Classifications

• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
• • 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
  • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
• • 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
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/102—Metallic powder coated with organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
  • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
  • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
• • 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
  • B22F1/14—Treatment of metallic powder
  • B22F1/148—Agglomerating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

• This invention generally relates to organic-material-doped metals, uses thereof and processes for their preparation.
• the preparation of metallic materials was based on a variety of metal-cation reduction methods in the presence of the organic component to be entrapped.
• Reduction methods have included the use of water soluble reducing agents, reducing metals, reducing solvents, and electrochemical reduction - all of which were applied on ions of coin metals and noble metals.
• US patent application no. 2010/0297724 [1] to inventors of the present application concerns a composition of matter comprising a hydrophobic organic substance entrapped in metal, produced by reducing the metal of the metal salt in the presence of dissolved hydrophobic moiety, entrapping the hydrophobic moiety in the metal.
• This technology is readily applicable to easily reduced metals such as silver, gold, copper and platinum.
• International patent application no. WO 2011/135563 [2] concerns a similar concept of easily reduced metals (such as silver), entrapping therapeutically active agents, such as biocides and releasing the active agents over prolonged periods of time.
• the presently known composites of a metal entrapping (doped with) organic materials do not include composites of metals characterized by small positive or negative reduction potentials, i.e., corrodible, non-noble metals. This is mainly due to the fact that existing processes for the production of such composites are inadequate for obtaining non-corroding metal composites.
• An object of the invention is to provide novel composites comprising each a corrodible metal doped with an organic material, the organic material endowing the corrodible metal with corrosive -resistance properties.
• Another objective of the present invention is to provide novel composites comprising a metal at the zero oxidation state and an organic material, wherein said composite being substantively free of the metal in a positive oxidation state.
• a corrodible metal doped (entrapped, embedded) with at least one organic material said composite being resistant to corrosion.
• the metal doped with said organic material may be in the form of a composite material, which may or may not comprise additional components.
• the composite comprises a corrodible metal and at least one organic material, and in other embodiments, the composite consists a corrodible metal and at least one organic material; in either of the two cases, said composite exhibits resistant to corrosion.
• the at least one organic material endows the corrodible metal with the resistance to corrosion. While the observed resistance is dependent on the organic material present, the amount of the organic material, relative to the amount of the corrodible metal is small.
• the metal is in the form of a metallic matrix and the organic material dopes the metal in the matrix.
• the "composite" of the present invention comprising a corrodible metal is a material composition having one or more component domains, comprising a metal and an organic material capable of decreasing or preventing corrosion of said metal.
• the composite material is characterized by having the organic material entrapped (embedded) in the metal (e.g., being typically in the form of a metallic matrix), which would have been susceptible to corrosion if not for the presence of said organic material.
• the metal is in the form of a metallic matrix having a continuous phase domain, namely demonstrating material continuity.
• the composite of the invention may be formed in any solid state form.
• the composite is in one or more of the following forms: granules, powders, sub-micron particles, clusters, or thin films.
• the different forms of the composite of the invention may be in any size or shape.
• the composite is in the form of particles.
• the particle diameter (one dimension of the particles) is in the nanometric scale. In some embodiments, the particles diameter is less than 100 nm. In other embodiments, the particle diameter is less than 10 nm. In further embodiments, the particles diameter is between 5 to 100 nm.
• the particles are formed in clusters; the clusters size may be in the range of a micrometer or in the nanometer scale. In some embodiments, the cluster size is less than 1,000 nm. In other embodiments, the cluster size ranges from 200 to 500 nm.
• the composite of the invention constitutes an organic material which is entrapped (embedded) within a metallic "matrix" comprising at least one metal.
• the matrix may be formed as a continuous form of aggregates or particles of a metallic material, which may be in a crystalline phase.
• the aggregates or particles may be associated to each other via physical and/or chemical bonds, such as electrostatic and/or Van der Waals forces, forming a porous matrix characterized by pores and inner voids.
• the matrix may additionally be characterized by a plurality of inner pores (inner voids, holes), which may be randomly distributed within the matrix.
• the pores may be nanometric in size, namely having a mean diameter smaller than 1,000 nm.
• the mean pore diameter is between about 10 nm and 500 nm.
• the mean pore diameter is between about 10 nm and 100 nm.
• the mean pore diameter is between about 20 nm and 50 nm.
• the pores size There may be several parameters affecting or determining the pores size, such as the size of the entrapped material; the quantity of entrapped material within a pore; molecular weight of the entrapped material; conditions of production, e.g., temperature may affect the density and arrangement of the matrix particles/aggregate within the composite; and others.
• the organic material is said to be entrapped in the metal, if the organic material is surrounded by metallic particles and immobilized to the metal by forces other than covalent bonding; for example, the force holding the two components together may be selected from multiple physical and chemical adsorptive interactions such as electrostatic and Van-der- Waals, ⁇ - ⁇ and/or ⁇ - ⁇ interactions, charge-transfer interactions and hydrophobic or hydrophilic interactions.
• the organic material does not coat the bulk of the metallic matrix, but is rather incorporated therein.
• the corrosion resistance is a property of the material down to its smallest nanometric level, the corrosion resistance property remains unchanged upon mechanical damages or upon impact. Whenever an inner portion or region of the material becomes exposed to air, below the impact scratch or break, the exposed material remains corrosion resistant.
• This unique characteristic of a composite according to the invention allows for corrosion resistance properties, which are not known in articles or composites simply coated with an anticorrosive film or coat. Because the presence of surface defects known in coating technologies, such as pitting corrosion defects generated on a surface of a corrodible metal, are avoided or greatly minimized (or diminished) in composites according to the invention, the improvement in the fatigue properties is substantially maintained, with a clear improvement in the corrosion resistance.
• At least some of the metal entrapping the organic material may be in a metallic form, i.e., in zero oxidation state. In some embodiments, substantially all (e.g., between 95-100% of) the metal within the matrix is in zero oxidation state. In other embodiments, a large portion of the metal (e.g., between 50-95%) within the matrix is in zero oxidation state.
• 100% of the metal in the matrix having a zero oxidation state In other embodiments, more than 90% of the metal within the matrix having a zero oxidation state. In additional embodiments, more than 80% of the metal within the matrix having a zero oxidation state. In further embodiments, more than 70% of the metal within the matrix having a zero oxidation state. In still additional embodiments, more than 60% of the metal within the matrix having a zero oxidation state. In other embodiments, more than 50% of the metal within the matrix having a zero oxidation state. In additional embodiments, more than 30% of the metal within the matrix having a zero oxidation state.
• the composite comprises in addition to the metal forming the matrix at least one additional metal component, not part of the metal- forming matrix
• the at least one additional metal component may be in any form selected from a metal having a zero oxidation state, metal salt, metal alloy, metal oxide, and others.
• the matrix or the metal entrapping the organic material retains its metallic characteristics, e.g., appearance, for example, its metallic luster, color; electronic characteristics, thermal conductivity; and malleability.
• the metallic characteristics are maintained after subjecting the composite to pressure, forming from the powder full bodies of a variety of articles.
• the matrix of the invention comprises two or more metals (together forming the matrix).
• the two or more metals may be in the form of a mixture of said metals or metallic alloys, said alloy may be in the form of a partial (two or more phases that may be homogeneous and/or heterogeneous in distribution) or a complete blend of one or more elements in the metallic matrix (exhibiting a single solid phase microstructure).
• the term "corrodible, non-noble metal” refers to a metal that readily (easily) corrodes, i.e., has a tendency to corrode, or has low resistance to oxidation, even at mild environment conditions, such as, at room temperature.
• the corrodible metal is one which would have undergone corrosion (oxidation) if not for the at least one organic material present in a composite according to the invention.
• the corrodible metal is a metal that is high on the electrochemical series, namely that is of a small positive reduction potential or a negative reduction potential.
• the corrodible metal is selected from metals having a positive reduction potential.
• said positive reduction potential is smaller than 0.15V.
• the corrodible metal is selected from metals having a reduction potential smaller than 0.1V.
• the corrodible metal is selected from metals having a reduction potential smaller than 0.05V.
• the corrodible metal is selected from metals having a negative reduction potential. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.1V. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.15V. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.2V. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.4V. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.5V. In some embodiments, the corrodible metal is selected from metals having a reduction potential smaller than -0.7V.
• the corrodible metal is selected from Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti, Zn and Pd, or any combination thereof. In further embodiments, the metal is selected from Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti and Zn or any combination thereof. In additional embodiments, the metal is selected from Fe, Al, Ga, Ge, Ni, Cr and Mn, or any combination thereof. In further embodiments, the metal is selected from Fe, Al, Ni and Cr.
• the metal is selected from Fe, Al and Cr. In additional embodiments, the metal is Fe.
• the "organic material" entrapped within a matrix comprising the at least one corrodible metal refers to any compound that endows the corrodible metal with corrosive -resistance properties, namely which is capable of decreasing or preventing corrosion of said corrodible metal.
• the organic material may be a small, medium or large organic molecule; it may be a mixture of two or more different organic molecules, a complex, a conjugate, a bundle or any other form of compounds or combinations thereof.
• the organic molecule is selected amongst reducing agents or molecules that affect the redox potential of the corrodible metal.
• the organic material is selected from hydrophobic organic molecules.
• the organic material is selected from organic acids, such as oxalic acid and formic acid; phenolic oxidation inhibitors, such as 2,6-di-tert-butyl paracresol (BHT); hydrides such as Hantzsch ester and polysilanes of the general formula (Si(RiR 2 )-0-)n, wherein each of Ri and R 2 are selected independently from H, Ci-Cealkyl and Ce-Cioaryls; and n is an integer between 1 and 100, or between 1-50, or between 1-30, or between 1-10.
• organic acids such as oxalic acid and formic acid
• phenolic oxidation inhibitors such as 2,6-di-tert-butyl paracresol (BHT)
• BHT 2,6-di-tert-butyl paracresol
• hydrides such as Hantzsch ester and polysilanes of the general formula (Si(RiR 2 )-0-)n, wherein each of Ri and R
• the organic material is selected amongst conducting polymers which may short-circuit metal defects of different electric potentials.
• the conductive polymer is polyaniline (PANI).
• the organic material is selected from dyes, such as Congo red (CR), Safranin-0 (SaO), thionine (Th) and sudan III (S-III).
• dyes such as Congo red (CR), Safranin-0 (SaO), thionine (Th) and sudan III (S-III).
• the organic material is l-butyl-3-methylmidiazolium nitrate.
• the organic material is selected amongst hydrophobic organic molecules, which may enhance the hydrophobicity of the corrodible metal.
• hydrophobic organic molecules include poly- (dimethylsiloxane) (PDMS), poly(acrylonitrile) (PAN), polyethylene, polypropylene, polycarbosilanes and fluorinated polyalkenes.
• the organic material is selected from polysterene (PS), polystyrene sulfonic acid (PSSA), poly (vinyl alcohol) (PVA) and poly(vinylbenzyl trimethyl ammonium hydroxide).
• the amount of the entrapped organic moiety in the corrodible metal is less than 20% w/w. In some embodiments, the amount is less than 10%. In other embodiments, the amount is between 0.05% to 20% w/w. In some other embodiments, the amount is between 0.1% to 15% w/w.
• the composite of the invention comprises iron and PANI.
• the composite of the invention comprises iron and polydimethylsiloxane (PDMS).
• the iron is metallic iron.
• the composite of the invention comprises at least one organic material selected from PANI and PDMS.
• the composite comprises iron, e.g., metallic iron as the corrodible metal.
• the composite of the invention exhibits resistance to corrosion.
• the resistance to corrosion reflects on the property of a composite according to the invention to resist to corrosion attack in a particular environment at defined operating conditions, pressure, temperature, presence of oxidizing materials and others. Without wishing to be bound by theory, this resistance stems from the presence of the organic material in the metallic matrix.
• the corrosion resistance is reflected in any one of the following:
• a composite of at least one metal and at least one organic material the composite being substantially free of the metal in a non-zero oxidation state.
• the composite of this aspect of the invention (namely that which is substantially free of metal in a non-zero oxidation state) is a material composition having one or more component domains, comprising said metal and an organic material.
• the composite material is characterized by having the organic material entrapped (embedded) in the metal, typically in the form of a metallic matrix in a zero oxidation state.
• the metallic matrix is in the form of a continuous phase domain, namely demonstrating material continuity.
• the composite of the invention may be formed in any solid state form.
• the composite is in one or more of the following forms: granules, powders, sub-micron particles, clusters, or thin films.
• the different forms of the composite of the invention may be in any size or shape.
• the composite is in the form of particles.
• the particle diameter (one dimension of the particles) is in the nanometric scale. In some embodiments, the particles diameter is less than 100 nm. In other embodiments, the particle diameter is less than 10 nm. In further embodiments, the particles diameter is between 5 to 100 nm.
• the particles are formed in clusters; the clusters size may be in the range of a micrometer or nanometer scale. In some embodiments, the cluster size is less than 1,000 nm. In other embodiments, the cluster size ranges from 200 to 500 nm.
• the composite of the invention constitutes an organic material which is entrapped (embedded) within the metallic "matrix" comprising at least one metal at a zero oxidation state.
• the matrix may be formed as a continuous form of aggregates or particles of a metallic material, which may be in a crystalline phase.
• the aggregates or particles may be associated to each other via physical and/or chemical bonds, such as electrostatic and/or Van der Waals forces, forming a porous matrix characterized by pores and inner voids.
• the zero oxidation state metallic matrix may additionally be characterized by a plurality of inner pores (inner voids, holes), which may be randomly distributed within the matrix.
• the pores may be nanometric in size, namely having a mean diameter smaller than 1 ,000 nm.
• the mean pore diameter is between about 10 nm and 500 nm.
• the mean pore diameter is between about 10 nm and 100 nm.
• the mean pore diameter is between about 20 nm and 50 nm.
• the pores size There may be several parameters affecting or determining the pores size, such as the size of the entrapped material, the quantity of entrapped material within a pore, molecular weight of the entrapped material, conditions of production e.g., temperature may affect the density and arrangement of the matrix particles/aggregate within the composite.
• an organic material is said to be entrapped in the metal if the organic material is surrounded by metallic particles and immobilized to the metal by forces other than covalent bonding; for example, the force holding the two components together may be selected from multiple physical and chemical adsorptive interactions such as electrostatic and Van-der-Waals, ⁇ - ⁇ and/or ⁇ - ⁇ interactions, charge-transfer interactions and hydrophobic or hydrophilic interactions.
• substantially all of the metal within the matrix is in zero oxidation state.
• the composite of this aspect of the invention is substantially free of a metal in a non-zero oxidation state.
• substantially free of metal in a non-zero oxidation state refers to a composite in which the metal cation content is less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% of the metal content in the composite of the invention.
• substantially metal at a zero oxidation state refers to the composite in which the metal is all or nearly all in zero oxidation state, e.g., between 95% and 100% of the metal content in the matrix is in a zero oxidation state; or between 96 and 100%; or between 97 and 100% or between 98 and 100%; or between 99 and 100% or between 99.5 and 100%.
• the metal may be selected from any metal of the Periodic Table.
• the metal is selected from Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Au, Pt, Pd, Ag, Mn, Co, Cd, Hf, Ta, Re, Os, Ir, Hg, Al, Ga, In, Sn, Tl, Pb, Bi, Ge, Sn or any combination thereof.
• the metal is Sc, and/or Ti, and/or V, and/or Cr, and/or Mn, and/or Fe, and/or Ni, and/or Cu, and/or Zn, and/or Y, and/or Zr, and/or Nb, and/or Tc, and/or Ru, and/or Mo, and/or Rh, and/or W, and/or Au, and/or Pt, and/or Pd, and/or Ag, and/or Mn, and/or Co, and/or Cd, and/or Hf, and/or Ta, and/or Re, and/or Os, and/or Ir, and/or Hg, and/or Al, and/or Ga, and/or In, and/or Sn, and/or Tl, and/or Pb, and/or Bi, and/or Ge, and/or Sn.
• the metal is selected from Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti, Zn and Pd, or any combination thereof. In further embodiments, the metal is selected from Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti and Zn or any combination thereof. In additional embodiments, the metal is selected from Fe, Al, Ga, Ge, Ni, Cr and Mn, or any combination thereof. In further embodiments, the metal is selected from Fe, Al, Ni and Cr. In still additional embodiments, the metal is Fe.
• the matrix of the invention comprises two or more metals.
• the two or more metals may be in the form of a mixture of said metals or metallic alloys, said alloy may be in the form of a partial (two or more phases that may be homogeneous and/or heterogeneous in distribution) or a complete blend of one or more elements in the metallic matrix (exhibiting a single solid phase microstructure).
• the organic material entrapped within a matrix comprising at least one metal may be any organic material which endows the metal with added characteristics or for which the metallic matrix acts as a carrier.
• the organic material may be small, medium or large organic molecule, it may be a mixture, a complex, a conjugate, a bundle or any other form of compounds or combinations thereof.
• the organic molecule is selected from reducing agents or molecules that affect the redox potential of the corrodible metal.
• the organic material may be selected from hydrophobic organic molecules.
• the organic material is selected from organic acids, such as oxalic acid and formic acid; phenolic oxidation inhibitors, such as 2,6-di-tert-butyl paracresol (BHT); hydrides such as Hantzsch ester and polysilanes.
• the organic material is selected from conducting polymers which may short-circuit metal defects of different electric potentials.
• the conductive polymer is polyaniline (PANI).
• the organic material is selected from dyes, such as congo red (CR), Safranin-0 (SaO), yhionine (Th) and sudan III (S-III).
• dyes such as congo red (CR), Safranin-0 (SaO), yhionine (Th) and sudan III (S-III).
• the organic material is l-butyl-3-methylmidiazolium nitrate.
• the organic material is selected from hydrophobic organic molecules, which may enhance the hydrophobicity of the corrosivable metal.
• hydrophobic organic molecules include poly(dimethylsiloxane) (PDMS), poly(acrylonitrile) (PAN), polyethylene, polypropylene, polycarbosilanes and fluorinated polyalkenes.
• the organic material is selected from polysterene (PS), polystyrene sulfonic acid (PSSA), poly (vinyl alcohol) (PVA) and poly(vinylbenzyltrimethylamonium hydroxide) .
• the ratio of the entrapped organic material in the metal is less than 20% w/w. In some embodiments, the ratio is less than 10%. In other embodiments, the ratio is between 0.05% to 20% w/w. In some other embodiments, the ratio is between 0.1% to 15% w/w.
• the composite of the invention comprises iron and PANI. In some embodiments, the composite of the invention comprises iron and polydimethylsiloxane (PDMS). In some embodiments, the iron is metallic iron.
• PDMS polydimethylsiloxane
• a composite of a metal e.g., at the zero oxidation state; and at least one organic material.
• the integrity of the at least one organic material is not affected.
• the mixture formed is a solution in said at least one solvent; the solvent being aqueous or non-aqueous (organic).
• the solvent is a non-aqueous solvent.
• the non-aqueous solvent may be selected from methanol, propanol, acetone, acetonitrile, chloroform, dimethyl sulfoxide, ethyl acetate, hexane, tetrahydrofuran, toluene and xylene.
• the non-aqueous solvent is xylene.
• the at least one solvent is a mixture of two or more different solvents.
• the process for manufacturing a composite of the invention (whether that which comprises a corrodible metal or a metal at a zero oxidation state) comprises:
• metal source being selected from:
• a metallic salt e.g., capable of disproportionation upon heating; -mixing the metal source with at least one organic material to be entrapped in a metallic mixture;
• thermolysis thermolysis
• photolysis ultrasonic treatment
• microwave treatment e.g., thermolysis conditions
• the process comprises:
• the metal in said metallic matrix is substantially at zero oxidation state; the composite being free of the metal in non-zero oxidation state.
• the process comprises:
• thermolysis conditions e.g., thermolysis conditions
• conditions for obtaining a composite according to the invention include thermal treatment under an elevated temperature.
• the conditions involve thermal treatment at a temperature of between 30°C and 500°C .
• the temperature is in the range of 40°C and 300°C. In other embodiments, the temperature is in the range of 50°C and 150°C.
• the temperature is above 100°C or above 150°C.
• reaction steps of the invention may be carried out under stirring and for a period which may range from minutes to several hours.
• the metal source may be one of:
• the metal source may be of any of the metals disclosed hereinabove.
• the metal source is a source of a corrodible metal, such as Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti, Zn and Pd.
• said metal is selected from Fe, Al, Ga, Ge, Ni, Cr, Mn, Ti and Zn.
• the metal is selected from Fe, Al, Ga, Ge, Ni, Cr and Mn.
• the metal is selected from Fe, Al, Ni and Cr, or from Fe, Al and Cr.
• the metal is Fe.
• metal complex encompasses compounds having at least one metal species at any form or oxidation state, bonded to non-metallic species (ligands), typically through coordinative bond.
• the non-metallic species is organic.
• the metal species is bonded to the carbon atom(s) in the non-metal species.
• the organic species may be selected from one or more of the following ligands carbonyl, phenyl, alkyl, keton, alkoxide, etc, and any combination thereof.
• the metal complex is selected from triirondodecacarbonyl, diironnonacarbonyl, bis(acetylcyclopentadienyl)iron, bis(methylcyclopentadienyl)iron, bis(l ,5-cyclooctadiene)nickel(0), tetrakis(triphenyl phosphite)nickel(O), bis(triphenylphosphine)nickel(0)dicarbonyl, chromium(O) hexacarbonyl, bis(benzene)chromium(0), tricarbonyl(cycloheptatriene) chromium(O), tricarbonyl(naphthalene)chromium(0), tricarbonyl(N-methylaniline) chromium(O) and manganese(0)carbonyl.
• the metal source is selected from iron pentacarbonyl (Fe(CO)s), Fe(C 5 H 5 ) 2 , Fe 2 (CO)4(C 5 H 5 )2, Ni(CO) 4 , NiCl 2 (PPh 3 ) 2 , Ni(cod) 2 Co 2 (CO) 8 , Mn 2 (CO)io, Cr(CO) 6 , Cr(CO) 4 (PPh 3 ) 2 and Cr(C 6 H 6 ) 2 .
• Fe(CO)s iron pentacarbonyl
• Fe(CO)s) Fe(C 5 H 5 ) 2
• Fe 2 (CO)4(C 5 H 5 )2 Fe 2 (CO)4(C 5 H 5 )2
• Ni(CO) 4 NiCl 2 (PPh 3 ) 2
• Ni(cod) 2 Co 2 (CO) 8 Mn 2 (CO)io, Cr(CO) 6 , Cr(CO) 4 (PPh 3 ) 2 and Cr(C 6 H 6 ) 2 .
• the metal source is selected from Fe(CO)s, Fe(CsH5) 2 and Fe 2 (CO) 4 (C 5 H 5 ) 2 .
• the metal complex is iron pentacarbonyl (Fe(CO)s).
• the process involves the thermolysis of two or more metal sources; e.g., may be a metal complex and the other a metal salt, or both may be metal complexes or metal salts.
• the ratio of the metal source, e.g., metal complex, to the organic material in a reaction mixture may a ratio determined by the final intended use of the composite.
• the ratio of the metal source to the organic material is in the range of 1000:1 to 1 : 1.
• the ratio is in the range of 100: 1 to 1 : 1.
• the ratio is in the range of 10:1 to 1 :1.
• the process comprises reducing a cation of the metal in the presence of the organic material.
• the reduction process is arrested after at least 50% of the material is entrapped.
• the reduction is carried out under such conditions that leave most of the salt reduced. In some embodiments, only 10% or less of the salt is reduced. In other embodiments, 1% or less of the salt is reduced.
• a composite manufactured according to a process of the invention may be processed to provide different composite form, which may range up to several centimeters in diameter. None-limiting examples of such processing comprises compressing, annealing, sintering, or any combination thereof.
• the particles are pressed and may be accompanied with heating to form disks.
• the pressed disks may be in various sizes, e.g., having thickness of several millimeters.
• the composite of the invention may be used in a variety of industrial applications, as the composites exhibit high resistance to corrosion. Therefore, in another aspect, the invention provides a composite for use in the manufacture of products (articles, devices, parts, elements) for industrial use.
• the composite of the invention may be used in an industry where metallic elements are employed.
• the industry may be the iron industry, for the production of e.g., construction or infrastructure elements, transportation, e.g., car parts, aerospace parts and plains, utilities, production facilities and home applications.
• the invention provides an article comprising a composite of the invention.
• the article may be a structural member that includes a metal member produced with a composite of the invention or a composite manufactured according to a process of the invention.
• the structural member not only has excellent fatigue properties, but also exhibits improved corrosion resistance as compared with the metal.
• the composite may be used in medicine, e.g., implants, dentistry devices etc.
• the present invention provides means for the inhibition of corrosion of various metals.
• the inhibition is achieved by doping the metal with redox-altering molecules; with reducing agents; with agents that affect the oxidation of the metal; or with agents that short-circuit metal defects of different electric potential.
• organic materials such as small organic molecules or polymers, may be used to enhance the metal stability to oxidative corrosion.
• Modified- metal powders for high-pressure articles production (“greens"), and modified-metal powders used for thin film protective coatings are material products of this methodology. While the iron may be the industrially most important corrodible metal, oxidation inhibition has also been observed in other metals as well.
• Figs. 1A-D present SEM images of the pristine Fe matrix (Fig. 1A); PANI@Fe (Fig. IB); PAN@Fe (Fig. 1C); and PDMS@Fe (Fig. ID).
• Fig. 2 presents XRD patterns of the powders PAN@Fe, Fe, PANI@Fe, PDMS@Fe, all produced at 100°C.
• the bottom pattern is the pattern for PANI@Fe produced at a lower temperature of 60°C.
• Figs. 3A-C present conducting tip AFM images of a PDMS@Fe disk showing the surface morphology (Fig. 3A) and the conduction areas (Fig. 3B). A higher magnification of the marked part in Fig. 3B is shown in Fig. 3C, revealing non-uniform conduction regions.
• Figs. 4A-B present curves of weight changes during thermogravimetric analysis (Fig. 4A) and its first derivative (Fig. 4B) for Fe powders: pristine Fe produced in the entrapment condition, PANI@Fe, PAN@Fe, and PDMS@Fe.
• Figs. 5A-B are photos of Fe and PANI@Fe disks after 2 h of immersion in 1M NaCl. The photos demonstrate corrosion inhibition.
• Figs. 6A-D are microscope images of 10mm diameter disks after 72 hours of immersion in 1M NaCl: Fe matrix (Fig. 6A); PAN@Fe (Fig. 6B); PANI@Fe (Fig. 6C); and PDMS@Fe (Fig. 6D).
• Figs. 7A-D present XRD patterns taken of the disk surfaces after immersion in 1M NaCl for 3 weeks: Fe matrix (Fig. 7A); PAN@Fe (Fig. 7B); PANI@Fe (Fig. 7C); and PDMS@Fe (Fig. 7D).
• Figs. 8A-D are SEM images of inner sections of the disks of: Fe made under the entrapment conditions (Fig. 8A), PANI@Fe (Fig. 8B), PAN@Fe (Fig. 8C) and PDMS@Fe (Fig. 8D).
• Fig. 9 presents curve of weight gain of disks during immersion in 1M NaCl.
• Figs. 10A-B present XPS spectra for the Fe 2p electrons of the disks of Fe (Fig. 10A) and PDMS@Fe (Fig. 10B) after 3 weeks of immersion.
• the present invention is thus based on the realization that it is possible to entrap organic materials in metals, by employing a process that provides the metal zero oxidation state. This was achieved by either having the desired metal in a zero oxidation state in the complex, or by having the desired metal in a complex which provides the metal at zero oxidation state by a thermal disproportionation reaction of the cation with it ligands, in the presence of the organic material to be entrapped.
• Iron penta-carbonyl decomposes easily through a range of intermediate iron carbonyls, forming magnetic iron clusters.
• thermolysis is carried out at 100°C, in solution in the presence of a dissolved polymer, a composite powdered material, polymer@iron, forms.
• TGA indicates that under the experimental conditions described below, the composites contain 1.5% of PANI, 2% of PAN and 7% by weight of PDMS.
• the microscopic morphology of these materials is shown in Fig. 1A. It can be seen that pure Fe aggregates from small particles -20 nm in size, to form large spherical clusters of 200-500 nm in size. In the composites, the added polymer reduces these dimensions significantly.
• PDMS@Fe Fig. ID
• the aggregates are as small as 20-30 nm and they are formed by even smaller particles with a diameter lower than 5 nm. This effect is attributed to the surfactant-like interaction between the polymer and the metallic nanocrystal, an effect which has been observed in other metal- entrapment studies.
• Figs. 3 A and 3B show, respectively, the morphology and the conductivity of a typical point on the surface. It can be seen that while the surface is quite flat, the conductivity map indicates that it is formed of aggregates of iron that encapsulate the polymer within.
• Fig. 3C shows a large magnification of the marked part of Fig. 3B and it reveals that the aggregates themselves are not uniform in nature and that there are conductive and non-conductive parts within the aggregates, with iron particles as small as 5 nm that entrap polymer between them. This observation reveals for the first time polymer entrapment within metals on scales smaller than 100 nm, and it implies that the obtained composite is a genuine blend between the metal and the polymer.
• the composite disks were immersed in 1M NaCl solution and the corrosion development was determined. Expectedly, the NaCl solution accelerates iron corrosion by cathodic oxygen reduction and anodic metal dissolution followed by the formation iron oxide. After 2 h of immersion extensive bubbling was observed in the Fe disk while no bubbles were observed in the doped disks (Fig. 5). The appearance of bubbles instantly upon immersion of the Fe disc indicated the availability of a large number of active sites on the iron surface which are shielded in the doped disked. This was a direct indication of the onset of corrosion on the surface of the Fe disk and of its inhibition in the PANI@Fe disk. The same results were obtained with the other composites.
• Figs. 7A-C show that the surfaces of Fe, PANI@Fe and PAN@Fe are composed of the Fe 3 0 4 oxide (Figs. 7A-C).
• PDMS@Fe retained its amorphous structure as in the powder form (Fig. 2).
• the XPS (X-ray photoelectron spectroscopy) measurements were performed on a Kratos Axis Ultra X-ray photoelectron spectrometer. Spectra were acquired with a monochromated Al KR (1486.7 eV) X-ray source with a 0° takeoff angle. The pressure in the test chamber was maintained at 1.5*10 ⁇ 9 Torr during the acquisitionprocess. High-resolution XPS scans were collected for C Is, O Is, Si 2p and Fe 2p peaks with pass energy of 20 eV and a step size of 0.1 eV. Data analysis and processing were performed with Vision processing data reduction software (Kratos Analytical Ltd.) and CasaXPS (Casa Software Ltd.). Conductive tip atomic force microscopy images were taken by Scaning Probe Microscopy - Nanoscope Dimension 3100 using the supplied TUNA program.

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