CN101358369A - Functionalized carbon nanotube coating and use thereof - Google Patents
Functionalized carbon nanotube coating and use thereof Download PDFInfo
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- CN101358369A CN101358369A CNA2008101349207A CN200810134920A CN101358369A CN 101358369 A CN101358369 A CN 101358369A CN A2008101349207 A CNA2008101349207 A CN A2008101349207A CN 200810134920 A CN200810134920 A CN 200810134920A CN 101358369 A CN101358369 A CN 101358369A
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Abstract
The invention discloses a method for preparing CNT coating on a substrate, which comprises the following steps: (a) the CNT receives carboxylic acid treatment; and (b) in the solvent containing a plurality of hydroxide radical and/or amino group substances, the CNT which receives carboxylic acid treatment is electrodeposited on the surface of the substrate at low pressure. The invention also discloses a method for preparing CNT composite coating on the substrate, coating compounds, products containing the substrate coated through the method, functional carbon nano tube coatings and an application thereof.
Description
Quoting of related application
The application requires in the right of priority of No. 200710138018.8 China's application that is entitled as " functionalized carbon nanotube coating and application thereof " of submission on August 2nd, 2007, and its integral body is hereby incorporated by.
Background of invention
1.
Invention field
The present invention relates to carbon nanotube, particularly the novel preparation method and the application thereof of functionalized carbon nano-tube (f-CNT) coating.
2.
Association area is described
Since being found first by Iijima, carbon nanotube (CNT) enjoys always shows great attention to.CNT has the characteristic of multinomial uniqueness, for example good conductivity, stable chemical properties and high physical strength (for example high modulus and hardness).The machinery of these brilliances and electric property make CNT have huge application potential.
Mention all that in a lot of research reports utilization CNT improves the physical strength of various materials.Yet these researchs mainly concentrate on the application in matrix material.For example CNT is joined (as aluminium alloy or copper alloy) in the metal alloy.Because CNT is often used as the stiffener (reinforcement) in the metal matrix composite materials, therefore the shared component of CNT is quite few in matrix material, is no more than 10% usually.Typical composite material and preparation method thereof is adopted in the preparation of CNT coating usually, and its step and preparation cycle that relates to a plurality of complexity is long.But the rarely seen report for preparing the CNT coating with electroplating technology.
The invention summary
Therefore, the contriver is intended to by the present invention deficiency of the prior art be improved.
A first aspect of the present invention relates to the method for preparing carbon nanotube (CNT) coating on matrix, and it comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains material with a plurality of hydroxyls and/or amino group, under the low pressure with carboxylic acidifying CNT galvanic deposit in matrix surface.
A second aspect of the present invention relates to the method for preparing carbon nanotube (CNT) compound coating on matrix, and it comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains material with a plurality of hydroxyls and/or amino group, under the low pressure with many galvanic deposit of carboxylic acidifying CNT in matrix surface.
A third aspect of the present invention relates to coating composition, the material that it comprises carboxylic acidifying CNT and has a plurality of hydroxyls and/or amino group.
A fourth aspect of the present invention relates to goods, and it comprises the matrix of the method according to this invention galvanic deposit.
In some preferred embodiment of the present invention, with the CNT coating preparation on the metal clockwork spring of clock and watch.
Up to now, the low voltage electro-deposition method is not widely used in preparing the CNT coating as yet.Yet the present invention uses electro-deposition method simple and with low cost to prepare matrix such as metal clockwork spring surface that CNT applies, and galvanic deposit is under low pressure carried out.This method can effectively and apace prepare successive CNT coating.
For preventing that metallic matrix from producing corrosion reaction in the aqueous solution, the present invention adopts organic solution as electrolytic solution.Have the material of a plurality of hydroxyls and/or amino group and the functional group on the CNT in the organic solution and react, thereby prepare continuous and fine and close coating.
The thickness of floating coat of the present invention can be controlled by time and the voltage of regulating the galvanic deposit operation, thereby can prepare the coating with different thickness and mechanical property.
The accompanying drawing summary
Fig. 1 is a galvanic deposit operation chart of the present invention, and wherein 1 is reference electrode, and 2 is the Pt electrode, and 3 is ionogen, and 4 is matrix.
Fig. 2 is the socle girder Road test synoptic diagram of the matrix of coating according to the present invention.
Detailed Description Of The Invention
Following description comprises some detail in order to thoroughly understand various disclosed embodiments. Yet various equivalent modifications should be appreciated that and can need not one or more these details, perhaps can use other method, composition, material etc. to put into practice embodiment.
Unless context has requirement in addition, in the following description book and claims, word " comprises (comprise) " and variation should be interpreted as implication open, that comprise such as " comprising (comprises) " and " comprising (comprising) ", namely should be interpreted as " including, but are not limited to ".
Mentioned " embodiment (one embodiment) " in the whole specification, or " embodiment (an embodiment) ", or " in another embodiment ", or " some embodiment ", or " in certain embodiments " refers to that the described feature that be specifically related to, structure or the characteristic relevant with described embodiment are included at least one embodiment. Therefore, phrase " in one embodiment ", " in embodiments ", " in another embodiment " or " in certain embodiments " of the local appearance of each in whole specification needn't all refer to identical embodiment. In addition, specific features, structure or characteristic can combine in one or more embodiments in any suitable manner.
Should be noted that as used in this specification and the appending claims " a " of singulative, " an " and " the " comprise the thing of mentioning of plural form, unless context refers else clearly. Therefore, for example, the solvent that contains " material with a plurality of hydroxyls and/or amino group " that this paper relates to comprises separately a kind of material with a plurality of hydroxyls and/or amino group, and perhaps two or more have the material of a plurality of hydroxyls and/or amino group. Shall also be noted that the term "or" usually with comprise " and/or " implication use, unless context refers else clearly.
A first aspect of the present invention is provided at the method for preparing the CNT coating on the matrix. The method comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains the material with a plurality of hydroxyls and/or amino group, under the low pressure with the CNT electro-deposition of carboxylic acid in matrix surface.
In the present invention, CNT includes but not limited to SWCN (SWNTs), multi-walled carbon nano-tubes (MWNTs), double-walled carbon nano-tube, Baji-tube, fullerene pipes (fullerene tubes), tubelike fullerene (tubular fullerenes), graphite fento (graphite fibrils), carbon whisker, gas-phase growth of carbon fibre and combination thereof. Such CNT can be by any known technique preparation, include but not limited to arc discharge method, laser oven process (laser oven), thermal decomposition method, combustion synthesis method, chemical vapour deposition technique and combination thereof, can also the metallic catalyst working load type or non-loading type in the described chemical vapour deposition technique.
In certain embodiments, CNT classifies according to the number of chirality, electrical conductivity, thermal conductivity, diameter, length, wall and the character of combination thereof.
In some preferred embodiment, use in the present invention the MWNT that is purchased.
Because the CNT of commerical grade can be polluted during its preparation usually, therefore in case of necessity, before being applied to the present invention, CNT need carry out purifying removing impurity, such as metal and other impurity of comprising carbon (for example carbon compound of noncrystalline shape). Any conventional purification process can both be used for the present invention.
In some preferred embodiment, CNT is purified. Exemplary purifying process includes but not limited to the people such as Chiang, J.Phys.Chem.B, 105, pp.1157-1161,2001; The people such as Chiang, J.Phys.Chem.B, 105, pp.8297-8301,2001, both be hereby incorporated by.
In some preferred embodiment, CNT is placed in the baking oven heating a period of time then washs with HCl.
In some preferred embodiment, the CNT that is purchased is placed in the baking oven heating a few hours washs with HCl then.
In the most preferred embodiment, the MWNT that is purchased is placed in baking oven in 400 ℃ of heating washed with HCl then in about 2 hours.
The matrix that is used for the present invention comprises that various hope deposit parts or the part of CNT with the goods that increase its physical strength thereon.In certain embodiments, the micromachine part is used as matrix.In some preferred embodiment, clockwork feed is used as matrix.
According to the present invention, the carboxylic acid processing is intended to-COOH group is added to the CNT surface to realize the functional modification to the CNT surface.Usually can use the CNT that the mixture process purifying of strong oxidizing property aqueous acid or multiple strong oxidizing property aqueous acid crosses and carry out reflux, thereby realize functional modification.
Acid with strong oxidizing property includes but not limited to the strong oxidizing property mineral acid, as nitric acid, nitrous acid, sulfuric acid, peroxy-disulfuric acid, pyrosulfuric acid, perchloric acid, hydrochloric acid, chlorous acid, hypochlorous acid, Hydrogen bromide, hypobromous acid, hydroiodic acid HI etc., with the strong oxidizing property organic acid, as organic peracid.Can be used in exemplary organic peracid of the present invention and include but not limited to peroxyformic acid, Peracetic Acid, peroxy trifluoroacetic acid, Perpropionic Acid, benzoyl hydroperoxide etc.
In certain embodiments of the invention, working concentration is approximately 65% aqueous nitric acid and realizes functional modification to the CNT surface.In certain embodiments of the invention, the mixed acid solution of forming with 3: 1 volume ratio with the nitric acid of 98% sulfuric acid and 70% is handled CNT.In certain embodiments of the invention, the mixed acid solution of forming with 7: 3 volume ratio with the dense perchloric acid of 65% concentrated nitric acid and 60% is handled CNT.
In some preferred embodiment of the present invention, be approximately 65% aqueous nitric acid processing CNT with concentration, heated 2 to 5 hours, be cooled to room temperature then to realize the functional modification on CNT surface.
In some preferred embodiment of the present invention, handle the MWNT of prepurification with the aqueous nitric acid of concentration about 65%, about 3 hours of reflux is cooled to room temperature then to realize the functional modification on MWNT surface.
Is neutral with deionized water wash f-CNT until pH, and centrifugal heating, drying then is used for next step.
With f-CNT powder and other material of gained, the material that comprises ionogen (randomly being used for the present invention) and have a plurality of hydroxyls and/or an amino group is scattered in the organic solvent.
Can be used in solvent of the present invention and include but not limited to carbonates, as methylcarbonate, diethyl carbonate, dipropyl carbonate, n-butyl carbonate and propylene carbonate; The low-grade fatty acid ester class is as methyl-formiate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate and butylacetate; Rudimentary lactone is as gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, γ-Ji Neizhi, δ-caprolactone, 6-caprolactone; Nitrile is as acetonitrile, propionitrile, butyronitrile, valeronitrile; Ethers, as 1,2-glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran (THF); Amides, as N, dinethylformamide (DMF) and N,N-dimethylacetamide (DMAC); The sulfone class is as dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone; And combination.
In certain embodiments, carbonic ether is used as solvent of the present invention.In some preferred embodiment of the present invention, propylene carbonate (PC) is used as solvent.
In some preferred embodiment of the present invention, being dispersed under hyperacoustic the assisting of CNT carried out.
In some preferred embodiment of the present invention, with the f-MWNT powder in ultrasonic bath with ultrasonic about 1 to 10 minute of the audio frequency of 50 to 100W power and 30 to 60kHz, the f-MWNT powder is dispersed in the organic solvent of propylene carbonate.
The ionogen that can be used among the present invention comprises those inorganic electrolytes that this area is commonly used.
In certain embodiments of the invention, alkali-metal inorganic salt are used as ionogen.
In some preferred embodiment, lithium salts is used as ionogen of the present invention.Can be used in electrolytical specific examples of the present invention and include but not limited to lithium perchlorate (LiClO
4), Quilonum Retard (Li
2CO3), Trilithium phosphate (Li
3PO
4), monometallic (LiH
2PO
4), Lithium Sulphate (Li
2SO
4), lithium nitrate (LiNO
3), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), tetrachloro-lithium aluminate (LiAlCl
4), tetrachloro arsenic acid lithium (LiAsCl
4), lithium fluoride (LiF), lithium chloride (LiCl), lithiumbromide (LiBr), lithium iodide (LiI) etc.
In some preferred embodiment of the present invention, with lithium perchlorate (LiClO
4) as ionogen.
According to the present invention, the material with a plurality of hydroxyls and/or amino group includes but not limited to that polyalcohols aminated compounds, natural and synthetic polyol and other have the organic polymer of a plurality of hydroxyls and/or amino group.Owing to be rich in great amount of hydroxy group and amino group, these materials can form chemical bond with carboxylic acidifying f-CNT, thereby help CNT stably to be scattered in the solution.
In certain embodiments of the invention, use the water-soluble poly alcamine compound.Can be used in exemplary polyalcohols aminated compounds of the present invention and include but not limited to diethanolamine (DEA), trolamine (TEA), tri-isopropanolamine, N, two (2-the hydroxyethyl)-2-Propanolamines of N-, N methyldiethanol amine etc.
In certain embodiments of the invention, exemplary natural polyhydroxy compound includes but not limited to polysaccharide, saponin(e, and xanthosine, such as the flavonoid of violaguercitrin, baicalin, catechol etc., alkaloid, sterol, sesquiterpene, arbutin, Fructus Sophorae glycosides etc.
In certain embodiments, can be used in polyhydroxylated polymer of the present invention and include but not limited to various polyvinyl alcohol, starch (unmodified type, modified version and substituted type), dextrin, natural gum, derivatived cellulose etc.
The limiting examples of polyhydroxylated polymer is the various partly or entirely hydroxylated polyvinyl acetate of selling as the polyvinyl alcohol of different molecular weight ranges, W-Gum, Sumstar 190, sour treated starch, hydroxyethylamyle, cyanoethyl starch, Sudan Gum-arabic, methylcellulose gum, Natvosol, hydroxypropylcellulose, methyl hydroxyethylcellulose etc.
In certain embodiments, the form that to can be used in polyamino polymkeric substance of the present invention can be straight-chain polymer, hyperbranched polymer or branch-shape polymer.
In some preferred embodiment of the present invention, the polyamino polymkeric substance includes but not limited to polymine, polyvinyl imidazole, polyvinyl pyridine, polymine and the monomeric adduct of 1-vinyl imidazole, based on cross-linked derivant of the polymer of amino acid that contains basic side chain, aforementioned polyamino polymkeric substance etc.
Exemplary polymine includes but not limited to polymine, the alkyl derivative of polymine, the adduct of polymine and alkyl carboxylic acid, the adduct of polymine and ketone and aldehyde, the adduct of polymine and isocyanic ester and lsothiocyanates, the adduct of polymine and alkylene oxide and poly-(alkylene oxide) segmented copolymer, the quaternary ammonium derivative of polymine, the adduct of polymine and silicone, the multipolymer of polymine and dicarboxylic acid, hyperbranched polyethyleneimine etc.
Can be used in the specific examples with material of a plurality of hydroxyls and/or amino group of the present invention and include but not limited to gather (2-acryl amino-2-methyl-1-propanesulfonic acid), polyoxyethylene glycol, polyacrylamide and chitosan.
In certain embodiments of the invention, the material with a plurality of hydroxyls and/or amino group is selected from polysaccharide or polyalcohols aminated compounds.In some preferred embodiment, chitosan is used for the present invention.
Usually, target CNT coating can be by having the material of a plurality of hydroxyls and/or amino group and preparation effectively in galvanic deposit operating period adding on a small quantity.In certain embodiments of the invention, organic solvent can comprise the material that 0.01 to 10.0 μ M has a plurality of hydroxyls and/or amino group.In some preferred embodiment of the present invention, organic solvent can comprise the material that 0.05 to 3.0 μ M has a plurality of hydroxyls and/or amino group.In some preferred embodiment of the present invention, organic solvent can comprise the material that 0.1 to 2.0 μ M has a plurality of hydroxyls and/or amino group.
Can be used in chitosan of the present invention can be natural or synthetic.Chitosan can obtain by the N-deacetylation of chitin polymkeric substance.
Chitin is a natural polysaccharide, is present in multiple ocean and the terrestrial life body, and it comprises crustacean, insect, mollusk and microorganism such as fungi.Chitinous structure is the unbranched polymkeric substance of 2-acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose (N-ethanoyl-D-glycosamine).
Chitin is generally insoluble,practically amorphous solid in water, rare bronsted lowry acids and bases bronsted lowry.Although chitin has multiple commercial applications,, found that bigger commercial exploitation is worth by converting it into deacetylated product chitosan.
Chitosan also is an insoluble,practically amorphous solid in water, but dissolves in aqueous solutions of organic acids, as formic acid and acetate.Yet deacetylation is incomplete usually, and some ethanoyl still is retained in most of chitosan composition.
Chitosan is the straight-chain polysaccharide polymkeric substance.The chitosan molecule chain is intertwined each other, thereby forms the three-dimensional CNT of interweaving coating at matrix surface.In galvanic deposit operating period, in organic solvent, only add a spot of chitosan usually.In some preferred embodiment of the present invention, in the galvanic deposit chitosan adding organic solvent of operating period with 0.1 to 0.5 μ M.In some preferred embodiment of the present invention, in the galvanic deposit chitosan adding propylene carbonate (PC) of operating period with 0.1 to 0.5 μ M.In some preferred embodiment of the present invention, galvanic deposit operating period is that the chitosan of 85% 0.3 μ M adds in the propylene carbonate (PC) with deacetylation.
Then with the pH regulator of dispersion liquid to about 4.0.Can regulate pH with mineral acid.Exemplary inorganic acid includes but not limited to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and composition thereof.In certain embodiments of the invention, preferably use the mixture of sulfuric acid and nitric acid.
When regulating the pH of dispersion liquid, can use any technology of monitoring organic solution pH well known by persons skilled in the art.For example, can use the pH of various indicator or potentiometer monitoring dispersion liquid of the present invention.In certain embodiments of the invention, use potentiometer to monitor the pH of dispersion liquid of the present invention.
Galvanic deposit of the present invention operates under the lower voltage to be carried out.In certain embodiments of the invention, application is less than the voltage of 10V.
In some preferred embodiment of the present invention, galvanic deposit operates under the negative pressure (with respect to reference electrode) to be carried out.Although the present invention can carry out with the electric current of milliampere(mA) level, should be appreciated that and also should consider not destroy the related material of galvanic deposit.Therefore, subject to the foregoing, above-mentioned in the present invention galvanic deposit can carried out under the negative pressure arbitrarily.
Yet in some preferred embodiment of the present invention, galvanic deposit operation is carried out to the voltage of-10V at-0.1V usually as required.In some preferred embodiment of the present invention, galvanic deposit operates in-and 0.5V carries out to the voltage of-6V.In some preferred embodiment of the present invention, galvanic deposit operates in-and 1V carries out to the voltage of-6V.In some preferred embodiment of the present invention, galvanic deposit operates in-and 2V carries out to the voltage of-5V.
The thickness that should be appreciated that the expectation coating can be controlled by various factors, as the voltage of galvanic deposit and time, the type of organic solvent, the type of used carbon nanotube etc.Usually, those skilled in the art can be according to above-mentioned factor control coating thickness easily.In certain embodiments of the invention, the voltage of use-3V, but the just coating of precipitation number micron thickness of about 10 minutes time.
In some preferred embodiment of the present invention, in propylene carbonate (PC), the f-CNT coating of the about 0.6 μ m of thickness under the voltage of-3V in about 5 minutes galvanic deposit to the clockwork spring surface.In some preferred embodiment of the present invention, in propylene carbonate (PC), the f-CNT coating of the about 1.6 μ m of thickness under the voltage of-3V in about 10 minutes galvanic deposit to the clockwork spring surface.In some preferred embodiment of the present invention, in propylene carbonate (PC), the f-CNT coating of the about 5.0 μ m of thickness under the voltage of-3V in about 30 minutes galvanic deposit to the clockwork spring surface.
A second aspect of the present invention is provided at the method for preparing the CNT compound coating on the matrix.Described method comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains material with a plurality of hydroxyls and/or amino group, under the low pressure with many galvanic deposit of carboxylic acidifying CNT in matrix surface.
This aspect of the present invention and above-described similar, just with carbon nanotube repeatedly galvanic deposit in matrix surface.In the method, the present invention uses structure preparation (compound) multiwalled f-CNT coating of stacked (layer-by-layer).Utilize the f-CNT coating structure of multi-layer type to reduce the integral thickness of coating, strengthened the mechanical property of coating simultaneously.
In order further to strengthen the intensity of matrix, the present invention also is included in the step of another metals like gold of deposition on every layer of CNT coating.This step can be undertaken by the ordinary method of this area, as sputtering sedimentation, plating etc.Sputtering sedimentation can carry out as follows.CNT coating and gold target are placed face-to-face.System is vacuumized, inject argon gas then.CNT coating and gold target are placed under the high pressure to produce plasma body so that gold can be splashed on the CNT coating.
The thickness of gold layer can be by the sputtering time adjustment.It will be appreciated by those skilled in the art that the present invention is not limited to use the method and the gold plating of d.c. sputtering.
A third aspect of the present invention provides coating composition, and it comprises carboxylic acidifying CNT and the above-mentioned material with a plurality of hydroxyls and/or amino group that contains.
In composition of the present invention, carboxylic acidifying CNT coating can account for 40% to 60% of coating wt usually.
A fourth aspect of the present invention provides goods, and it comprises the matrix that the method according to this invention applies.
In a preferred embodiment of the invention, described matrix is the clockwork spring of clock and watch, thereby goods are clock and watch.
Hereinafter, the present invention explains so that understand all respects of the present invention and advantage better in detail by following embodiment with reference to the accompanying drawings.But, should be appreciated that following embodiment is nonrestrictive and only is used to illustrate certain embodiments of the present invention.
Embodiment
Embodiment 1-3
The conventional CNT that the present invention uses, it buys (model: MWNT (non-array) from Nanometer Port Co., Ltd., Shenzhen; External diameter: 10 to 20nm; Length: 5 to 15 μ m; Specific surface area: 160 to 180m
2/ g; Bulk density 6 is to 8mL/g).As needs, can be by ordinary method with the CNT purifying.For example CNT can be placed and be warming up to 400 ℃ in the baking oven, heat and also cleaned in about 2 hours with 6M HCl.
HNO with the CNT behind the purifying and 65%
3Mix, then with HNO
3With the CNT mixed solution in about 3 hours of 140 ℃ of thermostatically heating, slowly be cooled to room temperature then.
With the carbon nanotube washed with de-ionized water after the acid treatment, be neutrality, centrifugation heating, drying then until pH.F-CNT powder (0.2mg/mL) is about in the ultrasonic bath that 70W, audio frequency are 40kHz at power handled about 3 to 5 minutes, so that it is scattered in the organic solvent propylene carbonate.Use the pH to 4 of the mixed solution adjusting dispersion liquid of sulfuric acid and nitric acid.In dispersion liquid, add LiClO
4The aqueous solution is as supporting electrolyte, and with LiClO
4Ultimate density remain on 0.05M, add deacetylation then and be the carbonic allyl ester solution of 85% chitosan.The ultimate density of chitosan is remained on 0.30 μ M.
Referring to Fig. 1, at room temperature, be negative pole with the platinum electrode, the stainless steel clockwork spring (can be available from the Zhejiang Elastic Factory of China, model: stainless steel 304; Width: 1mm; Thickness 0.095mm) be anodal.In the electroplate liquid of preparation as stated above, under the voltage of-3V, with the CNT galvanic deposit in the clockwork spring surface.Deposit to the thickness on clockwork spring surface as required, can use control device (for example computer) control electrodeposition time.After the galvanic deposit clockwork spring is placed in the baking oven about 12 hours of 60 ℃ of following heating.On clockwork spring, be respectively and make the CNT coating that thickness is 5 μ m, 1.5 μ m and 0.6 μ m.
Then, on each the CNT coatingsurface that makes, use the gold plating (about 20nm) of the method deposition of thin of d.c. sputtering.
The method that can be used in d.c. sputtering commonly used of the present invention is as described below.CNT coating and gold target are placed face-to-face.System is vacuumized, inject argon gas then and reach 10Torr until the pressure of system.CNT coating and gold target are applied the voltage of about 800V to produce plasma body, so that gold can be splashed on the CNT coating.The thickness of gold plating can be controlled by sputtering time.It will be appreciated by those skilled in the art that the purpose of using d.c. sputtering be metal deposition on the CNT coating, so the present invention is not limited to use the method and the gold plating of d.c. sputtering.Afterwards clockwork spring was annealed about 5 hours down in 450 ℃, make tiny gold particle be penetrated in the CNT coating.
After the deposition of gold, each coating is carried out the Young's modulus test.Referring to Fig. 2, this test adopts the method for socle girder to carry out.Toward pressing down, the other end then is placed on the gravity probe and goes up the reactive force of measuring it with an end of clockwork spring.Calculate the Young's modulus E of the clockwork spring of surveying based on following formula by slope (F/D) and reactive force:
L wherein, b and t are respectively length, width and the thickness of sample, and unit is a rice (m); F is downward pressure (bearing capacity), and unit is newton (N); D is downward displacement, and unit is a rice (m).
The socle girder test result is as shown in table 1.
The Young's modulus of the clockwork spring of table 1. deposited monolayers f-CNT and different thickness chitosan coat
| |
|
|
Uncoated clockwork spring | |
| Coat-thickness (μ m) | About 5.0 | About 1.5 | About 0.6 | - |
| Electrodeposition time (minute) | 30 | 10 | 5 | - |
| Young's modulus (GPa) | 311 | 255 | 236 | 220 |
| The percentage ratio that Young's modulus increases | 41.60 | 15.90 | 7.27 | - |
As shown in Table 1, the single CNT coating that 0.6 μ m is thick makes the Young's modulus of clockwork spring increase by 7.27%.1.5 making the Young's modulus of clockwork spring increase the thick single CNT coating of 15.90%, 5.0 μ m, the single CNT coating that μ m is thick make the Young's modulus of clockwork spring increase by 41.60%.
Be similar to the operation of embodiment 1 to 3, just embodiment 4 to 7 places electroplating solution as required once more with the clockwork spring behind the deposition of gold, so that galvanic deposit new one deck CNT coating and the new one deck gold of the clockwork spring electroplating surface behind deposition of gold.With the gauge control of every layer of single coating (CNT deposition+gold plating+thermal treatment) in 2.0 μ m.Multilayered structure obtains by the repeated deposition circulation.Obtaining 5,3,2 and 1 layers of compound coating respectively and after deposited gold on each coating, using the method identical to carry out Young's modulus and test with embodiment 1 to 3.
The socle girder test result is as shown in table 2.
The Young's modulus of the clockwork spring of table 2. deposit multilayer f-CNT and different thickness chitosan coat
| |
Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Coat-thickness (μ m) | About 2.0 | About 1.0 | About 0.7 | About 0.2 |
| Electrodeposition time (minute) | 18 | 8 | 6 | 2 |
| The percentage ratio that Young's modulus increases | 28.9 | 19.9 | 15.4 | 7.8 |
As shown in Table 2, single CNT coating (embodiment 7, and thickness is 200nm) makes the Young's modulus of clockwork spring increase by 7.8%.Two-layer CNT coating (embodiment 6, and thickness is 700nm) makes the Young's modulus of clockwork spring increase by 15.4%.(embodiment 5, and thickness is 1, and (embodiment 4, and thickness is 2,000nm) make the Young's modulus of clockwork spring increase by 28.9% 000nm) to make the Young's modulus of clockwork spring increase by 19.9%, five layer CNT coating for trilaminar CNT coating.
Can carry out these and other change according to foregoing description.Usually, in following claims, used term should not be interpreted as the qualification to disclosed specific embodiments in this specification sheets and claims, and should be interpreted as comprising all systems, device and/or the method for operating according to claims.Therefore, scope of the present invention is not subjected to the restriction of present disclosure, but is determined by the integral body of following claims.
All above-mentioned United States Patent (USP)s, U.S. Patent application publication, U.S. Patent application, foreign patent, foreign patent application and the non-patent publications that this specification sheets relates to all integral body is hereby incorporated by.
Although described specific embodiments of the present invention, but still can carry out various changes and without prejudice to the spirit and scope of the present invention at this according to described should be appreciated that for the purpose of explaining of preamble.Therefore, the present invention only is subjected to the restriction of appended claims.
Claims (19)
1. prepare the method for carbon nanotube (CNT) coating on matrix, it comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains material with a plurality of hydroxyls and/or amino group, under the low pressure with carboxylic acidifying CNT galvanic deposit in matrix surface.
2. the method for claim 1, wherein said CNT is selected from Single Walled Carbon Nanotube (SWNTs), multi-walled carbon nano-tubes (MWNTs), double-walled carbon nano-tube, Baji-tube, fullerene pipes, tubelike fullerene, graphite fento, carbon whisker or gas-phase growth of carbon fibre.
3. method as claimed in claim 1 or 2, wherein said material is the organic polymer with a plurality of hydroxyls and/or amino group, has the organic polymer of a plurality of hydroxyls and/or amino group as polyalcohols aminated compounds, natural and synthetic polyol and other, and preferred polysaccharide compounds, more preferably chitosan.
4. as claim 1 or 2 or 3 described methods, wherein said organic solvent also comprises inorganic electrolyte, preferably contains the inorganic salt of lithium, as lithium perchlorate (LiClO
4), Quilonum Retard (Li
2CO3), Trilithium phosphate (Li
3PO
4), monometallic (LiH
2PO
4), Lithium Sulphate (Li
2SO
4), lithium nitrate (LiNO
3), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), tetrachloro-lithium aluminate (LiAlCl
4), tetrachloro arsenic acid lithium (LiAsCl
4), lithium fluoride (LiF), lithium chloride (LiCl), lithiumbromide (LiBr), lithium iodide (LiI), and more preferably lithium perchlorate (LiClO
4).
5. as the described method of arbitrary claim in the claim 1 to 4, wherein said organic solvent is selected from carbonates, the low-grade fatty acid ester class, rudimentary lactone, nitrile, ethers, amides or sulfone class, as methylcarbonate, diethyl carbonate, dipropyl carbonate, n-butyl carbonate and propylene carbonate, methyl-formiate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate and butylacetate, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, γ-Ji Neizhi, δ-caprolactone, 6-caprolactone, acetonitrile, propionitrile, butyronitrile, valeronitrile, 1, the 2-glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran (THF), N, dinethylformamide (DMF) and N, N-N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone, preferred propylene carbonate.
6. as the described method of arbitrary claim in the claim 1 to 5, it also is included in hyperacoustic auxiliary CNT that will handle down and is scattered in step in the solution.
7. as the described method of arbitrary claim in the claim 1 to 6, wherein said electrodeposition step is carried out under negative pressure, and is preferred-3V.
8. as the described method of arbitrary claim in the claim 1 to 7, wherein said matrix is a clockwork feed.
9. prepare the method for CNT compound coating on matrix, it comprises:
(a) CNT is carried out the carboxylic acid processing; And
(b) in the solvent that contains material with a plurality of hydroxyls and/or amino group, under the low pressure with many galvanic deposit of carboxylic acidifying CNT in matrix surface.
10. method as claimed in claim 9, wherein said CNT is selected from Single Walled Carbon Nanotube (SWNTs), multi-walled carbon nano-tubes (MWNTs), double-walled carbon nano-tube, Baji-tube, fullerene pipes, tubelike fullerene, graphite fento, carbon whisker or gas-phase growth of carbon fibre.
11. as claim 9 or 10 described methods, wherein said material is the organic polymer with a plurality of hydroxyls and/or amino group, has the organic polymer of a plurality of hydroxyls and/or amino group as polyalcohols aminated compounds, natural and synthetic polyol and other, and preferred polysaccharide compounds, more preferably chitosan.
12. as claim 9 or 10 or 11 described methods, wherein said organic solvent also comprises inorganic electrolyte, preferably contains the inorganic salt of lithium, as lithium perchlorate (LiClO
4), Quilonum Retard (Li
2CO3), Trilithium phosphate (Li
3PO
4), monometallic (LiH
2PO
4), Lithium Sulphate (Li
2SO
4), lithium nitrate (LiNO
3), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), tetrachloro-lithium aluminate (LiAlCl
4), tetrachloro arsenic acid lithium (LiAsCl
4), lithium fluoride (LiF), lithium chloride (LiCl), lithiumbromide (LiBr), lithium iodide (LiI), and more preferably lithium perchlorate (LiClO
4).
13. as the described method of arbitrary claim in the claim 9 to 12, wherein said organic solvent is selected from carbonates, the low-grade fatty acid ester class, rudimentary lactone, nitrile, ethers, amides or sulfone class, as methylcarbonate, diethyl carbonate, dipropyl carbonate, n-butyl carbonate and propylene carbonate, methyl-formiate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate and butylacetate, gamma-butyrolactone, γ-Wu Neizhi, δ-Wu Neizhi, γ-Ji Neizhi, δ-caprolactone, 6-caprolactone, acetonitrile, propionitrile, butyronitrile, valeronitrile, 1, the 2-glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran (THF), N, dinethylformamide (DMF) and N, N-N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO) and tetramethylene sulfone, preferred propylene carbonate.
14. as the described method of arbitrary claim in the claim 9 to 13, it also is included in hyperacoustic auxiliary CNT that will handle down and is scattered in step in the solution.
15. as the described method of arbitrary claim in the claim 9 to 14, wherein said electrodeposition step is carried out under negative pressure, and is preferred-3V.
16. as the described method of arbitrary claim in the claim 9 to 15, its cycle period that also is included in each described galvanic deposit operation deposits the step of another metals like gold at described matrix surface.
17. as the described method of arbitrary claim in the claim 9 to 16, wherein said matrix is a clockwork feed.
18. coating composition, it comprises:
(a) carboxylic acidifying CNT; And
(b) has the material of a plurality of hydroxyls and/or amino group.
19. goods, it comprises the matrix that applies according to the described method of the arbitrary claim in claim 1 to 8 and the claim 9 to 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101349207A CN101358369B (en) | 2007-08-02 | 2008-07-31 | Functionalized carbon nanotube coating and use thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710138018.8 | 2007-08-02 | ||
| CN200710138018 | 2007-08-02 | ||
| CN2008101349207A CN101358369B (en) | 2007-08-02 | 2008-07-31 | Functionalized carbon nanotube coating and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101358369A true CN101358369A (en) | 2009-02-04 |
| CN101358369B CN101358369B (en) | 2011-05-25 |
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ID=40330965
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|---|---|---|---|
| CN2008101349207A Expired - Fee Related CN101358369B (en) | 2007-08-02 | 2008-07-31 | Functionalized carbon nanotube coating and use thereof |
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| Country | Link |
|---|---|
| CN (1) | CN101358369B (en) |
| CH (1) | CH697740B1 (en) |
| HK (1) | HK1125140A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041543B (en) * | 2009-10-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN107099834A (en) * | 2017-03-29 | 2017-08-29 | 广东工业大学 | A kind of copper radical self-lubricating composite coating and preparation method thereof |
| CN107099833A (en) * | 2017-03-29 | 2017-08-29 | 广东工业大学 | A kind of composite plating solution and preparation method thereof |
| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of the electrochemical oxidation synthetic method and its application of amide |
-
2008
- 2008-07-18 CH CH01124/08A patent/CH697740B1/en not_active IP Right Cessation
- 2008-07-31 CN CN2008101349207A patent/CN101358369B/en not_active Expired - Fee Related
-
2009
- 2009-03-24 HK HK09102831.0A patent/HK1125140A1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041543B (en) * | 2009-10-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN107099834A (en) * | 2017-03-29 | 2017-08-29 | 广东工业大学 | A kind of copper radical self-lubricating composite coating and preparation method thereof |
| CN107099833A (en) * | 2017-03-29 | 2017-08-29 | 广东工业大学 | A kind of composite plating solution and preparation method thereof |
| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of the electrochemical oxidation synthetic method and its application of amide |
Also Published As
| Publication number | Publication date |
|---|---|
| CH697740B1 (en) | 2009-08-31 |
| CH697740A2 (en) | 2009-02-13 |
| HK1125140A1 (en) | 2009-07-31 |
| CN101358369B (en) | 2011-05-25 |
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