CN102471050A - 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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- CN102471050A CN102471050A CN2010800316269A CN201080031626A CN102471050A CN 102471050 A CN102471050 A CN 102471050A CN 2010800316269 A CN2010800316269 A CN 2010800316269A CN 201080031626 A CN201080031626 A CN 201080031626A CN 102471050 A CN102471050 A CN 102471050A
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- steering wheel
- complex composition
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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
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- 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
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- 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
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- 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
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- 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 Nano carbon tube-metal particle complex composition and comprise the heating steering wheel of the CNT heating coating that forms by this complex composition.
Background technology
In general; The steering wheel of vehicle (steering wheel) is installed in a side leading section of the steering spindle that is connected with tooth sector; The rotation amount of steering wheel passes to tooth sector and turn wheel through 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.
Under the long-time in the winter time situation of stopping outside of above-mentioned steering wheel, steering wheel is cooled by the cold air of periphery, feels when controlling steering wheel that hand is cold, needs to start warm-air drier and promotes temperature or alleviate ice-cold sensation with the heat insulation effect of the grip of skin or cloth material.But under the situation of using warm-air drier, the driver needs the wait as long for temperature to 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 regulate the heating steering wheel of the temperature of steering wheel through temperature-adjusting device.
Disclose multiple structure in the heating steering wheel of prior art; Shown in its part that illustrates among Fig. 1; Constitute the synthetic resin part 20 that takes shape in the outside portion of core 10 with heater wire packing ring 30 parcels; With the structure of the above-mentioned heater wire packing ring 30 of the grip of skin or cloth material 40 parcels, above-mentioned heater wire packing ring 30 constitutes as required, is furnished with heater wire 31 (heater) and regulates the electro-heat equipment of temperature by thermoregulator 32.Above-mentioned heater wire 31 is generally by formations such as 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,, and hold sense (grip) (too soft) owing to packing ring reduces because the operation of making heater wire packing ring and parcel etc. make manufacturing process become complicated.The pattern-transferringlayer layer of timber or metal etc. is (water-soluble with transfer membrane through the hydraulic pressure transfer method; And utilize the soft property of water on object, to shift method of patterning) form, in the steering wheel that adheres to the heater wire packing ring, can't 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 of regulating the heater wire packing ring.
And the heating steering wheel of prior art directly is contacted with the hand to tactile sensing, therefore, preferably avoids resistance value to continue to change or the material of negative electricity change in resistance, so that minimize the phenomenon that temperature rises sharp or descend sharp.For this reason, can the heating steering wheel in applied for transparent CNT (CNT) as heater.
Wherein, CNT is its dispersion importantly, and, to reducing more research is arranged on the contact resistance between CNT and the CNT.If reduce the contact resistance between CNT and the CNT, when then conductance is with reduction, also can use as the transparency electrode material, following described prompting also arranged this.
In korean patent application 10-2008-0112799 number, as the method that reduces contact resistance, its main purpose is to produce the CNT-metal nanoparticles mixture, on plastic base, to make film.Said mixture shows as, in carbon nano tube surface absorption metal precursor, to reduce the overall electrical resistance of carbon nano-tube film.And, record and utilize Nano silver grain to grow into bunch mechanism of (Cluster) (Mechanism) on a part of surface of absorption through heat treatment.Under the situation of the Nano carbon tube-metal nanoparticle mixture that forms thus; Though can reduce resistance value; Nano silver grain is difficult to be adsorbed in equably the CNT (CNT) that constitutes stable wall (Wall) structure, causes the uneven result of detected value at each position.
For with above-mentioned CNT as the heater utilization; Under the situation of using the Nano carbon tube-metal nanoparticle mixture that forms by above-mentioned adsorption method; In the time of can confirming on having the plastics of three dimensional tortuous (Plastic) grip surfaces, to apply (Coating); Can't bring into play uniform heat generation characteristic, and along with the continuous Open-closure (On-Off) of power supply (Power), resistance value changes.
The heating handle directly is 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, so that minimize the phenomenon that temperature rises sharp or descend sharp.
CNT is being disperseed individually and be coated under the situation on the heating handle; Owing to high contact resistance is difficult to aim at the desired caloric value of heating handle; Nano metal is being disperseed individually and be coated under the situation on the heating handle, owing to low resistance coefficient causes initial heating.
Do not use under the situation of carbon not using CNT, because big, needing to be not suitable for the heating handle purposes of accurate temperature control (Control) based on the variation of the resistance value of temperature.
Along with the temperature that continues rises, resistance value will rise.The lasting rising of resistance value brings mobile the reducing of electric current, and the result can cause opening circuit, and as the method that prevents that this phenomenon from taking place, suitably uses carbon element to realize complementary each other characteristic.
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, thermoregulator needn't be arranged, 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 in the CNT dispersion soln, pasting to chemical; The Nano carbon tube-metal particle complex composition that makes conductance continue and be formed uniformly in front; And through using this Nano carbon tube-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 Nano carbon tube-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, thus through with the adhesive force of plastic handles, in the temperature range of precision, have 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 present invention provides a kind of Nano carbon tube-metal particle complex composition, comprising: the step of a) making the CNT dispersion soln that is dispersed with CNT; B) above-mentioned steps CNT dispersion soln a) is carried out acid-treated step; C) to above-mentioned steps b) the CNT dispersion soln carry out the step of neutralisation treatment; D) mixing above-mentioned steps c) CNT dispersion soln and the metallic solution that comprises metallic are in the step of carbon nano tube surface combination metallic.
The present 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 Nano carbon tube-metal particle complex composition; Electrode is electrically connected on above-mentioned CNT heating coating, is used for the guiding heating.
The effect of invention
According to heating steering wheel of the present invention; Form the heating coating through spraying dispersion liquid, it is simple to have a manufacturing process, the heating coating to hold sense good; Can form the pattern-transferringlayer layer of timber or metal etc. in the outside of heating coating; Thermoregulator needn't be arranged, and the heat transference efficiency of heating coating is outstanding, prevents the effect of thermal-arrest phenomenon.
And; A kind of metal nanoparticle of in the CNT dispersion soln, chemically pasting is provided; The Nano carbon tube-metal particle complex composition that makes conductance continue and be formed uniformly in front; And through using this Nano carbon tube-metal particle complex composition, the heating steering wheel that the resistance value of electricity does not change.
And; A kind of hybrid adhesive in Nano carbon tube-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, thus through with the adhesive force of plastic handles, in the temperature range of precision, have heat generation characteristic; And under the variations in temperature below 160 ℃, the heating steering wheel that resistance value does not change.
Description of drawings
Fig. 1 is the structure chart of the heating steering wheel of expression prior art.
Fig. 2 is the vertical view that expression is suitable for heating steering wheel of the present invention.
Fig. 3 is the cutaway view along arrow A-A line in the presentation graphs 2.
Fig. 4 is a cutaway view of representing heating steering wheel according to another embodiment of the present invention.
Fig. 5 is the manufacturing procedure picture that expression is suitable for heating steering wheel of the present invention.
Fig. 6 is the manufacturing flow chart that expression is suitable for heating steering wheel of the present invention.
(a) part of Fig. 7 is the particle model of the common CNT heater of expression.
(b) part of Fig. 7 is the particle model of expression by the heater of the electric conductor formation of CNT (CNT) and silver (Ag) particle or metallic etc.
(a) part of Fig. 8 is the electrical network model of the common carbon of expression.
(b) part of Fig. 8 is the electrical network model of expression CNT (CNT).
Fig. 9 is the figure of the process of expression embodiments of the invention 1.
Figure 10 is the photo of heating steering wheel of indicating to apply the solution of embodiments of the invention 1 and comparative example 1～2.
Figure 11 is the photo that the handle that is illustrated in Figure 10 coats the finished product of skin material.
Figure 12 is the durability test result of expression 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
Nano carbon tube-metal particle complex composition in according to the present invention comprises: the step of a) making the CNT dispersion soln that is dispersed with CNT; B) above-mentioned steps CNT dispersion soln a) is carried out acid-treated step; C) to above-mentioned steps b) the CNT dispersion soln carry out the step of neutralisation treatment; And d) mixing above-mentioned steps c) CNT dispersion soln and the metallic solution that comprises metallic are in the step of carbon nano tube surface combination 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 among TWNT (Thin wall nanotube, thin wall carbon nano-tube) and the SWNT (single wall nanotube, SWCN).
Above-mentioned steps a) in, make dispersion soln through above-mentioned CNT is scattered in solvent.
At above-mentioned steps b) in, add more than one acid that are selected from nitric acid, sulfuric acid, hydrochloric acid and the 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 the ammonium hydroxide aqueous solution and carry out neutralisation treatment.
In general, when CNT is carried out acid treatment, generate carboxyl randomly, the pH value descends and has acidity simultaneously.In that it is filtered under the situation about using, there is countless defective (defected) on the carbon nanotube molecule structure owing to the erosion that receives acid, have the characteristic of electric conductivity variation.In order to address the above problem, implement neutralisation treatment among the present invention, pH is reduced to more than 6.PH preferably reaches 7 for well.
After acid treatment, even only filtering carbon nanotube uses, also will there be the acid ion of trace in periphery, and therefore when adding metal nanoparticle, it may be easily by the residue acidifying.Because the mode manufacturing to obtain the simple metal nano particle and to be mixed in above-mentioned acid-treated CNT forms; Therefore under the state of not considering pH; When metal nanoparticle is mixed with CNT; Before metal nanoparticle carries out physical absorption through the Coulomb force, may be by remaining acid ion by acidifying.
Therefore; In the present invention; For chemical ground binding metal particle in the CNT that carboxyl is arranged in importing;, do not cause the stabilisation of CNT and make acid ion in the process that metallic chemical ground combines, not participate in reaction after carrying out neutralisation treatment for metallic does not receive the attack of acid ion.
At above-mentioned steps c) in, utilize ultrasonic wave to mix above-mentioned steps b) the CNT dispersion soln be selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and the ammonium hydroxide aqueous solution more than one.
At above-mentioned steps d) in, comprise in the metallic solution of metallic and comprise: solvent; Be selected from four octyl group ammonium bromides (TOAB), 1; 2-dichloro-benzenes (1; 2-dichlorobenzene), N-methyl pyrrolidone (NMP:N-methylpyrrolidone) and N; Dinethylformamide (DMF:N, more than one solution that mix with formaldehyde (formaldehyde) or acetaldehyde (acetaldehyde) in N-dimethylformamide); 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 be not to be defined in this, above-mentioned slaine more preferably is dissolved in HNO
3Behind the lysate, add little amount of N H
3Use.
At above-mentioned steps d) in, the metallic of carbon nano tube surface can be to be selected among Ag, Pt, Pd, Au, Cu, Ni, Al, Ag/Cu, Ag/Ni and the Cu/Ni more than one.And the diameter of the metallic of carbon nano tube surface is preferably 10 to 300nm.
Also comprise among the present invention: with above-mentioned steps d) solution be scattered in be selected from methyl ethyl ketone (MEK), 4-methyl-2 pentanone (MIBK), acetone (acetone), cyclohexanone (cyclohexanone), ketone be in solution, 2-Butoxyethyl acetate (butoxyethyl acetate), BC acetate (BCA:butyl carbitol acetate), the acetic acid saline solution more than one and make the step of dispersion soln; And the step of mixing above-mentioned dispersion soln and binding agent.
Wherein, have as binding agent and be selected from polyurethane resin (Poly Urethane resin), mylar (Poly ester resin) and the acrylic resin (Acryl resin) more than one.
With 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 the CNT dispersion soln.And, the ultrasonic wave that was undertaken 1 hour by the aqueous solution that mixes sulfuric acid and nitric acid at 3: 1 is mixed with sonicator (Sonicator (ULH-700)).
Then, after neutralizing with the NaOH aqueous solution, be mixed in four octyl group ammonium bromides and toluene 10ml on the DMF aqueous solution, acetaldehyde 1ml after, in aqueous solution of nitric acid, add the AgCl of 0.1g after, slowly add dense NH
3, preparation comprises the mixed solution of RX.Subsequently, the mixed solution of the above-mentioned RX of comprising is mixed in 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 and separates out the Ag particle on the CNT surface and combine.With the above-mentioned solution that reacts at aluminium film (anodisc; Utilize filter to filter 200nm); After being scattered in methyl ethyl ketone solution, adding binding agent (LG chemistry EXP-7) and mix, produce according to Nano carbon tube-metal particle complex composition of the present invention (with reference to Fig. 9).
Comparative example 1
With 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 the CNT dispersion soln.Wherein, put into NMP (n-methylpyrrolidone, n-methyl pyrrolidone) 10ml, the ultrasonic wave that carried out 10 hours with sonicator (Sonicator (ULH-700)) mixes.
(anodisc after filtering through filter in 200nm), then filters through silver-colored precursor solution (silver nitrate 5g and butylamine 4.5ml are mixed in toluene 60ml to be made), produces the CNT-metal nanoparticles mixture at the aluminium film with it.
With it after carrying out 2 hours heat treatment below 120 ℃, it is scattered in methyl ethyl ketone solution after, add binding agent (LG chemistry EXP-7) and mix, produce CNT-metal nanoparticles mixture solution.
Comparative example 2
With MWNT (multi wall nanotube; Multi-walled carbon nano-tubes) 2mg puts into glass beaker with the 100ml methyl ethyl ketone; Utilize microjet homogenizer (Microfluidizer (M-110S)) under 15000psi pressure, to implement the dispersion of physical property; After obtaining the CNT dispersion soln, add binding agent (LG chemistry EXP-7) and produce solution.
Experimental example 1
With the solution of embodiment 1 and comparative example 1～2 equably spraying and applying on the plastic handles with 3D shape (Urethane) surface.Consider the Dereadation deformation temperature of carbamate (Urethane) handle; With it after carrying out 2 hours drying below 100 ℃; 3 points (Point) (with reference to Figure 10 and Figure 11) of stepping up handle also detect 2 times with sheet resistance detector (MCP-HT450) repeatedly, and its result is illustrated in the table 1.
(table 1)
As stated; Under the situation of only using CNT individually (comparative example 2); Show the high face resistance value more than 106, be unfavorable for realizing, under the situation of CNT-metal nanoparticles mixture (comparative example 1) as the heating handle; Can confirm that because the degree of scatter of Ag is inhomogeneous, floating of corresponding value is bigger with detecting.That is,, only utilize, just can obtain the resistance value of the equalization on surface with CNT-metal nanoparticle synthetic state in order to use as exothermic material.
Experimental example 2
After coating skin material formation finished product (with reference to Figure 11), utilize IT6720 power supply (Power Supply) to insert DC 12 volts (Volt) and implement temperature rising test through handle according to embodiments of the invention 1 making.Form finished product though coat the skin material, and utilize IT6720 power supply (Power Supply) to insert DC12 volt (Volt), after temperature rises through 2 minutes (min) time, open circuit and fail running at comparative example 1.And in comparative example 2, under DC 12 volts (volt), flowing has electric current.
Experimental example 3
After coating skin material formation finished product, in-20 ℃ cryogenic chamber, place 6 hours (hr) and cool off through the handle of making according to embodiments of the invention 1.Subsequently, product is taken out 25 ℃ normal temperature, utilize IT6720 power supply (Power Supply) to insert DC12 volt (Volt), detect the variations in temperature of grip surface by thermoelectric couple (thermocouple).Shown in the durability test result of Figure 12, via 1 minute the time, rise to the temperature more than 25 ℃, begin to feel warm from grip surface, reach about 35 ℃ at time point through 5 minutes..Satisfied 40 ℃ the heating handle standard (ES56110-05) that reached with interior needs in 15 minutes; The result who is used to keep the long term stability tests under the state of PID controller of certain temperature of handle in removal; Under the situation of 50～53 ℃ of maintenances, the not distortion of breaking out of fire or skin material surface.
As stated, in the present invention, metal nanoparticle is establishment equably in CNT, in order when making dispersion soln, to prevent that metal nanoparticle from spinning off, can produce the Nano carbon tube-metal particle complex composition that utilizes displacement reaction.
When producing above-mentioned Nano carbon tube-metal particle complex composition; On as total integrated structure of the carbon-to-carbon of the inherent characteristic of CNT and the characteristic that moves based on this electric current; Intrinsic resistance will disappear; The current density of 1000 times of degree of copper cash can be accessed, and, the characteristic of contact resistance can be obtained reducing simultaneously by the charge transfer passage of the metal nanoparticle that combines with CNT.
Can access the characteristic that metallic is organized into each particle of CNT equably through the present invention; And, metal nanoparticle is incorporated into CNT because being reinforced the property learned; In the coating solution of hybrid adhesive, the segregation phenomenon between CNT and the metal nanoparticle does not take place.And, because the Nano carbon tube-metal particle synthetic that is coated on the plastic handles shape of 3D equably bondd by force (Binding), prevent to produce negative resistance, or metal nanoparticle separates and causes contact resistance along with the process of time., can in the heating claimed range of required heating handle, necessarily keep equably again in order to reduce conductance compared with merely.
In addition, the heating steering wheel in according to the present invention comprises: 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 Nano carbon tube-metal particle complex composition of the present invention; Electrode is electrically connected on above-mentioned CNT heating coating and guiding heating.
CNT heating coating of the present invention is characterized in that the Nano carbon tube-metal particle complex composition that is combined by CNT particle and metallic chemical ground applies.
The outside in above-mentioned CNT heating coating is enclosed with grip.
Above-mentioned grip is by a certain formation that is selected among skin, cloth material and the PU (polyurethane).
The outside in above-mentioned CNT heating coating is formed with the transfer layer based on the hydraulic pressure transfer method.
Be formed with external skin in the above-mentioned transfer layer outside.
Below, with reference to accompanying drawing embodiments of the invention are carried out detailed explanation.
Fig. 2 is the vertical view (removing the state of grip in the spoke) that expression is suitable for heating steering wheel of the present invention, and Fig. 3 is along the cutaway view of arrow A-A line in the presentation graphs 2.As shown in the figure; The structure that is suitable for heating steering wheel 100 of the present invention is following: form synthetic resin part 120 in the outside portion of the core that is made up of steel or light-alloy 110; Lateral surface at above-mentioned synthetic resin part 120 forms the CNT heating coating 130 that coating is formed with Nano carbon tube-metal particle complex composition, is enclosed with grip 140 in the outside of above-mentioned CNT heating coating 130.
Above-mentioned core 110 is made up of wheel rim 111 and spoke 112, and constitutes multiple profile morphologies such as circular section, ㄈ section or H section.
Above-mentioned synthetic resin part 120 uses PU (polyurethane), EPS (expanded polystyrene) or EPP (expansioning polypropylene) and foamed (Foam:expanded plastic) and forming as raw material, or uses synthetic resin such as ABS and ejection formation and form.
Above-mentioned CNT heating coating 130 is that Nano carbon tube-metal particle complex composition is ejected into above-mentioned synthetic resin part 120 and the layer of coating; Particularly preferably, spray and apply the Nano carbon tube-metal particle complex composition that metallics such as being combined silver (Ag) particle by chemical ground in the above-mentioned CNT (CNT) forms.
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 and guides heating with above-mentioned CNT heating coating 130.Also can connect thermoregulator 132 as required in the above-mentioned electrode 131, but, also can need not to be provided with other thermoregulator 132 because the inherent characteristic (quantity of electric charge control) that self has through CNT (CNT) can realize temperature control.In said temperature adjuster 132, connect power connector 133.
CNT (CNT) is to have number to the diameter of hundreds of microns (μ m) and the anisotropic former material of length.In CNT, carbon element atom combines with 3 other carbon element atoms and constitutes hexagonal honeycomb pattern.On smooth paper, draw when circle is rolled paper behind the above-mentioned honeycomb pattern, will constitute 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 that it is less that the diameter of this pipe is generally 1 nanometer (1/1000000000th meter) degree.On paper, draw honeycomb pattern and circular roll time-out will constitute nanotube, at this moment; According to which kind of angle to roll paper according to, CNT will become the electric conductor (Armchair, armchair) as metal; Or become semiconductor (ZigZag structure, mechanism in a zigzag).
Above-mentioned grip 140 is by skin or the cloth material or the ornament materials of PU (polyurethane) formation; Above-mentioned skin or cloth material are wrapped up CNT heating coating 130 and are combined by modes such as tailors; Above-mentioned PU (polyurethane) is combined by modes such as coatings, with parcel CNT heating coating 130).
Because open in No. 0749886 grade of Korean Patent mandate, will omit for the detailed description of the formation of CNT heating coating for the general known technology of the heater that utilizes CNT.
Constitute as stated according to heating steering wheel of the present invention in, shown in the flow chart of the process chart of Fig. 5 and Fig. 6, make synthetic resin part 120 shapings (S1) in the outside of core 110.Subsequently,, spray the dispersion liquid (Lq) of the Nano carbon tube-metal particle complex composition that combines on carbon nano tube surface chemical ground as metallic, form CNT heating coating 130 (S2) in the outside of above-mentioned synthetic resin part 120.In above-mentioned CNT heating coating 130, form electrode 131 (S3), as required thermoregulator 132 is set after, combine grip 140 to accomplish through outside parcel in above-mentioned CNT heating coating 130.
On the other hand, as among Fig. 4 with shown in the section, as another embodiment of the present invention, form synthetic resin part 120 in the outside of core 110, form CNT heating coating 130 at the lateral surface of above-mentioned synthetic resin part 120.Form the pattern-transferringlayer layer 150 of timber or metal etc. in the outside of above-mentioned CNT heating coating 130, form external skin 160 with appending in the outside of above-mentioned transfer layer 150.The pattern-transferringlayer layer 150 of above-mentioned timber or metal etc. forms through known hydraulic pressure transfer method, and said external coating 160 applies through known various material and several different methods.
In the heater wire heater that in the heating steering wheel in prior art, is suitable for, because the contact-making surface of calandria and heater wire belongs to contacting of locality, therefore reduction is for the heat transference efficiency of heated object, and it is slow to reach heating-up time of maximum temperature.But in the CNT heater that in heating steering wheel of the present invention, is suitable for, because the contact-making surface of heated object and heating layer belongs to comprehensive contacting, so outstanding for the heat transference efficiency of heated object, and it is fast to reach heating-up time of maximum temperature.
In addition, because the normal carbon heater (fluorenes, agraphitic carbon, graphite) shown in (a) part of Fig. 7 (a) part and Fig. 8 has 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 the resistance value rising and is difficult to guarantee reliability; But in the CNT (CNT) shown in Fig. 7 (b) part and Fig. 8 (b) part, because it is linear structure rather than sphere on molecular structure, the part that opens circuit less and more stable on resistance value.Particularly; The heater that the Nano carbon tube-metal particle complex composition that is combined on carbon nano tube surface chemical ground by metallic constitutes will keep PTC (positive temperature coefficiency; Positive temperature coefficient) character; Therefore temperature resistance coefficient almost is bordering on 0, and use does not repeatedly have the variation of resistance value yet and guarantees reliability easily.This can not merely come revisal by the carbon of the temperature resistance coefficient with the moon (-) and the mixing of the metal of the temperature resistance coefficient with sun (+); But the combination of the electric conductor through the metallic that combines in CNT (CNT) surface by utilizing chemical etc. realizes aforesaid characteristic.
In addition, shown in power utilization network model in Fig. 8 (a) part, common carbon has only carbon to contact with carbon particle in binding agent could to switch on; Therefore; When being suitable for coating, having the possibility that carbon particle converges in privileged site, thereby generate more heat at privileged site.Contrast therewith shown in power utilization network model in (b) part of Fig. 8, in CNT (CNT), does not have standoff distance to a certain degree even do not paste between the particle, will realize the electric network phenomenon of energising yet.Thus, only use with the content of common carbon and compare content seldom, also can realize equal above performance, get rid of CNT (CNT) particle, possess impartial heating and distribute, and do not have the thermal-arrest phenomenon in the possibility that privileged site converges.
In aforesaid heating steering wheel of the present invention; The operation of adhering to the heater wire packing ring in the heating steering wheel with prior art; Replace operation, compared with prior art save manufacturing expense significantly for the electric conductor that sprays CNT (CNT) and metallic etc.And, can form the pattern-transferringlayer layer of timber or metal etc., keep the good sense of holding, realize shape and resistive arrangement freely, relatively the time, can realize significant energy saving with prior art.In addition, on the characteristic (quantity of electric charge control) of CNT (CNT) material, other thermoregulator needn't be arranged.
Claims (14)
1. a Nano carbon tube-metal particle complex composition is characterized in that, comprising:
A) manufacturing is dispersed with the step of the CNT dispersion soln of CNT;
B) the CNT dispersion soln to said step a) carries out acid-treated step;
C) the CNT dispersion soln of said step b) is carried out the step of neutralisation treatment;
D) the CNT dispersion soln of the said step c) of mixing and the metallic solution that comprises metallic are in the step of carbon nano tube surface combination metallic.
2. Nano carbon tube-metal particle complex composition according to claim 1 is characterized in that, the CNT of said step a) is more than one the nanotube that is selected from multi-walled carbon nano-tubes, thin wall carbon nano-tube and the SWCN.
3. Nano carbon tube-metal particle complex composition according to claim 1 is characterized in that, in said step a), makes dispersion soln through said CNT is scattered in solvent.
4. Nano carbon tube-metal particle complex composition according to claim 1 is characterized in that, in said step b), adds to be selected from nitric acid, sulfuric acid, hydrochloric acid and the perchloric acid more than one and to carry out acid treatment.
5. Nano carbon tube-metal particle complex composition according to claim 1 is characterized in that, in said step c), adds to be selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and the ammonium hydroxide aqueous solution more than one and to carry out neutralisation treatment.
6. Nano carbon tube-metal particle complex composition according to claim 5; It is characterized in that; In said step c), utilize CNT dispersion soln that ultrasonic wave mixes said step b) and be selected from more than one aqueous solution in sodium hydrate aqueous solution, potassium hydroxide aqueous solution and the ammonium hydroxide aqueous solution.
7. Nano carbon tube-metal particle complex composition according to claim 1; It is characterized in that in said step d), the metallic solution that comprises metallic passes through solvent; Be selected from four octyl group ammonium bromides, 1; 2-dichloro-benzenes, N-methyl pyrrolidone and N, the solution that a kind of and formaldehyde in the dinethylformamide 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 make and form.
8. Nano carbon tube-metal particle complex composition according to claim 1; It is characterized in that; In said step d), the metallic of carbon nano tube surface is more than one metal ions that are selected among Ag, Pt, Pd, Au, Cu, Ni, Al, Ag/Cu, Ag/Ni and the Cu/Ni.
9. Nano carbon tube-metal particle complex composition according to claim 1 is characterized in that, also comprises:
The solution of said step d) is scattered in more than one solution that are selected from methyl ethyl ketone, 4-methyl-2 pentanone, acetone, cyclohexanone, ketone class solution, 2-Butoxyethyl acetate, BC acetate, the acetic acid saline solution and makes the step of dispersion soln; And
The step of mixing said dispersion soln and binding agent.
10. 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 said core;
CNT heating coating, at the lateral surface of said synthetic resin part, coating is formed with each described Nano carbon tube-metal particle complex composition in claim 1 to the claim 9;
Electrode is electrically connected on said CNT heating coating, is used for the guiding heating.
11. heating steering wheel according to claim 10 is characterized in that, is enclosed with grip in the outside of said CNT heating coating.
12. heating steering wheel according to claim 11 is characterized in that, said grip constitutes by being selected from a kind of in skin, cloth and the polyurethane.
13. heating steering wheel according to claim 10 is characterized in that, is formed with the transfer layer based on the hydraulic pressure transfer method in the outside of said CNT heating coating.
14. heating steering wheel according to claim 13 is characterized in that, is formed with external skin in the said transfer layer outside.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090077258A KR101116472B1 (en) | 2009-02-06 | 2009-08-20 | carbon nanotube-metal particle complex composition and steering wheel with heating element using the same |
| KR10-2009-0077258 | 2009-08-20 | ||
| 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 true CN102471050A (en) | 2012-05-23 |
| CN102471050B 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 DE DE112010003312T patent/DE112010003312T8/en not_active Expired - Fee Related
- 2010-07-30 JP JP2012524632A patent/JP5603939B2/en not_active Expired - Fee Related
- 2010-07-30 CN CN201080031626.9A patent/CN102471050B/en not_active Expired - Fee Related
- 2010-07-30 WO PCT/KR2010/005041 patent/WO2011021794A2/en active Application Filing
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 |
|---|---|
| CN102471050B (en) | 2014-08-06 |
| JP5603939B2 (en) | 2014-10-08 |
| JP2013501703A (en) | 2013-01-17 |
| DE112010003312T8 (en) | 2012-11-29 |
| WO2011021794A2 (en) | 2011-02-24 |
| WO2011021794A3 (en) | 2011-06-30 |
| DE112010003312T5 (en) | 2012-06-28 |
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