下する。熱処理(空気中)を130℃で10分間、その後640℃で20分間行う。熱的に焼結したサンプルをオーブンから直ちに除去する。典型的には、フィルム厚は約10μmである。
実施例17
(1)固体粒子(酸化銀、銀)の代表的なサンプルを採取する;
(2)分析をそれぞれの液体中の固体粒子の分散系において実施する;
(3)分析を室温で実施する;
(4)走査角度は90度である。
Claims (3)
- ナノ銀粒子の分散系を生成するための方法であって:
(a)第1分散剤の存在下、水性媒体において少なくとも1種の可溶性銀化合物をアルカリ金属水酸化物と反応させて、1200nm未満の平均二次粒径を有する酸化銀固体を生成する工程と;
(b)第2分散剤の存在下、水性媒体において酸化銀固体を少なくとも1種の還元剤と反応させて、300nm未満の平均二次粒径を有する銀粒子の第1分散系を生成する工程と;
(c)水性媒体の少なくとも1部分を粒子から除去して分散系を生成する工程と
を含む方法。 - 粒子を濃縮して、第1分散系よりも濃縮された第2分散系を形成する工程をさらに含み、分散系中のナノ銀粒子の濃度が、30重量%〜75重量%の範囲内である、請求項1
に記載の方法。 - 前記分散系が、少なくとも9ヶ月間熟成されている、請求項1または2に記載の方法。
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US9556350B2 (en) | 2017-01-31 |
GB2486190A (en) | 2012-06-13 |
US20130270490A1 (en) | 2013-10-17 |
WO2012078590A2 (en) | 2012-06-14 |
GB201020556D0 (en) | 2011-01-19 |
KR101932781B1 (ko) | 2018-12-27 |
EP2649621A4 (en) | 2018-04-04 |
BR112013013885A2 (pt) | 2016-09-13 |
RU2013130145A (ru) | 2015-01-20 |
US20220044838A1 (en) | 2022-02-10 |
US11958116B2 (en) | 2024-04-16 |
KR20140010935A (ko) | 2014-01-27 |
CN103282969B (zh) | 2016-08-10 |
EP2649621A2 (en) | 2013-10-16 |
EP2649621B1 (en) | 2020-08-12 |
US10984920B2 (en) | 2021-04-20 |
US20170128900A1 (en) | 2017-05-11 |
RU2593311C2 (ru) | 2016-08-10 |
CN103282969A (zh) | 2013-09-04 |
BR112013013885B1 (pt) | 2020-12-22 |
JP2014505784A (ja) | 2014-03-06 |
WO2012078590A3 (en) | 2012-08-16 |
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