WO2013171542A1 - Matériaux hybrides de polymère-nanoparticules métalliques - Google Patents

Matériaux hybrides de polymère-nanoparticules métalliques Download PDF

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WO2013171542A1
WO2013171542A1 PCT/IB2012/052408 IB2012052408W WO2013171542A1 WO 2013171542 A1 WO2013171542 A1 WO 2013171542A1 IB 2012052408 W IB2012052408 W IB 2012052408W WO 2013171542 A1 WO2013171542 A1 WO 2013171542A1
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polymer
metal
poly
amide
imide
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Carmen Mabel GONZALEZ HENRIQUEZ
Claudio Alberto TERRAZA INOSTROZA
Ulrich Georg VOLKMANN
Alejandro Leopoldo CABRERA OYARZUN
Maria Jose RETAMAL PONCE
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Pontificia Universidad Catolica De Chile
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals

Definitions

  • the present invention relates to material sciences field describing polymeric matrices (organo- heteroatom (silicon or germanium) polymers (poly(amide-imide)s or poly(amide)s)) that incorporates different metals, such as, copper, silver or gold, adding structural, thermal, optical, and electrical characteristics from the metals to the polymer.
  • polymeric matrices organo- heteroatom (silicon or germanium) polymers (poly(amide-imide)s or poly(amide)s)) that incorporates different metals, such as, copper, silver or gold, adding structural, thermal, optical, and electrical characteristics from the metals to the polymer.
  • the synergism or integration of metallic particles into a polymer matrix produces changes or modifications of the initial properties of the systems. Therefore, the new polymer-metallic nanoparticle hybrid materials constitute a kind of advanced composite with interesting properties which can be also used in a broad range of applications such as: electronic and magnetic devices, optoelectronic industry, copper corrosion applications, medical applications, imaging, cata
  • Polymers have been used in a broad range of applications. In electronic devices, such as, field- effect transistors, sensors, light emitting diodes, LED screens, in the medical field, for tissue regeneration, drugs and active principles controlled release, among others. Nevertheless, the field where these materials can be use as conductors, with embedded metals into the polymeric matrix, has been poorly researched. Only researches describing the use of polymeric matrices with metallic particle groups, forming a composite are currently known.
  • the polymer-metallic nanoparticle hybrid materials have recently attracted considerable attention owing to their potential application in the catalysis, sensors, memory devices, nonlinear optics and optical filters fields (Raffa P, Evangelisti C, Vitelli G, Salvatori P. (2008). First examples of gold nanoparticles catalyzed sihne alcoholysis and silylative pinacol coupling of carbonyl compounds. Tetrahed. Letter., 49: 3221-3224; Arcadi A. (2008). Alternative Synthetic Methods through New Developments in Catalysis by Gold. Chem. Rev., 108: 3266-3325 5 Lin P, Yan F, Yu J, Chan HLW, Yang M. (2010). The Application of Organic Electrochemical Transistors in Cell-Based Biosensors.
  • the first method consists in the "in-situ" preparation of nanoparticles in the matrix, either by the reduction of metal salts dissolved in the polymer matrix (Mayer A. B. R. (1998). Formation of noble metal nanoparticles within a polymeric matrix: nanoparticle features and overall morphologies. Mater. Sci. Eng. C, 6: 155-166; Selvan ST, Spatz JP, Klok HA, Moller M. (1998). Gold-Polypyrrole Core-Shell Particles in Diblock Copolymer Micelles. Adv. Mater., 10(2): 132-134; Watkins JJ, McCarthy TJ. (1995).
  • the third technique is the blending of pre-made metallic nanoparticles with pre-made polymer since this method provides full synthetic control over both the nanoparticles and the polymer matrix (Mallick K, Witcomb MJ, Erasmus R, Strydom A. (2009). Low- temperature magnetic property of polymer encapsulated gold nanop articles. J. Appl. Phys., 106: 074303-074308).
  • the metallic nanoparticles can be blended with a variety of polymers.
  • the dispersion of the nanoparticles in the system is incompatible nature due to the hydrophobic characteristics of the polymer.
  • Document US7750076B2 describes a polymer layer comprising silicone contains oxide particles of S1O 2 , T1O 2 , Sb 2 0 3 , SnC> 2 , AI 2 O 3 , ZnO, Fe 2 0 3 , Fe 3 0 4 , talc, hydro xyapatite or mixtures thereof and one or more metal traces embedded in the polymer layer, where the metal trace is bonded to the polymer silicon metal bond.
  • the polymer can be other than silicone and the metal traces can include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver or gold, or an alloy of two or more metals, or a combination of two or more alloys or metal layers thereof.
  • Document WO2006131616A1 relates to a new type of molecular junction in which molecules belonging to the families of 7-dialkylamino phenothiazines, 7-dialkylamino phenoxazines and of 5-alkyl or 5-aryl, 7-dialkylamino phenazines are grafted to a semiconductor by establishing a covalent bond between their carbon 3 and a surface atom of a semiconductor that can be a silicon atom, arsenic atom or germanium atom, and in which a metal is then electrolytically deposited onto the grafted surface of the semiconductor.
  • the document also relates to a new type of molecular junction in which the grafting of preceding organic molecules to a semiconductor is followed by the polymerization of acrylonitrile or N-vinyl-imidazole forming a polymer connected by a covalent bond to the grafted molecules and in which a metal, preferably copper, is then electrolytically deposited onto the grafted surface of the semiconductor.
  • the inventive devices are particularly used for producing new types of electronic components and for realizing copper deposits in the submicronic semiconductor structures.
  • the present invention discloses new materials having the processability and malleability of a polymer and the structural, thermal, optical, and electrical characteristics from the metals that it absorbs (such as copper, silver or gold).
  • the present invention uses an organo-heteroatom (silicon or germanium) polymer (poly(amide-imide)s or poly(amide)s) and a metal film as substrates for a process at room temperature, humidity and pressure generating polymer-metallic nanoparticle hybrid materials.
  • the new materials are conductors that can be used in electronic and magnetic devices, optoelectronic industry, copper corrosion applications, medical applications, imaging, catalysis and adhesives.
  • the present invention is also related to a new method to prepare polymer-metallic nanoparticle hybrid materials.
  • the present invention discloses new materials elaborated upon organo-heteroatom (silicon or germanium) polymers (poly(amide-imide)s or poly(amide)s) and a metallic film, such as, but not limited to copper, silver or gold, having the processability and malleability of a polymer and the structural, thermal, optical, electrical and other characteristics from the metals that it absorbs.
  • the polymers of the invention have the capacity to incorporate, with covalent bonds, in coordinated and arranged form, the metals to its structure, generating a new macromolecular material, keeping or improving the original properties of the polymers, adding the properties of the coordinated metal.
  • the organo-heteroatom (silicon or germanium) polymer for the new macromolecular material is selected among poly(amide-imide) or poly(amide) and the metal is selected among, but not limited to copper, gold, or silver.
  • the new materials are poly(amide-imide)-metallic nanoparticle hybrids and poly(amide)- metallic nanoparticle hybrids, using different kinds of pure metals, such as, but not limited to copper, silver, or gold.
  • the characterization experimental techniques involve the use of solid UV-vis and Raman spectroscopy, X-ray diffraction and Scanning Electronic Microscopy (SEM). All these techniques contribute to discover a possible mechanism of interaction between the metal cluster and the capping polymer and shed light on the relationship between polymer adsorption and the cluster size and distribution.
  • the present invention is also related to a new method at room temperature, humidity and pressure to prepare polymer-metallic nanoparticle hybrid materials.
  • the method for preparing the polymer-metallic nanoparticle hybrid materials comprises the steps of a) providing a polymer solution dissolving the organo-heteroatom (silicon or germanium) polymer (poly(amide-imide)s or poly(amide)s) in an aprotic polar organic solvent; b) providing a metal film from the selected metal; c) dispersing the polymer solution by spin coating on the metal film; and d) simultaneous absorption, nano-encapsulation or incorporation of the metal into the polymer matrix.
  • the preparation of the new materials starts with a polymeric solution, which is dispersed by spin coating on a metallic substrate (such as Cu, Ag or Au), previously deposited by physical vapor deposition (PVD). Additionally, metal film can be realized with other methods such as: Chemical vapor deposition (CVD) or sputtering. Immediately, when the polymer gets in contact with the metal, the nano-encapsulation, absorption or incorporation of the metal into the polymer matrix is produced. In addition, the objective of this invention enhances the understanding of the polymer-metal interaction.
  • the polymerization of the polymer matrix of the present invention is carried out by standard methods, known by a person having ordinary skill in the art ( Figure 1 and Figure 2) (Faghihi K, Shabanian M, Hajibeygi M. (2009). Optically Active and Organosoluble Poly(amide-imide)s Derived from N,N'-(Pyromellitoyl)bis-L-histidine and Various Diamines: Synthesis and Characterization. Macromolecular Research, 17 (11): 912-918; Yamazaki N., Matsumoto M., Higashi F. (1975). Studies on Reactions of the N-Phosphonium Salts of Pyridines. XW.
  • the organo-heteroatom (silicon or germanium) polymer (poly(amide-imide)s or poly(amide)s) is preparing upon a mixture of dicarboxylic acid, diamine, anhydrous calcium dichloride (CaC ⁇ ), triphenylphosphite (TPP), pyridine (Py) and N-methyl-2-pirrolydone ( ⁇ ) that is heated at 100-130 °C during 2-5 hours under stirring.
  • the stirring is performed at 110 °C. In another preferred embodiment, the stirring is performed during three hours.
  • the preparation of the metal films is realized by the following procedure: evaporation of metal grains with a purity of 99.90-99.95 % by Physical Vapor Deposition (PVD) in high vacuum onto a glass substrate at room temperature (20-30 °C) is performed.
  • the metal for the film is selected among, but not limited to copper, silver, or gold. In a preferred embodiment, the metal is copper, silver or gold. In another preferred embodiment, the metal has a purity of at least 99.90 %. In a preferred embodiment the glass substrate temperature is 25 °C.
  • Metal film thicknesses are between 30-70 nm. In a preferred embodiment, the thicknesses of the films are 50 nm.
  • the polymer dissolved in an aprotic polar organic solvent at concentration between 0.05-2.00 mgl ⁇ L is deposited by spin coating using rotation velocity ramps: 300-700 rpm for 5-25 s and 1000-2000 rpm for 5-25 s.
  • the polymers are dissolved in dimethylsulfoxide (DMSO) at 0.09 mgl ⁇ L and the spin coating process is developed using 500 rpm during 10 s and 1600 rpm for 10 s.
  • DMSO dimethylsulfoxide
  • incorporation of the metal into the polymer is produced immediately when the polymer gets in contact with the metal film.
  • the complete process can take from a few minutes to several hours.
  • This incorporation kinetic can be controlled, by modifying kinetic parameters (reaction conditions), and the specific structure of the polymer.
  • the new method is a promising alternative to existing conventional methods which need of a mixing device for a physical mixture of the solutions made at room temperature and thus producing the nano-encapsulation of the metals into the polymer.
  • the metallic nanoparticles are dispersed in the poly(amide-imide)s matrices due to the coordinate covalent bonds between the metal and the silicon or germanium atoms.
  • poly(amide)s with a thiophene moiety in the main chain produce the incorporation of the metal in their structure changing the crystalline pattern of the system.
  • the new materials severely increase their electric and thermal transport capacity.
  • the adhesive industry has not found an optimal way to produce the adhesion between polymer and metal, due to lack of strong interactions, such as covalent or ionic bonds.
  • the present invention provides a complete, stable and arranged inclusion of the metal into the polymer, a property that could be used in this industry.
  • a metal such as copper and silver
  • bactericide properties are very important for the medical industry.
  • the new material of the invention, with their high processability and malleability that also include bactericide properties from metal can certainly be used in medical applications.
  • the inclusion of gold into polymer can be used in biological sensors.
  • the low toxicity shown by this metal is an advantage in biological and medical application. Therefore, the modification of some initial optical properties such as fluorescence is widely used in biomarkers that allow the detection and quantification of biological systems, such as proteins.
  • the new polymer-metallic nanoparticle hybrid materials can be used in electronic and magnetic devices due to that the new materials are conductors of electricity, optoelectronic industry, copper corrosion applications, due to the protection that confers the polymeric matrix, medical applications due to that the new materials have bactericide and optical (absorption, transmittance and fluorescence) properties and adhesives due to that the covalent bonds between the polymer and the metal allow the interaction for a strong adhesion. Other possible applications would be related to the imaging and the catalysis fields.
  • Figure 3 Four point measurements of conductivity in polymers.
  • Figure 4 Raman spectroscopy of poly(amide-imide)s with the incorporation of copper (Cu), silver (Ag) and gold (Au): a) PALA; b) PALL; c) PALV and d) P ALPHA.
  • Figure 5 Raman spectroscopy of poly(amide)s with incorporation of copper (Cu), silver (Ag) and gold (Au): a) PAtSi and b) PAtGe.
  • Figure 6 XRD patterns of poly(amides-imide)s with incorporation of copper (Cu), silver (Ag) and gold (Au): a) PALA; b) PALL; c) PALV and d) PALPHA
  • Figure 7 X-Ray diffraction of poly(amide)s with incorporation of copper (Cu), silver (Ag) and gold (Au): a) PAtSi and b) PAtGe.
  • Figure 8 SEM micrographs of poly(amide-imide)-metal hybrids.
  • Figure 9 Poly(amides-imide)-metal hybrids: a) Nanoparticle areas and b) Elemental analysis results.
  • Figure 10 SEM micrographs of poly(amide) -metal hybrids.
  • Figure 11 Elemental analysis of poly(amide)-metallic nanoparticle hybrids.
  • Figure 12 Possible mechanism for generation of polymer-metallic nanoparticle hybrids: a) poly(amide-imide)s and b) poly(amide)s.
  • Example 1 Preparation of the metal films of silver, gold or copper
  • the polymer solution was deposited by spin coating using rotation velocity ramps: 500 rpm about 10 s and 1600 rpm for 10 s.
  • Polymer-metallic nanoparticle hybrid films prepared according to the present invention were characterized by UV-visible spectroscopy. These optical measurements were carried out by using UV-visible spectrophotometer (UV-2450 Shimadzu) and scanning the spectra between 200-800 nm at a resolution of 1 nm using barium sulfate as standard compound. To determine the resistance and conductivity in the hybrid films a four point probe system, connected to a multimeter (Keithley, Model 2000-200) was utilized (Figure 3).
  • the structural and vibration properties of the hybrid films were characterized by Raman spectroscopy with a Lab Ram 010 instrument from ISA equipped with a 5.5 mW HeNe laser beam (633 nm).
  • the Raman microscope uses a back- scattering geometry, where the incident beam is linearly polarized at 500:1 ratio.
  • the objective lens of the microscope was an Olympus Mplan lOOx (numerical aperture 0.9), which provide sufficient distance between the objective and the samples.
  • the integration time was 25 s for all the samples with an accumulation of 5 s.
  • the diffraction patterns were obtained in the usual ⁇ -2 ⁇ geometry.
  • the X-ray tube was operated at 40 kV and 40 mA.
  • the goniometer was swept between 5 ° and 140 ° at 0.02 7s over the whole 2 ⁇ interval.
  • the diffracted X-rays were detected with a scintillation detector.
  • the morphology of the hybrid films was examined with a scanning electron microscope (SEM), model LEO 1420VP, 100 ⁇ beam current and a working distance of 12-14 mm.
  • SEM scanning electron microscope
  • the microscope was operated at high vacuum ( ⁇ 10 ⁇ 5 mbar).
  • the main absorption band observed at 330 nm in the UV-vis spectrum of PALL is attributed to the ⁇ - ⁇ * transition.
  • PALL-Cu copper nanoparticles embedded in the polymeric matrix
  • PALA-Ag presented one broad absorption spectra in the UV and visible region that contribute the absorption bands at 387 and 459 nm, corresponding to the ⁇ - ⁇ * transition and the silver surface plasmon; respectively.
  • the absorption spectrum of PALL-Au showed two absorption maxima, one at 363 nm corresponding to the ⁇ - ⁇ * transition and a second at 449 nm, related to the surface plasmon resonance band.
  • PALV showed one maximum band at similar wavenumber than PALL (331 nm), corresponding to the ⁇ - ⁇ * transition.
  • PALV-Cu showed three absorption maxima at 350, 397 and 501 nm assigned to ⁇ - ⁇ *, ⁇ - ⁇ * and charge transfer transitions; respectively, and a lower band at 692 nm, corresponding to the copper surface plasmon.
  • silver nanoparticles are embedded in the polymeric matrices (PALV-Ag)
  • the absorption spectrum of PALV-Au showed two absorption maxima, at 363 nm, corresponding to the ⁇ - ⁇ * transition and at 449 nm, related to the surface plasmon resonance band.
  • PALPHA-Ag showed also one broad absorption spectra in the UV and visible region that contributes to the absorption bands at 394 and 454 nm, corresponding to ⁇ - ⁇ * transition and the silver surface plasmon. Finally, the spectrum of PALPHA-Au showed two absorption maxima at 364 nm, corresponding to the ⁇ - ⁇ * transition and at 454 nm, related to the surface plasmon resonance band.
  • PAtGe-Cu presented one weak band at 681 nm that involves the surface plasmon resonance band, characteristic of the copper nanoparticles.
  • PAtGe-Ag presented one broad absorption spectra in the UV and visible region where contribute the absorption bands at 371, 405, 491 and 538 nm corresponding to ⁇ - ⁇ *, ⁇ - ⁇ *, charge transfer transitions and the silver surface plasmon; respectively.
  • the absorption spectrum of PAtGe-Au showed two absorption maxima, at 369 nm corresponding to the ⁇ - ⁇ * transition, and 452 nm related to the surface plasmon resonance band.
  • the band related to the surface plasmon resonance is higher than the band of the polymer, with the exception of the hybrid polymer-copper nanoparticle systems.
  • the electrical conductivities of the polymers and the hybrid systems are shown in Table 2.
  • the conductivity increases with the incorporation of the metals.
  • PAtSi-Au hybrid showed conductivities one and three orders of magnitude higher than PAtSi-Ag and PAtSi-Cu; respectively.
  • These behaviors are related to the optical properties of the systems, thus when the wavelength moves to higher values, the electrical conductivity also increases.
  • the PAtGe presented an insulator behavior, similar to their hybrid systems.
  • Example 5 Structural and vibration properties
  • the Raman spectra obtained from thin pure metal films showed two vibrations for copper and silver; respectively.
  • at 628 cm “1 appears theoretically a band related to Cu-0 (Kazuo N, Infrared and Raman spectra of Inorganic and Coordination Compounds: Part A: Theory and Applications in Inorganic Chemistry. (1997). 5 th edition. John Wiley & Sons, Inc. New York, USA, p. 155), which is experimentally shown at 523 and 607 cm “1 .
  • the vibrations of the silver metal show two bands at 1356 and 1591 cm “1 .
  • vibrations are related to the process of thermal evaporation of the metal in high vacuum (PVD) and the deposition of amorphous carbon on the silver film (Itoh K, Kudryashov I, Yamagata J, Nishizawa T, Fujii M, Osaka N. (2005).
  • gold does not exhibit a vibration mode in the Raman spectrum, due to the intrinsic characteristics of the material; a noble metal.
  • the band at 1189 cm “1 is assigned to C-H ip bending, together with the 1027 cm “1 vibration.
  • the band at 1588 cm “1 in PALA-Ag presents the same behavior than PALA-Cu.
  • the areas of the vibrational modes decrease with respect to modes observed for PALA-Cu, due to the steric impediment produced by gold nanoparticles.
  • Raman spectra of the polymer designated as PALL represent a broad band assigned at 3050 cm “1 , corresponding to the aromatic C-H stretching vibration.
  • the C-H ip and oop bending are observed at 1028 cm “1 and 997 cm “1 , with a weak and strong intensity; respectively.
  • One C-H oop bending vibration band is assigned to 619 cm “1 , which is related to the movement of the hydrogen in the aromatic ring.
  • the detection of a weak, broad band at 1356 cm “1 is assigned to the silver residues in the film.
  • Raman spectra of PALV represent one strong band at 3054 cm “1 , corresponding to the aromatic C-H stretching vibration.
  • C-H ip and oop bending bands are assigned to three signs; 1194 cm “1 , 1030 cm “1 and 993 cm “1 , with weak and strong intensities; respectively.
  • the inclusion of the copper into the polymer showed a crystalline behavior, very different to the amorphous patterns of PALV.
  • the high intensity of the vibrational modes assigned to 520 and 611 cm “1 are related to the remainder CuO.
  • the bands at 3047 cm “1 corresponding to the aromatic CH stretching vibration, change its intensity in relation to the polymer (PALV) showing the loss of planarity and the resonance effect in the aromatic rings.
  • Raman spectra of PAtSi exhibit a weak band at 3050 cm “1 , due to the aromatic C-H stretching vibration and strong band related to C-H ip bending vibration at 995 cm “1 .
  • the carbon atoms present a radial ip movement, which is the in-phase ring stretching (or "breathing") mode.
  • Another interesting band at 1527 cm “1 corresponds to the Si-C arom.
  • the vibrations produced by the remainder CuO are assigned to 519 and 619 cm “1 with a strong intensity, in comparison to the other vibrations.
  • the inclusion of silver into the amorphous network of the polymer produces a crystalline behavior in the new structure formed.
  • the band at 3050 cm “1 is related to the aromatic C-H stretching vibrations.
  • PAtSi-Au showed a band at 3050 cm "1 associated to an increase of the crystalline degree.
  • the PAtSi-Au showed a displacement of Si-C arom. vibration, produced by the disturbance from the electronic distribution of the gold atom.
  • PAtGe (Figure 5b) presented three vibrational modes with strong, medium and weak intensities at 1583 cm “1 , 1334 cm “1 and 1086 cm “1 ; respectively.
  • the band at 1334 cm “1 possibly can be attributed to two vibrational modes, Ge-C arom. stretching and C-C intra-ring symmetric stretching vibration of the thiophene moiety.
  • Nanotechnology 17: 4929-4935) in the poly(amide-imide)s was further confirmed by X-ray diffraction (XRD) measurements, as it is shown in Figure 6 and Table 3.
  • XRD X-ray diffraction
  • the XRD pattern of Ag nanoparticles showed a strong peak with a maximum intensity at 38.09 °, representing Bragg 's reflection (111) planes of the standard cubic phase of Ag (Hu J, Cai W, Li C, Gan Y, Chen L. (2005).
  • the polymer-gold hybrid also exhibited the presence of a strong peak with a maximum intensity at 38.20 °, representing (111) planes of the standard cubic phase of Au.
  • Data of Figure 6 correspond to polymer-copper nanoparticle hybrids, with the presence of a significant diffuse X-ray amorphous component.
  • This spectrum confirms the presence of a disordered nanocrystalline phase, when the copper is incorporated to polymer.
  • this phase suggest that the amorphous state is relatively homogenous and restricted.
  • the phenyl rings around the silicon atom and the inclusion of the copper showed slower mobility than the chain carbons of the chiral groups which is consistent with the proposed packing model.
  • PALPHA-Au 90 4.07 4.07 4.07
  • the presence of Au nanoparticles in the polymeric matrix was observed by XRD, thus the strong peak with a maximum intensity is related to gold.
  • PAtGe-Cu presents an amorphous behavior similar to PAtSi-Cu.
  • poly(amide-imide)-Ag or poly(amide-imide)-Au hybrids it was confirmed the presence of the nanoparticles embedded in the polymeric matrix by a strong peak of maximum intensity.
  • the poly(amide)s with a thiophene moiety in the main chain showed coordinate bonds between the metal and the sulfur atom, which is related to change in the crystalline network of the system.
  • all polymer-Cu hybrids presented an amorphous behavior.
  • PAtGe -Ag (Weak Ag) 90 4.08 4.08 4.08
  • the preparation of polymer-metallic nanoparticles was carried out using 5,4 mg of polymer dissolved in 60 of DMSO. This solution was spin coated on a metallic substrate (Cu, Ag or Au), and afterwards the solvent was removed by a soft baking at 60 °C in vacuum.
  • Figure 8 shows the scanning electron microscopy SEM images of the surface of the polymer film-metallic nanoparticles at 5 kV magnification voltage.
  • the nanoparticles are uniformly dispersed in the polymeric matrix despite some agglomerated particles. MacroscopicaUy, the nanoparticles appear as a long chain of interacting particles, but at a higher magnification these chains appear to be composed of small nanoparticles with a calculated area of 92 to 45 nm 2 ( Figure 9a).
  • the relative standard deviation obtained from this analysis ranged from 68 to 18 %.
  • the nanoparticles are mostly exposed to the surface.
  • Figure 11 shows the atomic percentage of some elements in the poly(amide)-metal hybrid.
  • the significant amount of oxygen and silicon atoms is related to the glass (S1O 2 ) used as substrate.
  • Carbon signal is generally weaker than the oxygen signal due to its polymeric structure.
  • the significant metal atomic percentage within the polymer indicates its inclusion in the polymeric matrix.
  • Poly(amide-imide)s show the formation of spherical metallic nanoparticles, which are well distributed and stabilized by the polymer.
  • the particles are aggregated into dendrite-structures, that contain silicon atoms, where probably the coordinated covalent bonds are produced ( Figure 12a).
  • Figure 12b presents a different behavior for the poly(amide-imide)s.
  • the formation of nanoencapsulation of the metal is not observed.
  • the thiophenes stabilize the metallic nanoparticles by the interaction between the lone pairs of electrons on the central atom (-S-) and the metal, changing the crystalline network of the new system formed.
  • Example 8 Summary of characterization of polymer- metal hybrids
  • the thiophene moieties stabilize the metallic nanoparticles produced by the interaction between the lone pairs of electrons on the central atom (-S-) and the metal.
  • the formation of the hybrids was demonstrated by optical properties, Raman spectroscopy and X-ray diffraction.
  • the surface plasmon resonance bands related to metallic nanoparticles were observed. However, these bands are coupled to the ⁇ - ⁇ * transition observed for the polymers with the exception of the polymer-copper nanoparticle hybrids.
  • the metals embedded in the polymeric matrices produce a distortion around the silyl group and the aromatic rings, changing the vibration and intensities of these bands.

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Abstract

La présente invention porte sur de nouveaux matériaux élaborés à partir de polymères d'organo-hétéroatomes (silicium ou germanium) (polyamide-imides et polyamides) et d'un film métallique, tel que, sans caractère limitatif, le cuivre, l'argent ou l'or, ayant l'aptitude à la transformation et la malléabilité d'un polymère et les caractéristiques de structure, thermiques, optiques, électriques et d'autres caractéristiques des métaux qu'il absorbe. Les polymères de l'invention ont le pouvoir d'incorporer, avec des liaisons covalentes, sous forme coordinée et arrangée, les métaux dans leur structure, ce qui produit un nouveau matériau macromoléculaire. L'invention porte également sur un nouveau procédé pour préparer les matériaux hybrides de polymère-nanoparticules métalliques, comprenant les étapes consistant à a) utiliser une solution de polymère dissolvant le polymère d'organo-hétéroatome (silicium ou germanium) (polyamide-imides ou polyamides) dans un solvant organique polaire aprotique ; b) utiliser un film métallique produit à partir du métal choisi ; c) disperser la solution de polymère par revêtement par rotation sur le film métallique ; et d) absorber, encapsuler à l'échelle nanométrique ou incorporer simultanément le métal dans la matrice de polymère.
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN109916880A (zh) * 2019-04-22 2019-06-21 山东师范大学 一种单向静电纺丝三维拉曼增强基底及其制备方法和应用
JP2020139081A (ja) * 2019-02-28 2020-09-03 日立化成テクノサービス株式会社 金属ナノ粒子含有樹脂及び金属ナノ粒子含有樹脂の製造方法

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