EP3184206A1 - Dispersionen von metallen und/oder metallverbindungen - Google Patents

Dispersionen von metallen und/oder metallverbindungen Download PDF

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EP3184206A1
EP3184206A1 EP15202586.2A EP15202586A EP3184206A1 EP 3184206 A1 EP3184206 A1 EP 3184206A1 EP 15202586 A EP15202586 A EP 15202586A EP 3184206 A1 EP3184206 A1 EP 3184206A1
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Prior art keywords
metal
group
dispersion
compounds
atom
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French (fr)
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Nicolas DELIGNE
Victor SOLOUKHIN
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Solvay SA
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Solvay SA
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Priority to PCT/EP2016/082379 priority patent/WO2017109070A1/en
Publication of EP3184206A1 publication Critical patent/EP3184206A1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles

Definitions

  • the present invention relates to dispersions of solid particles made of a metal and/or a derivative thereof in a fluid dispersing medium with the help of a surfactant.
  • Dispersions of solid particles made of metals and dispersions of solid particles made of metal compounds have found increasing interest in the recent years for a multitude of different applications.
  • metal dispersions and metal oxide dispersions have been widely used for the manufacture of conductive or semiconductive films through facile deposition processes on substrates.
  • nanoparticulate dispersions of metals or of metal compounds are commonly used and it is important to avoid agglomeration of the nanoparticles. As long as the nanoparticles are not agglomerated, no or only little light diffusion occurs due to the small size of the particles which is beneficial for the transparency and for lower haze.
  • nanoparticulate dispersions of metals and nanoparticulate dispersions of various metal compounds are commonly used
  • the packing density of the particles can be higher and hence conductivity can be higher.
  • a further requirement is the stability of the dispersion. If the metal or the metal compound settles down too rapidly, no homogenous films can be obtained. Therefore, it is common to add a surfactant to the dispersion to stabilize same. However, addition of a surfactant leads to a number of issues.
  • the surfactant should be removed as completely as possible after deposition on the substrate as remaining surfactant is usually detrimental to the final film's properties. This is particularly the case when electrical, ionic and thermal conductivities are concerned. Remaining organics can also be detrimental to the thermal stability and stability over time of the films.
  • metal oxides can be used as anti-UV agents in polymers to decrease yellowing of the polymer on the mid-term caused by UV degradation.
  • Metal oxides e.g. alumina
  • various metal compounds including carbides (e.g. silicon carbide, boron carbide and tungsten carbide) and nitrides (e.g. boron nitride), can also be used as mechanical reinforcer in polymer matrices.
  • bipolar metal plates e.g. aluminum plates
  • a metal, a metal nitride or a metal carbide e.g. Ti, Au, Nb, TiN, TiC, TiCN, CrN
  • the so-treated bipolar plates have good strength, elasticity, dimensional stability, heat resistance, corrosion resistance, structural integrity, and core properties.
  • Metal nitrides and metal carbides provide superior corrosion resistance and wear resistance. Again, remain surfactants can affect the properties of the plate, in particular its heat resistance and its corrosion resistance.
  • Metal oxides, metal sulfides and other metal chalcogenides are commonly used as inorganic luminescent materials or pigments that can be deposited as thin films. Presence of residual organics severly impairs the color brightness of devices based on such films.
  • Numbers of metal, metal oxides and other metal compounds are used for their catalytic properties and can be used in heterogeneous catalysis in the gas and liquid phases.
  • These catalysts are usually deposited on a substrate in order to increase the surface area, to avoid leaching and, in some cases, to take advantage of the synergy of the two components (catalyst and substrate) for the catalytic reaction. Residual surfactants at the surface of the catalyst would obviously severly impair its catalytic performances by reducing the available surface for the catalytic reaction and by inducing secondary reactions. An energy and economically disadvantageous heat treatment is therefore required to remove the remaining surfactant.
  • the heat treatment can be responsible for reagglomeration of the metal-based particles reducing the surface area available for the reaction. If the dispersions are deposited on flexible substrates which are often based on polymers, the removability of the surfactant should be given at temperatures below the temperature of deformation of the substrate, and/or below the glass transition temperature thereof.
  • removal of the surfactant should be preferably performed at temperatures below the glass transition of the polymer itself and, in any cases, below the processing temperature.
  • EP-A 524 630 discloses compositions for use in a transparent and electrically conductive film.
  • the compositions comprise a composite compound based on an inorganic indium salt, an organic tin salt and an organic compound capable of coordinating with indium and tin.
  • the organic compound may be based on ⁇ or ⁇ -keto acid group containing compounds.
  • the dispersions are coated on substrates with high temperature resistance and a firing step at a temperature of 500 °C is necessary to obtain the desired oxide compounds from the salts.
  • the compositions of this reference are thus not suitable for substrates with deformation temperatures below 500°C.
  • WO 2005/105963 relates to the use of compounds having a hydrophobic moiety attached to a hydrophilic moiety, wherein the hydrophilic moiety comprises a ⁇ -keto carboxylic acid group, as a surfactant. Dispersions comprising solid particles and the said surfactant are also claimed. No dispersions comprising metals or metal compounds are disclosed or suggested.
  • WO 2010/071641 describes, inter alia, a process for the manufacture of cerium oxide nanoparticles. It is said that a stabilizer is normally needed during the manufacture of the nanoparticles to prevent undesirable agglomeration and a number of stabilizers are mentioned, including carboxylic acids, ⁇ -hydroxacarboxylic acids and ⁇ -ketocarboxylic acids or mixtures thereof.
  • the invented dispersion comprises solid particles dispersed, as an internal phase, in a fluid (preferably, in a liquid), as an external phase, by means of a surfactant, as a dispersing agent.
  • the dispersion in accordance with the present invention comprises at least metal and/or at least one metal compound.
  • the metal is selected from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides, (viii) actinides and (ix) mixtures thereof.
  • metals are the elements in the periodic system which are located left to the diagonal extending from boron (atomic number 5) to astatine (atomic number 85)).
  • Metals of group IA Li, Na, K, Rb, Cs, Fr are also known as alkali metals and metals of group IIA (Be, Mg, Ca , Sr Ba and Ra) are generally referred to as alkaline earth metals.
  • the metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals.
  • This group comprises the elements with atomic number 21 to 30 (Sc to Zn), 39 to 48 (Y to Cd), 72 to 80 (Hf to Hg) and 104 to 112 (Hf to Cn).
  • the lanthanides encompass the metals with atomic number 57 to 71 and the actinides the metals with the atomic number 89 to 103.
  • metalloids Some of the elements encompassed by the description above and understood to be metals for the purpose of the present inventon, are sometimes also referred to as metalloids.
  • the term metalloid is generally designating an element which has properties between those of metals and non-metals. Typically, metalloids have a metallic appearance but are relatively brittle and have a moderate electrical conductivity.
  • the six commonly recognized metalloids are boron, silicon, germanium, arsenic, antimony, and tellurium.
  • Other elements also recognized as metalloids include aluminum, polonium, and astatine. On a standard periodic table all of these elements may be found in a diagonal region of the p-block, extending from boron at one end, to astatine at the other (as indicated above).
  • all the solid particles comprising at least one metal element in elemental form and/or at least one metal compound of at least one metal element can be of the same chemical nature; for example, all the solid particles can consist of the same metal in elemental form, of the same metal alloy, of the same metal compound or of the same mixture of metal compounds (for example, core-shell particles wherein the shell is made of a first metal oxide and the core is made of another metal oxide).
  • the solid particles element can be of different chemical nature; for example, some solid particles can consist of a certain metal oxide while other particles consist of another metal oxide.
  • the solid particles comprise at least one metal element in elemental form.
  • the metal in elemental form can be :
  • the solid particles comprise one and only one metal element in elemental form.
  • the solid particles comprise a metal alloy comprising at least two metal elements in elemental form.
  • a metal alloy can be viewed as a solid metal-solid metal mixture wherein a primary metal acts as solvent while other metal(s) act(s) as solute; in a metal alloy and wherein the concentration of the metal solute does not exceed the limit of solubility of the metal solvent.
  • the metal alloy may be notably selected from the group consisting of Au-Pt, Pt-Pd, Sn-Ni, Pt-Bi and Pt-Fe alloys.
  • Metal alloy particles wherein the alloy is selected from this group may for example be used in catalyst and electrochemical storage applications.
  • the solid particles comprise at least one metal compound.
  • the chemical nature of the metal compound is not particularly limited.
  • the metal compound belongs to at least one class of compounds chosen from the class of metal hydride compounds, the class of metal beryllide compounds, the class of metal boride compounds, the class of metal aluminide compounds, the class of metal carbide compounds, the class of metal silicide compounds, the class of metal germanide compounds, the class of metal stannide compounds, the class of metal pnictide compounds, the class of metal oxide compounds, the class of metal chalchogenide compounds, the class of metal halide compounds and the class of intermetallic compounds. It often belongs to at least one class of compounds chosen from the class of metal boride compounds, the class of metal carbide compounds, the class of metal pnictide compounds, the class of metal oxide compounds and the class of metal chalchogenide compounds.
  • Some metal compounds useful for the invented dispersion can belong to several classes of compounds.
  • oxychalcogenides belong the class of metal oxide compounds and to the class of metal chalchogenide compounds
  • oxyhalides belong the class of metal oxide compounds and to the class of metal halide compounds
  • oxynitrides belong the class of metal oxide compounds and to the class of metal nitride compounds.
  • the metal compound is a metal hydride compound.
  • Metal hydride compounds comprise typically at least one metal atom (wherein the metal is as above defined) which is chemically bound to at least one hydrogen atom, wherein the electronegativity of the hydrogen atom is higher than the electronegativity of the metal atom.
  • Binary metal hydride compounds consist of at least one metal atom and at least one hydrogen.
  • An example thereof is beryllium hydride.
  • the metal compound is a metal beryllide compound.
  • Metal beryllide compounds comprise typically at least one beryllium atom and at least one other metal atom which is chemically bound to the beryllium atom, wherein the electronegativity of the beryllium atom is higher than the electronegativity of the other metal atom.
  • the (or at least one) other metal atom comprised in the metal beryllide compound can be notably :
  • Metal compounds useful for facet B of the present invention are metal icosagenide compounds.
  • Metal icosagenide compounds include metal boride compounds, metal aluminide compounds and metal gallide compounds such as vanadium gallide (V 3 Ga, which is an intermetallic compound).
  • the metal compound is a metal boride compound.
  • Metal boride compounds comprise typically at least one boron atom and at least one other metal atom which is chemically bound to the boron atom, wherein the electronegativity of the boron atom is higher than the electronegativity of the other metal atom.
  • the (or at least one) other metal atom comprised in the metal boride compound can be notably :
  • the metal compound is a metal aluminide compound.
  • Metal aluminide compounds comprise typically at least one aluminum atom and at least one other metal atom which is chemically bound to the aluminum atom, wherein the electronegativity of the aluminum atom is higher than or equal to the electronegativity of the other metal atom.
  • the (or at least one) other metal atom comprised in the metal aluminide compound can be notably :
  • Metal crystallogenide compounds include metal carbide compounds, metal silicide compounds, metal germanide compounds and metal stannide compounds.
  • the metal compound is a metal carbide compound.
  • Metal carbide compounds comprise typically at least one carbon atom and at least one metal atom which is chemically bound to the carbon atom; the electronegativity of the carbon atom is obviously higher than the electronegativity of the metal atom.
  • the (or at least one) metal atom comprised in the metal carbide compound can be notably:
  • the metal compound is a metal silicide compound.
  • Metal silicide compounds comprise typically at least one silicon atom and at least one other metal atom which is chemically bound to the silicon atom, wherein the electronegativity of the silicon atom is higher than or equal to the electronegativity of the other metal atom.
  • the (or at least one) other metal atom comprised in the metal silicide compound can be notably :
  • the metal compound is a metal germanide compound.
  • Metal germanide compounds comprise typically at least one germanium atom and at least one other metal atom which is chemically bound to the germanium atom, wherein the electronegativity of the germanium atom is higher than or equal to the electronegativity of the other metal atom.
  • metal germanide compounds are molybdenum germanide (MoGe 2 ) and the mixed germanides of manganese and of another metal of group IVB, such as ZrMnGe and TiMnGe.
  • the metal compound is a metal stannide compound.
  • Metal stannide compounds comprise typically at least one tin atom and at least one other metal atom which is chemically bound to the tin atom, wherein the electronegativity of the tin atom is higher than or equal to the electronegativity of the other metal atom.
  • metal stannides compounds examples are :
  • the metal compound is a metal pnictide compound, in particular a metal nitride compound or a metal phosphide compound.
  • Metal pnictide compounds comprise typically at least two different atoms, namely at least one first atom which is a pnictogen atom (which itself is or is not a metal atom) and at least one other atom which is a metal atom (which itself is or is not a pnictogen atom), wherein the electronegativity of the first atom is higher than or equal to the electronegativity of the other atom.
  • the first atom can be notably a nitrogen atom (the case being, the pnictide is a nitride), a phosphorus atom (the case being, the pnictide is a phosphide), an arsenic atom (the case being, the pnictide is an arsenide), an antimony atom (the case being, the pnictide is an antimonide) or a bismuth atom (the case being, the pnictide is an bismuthide).
  • Metal nitride compounds comprise typically at least one nitrogen atom and at least one metal atom which is chemically bound to the nitrogen atom; the electronegativity of the nitrogen atom is obviously higher than the electronegativity of the metal atom.
  • the (or at least one) metal atom comprised in the metal nitride compound can be notably:
  • transition metal nitrides such as TiN, VN, NbN, Mo 2 N, W 2 N and CrN, exhibit high chemical stability and functional physical properties such as hardness, high wear resistance, electrical conductivity, or even superconductivity.
  • the metal nitride is an oxynitride (i.e. a compound that qualifies as metal nitride compound and as metal oxide compound).
  • Metal phosphide compounds comprise typically at least one phosphorus atom and at least one metal atom which is chemically bound to the phosphorus atom, wherein the electronegativity of the phosphorus atom is higher than the electronegativity of the metal atom.
  • metal phosphides compounds examples are :
  • Metal arsenide compounds comprise typically at least one arsenic atom and at least one other metal atom which is chemically bound to the arsenic atom, wherein the electronegativity of the arsenic atom is higher than the electronegativity of the metal atom.
  • metal arsenide compounds examples include :
  • the metal compound is a metal oxide.
  • Metal oxide compounds comprise typically at least one oxygen atom and at least one metal atom which is chemically bound to the oxygen atom; the electronegativity of the oxygen atom is obviously higher than the electronegativity of the metal atom.
  • metal oxides are solid ionic compounds. In certain other metal oxides, the metal atom and the oxygen atom are covalently bonded.
  • the metal oxide compound itself is preferably selected from oxides, oxychalcogenides and oxohalides.
  • oxychalcogenides and oxohalides comprise respectively, in addition to the at least one oxygen atom in their chemical formula, at least one chalcogenide atom or at least one halide atom.
  • chalcogenide denotes an element of group VIA of the periodic system other than oxygen.
  • the metal oxide compound in the dispersions of the present invention may be a single oxide or a mixed oxide.
  • a single metal oxide is typically composed of one or more metal atom(s) of a same, unique metal element and one or more oxygen atom(s).
  • the metal atom comprised in the single metal oxide can be notably :
  • a mixed metal oxide is typically composed of one or more metal atom(s) of different metal elements and one or more oxygen atom(s). Many metals can form mixed oxides with one or more other metals. Mixed oxide minerals appear in a great variety in nature and synthetic mixed oxides find use as components of different materials used in advanced technological applications.
  • oxychalcogenides are the following:
  • the metal compound is a metal chalchogenide.
  • Chalcogenide is the designation for the elements of group VIA of the periodic system except oxygen.
  • Metal chalchogenide compounds comprise typically at least two different atoms, namely at least one first atom which is a chalcogen atom (which itself is or is not a metal atom) and at least one other atom which is a metal atom (which itself is or is not a chalcogen atom), wherein the electronegativity of the first atom is higher than or equal to the electronegativity of the other atom.
  • the first atom can be notably a sulphur atom (the case being, the chalcogen is a sulphide), a selenium atom (the case being, the chalcogen is a selenide), a tellurium atom (the case being, the chalcogen is an telluride) or a polonium atom (the case being, the chalcogen is a polonide).
  • metal sulphide compounds comprise typically at least one sulphur atom and at least one metal atom which is chemically bound to the sulphur atom; the electronegativity of the sulphur atom is obviously higher than the electronegativity of the metal atom.
  • the (or at least one) metal atom comprised in the metal sulphide compound can be notably :
  • Thin chalcogenide films are of particular interest for the fabrication of large area photodiode arrays, solar selective coatings, solar cells, photoconductors and sensors.
  • Metal sulphide compounds of choice for this application include Bi 2 S 3 , PbS, As 2 S 3 , Sb 2 S 3 , Ag 2 S, CdZnS, CuInS 2 , PbHgS and Cu 2 ZnSnS 4 (CZTS).
  • Metal selenide compounds comprise typically at least one selenium atom and at least one metal atom which is chemically bound to the selenium atom, wherein the electronegativity of the selenide atom is higher than the electronegativity of the metal atom.
  • the (or at least one) metal atom comprised in the metal selenide compound can be notably:
  • Metal telluride compounds comprise typically at least one tellurium atom and at least one other metal atom which is chemically bound to the tellurium atom, wherein the electronegativity of the selenide atom is higher than or equal to the electronegativity of the metal atom.
  • Non limitative examples of metal telluride compounds are Pb 2 Te 3 , CdTe, SbTe 3 and Bi 2 Te 3 .
  • the metal compound is a metal halide.
  • Metal halide compounds comprise typically at least one halogen atom other than astatine and at least one metal atom which is chemically bound to the halogen atom; the electronegativity of the halogen atom other than the astatine atom is obviously higher than the electronegativity of the metal atom.
  • the halogen atom can be a fluorine atom (the case being, the halide is a fluoride), a chlorine atom (the case being, the halide is a chloride), a bromine atom (the case being, the halide is a bromide) or an iodine atom (the case being, the halide is an iodide).
  • the (or at least one) metal atom comprised in the metal halide compound can be notably:
  • the metal compound is an intermetallic compound.
  • intermetallic compound are commonly used to denote a compound having at least one first metal atom as defined above which is at least partially chemically bound to at least one other metal atom.
  • the chemical bonding may be covalent and/or ionic, and is often at least partly ionic.
  • an intermetallic compound can be viewed as a solid metal-solid metal mixture wherein a primary metal acts as solvent while other metal(s) act(s) as solute; however, in an intermetallic compound and in contrast with what happens in an alloy, the concentration of the metal solute usually exceeds the limit of solubility of the metal solvent, causing a particular metal-metal arrangement.
  • the intermetallic compound can be a metal compound consisting of at least one first metal atom chosen from beryllium atom, aluminum atom and gallium atom on one hand and at least one second metal atom other than the first metal.
  • the intermetallic compound can be a metal compound consisting of at least one first metal atom chosen from beryllium atom, aluminum atom and gallium atom on one hand and at least one second metal atom chosen from transition metal atoms and lanthanide atoms on the other hand.
  • intermetallic compounds examples include LaBe 13 , ZrBe 13 , VBe 13 , CrBe 2 , MgAl, TiAl, Ni 3 Al, V 3 Ga and europium gallides such as EuGa 4 , EuGa 2 , Eu 3 Ga 5 , Eu 5 Ga 9 , EuGa, Eu 8 Ga 7 , Eu 3 Ga 2 and Eu 28 Ga 11 .
  • the solid particles comprised in the dispersion in accordance with the present invention are preferably nanoparticles.
  • nanoparticles denotes particles having an average particle diameter of less than than or equal to 300 nm, preferably of less than or equal to 200 nm and more preferably of less than or equal to 150 nm. In certain cases, it has proven advantageous that the average particle diameter be less than 100 nm, particularly preferred less than 50 nm. Normally, the average particle diameter is of at least 1 nm, or in some cases of at least 3 nm.
  • average particle diameter when used herein refers to the D 50 median diameter computed on the basis of the intensity weighed particle size distribution as obtained by the so called Contin data inversion algorithm. Generally said, the D 50 divides the intensity weighed size distribution into two equal parts, one with sizes (diameters) smaller than D 50 and one with sizes (diameters) larger than D 50 .
  • the average particle diameter as defined above is determined according to the following procedure.
  • the particles are isolated from a medium in which they may be contained (as there are various processes for the manufacture of such particles, the products may be available in different forms, e.g. as neat dry particles or as a suspension in a suitable dispersion medium.
  • the neat particles are then used for the determination of the particle size distribution preferably by the method of dynamic light scattering.
  • the method as described in ISO Norm Particles size analysis - Dynamic Light Scattering (DLS), ISO 22412:2008(E) is recommended to be followed.
  • This norm provides notably for instructions relating to instrument location (section 8.1.), system qualification (section 10), sample requirements (section 8.2.), measurement procedure (section 9 points 1 to 5 and 7) and repeatability (section 11).
  • Measurement temperature is usually at 25 °C and the refractive indices and the viscosity coefficient of the respective dispersion medium used should be known with an accuracy of at least 0.1 %. After appropriate temperature equilibration the cell position should be adjusted for optimal scattered light signal according to the system software.
  • the time averaged intensity scattered by the sample is recorded 5 times.
  • an intensity threshold of 1.10 times the average of the five measurements of the average scattered intensity may be set.
  • the primary laser source attenuator is normally adjusted by the system software and preferably adjusted in the range of about 10,000 cps. Subsequent measurements of the time autocorrelation functions during which the average intensity threshold set as above is exceeded should be disregarded.
  • a measurement consists of a suitable number of collections of the autocorrelation function (e.g. a set of 200 collections) of a typical duration of a few seconds each and accepted by the system in accordance with the threshold criterion explained above.
  • Data analysis is then carried out on the whole set of recordings of the time autocorrelation function by use of the Contin algorithm available as a software package, which is normally included in the equipment manufacturer's software package.
  • the particles in particular the nanoparticles, may have any shape, i.e. they may e.g. be particulate or fibrous, depending on the chemical composition of the oxide compounds.
  • the term "particulate” in this respect is to be understood as referring to particles having a more or less isometric structure like spherical, substantially spherical, ovoidal or substantially ovoidal particles.
  • Such particulate particles usually differ from acicular particles, platy particles as well as fibrous particles in the aspect ratio.
  • platy particles are well known by the persons skilled in the art. Typically, platy particles consist essentially of, or even consist of, particles having the shape of, or resembling to a plate, i.e. the particles are flat or substantially flat and their thickness is small in comparison with the other two dimensions.
  • acicular particles are also well known by the skilled in the art. Typically, acicular particles have the shape of, or resembling a needle.
  • the metal oxide compound may also be present in the form of fibrous particles, i.e. particles which are slender and greatly elongated, and their length is very high in comparison with the other two dimensions.
  • metal-based material denote a set of composed of at least one metal element in elemental form and/or at least one metal compound of at least one metal element.
  • the weight of the metal-based material is advantageously above 50 wt. %, preferably of at least 90 wt.% and more preferably of at least 99 wt. %; still more preferably, the solid particles consist essentially of or consist of the metal-based material.
  • the weight of the solid particles, based on the weight of the dispersion ranges advantageously from 0.5 to 75 wt. %.
  • the weight of the solid particles, based on the weight of the dispersion is preferably of at least 1 wt. %, more preferably of at least 5 wt. % and is possibly of at least 10 wt. %, at least 20 wt. % or even at least 35 wt. %.
  • the weight of the solid particles, based on the weight of the dispersion is preferably of at most 65 wt. %, possibly at most 55 wt. %.
  • the dispersion in accordance with the present invention comprises, as component b) at least one surfactant comprising a ⁇ -keto carboxylic acid group.
  • surfactant generally denotes a compound which lowers the surface tension between a liquid and a solid in a dispersion, thereby stabilizing the dispersion.
  • Preferred surfactants for use in the dispersions in accordance with the present invention are compounds having a hydrophobic moiety attached to a hydrophilic moiety, wherein the hydrophilic moiety comprises a ⁇ -keto acid group and the hydrophobic moiety is attached via a bond from a carbon or an oxygen of the hydrophobic moiety to a carbon of the ⁇ -keto acid group.
  • hydrophobicity is used herein to describe a property of a molecule which is seemingly repelled from a mass of water.
  • the hydrophobic interaction is mostly an entropic effect originating from the disruption of hydrogen bonds between liquid molecules of water by the non-polar hydrophobic solute.
  • hydrophobicity is the association of non-polar groups or molecules in an aqueous environment which arises from the tendency of water to exclude non-polar molecules.
  • the ⁇ -carbon of the ⁇ -keto acid group does not form part of a carboxyl or ester group, or a salt thereof.
  • Preferred surfactants for use in the dispersion in accordance with the present invention are represented by general formula (1) or a salt of such compounds.
  • Surfactants of this type are generally susceptible to temperature controlled decomposition, depending on pH, into volatile reaction products and an oil-like (if liquid), hydrophobic residue.
  • the temperature at which decomposition occurs is in most cases below 200 °C, preferably below 150 °C and even more preferably not significantly exceeding 100°C.
  • the decomposition products are volatile compounds which can be easily removed from the final products obtained from the dispersion.
  • surfactants which decompose to volatile products to at least 90 % in ten minutes at a temperature of not more than 150°C.
  • decomposition temperature is the temperature at which, in the thermal gravimetric analysis, a weight loss of 60% or more is observed when using a temperature gradient program starting at 25°C and an increase rate of 5°C/min.
  • the rate of decomposition of surfactants of this type can be effectively controlled by temperature.
  • the rate of decomposition generally increases with increasing temperature.
  • the decomposition rate of the surfactant may be accelerated by catalysts, such as decarboxylases, or simple amino acids, like glycine. Neither the attachment of the hydrophobic moiety to the hydrophilic moiety via a bond from a carbon of the hydrophobic moiety, nor from an oxygen of the hydrophobic moiety, are susceptible to premature degradation and/or thermally uncontrolled degradation under the above-presented conditions.
  • the hydrophobic moiety is preferably attached via a bond from a carbon of the hydrophobic moiety.
  • this is the equivalent of the hydrophobic moiety being -C-R 4 , wherein R 4 is a hydrophobic group.
  • hydrophobic groups exist and that their detailed structures are not always of critical importance.
  • any hydrophobic group, not itself susceptible to degradation in aqueous solution, creating an amphiphilic compound when attached to the hydrophilic moiety may be utilized in the present invention.
  • the hydrophobic moiety or moieties may independently be a straight-chain, branched-chain or cyclic, saturated or unsaturated, optionally substituted, aliphatic group; an optionally substituted aromatic group; an optionally substituted hydrophobic polyoxyalkylene group, such as an optionally substituted polyoxypropylene group; an optionally substituted perfluoroalkyl group; an optionally substituted polysiloxane group; a lignin or rosin derivative; or a combination thereof.
  • substituted in relation to the hydrophobic moiety or moieties, relates to the substitution of an organic group with any substituents not changing the hydrophobic nature of said moiety or the amphiphilic nature of the compound.
  • the hydrophobic moiety or moieties is/are preferably independently selected from a straight-chain, branched-chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group; an unsubstituted or substituted aromatic group; an unsubstituted or substituted hydrophobic polyoxyalkylene group; an unsubstituted or substituted perfluoroalkyl group; an unsubstituted or substituted polysiloxane group; a lignin or rosin derivative; and any combination thereof.
  • the hydrophobic moiety or moieties is/are independently selected from a straight-chain or branched-chain, saturated or unsaturated, optionally substituted C 1 -C 30 alkyl, preferably C 3 -C 22 alkyl and most preferably the hydrophobic residue comprises at least one aromatic ring system.
  • Suitable compounds which may be used as surfactants in accordance with the present invention are disclosed in WO2005/105963 starting on page 6 up to and including page 12, to which reference is made here for further details.
  • 3-oxo-5-phenyl pentanoic acid and benzoyl acetic acid are particularly preferred surfactants which may be used in the dispersions in accordance with the present invention.
  • benzoyl acetic acid has proven advantageous for certain preferred metal-based materials, namely for metal oxide compounds, especially for mixed oxides of indium and tin which find frequent use in the manufacture of transparent films in organic electronic devices.
  • the amount of surfactant can vary to a large extent.
  • the weight of the surfactant, based on the weight of the fluid dispersing medium is advantageously of at least 2 wt. %. It is preferably of at least 5 wt. %, possibly of at least 10 wt. % or of at least 15 wt. %, based on the weight of the fluid dispersing medium.
  • the weight of the surfactant, based on the weight of the fluid dispersing medium is advantageously of at most 50 wt. %. It is preferably of at most 35 wt. %, possibly of at most 30 wt. % or of at most 15 wt. %, based on the weight of the fluid dispersing medium.
  • the dispersion in accordance with the present invention comprise a fluid dispersing medium as component c).
  • the term fluid as generally understood, encompasses liquid and gaseous dispersing media.
  • the dispersing medium in the dispersion of the present invention is a liquid dispersing medium as described now in more details.
  • the liquid dispersing medium comprises advantageously one or more than one organic liquid(s) and is preferably capable of dissolving the surfactant used as component b) in the invented dispersion in the amount used so that there is no significant amount of dispersed, undissolved surfactant in the final dispersion which is visible.
  • the liquid dispersing medium may consist essentially of or may consist of one or more than one organic liquid(s).
  • the fluid dispersing medium c) may be contain water as additional component besides the organic liquid(s).
  • the skilled person will select the suitable liquid dispersing medium based on the requirements of the specific application case.
  • the organic liquid may be chosen from linear, branched or cyclic aliphatic or aromatic hydrocarbons e.g. pentane, hexane, heptane, 2,2,4-trimethyl pentane, cyclopentane, cyclohexane, cycloheptane, benzene, toluene or xylene, from carboxylic acids and their esters such as acetic acid, ethyl acetate and butyl acetate, alcohols such as ethanol, 1-propanol, 2-propanol, 2-isopropoxy ethanol or 1-butanol, ethers such as tert.-butyl methyl ether, diethyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2 dichloro ethane or trichloro ethylene, ketones such as acetone
  • Tetrahydrofuran, methyl ethyl ketone, 1-methyl-2-pyrrolidone, isopropanol and 2-isopropoxy ethanol and mixtures thereof, optionally mixed with water, have shown advantageous results in certain cases, notably when indium tin oxide is the metal-based material.
  • the dispersion in accordance with the present invention can be obtained by processes known to the skilled person for the manufacture of dispersion.
  • a general procedure for the preparation of nanoparticle dispersion is to weigh in the desired amount of metal-based material in a beaker in a fume hood.
  • the dispersing medium here a liquid dispersing medium, and the surfactant are weighed in.
  • the surfactant and the liquid dispersing medium may then be homogenized by hand mixing followed by stirring with a magnetic stirrer until the surfactant is fully dissolved.
  • particles of the metal-based material are added into the solution thus obtained gradually while stirring for about 30 min.
  • stirring can be prolonged for about 60 minutes to ensure the formation of a homogenous surfactant - dispersing medium - metal-based material suspension.
  • the dispersion in accordance with the present invention are advantageously used notably for all kinds of functional films, e.g. transparent and conductive, or opaque and insulating films, which may be deposited on solid substrates or in bulk form through methods based on using dispersions.
  • the dispersion in accordance with the present invention is preferably used notably for the manufacture of an ink suitable for being deposited into a functional film.
  • the dispersion in accordance with the present invention is notably suitable for the deposition of semiconductive, antistatic or dissipative films on solid substrates, for the deposition of insulating films on solid substrates, for the deposition of optically transparent, hazy or opaque films on solid substrates, for preparing luminescent films on solid substrates, for preparing pigment-based films on solid substrates or for preparing metal-based material catalysts in a bulk form or as films on solid substrates.
  • the dispersion in accordance with the present invention is also particularly suited for preparing a polymer - metal-based material composite.
  • the advantage of the invented dispersion for use in respective applications is the easy removability of the surfactant from the final product after deposition or processing into a bulk material. If such a final product is used as pigment, catalyst, luminescent material, ionic conductor or the like, the presence of residual surfactant in the film or other shaped article is usually detrimental and removal thereof is desired.
  • the film is preferably deposited on a solid substrate which may have a 1D, 2D or 3D structure.
  • the substrate may be porous or have a smooth surface without pores, depending on the targeted application.
  • substrate material metals, glass, ceramic materials, paper and hybrid materials may be mentioned here as suitable substrate material.
  • suitable substrate material metals, glass, ceramic materials, paper and hybrid materials. The skilled person will select the suitable substrate material in accordance with the final use.
  • Another embodiment of the present invention relates to the use of the dispersion in accordance with the present invention for the deposition of a conductive film on a solid substrate, in particular on a substrate having a deformation temperature of 400°C or less, particularly preferred on a polymeric substrate having a deformation temperature of 400°C or less.
  • deformation temperature denotes the temperature above which the substrate undergoes a dimensional deformation under a specified load as defined in ASTM D648 or ISO 75.
  • ASTM D 648 specifies two different loads thereby yielding two values for the material tested.
  • the deformation temperature denotes the value at a load of 0.455 MPa, i.e. at the lower weight specified in ASTM D 648.
  • Still another embodiment of the present invention relates to the manufacture of conductive films on a substrate having a temperature of deformation of less than 400 °C comprising
  • Benzoyl acetic acid was synthesized according to the procedure published WO 2010/120232 via saponification of ethyl benzoyl acetate.
  • ITO indium tin oxide
  • metal oxide a metal oxide
  • surfactant b benzoyl acetic acid
  • dispersing medium c dispersing medium
  • the surfactant and the dispersing medium were homogenized by hand mixing followed by stirring with magnetic stirrer until the benzoyl acetic acid was completely dissolved.
  • the ITO nanoparticles were added into the above solution gradually while stirring for about 30 min. In some cases stirring was prolonged for about 60 minutes to ensure that a homogenous stabilizer-organic liquid-nanoparticle suspension was obtained. This was due to solubility difference of benzoyl acetic acid in different dispersing mediums tested.
  • the suspension was moved to a glass beaker and a 13 mm Vibracell sonicator tip was immersed into the suspension and the suspension was sonicated for about 7 min in an ice bath with a power setting of 30% on the VC750 sonicator. (Pulse mode was not used).
  • the dispersions prepared are summarized in Table 1.
  • Table 1 Ex. Nature of the dispersing medium Amount of dispersing medium (g) Amount BA in (g) Amount of ITO (g) 1 THF 10 0,10 0,20 2 MEK 10 0,10 0,20 3 NMP 10 0,10 0,20 4 2-IPE 10 0,10 0,20 5 IPA 10 0,10 0,20 THF: Tetrahydrofuran, MEK: Methyl-ethyl-ketone, NMP: N-Methyl-2-pyrrolidone, 2-IPE: 2-Isopropoxy ethanol, IPA: 2-Hydroxypropane, BA: Benzoyl acetic acid
  • the dispersions showed a certain stability after 30 min but settled down after 4 days.
  • Example 1 was repeated with THF, 2-IPA and IPE as liquid dispersing medium and increasing the amount of BA to 5 wt. % (0.5 g) and the amount of ITO to 10 wt. % (1 g)
  • the Z-average particle size as defined in ISO 13321 and ISO 22412 was determined.
  • the Z-Average size or Z-Average mean used in dynamic light scattering is a parameter also known as the cumulants mean. It is the primary and most stable parameter obtainable by DLS.
  • ISO 22412 defines this value as the harmonic intensity averaged particle diameter.
  • the Z-average particle sizes were 210 nm for IPE , 228 nm for THF and 166nm for IPA dispersion, which is a clear indication that benzoyl acetic acid is able to stabilize ITO nanoparticles in these liquid dispersing media without significant agglomeration of the nanoparticles.
  • Dispersions with even higher amounts of ITO and benzoyl acetic acid as surfactant were prepared using the general method described above. The compositions are shown in Table 2.
  • Table 2 Ex. Nature of the dispersing medium Amount of dispersing medium (g) Amount BA in g Amount of ITO (g) 9 IPA 10 0,76 2.0 10 IPA 10 0.78* 5.0 11 2-IPE 10 1.52 2.0 12 2-IPE 10 1.55 5.0 13 THF 10 1.54 2.0 14 THF 10 1.49 5.0 * Limitation of solubility of BA in the dispersing medium
  • the dispersion showed a good stability for more than 10 days with THF overall showing the best results.
  • the ITO nanoparticles were well dispersed and aggregate size (determined by scanning electron microscopy) was less than 300 nm, i.e. the particles were still nanoparticulate.
  • Examples 15 to 20 - Dispersions were prepared in accordance with Table 3 using THF as dispersing medium Table 3 Ex.
  • Amount THF (g) Amount of surfactant (g) Amount of ITO (g) Concentration ITO wt. % 15 8.4 1.2 2.4 20 16 3 3.0 6.0 50 17C 8.4 1.2 2.4 20 18C 3.0 3.0 6.0 50 19C 9.6 0 2.4 20 20C 6 0 6.0 50
  • Examples 15 to 16 comprise benzoyl acetic acid in accordance with the present invention
  • examples 17C to 20C are comparative examples comprising [(2-(2-methoxyethoxy)ethoxy]acetic acid (MEA) as surfactant (Examples 17C and 18C) and no surfactant (Examples 19C and 20C).
  • MEA [(2-(2-methoxyethoxy)ethoxy]acetic acid
  • the samples of Examples 15 to 18 comprising a surfactant showed much better dispersion stability than those of Examples 19 and 20.
  • the samples of Examples 13 to 20 were analyzed using DLS as described hereinbefore. In this context, the samples were diluted as detailed hereinafter.
  • the concentrated sample was shaken by hand strongly to dissolve all the particles collected on the bottom of the vial during the storage time.
  • 2 droplets of the 20% concentrated suspension were diluted in 20ml of the liquid dispersing medium in a glass vial and the vial was shaken to dissolve the material and get a translucent sample. In case of 50% concentrated solution, only 1 droplet was used. All the measurement was done at 25°C, refractive index of ITO and dispersant was assumed to be 2,0 and 1,409, respectively, and viscosity of the THF was set to 0,4549.
  • Figure 1 shows a graphical representation of the results obtained for the dispersions. All dispersions were prepared with THF as dispersing medium.
  • the bars for the individual dispersions represent from left to right for each dispersion the values at the start, after 1 day, after 1 week and after 1 month.
  • ITO nanoparticles are in most cases, single crystalline nanoparticles of 20-30 nm. From high resolution TEM image of ITO nanoparticles, a superstructure that has d-spacing much larger than normal d-spacing in ITO crystals was observed in some of the samples. Thus, overall, BA and MEA seem to be suitable to stabilize nanoparticulate ITO dispersions in THF and to avoid aggregation of the nanoparticles.
  • the experiments were performed using an initial temperature of 25°C, a final temperature of 550°C and a temperature gradient of 5°C/min. Nitrogen was used as gas at a rate of 20 ml/min.
  • Figure 2 shows the TGA and DSC of the surfactants BA and MEA as such
  • Figure 3 shows the results for dispersions with 20 wt. % ITO and
  • Figure 4 shows the result for the dispersions with 50 wt. % ITO.
  • BA offers the same dispersion quality and stabilization but has the important advantage of easy removability at lower temperatures compared to MEA.
EP15202586.2A 2015-12-23 2015-12-23 Dispersionen von metallen und/oder metallverbindungen Withdrawn EP3184206A1 (de)

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CN111790905A (zh) * 2020-05-29 2020-10-20 北京理工大学 一种具有表面纳米结构的高热氧化活性铝粉及其制备方法
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