EP1818431B1 - Verfahren zur Herstellung eines Edelmetalls faseriger Morphology - Google Patents

Verfahren zur Herstellung eines Edelmetalls faseriger Morphology Download PDF

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Publication number
EP1818431B1
EP1818431B1 EP06425079A EP06425079A EP1818431B1 EP 1818431 B1 EP1818431 B1 EP 1818431B1 EP 06425079 A EP06425079 A EP 06425079A EP 06425079 A EP06425079 A EP 06425079A EP 1818431 B1 EP1818431 B1 EP 1818431B1
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European Patent Office
Prior art keywords
metal
process according
polymer
phase
polymer nanocomposite
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Not-in-force
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EP06425079A
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English (en)
French (fr)
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EP1818431A1 (de
Inventor
Gianfranco C/o C.R.F. Soc. Consortile Azi. Carotenuto
Brunetto C/o C.R.F. Soc. Consortile Azi. Martorana
Gianluca C/o C.R.F. Soc. Consortile Azi. La Peruta
Francesco C/o C.R.F. Soc. Consortile Azi. Butera
Piero C/o C.R.F. Soc. Consortile Azi. Perlo
Gianfranco C/o C.R.F. Soc. Consortile Azi. Innocenti
Luigi C/o C.R.F. Soc. Consortile Azi. Nicolais
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Centro Ricerche Fiat SCpA
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Centro Ricerche Fiat SCpA
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Priority to EP06425079A priority Critical patent/EP1818431B1/de
Priority to AT06425079T priority patent/ATE444382T1/de
Priority to DE602006009475T priority patent/DE602006009475D1/de
Publication of EP1818431A1 publication Critical patent/EP1818431A1/de
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material

Definitions

  • the present invention concerns a new process for the manufacture of metals with fibrous morphology, in particular a metallic material with fibrous morphology having fibres of nanometric thickness.
  • the marked difficulty of handling and using metallic nanostructures is chiefly connected to their very marked tendency to aggregation.
  • the aggregation of metallic nanoparticles represents a considerable drawback since it involves the complete loss of the mesoscopic characteristics (e.g. plasma absorption, fluorescence, etc.) and small metallic masses of sub-micrometric dimensions are formed that are arborescent (dendrites) that cannot in practice be used for any technological application.
  • mesoscopic characteristics e.g. plasma absorption, fluorescence, etc.
  • small metallic masses of sub-micrometric dimensions are formed that are arborescent (dendrites) that cannot in practice be used for any technological application.
  • the aggregation of metallic nanoparticles may bring about the development of particular fibrous structures that can have significant technological applications in various sectors (e.g. electrodes for batteries [9-11], electrostatic filters [12], oxygen sensors [13], sterilisers for the air [14], devices to dose ozone [15], heterogeneous catalysts [16], heat exchangers [17], membranes for ultrafiltration of biological liquids [17], etc).
  • These materials also enable the welding characteristics of electric contacts to be improved, reducing contact resistance and, thus, reducing wastage of electricity [18].
  • the polymeric bonding agent plays a very important role and is frequently comprised of polyvinyl pyrrolidone (PVP).
  • PVP polyvinyl pyrrolidone
  • the polymeric bonding agent plays a very important role and is frequently comprised of polyvinyl pyrrolidone (PVP).
  • PVP is an amorphous polymer that decomposes rapidly and quantitatively at relatively low temperatures (ca. 350-500°C). For this particular characteristic its use is widespread in the sector of sintering ceramic powders at low temperature [19-21].
  • the material is used as a bonding agent for fine-grain ceramic powders, whereby a precursor tape can be made, subsequently heated in air at 250-300°C to completely burn the polymer bonding agent and then heated to 900-1400°C to conclude the sintering-densification of the ceramic material.
  • the polymer burns in air without leaving any type of solid residue such that, at the completion of its combustion, the result is an intimately aggregated powder. Few other polymers present analogous characteristics (e.g. polyvinyl alcohol, PVA) and may thus be used in its place.
  • PVA polyvinyl alcohol
  • the purpose of the present invention is to develop a new economic and innovative process for the manufacture of a metallic material with fibrous morphology. According to the present invention, this purpose is achieved thanks to the solution described specifically in the attached claims.
  • the claims form an integral part of the technical instruction provided here in regard to the invention.
  • the invention relates to a process for the manufacture of metallic fibres as defined in the claims.
  • the fibres present nanometric thickness and thus the surface development of the solid metal is the maximum that can be achieved for a porous structure.
  • the fibrous morphology is only produced when the nanocomposite presents a relatively reduced nano-load of metal (approximately 5% by weight).
  • the fibrous metallic structure corresponding to a sort of metallic wool, has been obtained by burning a particular hybrid organic-inorganic nanostructured system in air, that is by burning a metal-polymer nanocomposite. From the structural standpoint this precursor is constituted of spherical metal nanoparticles with mean particle size of approximately 3-15 nm, not aggregated but dispersed uniformly within a continuous polymeric matrix in general comprised of polyvinyl pyrrolidine (PVP) of low molecular weight (10,000 u.m.a.).
  • PVP polyvinyl pyrrolidine
  • Two-phase systems of this type may be produced with a very high degree of purity, as will be described below.
  • Numerous catalytically-active noble metals e.g. Au, Ag, Pd, Pt, Rh, etc.
  • Au, Ag, Pd, Pt, Rh, etc. may be produced in the form of a colloidal suspension by reduction of the corresponding ions with alcohols [5-8,23].
  • These ions originate from the disassociation of electrolytes (ionic solids) typically consisting of inorganic salts (sulphates and nitrates) or organic salts (acetates).
  • electrolytes ionic solids
  • inorganic salts sulphates and nitrates
  • organic salts acetates
  • vicinal diols are usually preferred, since these chemical compounds possess a much greater reducing power than simple alcohols and thus the reduction may also be carried on at ambient temperature.
  • the reducing agent is introduced in larger than stoichiometric quantities, since it also acts as organic solvent in which the reaction takes place and is thus also the means of growth of the nanometric solid metallic phase.
  • a frequently-used reducing agent is ethylene glycol (1,2-ethanediol). With some metal salts (e.g. AgNO 3 ) the reduction reaction may easily be performed at ambient temperature and consists in dehydration of the glycol with formation of acetaldehyde and subsequent reduction of the metal ion by the acetaldehyde with formation of metallic atoms and molecules of acetylacetal.
  • the metal atoms form metallic clusters (aggregations of a small number of metal atoms) once the system exceeds the saturation limit.
  • the reduction reaction is carried on in presence of a protective agent whose function is to become adsorbed onto the surface of the metal particles, stabilising the surface and thus preventing particle aggregation, which would otherwise be made possible by their frequent collisions in the reaction environment due to Brownian motion.
  • stabilising agents are in general organic molecules able to be adsorbed with varying degree of stability onto the surface of the metal particles so as to comprise an organic coating.
  • Polymeric protective agents are particularly valid. Among these, those most frequently used are poly(vinyl pyrrolidone) (PVP) and polyvinyl alcohol (PVA). That is, the same polymers that are used as bonding agents in the sinteration of hyper-fine ceramic powders.
  • Ethylene glycol also shows some capability to be adsorbed onto metal surfaces; however, the protective power of this molecule is quite limited and thus inadequate in the presence of high concentrations of particles. Furthermore, the polymeric stabiliser is also able to favour the reduction reaction of the colloidal metal and the phase separation process.
  • the metallic nanoparticles may be isolated from the liquid medium in which they are dispersed, for example, through the co-precipitation technique, that is to say precipitation together with the polymeric stabiliser.
  • the metal particles are linked to the polymeric stabiliser in a stable fashion through a co-ordination link involving numerous lateral polar groups of the polymer, the particles are completely precipitated together with the polymer by varying the polarity of the liquid dispersing medium.
  • the polarity of ethylene glycol may be substantially varied by the addition of acetone.
  • the two solvents are miscible in all proportions and successive additions of acetone gradually lower the polarity of the resulting binary mixture. From this liquid phase that gradually becomes less polar, PVP ends up by precipitating, taking with it the metal nanoparticles, which are stably linked to its structure by non-bond interactions.
  • phase that coagulates initially consists of a sort of soft semisolid due to the presence of a large quantity of ethylene glycol that plasticises the PVP.
  • this material gradually becomes more solid as the last molecules of ethylene glycol diffuse outwards.
  • Figures 1 and 2 show the microstructures of two polymeric Ag/PVP nanocomposites obtained starting from different quantities of silver salt.
  • Figure 3a shows the XRD diffractogram of the Ag/PVP nanocomposite after drying, whereas figure 3b shows the diffractogram of a metallic silver standard; as may be seen, the metal produced by alcohol reduction of the corresponding salts is crystalline and nanometric (reflection broadening).
  • the dried nanocomposite material is then burned in air.
  • the process is conducted using a simple quartz kiln (or tubular quartz oven) operating in air flow.
  • thermogravimetric balance TGA, TA-Instrument Mod.Q500
  • TGA thermogravimetric balance
  • Figure 4a shows the TGA thermogram of a specimen of Ag/PVP heated in a flow of nitrogen (pyrolysis).
  • decomposition began at 350°C and was practically complete at approximately 470°C, with a single weight loss.
  • the residual weight was equal to 16% of the initial mass, and was found to be higher than the value obtained by combustion of the specimen in air under the same heating conditions. This may be attributed to the formation of carbon residue produced by thermal decomposition (pyrolysis) of the polymer.
  • the presence of this product of pyrolysis was confirmed by elemental analysis carried out on the residue through an X-ray microprobe (EDS, LINK AN10000) (see Figure 4b ). EDS analysis carried out on the residue showed the presence of elements that constitute the polymeric matrix (PVP), principally carbon and traces of nitrogen, in addition to the signal for silver.
  • EDS analysis carried out on the residue showed the presence of elements that constitute the polymeric matrix (PVP), principally carbon and traces of nitrogen, in addition to the signal for silver
  • Figure 5a shows the TGA thermogram of the Ag/PVP nanocomposite burned in air under the same conditions. In this case, a double weight loss was observed, respectively centred around 410°C and 490°C. Combustion of the Ag/PVP nanocomposite in air left a residue equal to 4% of the initial mass, suggesting complete decomposition of the polymeric matrix. Indeed, subsequent elemental analysis performed by EDS showed that the residue was exclusively comprised of metallic silver (see figure 5b ).
  • FIG. 6a shows the residue of the Ag/PVP specimen burned in nitrogen (pyrolysis).
  • the material presents a porous structure, but highly irregular. Particles of silver cannot be distinguished and thus must still be englobed in the carbon matrix generated during pyrolysis.
  • Combustion of the nanocomposite in air brought about the formation of a fibrous metallic structure, shown in figures 6a, 6c and 6d .
  • the fibres are practically continuous and have a diameter of approximately 2 ⁇ m. Furthermore, they are linked together to produce a network the average size of whose mesh is below 10 ⁇ m in diameter.
  • Combustion in air of Ag/PVP nanocomposites having a reduced nanometric metallic load leads to a fibrous-networked structure constituted of metal alone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Inorganic Fibers (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (17)

  1. Verfahren zur Herstellung von Metallfasern, umfassend die folgenden Phasen:
    i) Herstellung einer kolloidalen Suspension eines Metalls im Elementarzustand in Gegenwart eines Polymers, wobei die kolloidale Suspension durch Reduktion eines Salzes des Metalls mittels eines Reduktionsmittels in einem Lösungsmittel hergestellt wird, so dass eine kolloidale Suspension des Metalls im Elementarzustand in dem Lösungsmittel erhalten wird;
    ii) Abtrennung des Metalls im Elementarzustand und des Polymers von der Suspension mittels Kopräzipitation des Metalls im Elementarzustand und des Polymers, um einen Metall-Polymer-Nanokomposit zu erhalten;
    iii) Verbrennung der organischen Komponente des Metall-Polymer-Nanokomposits bei einer Temperatur zwischen 300 und 500 °C, um Metallfasern zu erhalten.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Lösungsmittel und das Reduktionsmittel die gleiche Zusammensetzung aufweisen.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Reduktionsmittel ein Alkohol, vorzugsweise ein vizinales Diol ist.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das vizinale Diol 1,2-Ethandiol ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Reduktionsmittel in größeren Mengen als den Mengen der stöchiometrischen Beziehung zwischen Metall und Reduktionsmittel verwendet wird.
  6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer in dem Lösungsmittel löslich ist.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Polymer ausgewählt ist aus Polyvinylpyrrolidon und Polyvinylalkohol.
  8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Phase i) der Herstellung der kolloidalen Suspension bei einer Temperatur im Bereich von 25-50 °C, vorzugsweise von 35-45 °C durchgeführt wird.
  9. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Metall-Polymer-Nanokomposit eine Metallmenge unter 10 Gew.-% enthält.
  10. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Metall-Polymer-Nanokomposit eine Metallmenge von weniger als 7 Gew.-% enthält.
  11. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Metall-Polymer-Nanokomposit eine Metallmenge enthält, die 5 Gew.-% entspricht.
  12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Phase ii) der Abtrennung durch Variieren der Polarität der Suspension erzielt wird.
  13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Phase ii) der Abtrennung des Metall-Polymer-Nanokomposits auch eine Phase der Trocknung des Metall-Polymer-Nanokomposits einschließt, welcher kopräzipitiert worden ist.
  14. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Phase iii) der Verbrennung des Metall-Polymer-Nanokomposits in Luft durchgeführt wird.
  15. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Metall ausgewählt ist aus Au, Ag, Pd, Pt, Rh, Ir.
  16. Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass das Metall im Elementarzustand eine teilchenförmige Morphologie aufweist.
  17. Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass die metallischen Teilchen einen mittleren Durchmesser zwischen 1 und 20 nm aufweisen.
EP06425079A 2006-02-13 2006-02-13 Verfahren zur Herstellung eines Edelmetalls faseriger Morphology Not-in-force EP1818431B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP06425079A EP1818431B1 (de) 2006-02-13 2006-02-13 Verfahren zur Herstellung eines Edelmetalls faseriger Morphology
AT06425079T ATE444382T1 (de) 2006-02-13 2006-02-13 Verfahren zur herstellung eines edelmetalls faseriger morphology
DE602006009475T DE602006009475D1 (de) 2006-02-13 2006-02-13 Verfahren zur Herstellung eines Edelmetalls faseriger Morphology

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06425079A EP1818431B1 (de) 2006-02-13 2006-02-13 Verfahren zur Herstellung eines Edelmetalls faseriger Morphology

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EP1818431A1 EP1818431A1 (de) 2007-08-15
EP1818431B1 true EP1818431B1 (de) 2009-09-30

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Publication number Priority date Publication date Assignee Title
CN102672196B (zh) * 2012-05-15 2014-12-24 大连理工大学 一种常温制备金属胶体的方法
CN110653380B (zh) * 2019-10-31 2022-08-19 合肥工业大学 一种常温下在醇相中快速制备金纳米颗粒的方法

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DE19639632B4 (de) * 1996-09-26 2005-10-13 Zenneck, Ulrich, Prof. Dr. Verfahren zur Herstellung ionenfreier Nanometall-Polymerverbunde und deren Verwendung
US6346136B1 (en) * 2000-03-31 2002-02-12 Ping Chen Process for forming metal nanoparticles and fibers
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

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EP1818431A1 (de) 2007-08-15
ATE444382T1 (de) 2009-10-15

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