CN102471050B - Carbon nanotube/metal particle complex composition and heated steering wheel using same - Google Patents
Carbon nanotube/metal particle complex composition and heated steering wheel using same Download PDFInfo
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- CN102471050B CN102471050B CN201080031626.9A CN201080031626A CN102471050B CN 102471050 B CN102471050 B CN 102471050B CN 201080031626 A CN201080031626 A CN 201080031626A CN 102471050 B CN102471050 B CN 102471050B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D1/00—Steering controls, i.e. means for initiating a change of direction of the vehicle
- B62D1/02—Steering controls, i.e. means for initiating a change of direction of the vehicle vehicle-mounted
- B62D1/04—Hand wheels
- B62D1/06—Rims, e.g. with heating means; Rim covers
- B62D1/065—Steering wheels with heating and ventilating means
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- 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
- B22F1/18—Non-metallic particles coated with metal
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- 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
- H05B3/40—Heating elements having the shape of rods or tubes
- H05B3/42—Heating elements having the shape of rods or tubes non-flexible
- H05B3/46—Heating elements having the shape of rods or tubes non-flexible heating conductor mounted on insulating base
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
-
- 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
- H05B2203/02—Heaters using heating elements having a positive temperature coefficient
-
- 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
Abstract
The present invention relates to a carbon nanotube/metal particle complex composition prepared by: a) a step of preparing a carbon nanotube solution in which carbon nanotubes are dispersed; b) a step of performing acid treatment on the carbon nanotube solution prepared in step a); c) a step of neutralizing the carbon nanotube solution prepared in step b); and d) a step of mixing the carbon nanotube solution prepared in step c) and a metal solution containing metal particles, in order to bond said metal particles to the surfaces of said carbon nanotubes. The present invention also relates to a heated steering wheel including a carbon nanotube heating coating layer formed from the composition.
Description
Technical field
The present invention relates to carbon nanotube/metal particle complex composition and comprise the heating steering wheel of the CNT heating coating being formed by this complex composition.
Background technology
In general, the steering wheel of vehicle (steering wheel) is arranged on a side leading section of the steering spindle being connected with tooth sector, the rotation amount of steering wheel passes to tooth sector turn wheel by steering spindle, in order to improve driver's the sense of holding, above-mentioned steering wheel is generally by making such as the PVC (polyvinyl chloride) of light-duty material or polyurethane.
Above-mentioned steering wheel is in the winter time in long-time situation of stopping outside, and steering wheel is cooled by the cold air of periphery, feels that hand is cold while controlling steering wheel, need to start warm-air drier and promote temperature or alleviate ice-cold sensation with the heat insulation effect of the grip of skin or cloth material.But, in the situation that using warm-air drier, driver need to wait as long for temperature and rise, and grip has the problem of heat insulation effect shortcoming, for this reason, disclose built-in heater wire parts (heater) in steering wheel, and by temperature-adjusting device, regulate the heating steering wheel of the temperature of steering wheel.
In the heating steering wheel of prior art, disclose various structures, as shown in its part illustrating in Fig. 1, form the synthetic resin part 20 that takes shape in the outside portion of core 10 with heater wire packing ring 30 parcels, as required by the structure of the above-mentioned heater wire packing ring 30 of grip 40 parcel of skin or cloth material, above-mentioned heater wire packing ring 30 is configured to, and is furnished with heater wire 31 (heater) and by thermoregulator 32, is regulated the electro-heat equipment of temperature.Above-mentioned heater wire 31 is generally by formations such as the metallic heating bodies such as nichrome wire or PTC (positive temperature coefficiency, positive temperature coefficient) ceramic heating elements.
But, in the heating steering wheel of prior art, owing to making the operation Deng Shi manufacturing process of heater wire packing ring parcel, become complicated, and hold sense (grip) (too soft) because packing ring reduces.The pattern-transferringlayer layer of timber or metal etc. is (water-soluble by transfer membrane by hydraulic rotation shifting method, and the mildness of utilizing water shifts the method for pattern on object) form, in the steering wheel that adheres to heater wire packing ring, cannot form the pattern-transferringlayer layer of timber or metal etc.In addition, have the problems such as thermoregulator that must be useful on the temperature that regulates heater wire packing ring.
And the heating steering wheel of prior art is directly contacted with the hand to tactile sensing, therefore, preferably avoid resistance value to continue to change or the material of negative electricity change in resistance, to minimize the phenomenon that temperature rises sharp or decline sharp.For this reason, can be in heating steering wheel applied for transparent CNT (CNT) as heater.
Wherein, importantly it disperses CNT, and, to reducing, on the contact resistance between CNT and CNT, there is more research.If reduce the contact resistance between CNT and CNT, when conductance is by reduction, also can use as transparency electrode material, to this, also there is prompting as described below.
In No. 10-2008-0112799, korean patent application, as the method that reduces contact resistance, its main purpose is to produce CNT-metal nanoparticles mixture, to manufacture film on plastic base.Said mixture shows as, at carbon nano tube surface adsorbing metal presoma, to reduce the overall electrical resistance of carbon nano-tube film.And, record and utilize Nano silver grain on the part surface of absorption, to grow into bunch mechanism of (Cluster) (Mechanism) by heat treatment.In the situation that the Nano carbon tube-metal nanoparticle mixture forming thus, although can reduce resistance value, Nano silver grain is difficult to be adsorbed in equably the CNT (CNT) that forms stable wall (Wall) structure, causes the inhomogeneous result of detected value at each position.
For using above-mentioned CNT as heater utilization, in the situation that use the Nano carbon tube-metal nanoparticle mixture being formed by above-mentioned adsorption method, in the time of can confirming to apply (Coating) on thering is the plastics of three dimensional tortuous (Plastic) grip surfaces, cannot bring into play uniform heat generation characteristic, and along with the continuous Open-closure (On-Off) of power supply (Power), resistance value changes.
Heating handle-bar is directly contacted with the hand to tactile sensing, therefore, should avoid resistance value to continue to change or the material of negative electricity change in resistance, to minimize the phenomenon that temperature rises sharp or decline sharp.
In the situation that CNT being disperseed individually and is coated on heating handle-bar, because high contact resistance is difficult to aim at the desired caloric value of heating handle-bar, in the situation that nano metal being disperseed individually and is coated on heating handle-bar, because low resistance coefficient causes initial heating.
The in the situation that of using carbon not using CNT, because the variation of the resistance value based on temperature is large, be not suitable for needing accurate temperature to control the heating handle-bar purposes of (Control).
Along with lasting temperature rises, resistance value will rise.The lasting rising of resistance value brings reducing of current flowing, and result can cause opening circuit, and as the method that prevents that this phenomenon from occurring, suitably uses carbon element to realize the characteristic of mutual complementation.
Summary of the invention
Technical problem
Therefore, in order addressing the above problem, to the object of the present invention is to provide a kind of manufacturing process simple, to hold sense well, can form pattern-transferringlayer layer, needn't have thermoregulator, heat transference efficiency is outstanding, prevents the heating steering wheel of thermal-arrest phenomenon.
And, the object of the present invention is to provide a kind of metal nanoparticle of pasting in carbon nanotube dispersed solution chemistry, the carbon nanotube/metal particle complex composition that makes conductance continue and be formed uniformly above, and by using this carbon nanotube/metal particle complex composition, the heating steering wheel that the resistance value of electricity does not change.
And, the object of the present invention is to provide a kind of hybrid adhesive in carbon nanotube/metal particle complex composition and make the solution of one-pack-type, it is disperseed to be coated on plastics (Plastic) grip surface of 3D structure equably, thereby by the adhesive force with plastic handles, in accurate temperature range, there is heat generation characteristic, and under the variations in temperature below 160 ℃, the heating steering wheel that resistance value does not change.
The means of dealing with problems
The invention provides a kind of carbon nanotube/metal particle complex composition, comprising: the step of a) manufacturing the carbon nanotube dispersed solution that is dispersed with CNT; B) above-mentioned steps carbon nanotube dispersed solution a) is carried out to acid-treated step; C) to above-mentioned steps b) carbon nanotube dispersed solution carry out the step of neutralisation treatment; D) carbon nanotube dispersed solution mixing above-mentioned steps c) and the metallic solution that comprises metallic, the step in carbon nano tube surface in conjunction with metallic.
The invention provides a kind of heating steering wheel, comprising: core, the rigidity of maintenance steering wheel; Synthetic resin part, is formed at the outside portion of above-mentioned core; CNT heating coating, at the lateral surface of above-mentioned synthetic resin part, coating is formed with above-mentioned carbon nanotube/metal particle complex composition; Electrode, is electrically connected on above-mentioned CNT heating coating, for guiding heating.
The effect of invention
According to heating steering wheel of the present invention, by spraying dispersion liquid, form heating coating, there is manufacturing process simple, holding of heating coating feels good, can form in the outside of heating coating the pattern-transferringlayer layer of timber or metal etc., needn't have thermoregulator, the heat transference efficiency of heating coating is outstanding, prevents the effect of thermal-arrest phenomenon.
And, a kind of metal nanoparticle of chemically pasting in carbon nanotube dispersed solution is provided, the carbon nanotube/metal particle complex composition that makes conductance continue and be formed uniformly above, and by using this carbon nanotube/metal particle complex composition, the heating steering wheel that the resistance value of electricity does not change.
And, a kind of hybrid adhesive in carbon nanotube/metal particle complex composition is provided and makes the solution of one-pack-type, it is disperseed to be coated on plastics (Plastic) grip surface of 3D structure equably, thereby by the adhesive force with plastic handles, in accurate temperature range, there is heat generation characteristic, and under the variations in temperature below 160 ℃, the heating steering wheel that resistance value does not change.
Accompanying drawing explanation
Fig. 1 means the structure chart of the heating steering wheel of prior art.
Fig. 2 means the top view of applicable heating steering wheel of the present invention.
Fig. 3 means the cutaway view along arrow A-A line in Fig. 2.
Fig. 4 means the cutaway view of heating steering wheel according to another embodiment of the present invention.
Fig. 5 means the manufacturing procedure picture of applicable heating steering wheel of the present invention.
Fig. 6 means the manufacturing flow chart of applicable heating steering wheel of the present invention.
(a) part of Fig. 7 means the particle model of common CNT heater.
(b) part of Fig. 7 means the particle model by the heater of the electric conductor formation of CNT (CNT) and silver (Ag) particle or metallic etc.
(a) part of Fig. 8 means the electrical network model of common carbon.
(b) part of Fig. 8 means the electrical network model of CNT (CNT).
Fig. 9 means the figure of the process of embodiments of the invention 1.
Figure 10 means the photo of the heating steering wheel of the solution that will apply embodiments of the invention 1 and comparative example 1～2.
Figure 11 means the photo at the finished product of the coated skin material of handle of Figure 10.
Figure 12 means the durability test result according to embodiments of the invention 1.
The explanation of Reference numeral
110: core 120: synthetic resin part
130: CNT heating coating 131: electrode
140: grip 150: transfer layer
160: external skin
The specific embodiment
Carbon nanotube/metal particle complex composition according to the present invention, comprising: the step of a) manufacturing the carbon nanotube dispersed solution that is dispersed with CNT; B) above-mentioned steps carbon nanotube dispersed solution a) is carried out to acid-treated step; C) to above-mentioned steps b) carbon nanotube dispersed solution carry out the step of neutralisation treatment; And d) carbon nanotube dispersed solution mixing above-mentioned steps c) and the metallic solution that comprises metallic, the step in carbon nano tube surface in conjunction with metallic.
Wherein, above-mentioned steps CNT a) is to be selected from MWNT (multi wall nanotube, multi-walled carbon nano-tubes), more than one nanotubes in TWNT (Thin wall nanotube; thin wall carbon nano-tube) and SWNT (single wall nanotube, SWCN).
Above-mentioned steps a) in, by above-mentioned carbon nanotube dispersed is manufactured to dispersion soln in solvent.
At above-mentioned steps b) in, add more than one acid that are selected from nitric acid, sulfuric acid, hydrochloric acid and perchloric acid and carry out acid treatment.
At above-mentioned steps c) in, add more than one aqueous solution that are selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide aqueous solution and carry out neutralisation treatment.
In general, when CNT is carried out to acid treatment, generate randomly carboxyl, simultaneously pH value decline and with acidity.Filtered use in the situation that, owing to being subject to there is countless defect (defected) in the carbon nanotube molecule structure of sour erosion, there is the feature of electric conductivity variation.In order to address the above problem, in the present invention, implement neutralisation treatment, pH is reduced to more than 6.PH preferably reaches 7 for well.
After acid treatment, even if only filtering carbon nanotube is used, also will there is micro-acid ion in periphery, therefore adding the metallic nanoparticle period of the day from 11 p.m. to 1 a.m, and it may be easily by residue acidifying.Because the mode manufacture to obtain simple metal nano particle and to be mixed in above-mentioned acid-treated CNT forms, therefore do not considering under the state of pH, when metal nanoparticle is mixed with CNT, before metal nanoparticle carries out physical absorption by Coulomb force, may be by remaining acid ion by acidifying.
Therefore, in the present invention, in order there to be chemistry ground binding metal particle in the CNT of carboxyl in importing, for metallic is not subject to the attack of acid ion, do not carry out after neutralisation treatment, cause the stabilisation of CNT and make acid ion metallic chemistry do not participate in reaction in the process of combination.
At above-mentioned steps c) in, utilize ultrasonic wave to mix above-mentioned steps b) carbon nanotube dispersed solution and be selected from more than one in sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide aqueous solution.
At above-mentioned steps d) in, in the metallic solution that comprises metallic, comprise: solvent; Be selected from four octyl group ammonium bromides (TOAB), 1,2-dichloro-benzenes (1,2-dichlorobenzene), 1-METHYLPYRROLIDONE (NMP:N-methylpyrrolidone) and N, the solution that more than one in dinethylformamide (DMF:N, N-dimethylformamide) mix with formaldehyde (formaldehyde) or acetaldehyde (acetaldehyde); And be selected from more than one the slaine in the salt of Ag, Pt, Pd, Au, Cu, Ni, Al, Ag/Cu, Ag/Ni.
Concrete example as above-mentioned slaine has AgCl, AgI, AgBr, AgNO
3, AgCN and KAg (CN)
2deng, but being not defined in this, above-mentioned slaine is more preferably dissolved in HNO
3after lysate, add a small amount of NH
3use.
At above-mentioned steps d) in, the metallic of carbon nano tube surface can be to be selected from more than one in Ag, Pt, Pd, Au, Cu, Ni, Al, Ag/Cu, Ag/Ni and Cu/Ni.And the diameter of the metallic of carbon nano tube surface is preferably 10 to 300nm.
In the present invention, also comprise: by above-mentioned steps d) Solution Dispersion in be selected from methyl ethyl ketone (MEK), 4-methyl-2 pentanone (MIBK), acetone (acetone), cyclohexanone (cyclohexanone), ketone be in solution, 2-Butoxyethyl acetate (butoxyethylacetate), BC acetate (BCA:butyl carbitol acetate), acetic acid saline solution more than one and manufacture the step of dispersion soln; And the step of mixing above-mentioned dispersion soln and binding agent.
Wherein, as binding agent, have and be selected from more than one in polyurethane resin (Poly Urethane resin), mylar (Poly ester resin) and acrylic resin (Acryl resin).
embodiment 1
By MWNT (multi wall nanotube, multi-walled carbon nano-tubes) 2mg and 100ml distilled water are put into glass beaker, utilize microjet homogenizer (Microfluidizer (M-110S)) under 15000psi pressure, to implement the dispersion of physical property, obtain CNT dispersion soln.And, with sonicator (Sonicator (ULH-700)) to mixing by mixing the ultrasonic wave that sulfuric acid and nitre aqueous acid carry out 1 hour at 3: 1.
Then, after neutralizing with the NaOH aqueous solution, be mixed in after the four octyl group ammonium bromides and toluene 10ml, acetaldehyde 1ml on the DMF aqueous solution, in aqueous solution of nitric acid, add after the AgCl of 0.1g, slowly add dense NH
3, prepare the mixed solution that comprises RX.Subsequently, the mixed solution of the above-mentioned RX of comprising is mixed in to the MWNT that comprises NaOH, the mixing of implementing 80 ℃, the 3 hours line replacement reaction (Phase Transfer Reaction) of going forward side by side, makes to separate out Ag particle combination on CNT surface.By the above-mentioned solution reacting at aluminium film (anodisc, 200nm), utilize filter to filter, be scattered in after methyl ethyl ketone solution, add binding agent (LG chemistry EXP-7) and mix, produce according to carbon nanotube/metal particle complex composition of the present invention (with reference to Fig. 9).
comparative example 1
By MWNT (multi wall nanotube, multi-walled carbon nano-tubes) 2mg and 100ml distilled water are put into glass beaker, utilize microjet homogenizer (Microfluidizer (M-110S)) under 15000psi pressure, to implement the dispersion of physical property, obtain CNT dispersion soln.Wherein, put into NMP (n-methylpyrrolidone, n-methyl pyrrolidone) 10ml, with the ultrasonic wave that sonicator (Sonicator (ULH-700)) carries out 10 hours, mix.
By it at aluminium film (anodisc, after filtering by filter 200nm), then by silver-colored precursor solution (silver nitrate 5g and butylamine 4.5ml are mixed in to toluene 60ml to be manufactured), filter, produce CNT-metal nanoparticles mixture.
It is carried out, after the heat treatment of 2 hours, being scattered in after methyl ethyl ketone solution at 120 ℃ below, add binding agent (LG chemistry EXP-7) and mix, produce CNT-metal nanoparticles mixture solution.
comparative example 2
By MWNT (multi wall nanotube, multi-walled carbon nano-tubes) 2mg puts into glass beaker with 100ml methyl ethyl ketone, utilize microjet homogenizer (Microfluidizer (M-110S)) under 15000psi pressure, to implement the dispersion of physical property, obtain after CNT dispersion soln, add binding agent (LG chemistry EXP-7) and produce solution.
experimental example 1
By the solution of embodiment 1 and comparative example 1～2 equably spraying and applying on plastic handles (Urethane) surface with 3D shape.Consider the Dereadation deformation temperature of carbamate (Urethane) handle, it is carried out after 2 hours dry below at 100 ℃, step up 3 points (Point) (with reference to Figure 10 and Figure 11) of handle and repeatedly detect 2 times with sheet resistance detector (MCP-HT450), the results are shown in table 1.
(table 1)
As mentioned above, in the situation that only using CNT individually (comparative example 2), show more than 106 high surface resistance values, be unfavorable for realizing as heating handle-bar, the in the situation that of CNT-metal nanoparticles mixture (comparative example 1), can confirm because the degree of scatter of Ag is inhomogeneous, floating of corresponding value is larger with detecting.That is,, in order to use as exothermic material, only with CNT-metal nanoparticle synthetic state, utilize, just can obtain surperficial impartial resistance value.
experimental example 2
By (with reference to Figure 11) after forming finished product according to the coated skin material of the handle of embodiments of the invention 1 making, utilize IT6720 power supply (Power Supply) access DC 12 volts (Volt) to implement temperature rising test.Although form finished product in the coated skin material of comparative example 1, and utilize IT6720 power supply (Power Supply) access DC12 volt (Volt), after temperature rises when through 2 minutes (min), open circuit and fail running.And, in comparative example 2, under DC 12 volts (volt), do not flow and have electric current.
experimental example 3
In the coated skin material of the handle by making according to embodiments of the invention 1, form after finished product, in the cryogenic chamber of-20 ℃, place 6 hours (hr) and carry out cooling.Subsequently, product is taken out to the normal temperature of 25 ℃, utilized IT6720 power supply (Power Supply) access DC12 volt (Volt), by thermoelectric couple (thermocouple), detected the variations in temperature of grip surface.As shown in the durability test result of Figure 12, when via 1 minute, rise to more than 25 ℃ temperature, from grip surface, start to feel warm, at the time point through 5 minutes, reach approximately 35 ℃..Meet 15 minutes and with interior needs, reached the heating handle standard (ES56110-05) of 40 ℃, removing for keeping the result of the long term stability tests under the state of PID controller of certain temperature of handle, in the situation that keeping 50～53 ℃, the not distortion of breaking out of fire or skin material surface.
As mentioned above, in the present invention, metal nanoparticle is establishment equably in CNT, in order to prevent that metal nanoparticle from spinning off when manufacturing dispersion soln, can produce the carbon nanotube/metal particle complex composition that utilizes displacement reaction.
When producing above-mentioned carbon nanotube/metal particle complex composition, in the characteristic moving at the total integrated structure of the carbon-to-carbon of the inherent characteristic as CNT and the electric current based on this, intrinsic resistance will disappear, can access the current density of 1000 times of degree of copper cash, and by the charge transfer passage of the metal nanoparticle of being combined with CNT, can obtain reducing the characteristic of contact resistance simultaneously.
By the present invention, can access the characteristic that metallic is organized into each particle of CNT equably, and because being reinforced the property learned, metal nanoparticle is incorporated into CNT, in the coating solution of hybrid adhesive, there is not the segregation phenomenon between CNT and metal nanoparticle.And, owing to being coated on equably the carbon nanotube/metal particle synthetic of the plastic handles shape of 3D, bondd by force (Binding), prevent from along with the process of time, producing negative resistance, or metal nanoparticle is separated and cause contact resistance.Compared with merely, in order to reduce conductance, can in the heating claimed range of required heating handle-bar, necessarily keep equably again.
In addition, the heating steering wheel according to the present invention, comprising: core, keeps the rigidity of steering wheel; Synthetic resin part, is formed at the outside portion of above-mentioned core; CNT heating coating, at the lateral surface of above-mentioned synthetic resin part, coating is formed with carbon nanotube/metal particle complex composition of the present invention; Electrode, is electrically connected on above-mentioned CNT heating coating guiding heating.
CNT heating coating of the present invention, is characterized in that, by CNT particle and metallic chemistry the carbon nanotube/metal particle complex composition of combination apply.
Outside at above-mentioned CNT heating coating is enclosed with grip.
Above-mentioned grip is by a certain formation being selected from skin, cloth material and PU (polyurethane).
In the outside of above-mentioned CNT heating coating, be formed with the transfer layer based on hydraulic rotation shifting method.
In above-mentioned transfer layer outside, be formed with external skin.
Below, with reference to accompanying drawing, embodiments of the invention are described in detail.
Fig. 2 means the top view (removing the state of grip in spoke) of applicable heating steering wheel of the present invention, and Fig. 3 means in Fig. 2 the cutaway view along arrow A-A line.As shown in the figure, the structure of applicable heating steering wheel 100 of the present invention is as follows: the outside portion at the core 110 consisting of steel or light-alloy forms synthetic resin part 120, lateral surface at above-mentioned synthetic resin part 120 forms the CNT heating coating 130 that coating is formed with carbon nanotube/metal particle complex composition, in the outside of above-mentioned CNT heating coating 130, is enclosed with grip 140.
Above-mentioned core 110 consists of wheel rim 111 and spoke 112, and forms the multiple profile morphologies such as circular section, ㄈ section or H section.
Above-mentioned synthetic resin part 120 is used PU (polyurethane), EPS (expanded polystyrene) or EPP (expansioning polypropylene) as raw material and foamed (Foam:expanded plastic) and forming, or uses the synthetic resin such as ABS ejection formation and form.
Above-mentioned CNT heating coating 130 is carbon nanotube/metal particle complex composition to be ejected into above-mentioned synthetic resin part 120 and the layer of coating, particularly preferably, spray and the coating carbon nanotube/metal particle complex composition that chemistry ground forms in conjunction with metallics such as silver (Ag) particles in above-mentioned CNT (CNT).
The coating quality of the unit are of above-mentioned CNT heating coating 130 is preferably 3～15g/m
2.
Form the electrode 131 that is electrically connected to and guides heating with above-mentioned CNT heating coating 130.In above-mentioned electrode 131, also can connect thermoregulator 132 as required, but because can realizing temperature, the inherent characteristic self having by CNT (CNT) (quantity of electric charge control) controls, and also can be without other thermoregulator 132 is set.In said temperature adjuster 132, connect power connector 133.
CNT (CNT) is to have number to hundreds of micron diameters of (μ m) and the anisotropic former material of length.In CNT, a carbon element atom is combined with 3 other carbon element atoms and forms hexagonal honeycomb pattern.On smooth paper, draw after above-mentioned honeycomb pattern when circle is rolled paper, will form nano tube structure.That is, nanotube have with the pipe of hollow or with cylinder identical apperance.The reason that is referred to as nanotube is, it is less that the diameter of this pipe is generally 1 nanometer (1/1000000000th meter) degree.When drawing honeycomb pattern circle rolling on paper, will form nanotube, now, according to which kind of angle to roll paper according to, CNT is by the electric conductor (Armchair, armchair) becoming as metal, or become semiconductor (ZigZag structure, in a zigzag mechanism).
Above-mentioned grip 140 is by skin or cloth material or the ornament materials of PU (polyurethane) formation, above-mentioned skin or cloth material parcel CNT heating coating 130 also carry out combination by modes such as tailors, above-mentioned PU (polyurethane) carries out combination by modes such as coatings, to wrap up CNT heating coating 130).
Due to open in No. 0749886 grade of Korean Patent mandate for utilizing the general known technology of heater of CNT, for the detailed description of the formation of CNT heating coating, will omit.
Form as mentioned above according in heating steering wheel of the present invention, as shown in the flow chart of the process chart of Fig. 5 and Fig. 6, in the outside of core 110, make synthetic resin part 120 be shaped (S1).Subsequently, in the outside of above-mentioned synthetic resin part 120, spray as metallic carbon nano tube surface chemistry the dispersion liquid (Lq) of carbon nanotube/metal particle complex composition of combination, form CNT heating coating 130 (S2).In above-mentioned CNT heating coating 130, form electrode 131 (S3), after set temperature adjuster 132, by the outside parcel at above-mentioned CNT heating coating 130, in conjunction with grip 140, complete as required.
On the other hand, as used in Fig. 4 as shown in section, as another embodiment of the present invention, in the outside of core 110, form synthetic resin part 120, at the lateral surface formation CNT heating coating 130 of above-mentioned synthetic resin part 120.In the outside of above-mentioned CNT heating coating 130, form the pattern-transferringlayer layer 150 of timber or metal etc., in the outside of above-mentioned transfer layer 150, append and form external skin 160.The pattern-transferringlayer layer 150 of above-mentioned timber or metal etc. forms by known hydraulic rotation shifting method, and said external coating 160 applies by known various material and several different methods.
In the heating steering wheel in prior art in applicable heater wire heater, because the contact-making surface of calandria and heater wire belongs to contacting of locality, therefore reduce the heat transference efficiency for heated object, and it is slow to reach heating-up time of maximum temperature.But, in heating steering wheel of the present invention in applicable CNT heater, because the contact-making surface of heated object and heating layer belongs to comprehensive contacting, therefore outstanding for the heat transference efficiency of heated object, and it is fast to reach heating-up time of maximum temperature.
In addition, because (a) part of Fig. 7 and the normal carbon heater (fluorenes, agraphitic carbon, graphite) shown in (a) part of Fig. 8 have the temperature resistance coefficient as the moon (-) of the characteristic of carbon, use repeatedly causes that resistance value reduces and is difficult to guarantee reliability.And, because the heater of metallicity material of the prior art has the temperature resistance coefficient of sun (+), so use repeatedly causes that resistance value rises and is difficult to guarantee reliability, but in the CNT (CNT) shown in (b) part of Fig. 7 (b) part and Fig. 8, because it is linear structure rather than spherical on molecular structure, the part opening circuit less and more stable in resistance value.Particularly, by metallic carbon nano tube surface chemistry the heater that forms of the carbon nanotube/metal particle complex composition of combination will retain PTC (positive temperaturecoefficiency, positive temperature coefficient) character, therefore temperature resistance coefficient is almost bordering on 0, and use does not repeatedly have the variation of resistance value yet and easily guarantees reliability.This can not be merely carrys out revisal by having the carbon of temperature resistance coefficient of the moon (-) and the mixing of metal with the temperature resistance coefficient of sun (+), but by utilize the combination of electric conductor of the metallic etc. of chemistry combination on CNT (CNT) surface, realize characteristic as above.
In addition,, as shown in power utilization network model in (a) part of Fig. 8, common carbon only has carbon to contact and could switch on carbon particle in binding agent, therefore, when applicable coating, have the possibility that carbon particle converges in privileged site, thereby generate more heat at privileged site.Contrast, as shown in power utilization network model in (b) part of Fig. 8, in CNT (CNT), has standoff distance to a certain degree even do not paste between particle therewith, also will realize the electric network phenomenon of energising.Thus, only use with the content of common carbon and compare content seldom, also can realize equal above performance, get rid of the possibility that CNT (CNT) particle converges at privileged site, possess impartial heating and distribute, and there is no thermal-arrest phenomenon.
In heating steering wheel of the present invention as above, the operation of heater wire packing ring will be adhered in the heating steering wheel of prior art, instead of the operation of spraying the electric conductor of CNT (CNT) and metallic etc., compared with prior art save significantly manufacturing expense.And, can form the pattern-transferringlayer layer of timber or metal etc., keep the good sense of holding, realize shape and resistive arrangement freely, in the time of compared with the prior art, can realize significant energy saving.In addition, upper in the characteristic (quantity of electric charge control) of CNT (CNT) material, needn't there is other thermoregulator.
Claims (13)
1. a heating steering wheel, is characterized in that, comprising:
Core, the rigidity of maintenance steering wheel;
Synthetic resin part, is formed at the outside portion of described core;
CNT heating coating, at the lateral surface of described synthetic resin part, coating is formed with carbon nanotube/metal particle complex composition;
Electrode, is electrically connected on described CNT heating coating, for guiding heating,
The coating quality of the unit are of wherein said CNT heating coating is 3～15g/m
2,
Wherein said carbon nanotube/metal particle complex composition is prepared by the method comprising the following steps:
A) manufacture the step of the carbon nanotube dispersed solution that is dispersed with CNT;
B) described step carbon nanotube dispersed solution a) is carried out to acid-treated step;
C) to described step b) carbon nanotube dispersed solution carry out the step of neutralisation treatment;
D) mix described step c) carbon nanotube dispersed solution and the metallic solution that comprises metallic, the step in carbon nano tube surface in conjunction with metallic, and
By described steps d) Solution Dispersion in acetic ester solution and manufacture the step of dispersion soln; And
The step of mixing described dispersion soln and binding agent.
2. heating steering wheel according to claim 1, is characterized in that, described step CNT a) is more than one the nanotube being selected from multi-walled carbon nano-tubes, thin wall carbon nano-tube and SWCN.
3. heating steering wheel according to claim 1, is characterized in that, described step a) in, by described carbon nanotube dispersed is manufactured to dispersion soln in solvent.
4. heating steering wheel according to claim 1, is characterized in that, at described step b) in, add to be selected from more than one in nitric acid, sulfuric acid, hydrochloric acid and perchloric acid and to carry out acid treatment.
5. heating steering wheel according to claim 1, is characterized in that, at described step c) in, add to be selected from more than one in sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide aqueous solution and to carry out neutralisation treatment.
6. heating steering wheel according to claim 5, it is characterized in that, at described step c) in, utilize ultrasonic wave to mix described step b) carbon nanotube dispersed solution and be selected from more than one aqueous solution in sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide aqueous solution.
7. heating steering wheel according to claim 1, it is characterized in that, in described steps d) in, the metallic solution that comprises metallic passes through solvent, be selected from four octyl group ammonium bromides, 1, the solution that a kind of and formaldehyde in 2-dichloro-benzenes, 1-METHYLPYRROLIDONE and DMF or acetaldehyde mix, and be selected from more than one slaine in the salt of Ag, Pt, Pd, Au, Cu, Ni, Al, Ag/Cu, Ag/Ni and mix to manufacture and form.
8. heating steering wheel according to claim 1, is characterized in that, in described steps d) in, the metallic of carbon nano tube surface is more than one metal ions that are selected from Ag, Pt, Pd, Au, Cu, Ni, A1, Ag/Cu, Ag/Ni and Cu/Ni.
9. heating steering wheel according to claim 1, is characterized in that, described acetic ester solution comprises and is selected from more than one in 2-Butoxyethyl acetate and BC acetate.
10. according to the heating steering wheel described in any one in claim 1 to 9, it is characterized in that, in the outside of described CNT heating coating, be enclosed with grip.
11. heating steering wheels according to claim 10, is characterized in that, described grip forms by being selected from a kind of in skin, cloth and polyurethane.
12. according to the heating steering wheel described in any one in claim 1 to 9, it is characterized in that, in the outside of described CNT heating coating, is formed with the transfer layer based on hydraulic rotation shifting method.
13. heating steering wheels according to claim 12, is characterized in that, in described transfer layer outside, are formed with external skin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2009-0077258 | 2009-08-20 | ||
| KR1020090077258A KR101116472B1 (en) | 2009-02-06 | 2009-08-20 | carbon nanotube-metal particle complex composition and steering wheel with heating element using the same |
| PCT/KR2010/005041 WO2011021794A2 (en) | 2009-08-20 | 2010-07-30 | Carbon nanotube/metal particle complex composition and heated steering wheel using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102471050A CN102471050A (en) | 2012-05-23 |
| CN102471050B true CN102471050B (en) | 2014-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080031626.9A Expired - Fee Related CN102471050B (en) | 2009-08-20 | 2010-07-30 | Carbon nanotube/metal particle complex composition and heated steering wheel using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5603939B2 (en) |
| CN (1) | CN102471050B (en) |
| DE (1) | DE112010003312T8 (en) |
| WO (1) | WO2011021794A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012214752B4 (en) | 2012-08-20 | 2014-09-25 | Takata AG | vehicle steering wheel |
| KR20140105640A (en) * | 2013-02-22 | 2014-09-02 | (주)엘지하우시스 | Thermal mat for car by using radiant heat |
| KR101447478B1 (en) | 2013-07-12 | 2014-10-06 | (주)바이오니아 | Ceramic paste using CNT or CNT-metal composition and conductive film including the same |
| DE102015206662B3 (en) * | 2015-04-14 | 2016-07-14 | Takata AG | steering wheel assembly |
| JP2019179726A (en) * | 2018-03-30 | 2019-10-17 | 古河電気工業株式会社 | heater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002202591A (en) * | 2000-12-28 | 2002-07-19 | Jsr Corp | Electrically conductive pattern forming method |
| KR20040106947A (en) * | 2003-06-05 | 2004-12-20 | 삼성전자주식회사 | Method for preparing a Conductive Film and a Pattern using Metallic Nano particle and Carbon Nanotube |
| KR20060005316A (en) * | 2005-12-27 | 2006-01-17 | 홍성태 | Vehicle handle thermostat |
| CN2763154Y (en) * | 2004-10-11 | 2006-03-08 | 万金林 | Nanometer rare-magnetism anti-fatigue automobile steering wheel and its cover |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2953996B2 (en) * | 1995-05-31 | 1999-09-27 | 日本電気株式会社 | Metal-coated carbon nanotube and method for producing the same |
| US6727467B1 (en) * | 2003-01-31 | 2004-04-27 | W.E.T. Automotive Systems Ag | Heated handle and method of forming same |
| KR100749886B1 (en) * | 2006-02-03 | 2007-08-21 | (주) 나노텍 | Heating element using Carbon Nano tube |
| JP2008133178A (en) * | 2006-10-25 | 2008-06-12 | Kuraray Co Ltd | Method for manufacturing carbon nanotube |
| KR100924766B1 (en) | 2007-06-22 | 2009-11-05 | 삼성전자주식회사 | Carbon nano-tubeCNT thin film comprising a metal nano-particle, and a manufacturing method thereof |
-
2010
- 2010-07-30 CN CN201080031626.9A patent/CN102471050B/en not_active Expired - Fee Related
- 2010-07-30 DE DE112010003312T patent/DE112010003312T8/en not_active Expired - Fee Related
- 2010-07-30 WO PCT/KR2010/005041 patent/WO2011021794A2/en active Application Filing
- 2010-07-30 JP JP2012524632A patent/JP5603939B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002202591A (en) * | 2000-12-28 | 2002-07-19 | Jsr Corp | Electrically conductive pattern forming method |
| KR20040106947A (en) * | 2003-06-05 | 2004-12-20 | 삼성전자주식회사 | Method for preparing a Conductive Film and a Pattern using Metallic Nano particle and Carbon Nanotube |
| CN2763154Y (en) * | 2004-10-11 | 2006-03-08 | 万金林 | Nanometer rare-magnetism anti-fatigue automobile steering wheel and its cover |
| KR20060005316A (en) * | 2005-12-27 | 2006-01-17 | 홍성태 | Vehicle handle thermostat |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112010003312T5 (en) | 2012-06-28 |
| WO2011021794A3 (en) | 2011-06-30 |
| JP5603939B2 (en) | 2014-10-08 |
| WO2011021794A2 (en) | 2011-02-24 |
| CN102471050A (en) | 2012-05-23 |
| JP2013501703A (en) | 2013-01-17 |
| DE112010003312T8 (en) | 2012-11-29 |
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