WO2015009182A1 - Method for preparing polymer composites comprising modified carbon nanotubes, polymer composite comprising modified carbon nanotubes and use of same - Google Patents
Method for preparing polymer composites comprising modified carbon nanotubes, polymer composite comprising modified carbon nanotubes and use of same Download PDFInfo
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- WO2015009182A1 WO2015009182A1 PCT/PL2014/050043 PL2014050043W WO2015009182A1 WO 2015009182 A1 WO2015009182 A1 WO 2015009182A1 PL 2014050043 W PL2014050043 W PL 2014050043W WO 2015009182 A1 WO2015009182 A1 WO 2015009182A1
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- Prior art keywords
- carbon nanotubes
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- 239000002071 nanotube Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 13
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 10
- 239000001739 pinus spp. Substances 0.000 claims description 10
- 229940036248 turpentine Drugs 0.000 claims description 10
- 239000003502 gasoline Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940067157 phenylhydrazine Drugs 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 nonane ethoxy silane Chemical compound 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001293 FEMA 3089 Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000005313 fatty acid group Chemical group 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000011110 re-filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/026—Heaters specially adapted for floor heating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/029—Heaters specially adapted for seat warmers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/036—Heaters specially adapted for garment heating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
- H05B2214/03—Heating of hydrocarbons
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
- H05B2214/04—Heating means manufactured by using nanotechnology
Definitions
- the present invention relates to a method for preparing polymer composites comprising modified carbon nanotubes, polymer composite comprising modified carbon nanotubes and use of same in floor heating, heating of car seats, operating tables and clothing.
- Carbon nanotubes are graphene layers rolled into hollow cylinders (typically single layer carbon atoms) . Due to their structure, they are also considered as one-dimensional objects, as the length to diameter ratio of nanotubes may be in the order of millions. Nanotubes have unusual properties, such as: very high tensile strength or unique electrical properties and very good thermal conductivity. With these unique characteristics they have a high application potential. Of particular interest are multi-walled carbon nanotubes made of concentric graphene layers. Due to the high chemical resistance, their properties can be modified by breaking some of the bonds between carbon atoms. The main challenge when using carbon nanotubes is the method of bonding them with the carrier material that may be subject to functionalization, such as polymer matrices .
- Patent PL392221 discloses a method to prepare a carbon nanotubes incorporated cellulose nanocomposite . Such material has better current-voltage performance in the case of pure and modified cellulose fibres, and has better mechanical performance as compared with pure and modified carbon nanotubes.
- the said method involves preparation of first solution of cellulose in a hydrophilic ionic liquid, preparation of the second solution of carbon nanotubes in a hydrophilic ionic liquid with anionic surfactant, followed by precipitation of the said nanocomposite from the solution with water.
- Tubes are dispersed in a hydrophilic liquid in the presence of an anionic surfactant by ultrasonic treatment, resulting in breaking up the nanostructure agglomerations with carbon nanofibres becoming separated from each other.
- Patent PL391415 discloses a method for preparing carboxylated or carboxylated and hydroxylated carbon nanotubes without impurities of oxidizing agents that are difficult to remove, by pre-oxidising carbon nanotubes in the solid phase in air atmosphere to red glowing heat at 500-700 °C in a microwave field. Then, nanotubes are further oxidized by exposing them to a cooling or cooling-oxidizing liquid medium, and the suspension is subjected to ultrasonic treatment. After the suspension is dispersed, the oxidized carbon nanotubes are filtered or centrifuged, washed and dried until a loose, free-flowing product is obtained.
- patent PL383273 discloses a method of using carbon nanotubes for the coating of fibres in particular intended for the manufacture of heating materials.
- the possess for using carbon nanotubes for fibre coating is characterized in that carbon nanotubes, after being purified from amorphous carbon, are enriched with hydrophilic functional groups, and then converted to the ammonium salt.
- the solution of modified carbon nanotubes is then used for coating fibres or fabrics.
- the method according to the said invention only involves coating of cellulose or cellulose/polymer substrates.
- the technical challenge of the present invention is to propose a polymer composition enriched with multi-walled carbon nanotubes to enable fabrication of low-voltage heating mats that would be resistant to mechanical and chemical damage, safe to use and at the same time flexible enough to allow for folding and unfolding in the full range from 0° to 360°, to apply and trim the heating module to suite the size of the area to be heated.
- the first object of the invention is a method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) diaminobenzene is added to a dispersion of nanotubes in heptanes until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein diaminobenzene from step a) is a 2% solution in isopentanol, halogenated silicon compounds from step b) are a 2% solution in heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes disper
- the method is characterized in that up to 5 wt% of ethanol or isobutanol is added to the dispersion of nanotubes during stirring on the magnetic stirrer in step c) .
- the method is characterized in that in step b) the tri (tri , 4, 7, 9-pentyl ) nonane ethoxy silane is used as a silicon compound.
- the method according to the invention is characterized in that the nonpolar solvent is selected from a group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate.
- the method according to the invention is characterized in that the ratio of dissolved chemically inert silicone preparation containing dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
- the second object of the invention is a method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) phenylhydrazine with ammonia is added a dispersion of nanotubes in heptane until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein the solution added in step a) is 5% phenylhydrazine with 27% concentrated ammonia solution, halogenated silicon compounds are a 2% solution in heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes dis
- phenylhydrazine is dissolved in butyl acetate. More preferably, the method according to the invention is characterized in that the organosilicon system is enriched with fatty acid chains.
- the nonpolar solvent is selected from a group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate.
- the method according to the invention is characterized in that the ratio of dissolved chemically inert silicone preparation containing dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
- the third object of the invention is a modified polymer composite comprising carbon nanotubes, wherein it has been prepared by a method as defined in the first or second object of the invention.
- the composite according to the invention is characterized in that the content of carbon nanotubes is from 0.5% to 15%, by weight. More preferably, the composite according to the invention is characterized in that it has a texture which is suitable for application to substrate by spray, roller, brush or other known method.
- the fourth object of the invention is the use of a polymer composite comprising modified carbon nanotubes as defined in any previous object of the invention for fabrication of flexible heating mats.
- the polymer composition with integrated multi-walled carbon nanotubes according to the invention allows to smoothly achieve the working temperature, depending on the applied voltage, current, and heating layer thickness and the type of nanotube medium applied to polymer matrix.
- the invention may be used to fabricate a heating film on the surface of hydrophobic silicones and mixtures of the same with other polymers.
- the specific surface structure and the dispersion method allow to fabricate nanostructured materials with very good electrical performance.
- FIG. 1 shows a heating mat with a power supply system, described in the third embodiment
- Fig. 2 shows a heating mat with a power supply system as described in the fourth embodiment .
- Raw carbon nanotubes (10 g) were placed in a round bottom flask (2 litres) and 300 ml of nitric acid was added. The whole was mixed in a high-speed mixer at 22 000 rev/min for 2 hours. 200 ml of 30% hydrogen peroxide was added to the dispersion so obtained and mixed again for 30 minutes. After this time the solution was placed in ultrasonic reactor for 6 hours. 200 ml of concentrated nitric acid and 150 ml of concentrated sulphuric acid were added to the obtained mixture. The whole was placed under a return cooler and then boiled for 4 hours.
- Example 2 The obtained mixture was filtered, the precipitate was transferred to a flat bottom flask (2 litres) poured over with 3% hydrobromic acid solution (1 litre) and placed in ultrasonic reactor for 20 minutes. Subsequently, the mixture was filtered, the precipitate was placed in a 500 ml flat-bottomed flask and 100 ml of concentrated HBr was added. The mixture was placed in a microwave reactor for 1 hour. After filtration, neutralization of excess HBr with ammonia to pH 10, re-filtration and drying - the material serves as an input material for further applications.
- Example 2 Example 2
- Raw carbon nanotubes (10 g) were placed in a round bottom flask (2 litres) and 300 ml of nitric acid and 100 ml of sulphuric acid was added. The whole was mixed in a high-speed mixer at 15 000 rev/min for 1 hour. 500 ml of water was added to the dispersion so obtained and filtered. Then, the precipitate was placed in a flat bottom flask, 200 ml of 30% hydrogen peroxide was added and placed in ultrasonic reactor for 30 min. After filtration, washing with water, the precipitate was placed in a 2000 ml round bottom flask and 400 ml of concentrated nitric acid and 150 ml of concentrated sulphuric acid was added.
- the whole was placed under a return cooler and boiled for 4 hours.
- the obtained mixture was filtered, the precipitate was transferred to a flat bottom flask (2 litres), poured over with demineralised water (600 ml), placed in ultrasonic reactor for 120 min. Subsequently, the mixture was filtered, the precipitate was placed in a 500 ml flat-bottomed flask and 100 ml of concentrated HBr was added.
- the mixture was placed in a microwave reactor for 2 hours. After filtration, neutralization of excess HBr with ammonia solution to pH 10, re-filtration and drying - the material serves as input material for further applications.
- the prepared solution was stirred with magnetic stirrer for 30 min at 2000 revolutions per minute to form an input material for bonding with inert silicon, not containing acidic and basic functional groups, but only methyl, ethoxyl and hydroxyl functional groups.
- inert silicon not containing acidic and basic functional groups, but only methyl, ethoxyl and hydroxyl functional groups.
- 5 wt% ethanol was added to the nanotubes dispersion.
- the Protectosil product i.e. tri (tri , 4, 7, 9-pentyl ) nonane ethoxy silane was used in the reaction.
- the so obtained preparation was dissolved in a nonpolar solvent, a 1:1 mixture of turpentine and dearomatised gasoline.
- the mat composite saturation with nanotubes was between 1% to 1.5%, with the layer thickness of 2 mm.
- the mat is supplied with 24V/3A AC voltage at a frequency of 50 Hz, using voltage control.
- the composite so obtained had a working range from 20 °C to 80 °C and 30 s time of reaching 80 °C.
- Example 4 100 ml of 5% phenylhydrazine in concentrated 27% ammonia solution was added to the dispersion of nanotubes in 200 ml of 4% heptane solution obtained in the second embodiment. After stirring and achieving pH 9 by means of diaminobenzene, halogenated silicon compounds with hydrocarbon systems attached were added, as in embodiment 3. Then, the prepared solution was stirred with magnetic stirrer for 30 min at 2000 revolutions per minute to form an input material for bonding with inert silicon, not containing acidic and basic functional groups, but only methyl, ethoxyl and hydroxyl functional groups. The so obtained preparation was dissolved in a nonpolar solvent, a 1:1 mixture of turpentine and butyl acetate.
- the chemically inert E80 silicone built of chains enriched with ethoxy groups, was dissolved in the same nonpolar solvent. Preparation with carbon nanotubes dissolved in nonpolar solvent was mixed with silicone dissolved in nonpolar solvent in a 100:1 ratio, and then applied to the desired surface by spraying and dried to produce a finished product. The achieved resistance of the applied layer was 20 ⁇ .
Abstract
The present invention relates to a method for fabricating a polymer composite comprising modified carbon nanotubes, involving the following steps: diaminobenzene is added to a dispersion of nanotubes in heptane to obtain a p H of the solution of 9, halogenated silicon compounds with attached hydrocarbon system are added to the solution, stirred on a magnetic stirrer, the obtained preparation is dissolved in a nonpolar solvent, the chemically inert silicone is dissolved in a nonpolar solvent, the dissolved mixture is a chemically inert silicone with dissolved preparation comprising carbon nanotubes, wherein carbon nanotubes are from 20 to 120 nm long with a diameter from 5 nm to 15 nm. The present invention also relates to a modified polymer composite comprising carbon nanotubes and use of same for the production of heating mats.
Description
Method for preparing polymer composites comprising modified carbon nanotubes, polymer composite comprising modified carbon nanotubes and use of same
The present invention relates to a method for preparing polymer composites comprising modified carbon nanotubes, polymer composite comprising modified carbon nanotubes and use of same in floor heating, heating of car seats, operating tables and clothing.
Carbon nanotubes are graphene layers rolled into hollow cylinders (typically single layer carbon atoms) . Due to their structure, they are also considered as one-dimensional objects, as the length to diameter ratio of nanotubes may be in the order of millions. Nanotubes have unusual properties, such as: very high tensile strength or unique electrical properties and very good thermal conductivity. With these unique characteristics they have a high application potential. Of particular interest are multi-walled carbon nanotubes made of concentric graphene layers. Due to the high chemical resistance, their properties can be modified by breaking some of the bonds between carbon atoms. The main challenge when using carbon nanotubes is the method of bonding them with the carrier material that may be subject to functionalization, such as polymer matrices . Solutions based on the use of carbon nanotubes as polymer fillers have been known for many years, however, a fundamental problem is to obtain a homogenous dispersion of carbon nanotubes in the polymer matrix. The existing solutions involve preparation of a dispersion by means of surfactants, followed by application of a mixture so obtained to the prepared polymer precursors or the final polymer dispersion. Because chemicals must be used to disentangle the fibres of carbon nanotubes, the composites are characterised by a limited mechanical strength and flexibility. Another solution is to disperse raw nanotubes in the polymer matrix, however, it is not possible to obtain a homogenous
structure of composites so prepared. Such a system exhibits good electrical performance with limited applicability due to poor mechanical characteristics. Patent PL392221 discloses a method to prepare a carbon nanotubes incorporated cellulose nanocomposite . Such material has better current-voltage performance in the case of pure and modified cellulose fibres, and has better mechanical performance as compared with pure and modified carbon nanotubes. The said method involves preparation of first solution of cellulose in a hydrophilic ionic liquid, preparation of the second solution of carbon nanotubes in a hydrophilic ionic liquid with anionic surfactant, followed by precipitation of the said nanocomposite from the solution with water. Tubes are dispersed in a hydrophilic liquid in the presence of an anionic surfactant by ultrasonic treatment, resulting in breaking up the nanostructure agglomerations with carbon nanofibres becoming separated from each other. In addition, the surfactants reduce viscosity of the liquid and lower the surface tension of nanotube agglomerates. Patent PL391415 discloses a method for preparing carboxylated or carboxylated and hydroxylated carbon nanotubes without impurities of oxidizing agents that are difficult to remove, by pre-oxidising carbon nanotubes in the solid phase in air atmosphere to red glowing heat at 500-700 °C in a microwave field. Then, nanotubes are further oxidized by exposing them to a cooling or cooling-oxidizing liquid medium, and the suspension is subjected to ultrasonic treatment. After the suspension is dispersed, the oxidized carbon nanotubes are filtered or centrifuged, washed and dried until a loose, free-flowing product is obtained. The said method is characterized by purity combined with the presence of hydrophilic groups on the surface. The main challenge is posed by the complicated purification process, the need to ensure anaerobic atmosphere and a large amount of carbon on the surface of nanotubes. On the other hand, patent PL383273 discloses a method of using carbon nanotubes for the coating of fibres in particular intended for the manufacture of heating materials. The possess for using carbon nanotubes for fibre coating is characterized in that carbon nanotubes, after being purified from amorphous carbon, are enriched with hydrophilic functional groups, and then converted to the ammonium salt. The solution of modified
carbon nanotubes is then used for coating fibres or fabrics. The method according to the said invention, only involves coating of cellulose or cellulose/polymer substrates. Due to the presence of hydroxyl groups on the surface of cellulose, they can be bonded with modified carbon nanotubes using a chemical catalyst. The patent application KR20120065494 presents a flexible heat mat of DC voltage, in the form of a thin fabric layer enriched with carbon nanotubes, eliminating the need for metallic conductors, such as copper. In the cited patent, carbon nanotubes are integrated with the fabric structure, which is characterized by a low mechanical strength, especially to puncture and tear, and is liquid-absorbing, thus offering limited applicability. The technical challenge of the present invention is to propose a polymer composition enriched with multi-walled carbon nanotubes to enable fabrication of low-voltage heating mats that would be resistant to mechanical and chemical damage, safe to use and at the same time flexible enough to allow for folding and unfolding in the full range from 0° to 360°, to apply and trim the heating module to suite the size of the area to be heated. The first object of the invention is a method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) diaminobenzene is added to a dispersion of nanotubes in heptanes until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein diaminobenzene from step a) is a 2% solution in isopentanol, halogenated silicon compounds from step b) are a 2% solution in
heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes dispersed in heptanes in step a) are from 20 nm to 120 nm long and have a diameter from 5 nm to 15 nm. In a further preferred embodiment of the invention, the method is characterized in that up to 5 wt% of ethanol or isobutanol is added to the dispersion of nanotubes during stirring on the magnetic stirrer in step c) . In a further preferred embodiment of the invention the method is characterized in that in step b) the tri (tri , 4, 7, 9-pentyl ) nonane ethoxy silane is used as a silicon compound. Even more preferably, the method according to the invention is characterized in that the nonpolar solvent is selected from a group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate. Most preferably, the method according to the invention is characterized in that the ratio of dissolved chemically inert silicone preparation containing dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
The second object of the invention is a method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) phenylhydrazine with ammonia is added a dispersion of nanotubes in heptane until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein the solution added in step a) is 5% phenylhydrazine with 27% concentrated ammonia solution, halogenated silicon compounds are a 2% solution in heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes dispersed in heptane
are from 20 nm to 120 nm long and have a diameter from 5 nm to 15 nm. Equally preferably, phenylhydrazine is dissolved in butyl acetate. More preferably, the method according to the invention is characterized in that the organosilicon system is enriched with fatty acid chains. In the further preferred embodiment of the invention, the nonpolar solvent is selected from a group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate. Most preferably, the method according to the invention is characterized in that the ratio of dissolved chemically inert silicone preparation containing dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
The third object of the invention is a modified polymer composite comprising carbon nanotubes, wherein it has been prepared by a method as defined in the first or second object of the invention.
Also preferably, the composite according to the invention is characterized in that the content of carbon nanotubes is from 0.5% to 15%, by weight. More preferably, the composite according to the invention is characterized in that it has a texture which is suitable for application to substrate by spray, roller, brush or other known method.
The fourth object of the invention is the use of a polymer composite comprising modified carbon nanotubes as defined in any previous object of the invention for fabrication of flexible heating mats.
The polymer composition with integrated multi-walled carbon nanotubes according to the invention allows to smoothly achieve the working temperature, depending on the applied voltage, current, and heating layer thickness and the type of nanotube medium applied to polymer matrix. The invention may be used to fabricate a heating film on the surface of hydrophobic silicones and mixtures of the same with other polymers. The specific surface structure and the
dispersion method allow to fabricate nanostructured materials with very good electrical performance.
Exemplary embodiments of the invention are illustrated on the drawing, where Fig. 1 shows a heating mat with a power supply system, described in the third embodiment and Fig. 2 shows a heating mat with a power supply system as described in the fourth embodiment .
Example 1
Raw carbon nanotubes (10 g) were placed in a round bottom flask (2 litres) and 300 ml of nitric acid was added. The whole was mixed in a high-speed mixer at 22 000 rev/min for 2 hours. 200 ml of 30% hydrogen peroxide was added to the dispersion so obtained and mixed again for 30 minutes. After this time the solution was placed in ultrasonic reactor for 6 hours. 200 ml of concentrated nitric acid and 150 ml of concentrated sulphuric acid were added to the obtained mixture. The whole was placed under a return cooler and then boiled for 4 hours. The obtained mixture was filtered, the precipitate was transferred to a flat bottom flask (2 litres) poured over with 3% hydrobromic acid solution (1 litre) and placed in ultrasonic reactor for 20 minutes. Subsequently, the mixture was filtered, the precipitate was placed in a 500 ml flat-bottomed flask and 100 ml of concentrated HBr was added. The mixture was placed in a microwave reactor for 1 hour. After filtration, neutralization of excess HBr with ammonia to pH 10, re-filtration and drying - the material serves as an input material for further applications.
Example 2
Raw carbon nanotubes (10 g) were placed in a round bottom flask (2 litres) and 300 ml of nitric acid and 100 ml of sulphuric acid was added. The whole was mixed in a high-speed mixer at 15 000 rev/min for 1 hour. 500 ml of water was added to the dispersion so obtained and filtered. Then, the precipitate was placed in a flat bottom flask, 200 ml of 30% hydrogen peroxide was added and placed in ultrasonic reactor for 30 min. After filtration, washing with water, the precipitate was placed in a 2000 ml round bottom flask and 400 ml of concentrated nitric acid and 150 ml of concentrated sulphuric acid was added. The whole was placed under a return cooler and boiled for 4 hours. The obtained mixture was filtered, the precipitate was transferred to a flat bottom flask (2 litres), poured over with demineralised water (600 ml), placed in ultrasonic reactor for 120 min. Subsequently, the mixture was filtered, the precipitate was placed in a 500 ml flat-bottomed flask and 100 ml of concentrated HBr was added. The mixture was placed in a microwave reactor for 2 hours. After filtration, neutralization of excess HBr with ammonia solution to pH 10, re-filtration and drying - the material serves as input material for further applications.
Example 3
50 ml of 2% diaminobenzene dissolved in isopentanol was added to the dispersion of nanotubes in 200 ml 4% heptane solution obtained in the first embodiment. After stirring and achieving pH 9 by means of diaminobenzene, halogenated silicon compounds containing triethylchlorosilane, dichlordimethylsilane, triheksylobromosilan with attached hydrocarbon systems in 20 ml of 2% heptane solution. Then, the prepared solution was stirred with magnetic stirrer for 30 min at 2000 revolutions per minute to form an input material for bonding with inert silicon, not containing acidic and basic functional groups, but only methyl, ethoxyl and hydroxyl functional groups. During stirring on magnetic stirrer, 5 wt% ethanol was added to the nanotubes dispersion. Then, the Protectosil product, i.e. tri (tri , 4, 7, 9-pentyl ) nonane ethoxy silane was used in the reaction. The so obtained preparation was dissolved in a nonpolar solvent, a
1:1 mixture of turpentine and dearomatised gasoline. The chemically inert FD80 silicone, built of chains enriched with ethoxy groups, was dissolved in the same nonpolar solvent. Preparation with carbon nanotubes dissolved in nonpolar solvent was mixed with silicone dissolved in nonpolar solvent in a 1:1 ratio, and then applied to the desired surface by a roller and dried to produce a finished product. Supplying electrodes (E), spaced at a distance K of 10 cm, were arranged on the obtained mat with two layers of heating composite, as shown in Fig. 1. The mat composite saturation with nanotubes was between 1% to 1.5%, with the layer thickness of 2 mm. The mat is supplied with 24V/3A AC voltage at a frequency of 50 Hz, using voltage control. The composite so obtained had a working range from 20 °C to 80 °C and 30 s time of reaching 80 °C.
Example 4 100 ml of 5% phenylhydrazine in concentrated 27% ammonia solution was added to the dispersion of nanotubes in 200 ml of 4% heptane solution obtained in the second embodiment. After stirring and achieving pH 9 by means of diaminobenzene, halogenated silicon compounds with hydrocarbon systems attached were added, as in embodiment 3. Then, the prepared solution was stirred with magnetic stirrer for 30 min at 2000 revolutions per minute to form an input material for bonding with inert silicon, not containing acidic and basic functional groups, but only methyl, ethoxyl and hydroxyl functional groups. The so obtained preparation was dissolved in a nonpolar solvent, a 1:1 mixture of turpentine and butyl acetate. The chemically inert E80 silicone, built of chains enriched with ethoxy groups, was dissolved in the same nonpolar solvent. Preparation with carbon nanotubes dissolved in nonpolar solvent was mixed with silicone dissolved in nonpolar solvent in a 100:1 ratio, and then applied to the desired surface by spraying and dried to produce a finished product. The achieved resistance of the applied layer was 20Ω. Supplying electrodes (E) , spaced at a distance L = 15 cm, were arranged on the obtained mat with 4 layers of heating composite, as shown in Fig. 2. The mat is supplied with 24V/3A AC voltage at a frequency of 50 Hz, using voltage control. The composite so obtained
enabled working temperatures up to 100 °C reached in no more than 20 seconds .
Claims
Claims 1. method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) diaminobenzene is added to a dispersion of nanotubes in heptanes until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein diaminobenzene from step a) is a 2% solution in isopentanol, halogenated silicon compounds from step b) are a 2% solution in heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes dispersed in heptanes in step a) are from 20 nm to 120 nm long and have a diameter from 5 nm to 15 nm
2 A method according to claim 1, wherein up to 5 wt% ethanol or isobutanol is added to the dispersion of nanotubes during stirring on the magnetic stirrer in step c) .
3. A method according to claims 1 or 2, wherein in step b) tri (tri , 4, 7, 9-pentyl ) nonane ethoxy silane is used as a silicon compound.
4. A method according to any claim from 1 to 3, wherein the nonpolar solvent is selected from the group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate.
5. A method according to any claim from 1 to 4, wherein the ratio of dissolved chemically inert silicone preparation containing dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
6. A method for fabricating a polymer composite, comprising modified carbon nanotubes, involving the following steps: a) phenylhydrazine with ammonia is added a dispersion of nanotubes in heptane until the pH value of the solution is 9, b) halogenated silicon compounds with hydrocarbon systems attached are added to the solution from step a, c) mixture from step b) is stirred on a magnetic stirrer, d) preparation from step c) is dissolved in a nonpolar solvent, e) chemically inert silicone is dissolved in a nonpolar solvent, f) chemically inert silicone is mixed with the dissolved preparation comprising carbon nanotubes, wherein the solution added in step a) is 5% phenylhydrazine with 27% concentrated ammonia solution, halogenated silicon compounds are a 2% solution in heptane, stirring in step c) is carried out for 30 min at 2000 rpm, wherein the carbon nanotubes dispersed in heptane are from 20 nm to 120 nm long and have a diameter from 5 nm to 15 nm .
7. A method according to claim 6, wherein phenylhydrazine is dissolved in butyl acetate.
8. A method according to claims 6 or 7, wherein silicon is enriched with fatty acid chains.
9. A method according to any claims from 6 to 8, wherein the nonpolar solvent is selected from a group consisting of hexane, toluene, dearomatised gasoline, mixture of dearomatised gasoline and turpentine, turpentine oil, mixture of turpentine and butyl acetate.
10. A method according to any claim from 6 to 9, wherein the ratio of dissolved chemically inert silicone preparation comprising dissolved carbon nanotubes is in the range from 1:1 to 1000:1.
11. A polymer composite comprising modified carbon nanotubes, wherein it has been prepared by a process as defined in any of the claims from 1 to 10.
12. A composite according to claim 11, wherein the content of carbon nanotubes is from 0.5% to 15%, by weight.
13. A polymer composite comprising modified carbon nanotubes according to claims 11 or 12, wherein it has a texture which is suitable for application to substrate by spray, roller, brush or other known method.
14. The use of a polymer composite comprising modified carbon nanotubes as defined in any claim from 11 to 13 for fabrication of flexible heating mats.
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| PL404703A PL404703A1 (en) | 2013-07-16 | 2013-07-16 | Method for producing polymer composites containing modified carbon nanotubes, polymer composite containing modified carbon nanotubes and its application |
| PLPL404703 | 2013-07-16 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050067406A1 (en) * | 2003-09-30 | 2005-03-31 | Shanmugam Rajarajan | Self heating apparatus |
| US20060217482A1 (en) * | 2004-07-09 | 2006-09-28 | Lukehart Charles M | Reactive graphitic carbon nanofiber reinforced polymeric composites showing enhanced flexural strength |
| PL383273A1 (en) | 2007-09-05 | 2009-03-16 | Nanoco Spółka Z Ograniczoną Odpowiedzialnością | The manner of application of carbon nanotubes for coating of fibres |
| PL391415A1 (en) | 2010-06-02 | 2011-12-05 | Politechnika Warszawska | Method for modification of carbon nanotubes, especially polyhedral |
| PL392221A1 (en) | 2010-08-25 | 2012-02-27 | Instytut Chemii Fizycznej Polskiej Akademii Nauk | Method of obtaining the cellulose nanocomposite with in-built carbon nanotubes and the cellulose nanocomposite with the in-built carbon nanotubes |
| KR20120065494A (en) | 2010-12-13 | 2012-06-21 | 김철웅 | Heat mat of dc-voltage using carbon-nanotube tread |
-
2013
- 2013-07-16 PL PL404703A patent/PL404703A1/en unknown
-
2014
- 2014-07-15 WO PCT/PL2014/050043 patent/WO2015009182A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050067406A1 (en) * | 2003-09-30 | 2005-03-31 | Shanmugam Rajarajan | Self heating apparatus |
| US20060217482A1 (en) * | 2004-07-09 | 2006-09-28 | Lukehart Charles M | Reactive graphitic carbon nanofiber reinforced polymeric composites showing enhanced flexural strength |
| PL383273A1 (en) | 2007-09-05 | 2009-03-16 | Nanoco Spółka Z Ograniczoną Odpowiedzialnością | The manner of application of carbon nanotubes for coating of fibres |
| PL391415A1 (en) | 2010-06-02 | 2011-12-05 | Politechnika Warszawska | Method for modification of carbon nanotubes, especially polyhedral |
| PL392221A1 (en) | 2010-08-25 | 2012-02-27 | Instytut Chemii Fizycznej Polskiej Akademii Nauk | Method of obtaining the cellulose nanocomposite with in-built carbon nanotubes and the cellulose nanocomposite with the in-built carbon nanotubes |
| KR20120065494A (en) | 2010-12-13 | 2012-06-21 | 김철웅 | Heat mat of dc-voltage using carbon-nanotube tread |
Non-Patent Citations (3)
| Title |
|---|
| AMIRI A ET AL: "One-pot, efficient functionalization of multi-walled carbon nanotubes with diamines by microwave method", APPLIED SURFACE SCIENCE, ELSEVIER, AMSTERDAM, NL, vol. 257, no. 23, 5 July 2011 (2011-07-05), pages 10261 - 10266, XP028264760, ISSN: 0169-4332, [retrieved on 20110714], DOI: 10.1016/J.APSUSC.2011.07.039 * |
| LAURENCE VAST ET AL: "Multiwalled carbon nanotubes functionalized with 7-octenyltrichlorosilane and n-octyltrichlorosilane: dispersion in Sylgard(R)184 silicone and Young's modulus", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, BO, vol. 44, no. 13, 21 April 2009 (2009-04-21), pages 3476 - 3482, XP019679823, ISSN: 1573-4803 * |
| VAST ET AL: "Preparation and electrical characterization of a silicone elastomer composite charged with multi-wall carbon nanotubes functionalized with 7-octenyltrichlorosilane", COMPOSITES SCIENCE AND TECHNOLOGY, ELSEVIER, UK, vol. 67, no. 5, 18 January 2007 (2007-01-18), pages 880 - 889, XP005835499, ISSN: 0266-3538, DOI: 10.1016/J.COMPSCITECH.2005.12.033 * |
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