Classifications

• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
• • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/382—Contact thermal transfer or sublimation processes
  • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • 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
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
• • 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
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • 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
  • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0052—Digital printing on surfaces other than ordinary paper by thermal printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers

Definitions

• the present invention relates to a composition comprising carbon nanotubes and conductive polyaniline in a matrix of insulating polymer and a process for making said composition. It has been found that first treating nanotubes with a polyaniline solution permits the use of a reduced quantity of nanotubes, in situations where the nanotubes are used to increase electrical conductivity. TECHNICAL BACKGROUND Over the last 30 years there has been considerable interest in developing polymers with conductive rather than insulating properties, such that they could be used in active electronic devices.
• Tailoring electrical properties of polymers has been achieved utilizing three different strategies: 1 ) Modifying the intrinsic bulk properties by altering the chemical composition and structure of the starting material 2) Altering the properties of the polymer at the molecular level incorporating dopants, which may form charge transfer complexes with the host polymer.
• This approach is molecular doping in which molecules such as AsFs and l 2 are incorporated into polymers such as polyactelyne and polycarbonate, and 3)
• the most commonly utilized strategy is the attainment of the desired conductivity by incorporating microscopic pieces such as metal flakes, carbon-black particulate into the host polymer to form conducting polymers.
• route (2) provides the most efficient pathways to polymeric synthetic metals, some materials tend to exhibit lack of stability under ambient conditions.
• Organic conductors such as polyacetylene, which have a jr-electron system in their backbone or like poly-(p-phenylene), and polypyrole consist of a sequence of aromatic rings and are excellent insulators in native state and can be transformed into complexes with metallic conductivity upon oxidation or reduction.
• the electrical conductivity of polyacetylene (CH) X increases by a factor of 10 11 when the polymer is doped with donor or acceptor molecules.
• Tailoring electrical properties of polymers has been achieved utilizing three different strategies: (1 ) Modifying the intrinsic bulk properties by altering the chemical composition and structure of the starting material (2) Altering the properties of the polymer at the mol ⁇ cular level incorporating dopants, which may form charge transfer complexes with the host polymer.
• This approach is molecular doping in which molecules such as AsF 5 and l 2 are incorporated into polymers such as polyactelyne and polycarbonate, and (3)
• the most commonly utilized strategy is the attainment of the desired conductivity by incorporating microscopic pieces such as metal flakes, carbon-black particulate into the host polymer to form conducting polymers.
• route (2) clearly provides the most efficient pathways to polymeric synthetic metals, materials tend to exhibit lack of stability under ambient conditions.
• poly(1 ,6-heptadiyne) and polypropyne the un-doped polymers are unstable in oxygen.
• poly-p-phenylene, poly-p-phenylene oxide and poly-p-phenylene sulfide are stable in oxygen they can only be doped with powerful acceptors such as AsF ⁇ and once doped they are susceptible to rapid hydrolysis under ambient conditions.
• polypyrole is stable under ambient conditions it lacks some of the other desirable characteristics, most notably variable conductivity. Alternatively more modest conductivity values (0.001 S/cm) can be achieved by filling inert polymers with conductors.
• Conductivities of 10 "10 to 10 "1 S/cm are readily achieved and can be tailor into the specifications.
• the electrical conductivity depends upon filler loading and there is a steep dependence of conductivity on filler load over a short filler concentration range above a critical level (percolation threshold). Since high levels of filler loading 10-40% are employed to achieve high conductivities, polymer processability is severely hindered.
• Typical fillers are PAN- derived C fibers, metallized glass fibers, Al flakes, Al rods and carbon black. Typical loading and resulting conductivivities are shown in the table below:
• the emeraldine base form of polyaniline can be doped to the metallic conducting regime by dilute non-oxidizing aqueous acids such as HCI to yield an emeraldine salt that exhibits metallic conductivity but is air stable and cheap to produce in large quantities.
• the emeraldine form of polyaniline is believed to show high conductivity because of the extensive conjugation of the backbone. Unlike all other conjugated polymers the conductivity of the material depends on two variables rather than one, namely the degree of oxidation of the PANI and the degree of protonation.
• PANI's are those cast from solutions of PANI camphosulfonate (PANI-CSA) in m-cresol ⁇ 10 2 S/cm about two order of magnitude higher than PANI's protonated with mineral acids which range from 10 "1 to 10 1 S/cm.
• PANI-CSA PANI camphosulfonate
• mineral acids which range from 10 "1 to 10 1 S/cm.
• Achieving stable polymeric materials with metallic conductivities that are processable and stable at ambient conditions is important for further enabling the use of conducting polymers in electronic applications. It has been previously shown that small amounts of carbon nanotubes increase the conductivity of PANI by 4-5 orders of magnitude. Since the nanotube concentration is considerably lower than that required of fillers, the processability of the host polymer can be maintained while the conductivity is increased.
• the printable formulations developed had some disadvantages as well.
• composition comprising conductive polyaniline and carbon nanotubes for laser printing.
• the present invention is a composition comprising carbon nanotubes dispersed with conductive polyaniline in an insulating polymer matrix.
• the dispersion of polyaniline with the carbon nanotubes allows percolation and hence metallic-like values of the electrical conductivity at lower volume fractions of carbon nanotubes than if the nanotubes had not been dispersed with the polyaniline.
• the present invention is also a process for making the above-described composition.
• This invention describes a composition comprising: a) An insulating polymer matrix b) 0.1 to 10 % by weight of carbon nanutubes dispersed in said insulating polymer matrix c) conductive polyaniline dispersed with said carbon nanotubes.
• the invention is also a process comprising: a) dispersing carbon nanotubes in a solvent also containing dissolved polyaniline to form a first liquid dispersion b) adding a solution of insulating polymer to said first liquid dispersion to form a second liquid dispersion c) depositing said second liquid dispersion on a substrate and allowing said solvent to evaporate.
• a) dispersing carbon nanotubes in a solvent also containing dissolved polyaniline to form a first liquid dispersion b) adding a solution of insulating polymer to said first liquid dispersion to form a second liquid dispersion c) depositing said second liquid dispersion on a substrate and allowing said solvent to evaporate.
• FIG. 3 is a graph of conductivity over %SWNT.
• Figure 4 is a graph of resistivity (ohm-square) over % filler.
• PANI polyaniline
• FIG. 4 is a graph of resistivity (ohm-square) over % filler.
• the present invention is a composition comprising an insulating polymer matrix of materials such as, but not limited to, polystrene, ethylcellulose, Novlac TM (DuPont, Wilmington, DE), poly hydroxy sytrene and its copolymers, poly methyl methacrylates and its copolymers and poly-ethyl methacrylate.
• an insulating polymer matrix of materials such as, but not limited to, polystrene, ethylcellulose, Novlac TM (DuPont, Wilmington, DE), poly hydroxy sytrene and its copolymers, poly methyl methacrylates and its copolymers and poly-ethyl methacrylate.
• Within the insulating polymer matrix is dispersed a mixture of carbon nanotubes and conductive polyaniline.
• the mixture of carbon nanotubes and conductive polyaniline is produced by dispersing carbon nanotubes in xylenes and then adding doped polyaniline ( doped with, for example, di-nonyl naphthalene sulfonic acid, benzyl sulfonic acid or camphor sulfonic acid to make the polyaniline conductive) to the dispersion.
• doped polyaniline doped with, for example, di-nonyl naphthalene sulfonic acid, benzyl sulfonic acid or camphor sulfonic acid to make the polyaniline conductive
• the polyaniline is added as a solution of polyaniline in xylenes.
• a solution of insulating polymer is then added to the dispersion.
• the deposit comprises the composition of the present invention, an insulating polymer matrix containing a dispersion of carbon nanotubes and doped polyaniiine.
• the amounts of nanotubes and polyaniline dispersed in the insulating polymer matrix can be varied by varying the ratios of the various components in the xylenes.
• a level of 0.25% by weight of carbon nanotubes is required to achieve percolation and obtain metallic conductivity.
• the present invention also comprises the process to obtain this composition as described above.
• the substrate for deposition of insulating polymer solution mixed with the polyaniline/carbon nanotube dispersion can be a donor element for thermal transfer printing.
• a transparent substrate such as MYLAR TM (Dupont, Wilmington, DE) can be used. After deposition of the dispersion, the solvent is allowed to evaporate.
• the donor element is positioned over a receiver element, which is to be patterned with the material to be transferred.
• a pattern of laser radiation is exposed to the donor element such that a pattern of the dried dispersion is transferred to the receiver.
• the insulating polymer solution mixed with the polyaniline/carbon nanotube dispersion can be patterned by a printing process such as ink jet printing, flexography or gravure prior to the evaporation of the solvent. The dispersion is patterned on to a substrate and then the solvent is allowed to evaporate.
• EXAMPLES EXAMPLES 1-2 This example shows the effect on conductivity of adding carbon nanotubes coated with DNNSA-PANI and incorporated the PANI coated tubes into an insulated matrix. The conductivity of carbon nanotubes in a conducting DNNSA-PANI matrix is also included for comparison.
• DNNSA Di- nonyl naphthalene sulfonic acid
• the polyaniline was protonated as reported in US. 5,863,465 (1999) (Monsanto patent) using di-nonyl naphthalene sulfonic acid.
• DNNSA-PANI with (single walled nano-tube) SWNT dispersions were created by using a total of 2.5% solids in xylenes with 20% of the solids being Hipco single wall carbon nanotubes (CNI incorporated, Houston TX) and 80% of the solids from DNNSA-PANI solution in xylenes with 34% solids.
• the composite was made following the following procedure: • The CNT were 1st dispersed into the xylenes using 10 minutes horn sonication at ambient temperature. • The DNNSA-PANI was dispersed into the CNT/xylenes solution using 5 minutes horn sonication at ambient temperature using a 4:1 PANI/SWNT ratio as specified above. • The insulator solution comprised 10 % by weight polystyrene (Aldrich) in xylenes. PAni/Hipco dispersions were dispersed in the Polystyrene solutions at 0.1 , 0.2, 0.3, 0.4, 0.5, 1 , 2, 3, 5, 10% NT concentration. The solution was then coated onto glass slides with Ag contacts and their conductivity measured.
• the Ag contacts were sputtered onto 2" x 3" microscope slides to 2000A in thickness through an aluminum mask using a Denton vacuum unit (Denton Inc. Cherry Hill, NJ). Films were coated onto the microscope slides with Ag contacts using a #4 Meyer rod and dried in a vacuum oven at 60°C for 45 seconds. The coated area was 1 " x 2" and the film thickness around 1 microns. Thicknesses were determined by profilometry.
• the film conductivity was measured using the standard 4- probe measurement technique. The current was measured at the two outer contacts. These contacts were separated by 1 " and connected to a Hewlett Packard power supply in series with an electrometer (Keithley, 617). The voltage was measured at the two inner contacts, separated 0.25" using a Keithley multimeter. The resistivity (in ohm-square) as a function of nanotube concentration is shown in the figure below.
• Example 3 shows the effect on conductivity of adding carbon nanotubes coated with DNNSA-PANI and incorporated the PANI coated tubes into an ethyl cellulose insulating matrix (example 4) relative to a DNNSA-PANI insulating matrix (example 3).
• the data in example 5 shows the conductivity of bare SWNT's dispersed in an ethyl cellulose matrix.
• the polyaniline was protonated as reported in US.
• PAni/Hipco dispersions were dispersed in the Polystyrene solutions at 0.1 ,
• Example 6 shows the effect on conductivity of adding carbon nanotubes coated with DNNSA-PANI into a poly-ethyl methacrylate matrix (example 6) relative to a DNNSA-PANI insulating matrix (example 3).
• the data in example 6 shows the conductivity of PANI coated SWNT's dispersed in an poly ethyl methacrylate matrix.
• the polyaniline was protonated as reported in US 5,863,465 (1999) (Monsanto patent) using di-nonyl naphthalene sulfonic acid.
• the DNNSA- PANI/SWNT dispersions were created by using a total of 2.5% solids in xylenes with 20% of the solids being Hipco (R0236) Carbon Nanotubes ( CNI incorporated, Houston TX) and 80% of the solids from DNNSA-PANI solution in xylenes with 34% solids.
• the composite was made following the procedure described in the previous example.
• PAni/Hipco dispersions were dispersed in the Polystyrene solutions at 0.1 , 0.5, 1 , 5, 10% NT concentration.
• Example 7 illustrates the advantage of using nanotubes to increase the conductivity of PANI relative to the use of carbon black ink and conducting Ag ink as fillers.
• a 2.60 W.% conductive polyaniline in xylenes was made by adding
• XICP-OSO1 14.36g xylenes (EM Science, purity:98.5%) to 0.9624 g XICP-OSO1 , a developmental conductive polyaniline solution from Monsanto Company.
• XICP-OSO1 contains approximately 48.16 W.% xylenes, 12.62 W.% butyl cellosolve, and 41.4 W.% conductive polyaniline.
• Nanotubes were dispersed in turpinol at 1.43% by weight. The nanotube/turpinol mixture was sonicated for 24 hours at ambient temperature prior to mixing with the 41.4 % solution of PANI- XICP-OSO1.
• the nanotube/PANI solutions at 0, 0.25, 0.5, 0.75, 1 , 1.25, 1.5, 1.75,2, 4, 6, 10, 20 and 40% nanotube concentration were coated onto microscope slides and dried in a vacuum oven at 60°C for 30 seconds.
• PANI-XICP-OSO1 was mixed with Graphitic ink PM- 003A (Acheson colloids, Port Hurom, Ml) at 0, 5, 10, 20, 40 and 100% by weight.
• PANI-XICP-OSO1 was mixed with Ag conducting ink # 41823 (Alfa-Aesar, Ward Hill, MA) at 0, 5, 10, 20, 40, 80 and 100% by weight.
• the coated area was 1" x 2". Film thickness was determined by optical interferometry.
• the Ag contacts for resistivity measurements were sputtered to 4000A in thickness through an aluminum mask using a Denton vacuum unit (Denton Inc. Cherry Hill, NJ).
• the film resistivity was measured using the standard 4-probe measurement technique.
• the current was measured at the two outer contacts. These contacts were separated by 1 " and connected to a Hewlett Packard power supply in series with an electrometer (Keithley, 617).
• the voltage was measured at the two inner contacts, separated 0.25" using a Keithley multimeter.
• the resistivity (in ohm-square) as a function of nanotube, graphitic ink and Ag ink concentrations are shown in the figure below.
• the resistivity of the film decreases by 4 orders of magnitude with only 2% loading of nanotubes while it does not change with less than 20% loading of a conducting graphitic or Ag inks.

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• 2004
  • 2004-10-20 US US10/969,422 patent/US20050165155A1/en not_active Abandoned
  • 2004-10-21 EP EP04796458A patent/EP1678250A1/en not_active Withdrawn
  • 2004-10-21 WO PCT/US2004/035486 patent/WO2005040265A1/en not_active Ceased
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  • 2007-07-19 US US11/779,901 patent/US20080241390A1/en not_active Abandoned

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