Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences

• US 9,717,170 B2
• Filed: 10/16/2013
• Issued: 07/25/2017
• Est. Priority Date: 10/16/2012
• Status: Expired due to Fees

• Current Assignee: Universita' Degli Studi Di Roma La Sapienza (Repubblica Italiana)
• Original Assignee: Universita' Degli Studi Di Roma La Sapienza (Repubblica Italiana)
• Inventors: Sarto, Maria Sabrina, De Bellis, Giovanni, Tamburrano, Alessio, D'Aloia, Alessandro Giuseppe
• Primary Examiner(s): Nguyen, Tri V
• Application Number:
  US14/435,835
• Publication Number:
  US 20150305212A1
• Time in Patent Office: 1,378 Days
• Field of Search: 252500-511, 423445 R-448
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: B82Y 99/00 Subject matter not provided for in other groups of this subclass
• CPC Class Codes: C01B 32/182 Graphene
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01Q 17/00 Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
• CPC Class Codes: H05K 9/0083 comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers H05K9/0086 takes precedence
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.

Abstract

A process for producing GNP-based polymeric nanocomposites for electromagnetic applications such as shielding and/or absorption of the energy associated to electromagnetic fields envisages a plurality of steps that include: controlled synthesis, for optimizing the morphological and electrical properties thereof, of graphene nanoplatelets (GNPs) to be used as nanofillers in a polymeric matrix; selection of the polymeric matrix so as to optimize its chemical compatibility with the type of GNPs thus obtained; production via the solution-processing technique of GNP-based polymeric nanocomposites with dielectric permittivity and electric conductivity controlled and predictable via the equivalent-effective-medium model by calibrating the parameters of the model for the specific type of polymeric matrix and GNPs used.

Claims

1. A process for producing a polymeric nanocomposite with electrical and electromagnetic properties controlled and predictable by applying the equivalent-effective-medium model, for electromagnetic applications, shielding and/or absorption of the energy associated to electromagnetic fields, comprising the following steps:

a) carrying out a synthesis of graphene nanoplatelets through liquid phase exfoliation of thermally expanded graphite, modifying, through parameters of the production process, morphological and electrical properties thereof, said parameters of the production being;

i) a temperature-to-time expansion rate higher than 2000°

C./min and up to 45000°

C./min;

ii) a dispersion of thermally expanded graphite in organic solvents or their appropriate mixture matching Hansen'"'"'s solubility parameters of graphite; and

iii) sonication with an ultrasound tip at a power in a range of 20%-100%, in pulse mode between 1 s ON-2 s OFF and 4 s ON-1 s OFF, with total ON time of 20 min, at a temperature below a boiling point of the solvent, in a range of 14°

C.-20°

C. in order to keep the ultrasound tip resonating throughout the dispersion of step ii);

b) using said graphene nanoplatelets as nanofillers in a polymeric matrix selected on a basis of chemical compatibility with the graphene nanoplatelets, distributing said graphene nanoplatelets and dispersing said graphene nanoplatelets in an entire mass of the matrix in a weight percentage by a magnetic stirring technique which imparts on a magnetic anchor a motion of revolution in addition to a rotation around the magnetic anchor'"'"'s own axis so as to prevent formation of graphene nanoplatelet aggregates in the mixture during complete solvent evaporation, wherein;

i) control of the solvent evaporation rate in a range 0.05-0.2 ml/min and corresponding to a total duration between 0.5 and 24 h in order to avoid formation of graphene nanoplatelet aggregates and trapping of molecules of solvent in the nanocomposite,

ii) utilizing a device adapted to impart on the magnetic anchor a motion of revolution in addition to the rotation around the magnetic anchor'"'"'s own axis in order to avoid formation of graphene nanoplatelet aggregates and to obtain a dispersion of the nanofiller in the polymer matrix,

wherein said mixing process and preventing aggregate formation, produces a nanocomposite in which an imaginary part of an effective permittivity is controlled independently of a real part through a nanometric thickness of the nanofiller, which activates electron transport between the nanofiller and a polymer matrix, whereas the real part of the effective permittivity is controlled independently of the imaginary part through a surface extension of the graphene nanoplatelets, which affects properties of polarization of the material but not the material'"'"'s electrical conductivity, and

wherein an expansion temperature of graphite intercalated compound is made using a regression line

R=−

0.0002T+0.3357

where T is expressed in degrees centigrade and R in ohms,

said regression line expressing analytically, as a function of the expansion temperature, a resistance of the graphene nanoplatelets films measured using the four-tip technique;

said regression line being obtained by interpolation of experimental data.

2. The process for producing polymeric nanocomposites as per claim 1, wherein the graphene nanoplatelets are produced by thermochemical exfoliation of graphite intercalated compound, by liquid-phase exfoliation of thermally expanded graphite using as solvent acetone or dimethyl formamide, or a mixture of acetone and dimethyl formamide in amounts ranging between 5 and 15 parts out of 100 of dimethyl formamide, and between 95 and 85 parts out of 100 of acetone, and

wherein a ratio of dimethyl formamide:

Acetone is 1;

9.

3. A process for producing a polymeric nanocomposite with electrical and electromagnetic properties controlled and predictable by applying the equivalent-effective-medium model, for electromagnetic applications, shielding and/or absorption of the energy associated to electromagnetic fields, comprising the following steps:

a) carrying out a synthesis of graphene nanoplatelets through liquid phase exfoliation of thermally expanded graphite, modifying, through parameters of the production process, morphological and electrical properties thereof, said parameters of the production being;

i) a temperature-to-time expansion rate higher than 2000°

C./min and up to 45000°

C./min;

ii) a dispersion of expanded graphite in organic solvents or their appropriate mixture matching Hansen'"'"'s solubility parameters of graphite; and

iii) sonication with an ultrasound tip at a power in a range of 20%-100%, in pulse mode between 1 s ON-2 s OFF and 4 s ON-1 s OFF, with total ON time of 20 min, at a temperature below a boiling point of the solvent, in a range of 14°

C.-20°

C. in order to keep the ultrasound tip resonating throughout the dispersion of step ii);

b) using said graphene nanoplatelets as nanofillers in a polymeric matrix selected on a basis of chemical compatibility with the graphene nanoplatelets, distributing said graphene nanoplatelets and dispersing said graphene nanoplatelets in an entire mass of the matrix in a weight percentage by a magnetic stirring technique which imparts on a magnetic anchor a motion of revolution in addition to a rotation around the magnetic anchor'"'"'s own axis so as to prevent formation of graphene nanoplatelet aggregates in the mixture during complete solvent evaporation, wherein;

i) control of the solvent evaporation rate in a range 0.05-0.2 ml/min and corresponding to a total duration between 0.5 and 24 h in order to avoid formation of graphene nanoplatelet aggregates and trapping of molecules of solvent in the nanocomposite,

ii) utilizing a device adapted to impart on the magnetic anchor a motion of revolution in addition to the rotation around the magnetic anchor'"'"'s own axis in order to avoid formation of graphene nanoplatelet aggregates and to obtain a dispersion of the nanofiller in the polymer matrix,

wherein said mixing process and preventing aggregate formation, produces a nanocomposite in which an imaginary part of an effective permittivity is controlled independently of a real part through a nanometric thickness of the nanofiller, which activates electron transport between the nanofiller and a polymer matrix, whereas the real part of the effective permittivity is controlled independently of the imaginary part through a surface extension of the graphene nanoplatelets, which affects properties of polarization of the material but not the material'"'"'s electrical conductivity, and

wherein a rate of expansion of graphite intercalated compound is made using a regression line

R=−

4.10<sup>−

6</sup>r+0.1646

where r is expressed in degrees centigrade per minute and R in ohms;

said regression line being obtained by interpolation of experimental data.

4. The process for producing polymeric nanocomposites as per claim 3, wherein the graphene nanoplatelets are produced by thermochemical exfoliation of graphite intercalated compound, by liquid-phase exfoliation of thermally expanded graphite using as solvent acetone or dimethyl formamide, or a mixture of acetone and dimethyl formamide in amounts ranging between 5 and 15 parts out of 100 of dimethyl formamide, and between 95 and 85 parts out of 100 of acetone, and

wherein a ratio of dimethyl formamide:

Acetone is 1;

9.