CN101198542A

CN101198542A - Product including carbon nano-tube and method for purifying fluid with the carbon nano-tube

Info

Publication number: CN101198542A
Application number: CN200580050073.0A
Authority: CN
Inventors: 克里斯托弗·H·库珀; 艾伦·G·卡明斯; 米哈伊尔·Y·斯塔罗斯京; 查尔斯·P·洪辛格
Original assignee: Seldon Technologies LLC
Current assignee: Seldon Technologies LLC
Priority date: 2005-04-22
Filing date: 2005-04-22
Publication date: 2008-06-11
Also published as: WO2006115486A1; EP1885647A1; JP2008538531A

Abstract

Disclosed herein are articles for removing contaminants from a fluid, such as a liquid or gas, the article comprising carbon nanotubes, which comprise at least one molecule or cluster attached thereto or located therein, wherein the carbon nanotubes are present in the article in an amount sufficient to reduce the concentration of contaminants in fluid that come into contact with the article. A method of making the nanomesh material used in such articles is also disclosed, as are methods of purifying fluids using these articles.

Description

Comprise the product of CNT and use the method for described CNT bodies for purifying fluids

This paper is the Application No. No.10/794 that submits on March 8th, 2004,056 part continuation application, and require the following this country priority: in the U.S. Provisional Patent Application sequence number 60/452 of submission on March 7th, 2003,530, the U.S. Provisional Patent Application sequence number of submitting on May 6th, 2,003 60/468,109, the U.S. Provisional Patent Application sequence number of submitting on September 3rd, 2,003 60/499,375, all these are included in this paper as a reference in full with it.

The disclosure relates to from remove the product of pollutant such as fluids such as liquid or gases, and wherein said product comprises CNT.The disclosure also relates to the method for making such product and uses described product to remove the method for pollutant from fluid.In some embodiment, disclosed product is used to from being made drinking water or be used to make salt solution to remove freshen by the water of microbial contamination.

There are many steps and method to handle to be used to and consume, use, handle and the fluid of other needs.Be chemical treatment among the most general step with disinfectant, distillation with purify waste water, centrifugal and filter with remove particulate (both in liquid also in air), decant with two-phase, counter-infiltration and the electrodialysis of separation of the fluid so that liquid deionization, pasteurization with sterilized food, and catalytic process be converted into useful products with the reactant that will not expect.Because each of these methods is designed to application-specific, the combination that needs method usually is to realize end-product.

When handling fluid, will balanced factor comprise fluid-flow rate, flow resistance and pollutant removal level.Desirable will be have can preceding two factors of balance material, realize simultaneously than before possible higher levels of pollutant removal.

The hope of nanometer technology material is that it will make us can accomplish the thing of using more other materials of traditional macro level not accomplish, such as fluid purification.Many existing methods can comprise that product or filter such as nano materials such as CNTs improve by use.Foundly be that the suitably prepd net (" nanometer net (nanomesh) ") of CNT that comprises can be used to remove various pollutant from fluid, the particulate, chemicals (natural and synthetic) that comprise virus, bacterium, organic and inorganic pollution, salt ion, nanometer or micron-scale, realize at least a additional benefits simultaneously, such as the weight that keeps or improve the fluid-flow rate by product, the flow resistance that reduces the leap product or reduction products obtained therefrom.

As the term " nanometer " that is used for this paper relates to material or structure, and its size is in the scope of about part per billion meter (being nanometer), such as at molecular level.For example, term " nanometer technology " is usually directed to have 1 to 500nm, and the technology of at least one size grades such as 1 to 100nm presents at least one character or function as the result of described little grade, and can control or operate independent atom or molecule.

Summary of the invention

More than realizing, a kind of product that generally includes CNT is provided, wherein at least one CNT is added or is connected to another CNT or arrived other materials, such as fiber, particle or matrix." CNT " is meant the nanoscale tubular construction, and it is made up of the hexatomic ring of carbon substantially, and its one-tenth key pattern forms hexagonal lattice, with the wall of closed in itself with the formation cylindrical structural.This interconnect architecture that comprises nanotube to small part is called as " nanometer net " in this paper.

This paper has disclosed a kind of being used for from remove the product of pollutant such as fluids such as water or air.Described product generally includes nanotube, and can or can not comprise be connected thereto or be positioned at wherein at least one molecule or bunch, wherein said CNT with enough make with the product fluid in contact in the amount that reduces of pollutant levels be present in the described product.

A kind of method that reduces amount of pollutants in the fluid also is provided, and described method comprises fluid is reached enough a period of time of separating, remove, fix, modifying or destroying at least a pollutant in the fluid with product described herein contact.In the embodiment, described method can be used to remove pollutant from water or air.

Further provide a kind of preparation to comprise the method for the nano material of CNT.Described method comprises machinery, chemistry or radiation treatment, or its any combination, and CNT forms functionalized carbon nanotubes thereby described medium is enough to make at least a sense chemical group to be connected to carbon nano tube surface in certain medium.Described method also comprises functionalized carbon nanotubes rinsing and/or dispersion at least a solvent that is selected from moisture, inorganic and organic solvent.Described method also comprises the eurypalynous CNT that can have the different chemical functionalization of combination, to assist in removing, to destroy or to change pollutant.

In the embodiment, described method also comprises functionalized carbon nanotubes and fiber and at least one solvent to form the suspension of functionalized carbon nanotubes and fiber.By suspension being deposited on the matrix, and on porous matrix, form the nanometer stratum reticulare usually such as any standard methods such as vacuum filtrations.

Except that above main topic of discussion, the disclosure comprises that many other can imitate feature, such as those in explanation hereinafter.Be above-mentioned explanation and the following narration that to be understood all only are exemplary.

Brief Description Of Drawings

Described accompanying drawing is merged in this specification and constitutes the part of this specification.

Fig. 1 is the bonding structure of SWCN and the schematic diagram of shape.

Fig. 2 represents the lattice deformation of defective CNT.

Fig. 3 represents to make the functionalized sectional view of CNT with carboxyl functional group.

Fig. 4 represents the CNT that is full of.

Fig. 5 not sectional view of homoatomic CNT of representing to mix.

Fig. 6 represents to comprise the fluid purifying apparatus of CNT, and wherein said matrix has the pleated design.

Fig. 7 is illustrated in the method for deposition of carbon nanotubes on the rolling matrix, and described matrix can center on cylinder, wooden unit or other bulk materials and twine.

Fig. 8 has schematically represented to show the desalter that is electrically connected to the nanometer stratum reticulare.

Fig. 9 represents to use the sequence of crossing the nanometer nethike embrane to apply low frequency, three-phase AC signal (driving ion motion) and high-frequency AC signal (destroy debye atmosphere (debye atmosphere)), the dynamics of the ion motion by the nanometer nethike embrane sequence in active pattern.

Figure 10 illustrates that schematically the ion neighborhood in the aqueous solution also shows the polarization property owing to hydrone, by the electron screening thing of molecular cloud (debye atmosphere) formation.

Figure 11 is the flow chart that is used to make the fluid purifying apparatus method.Present embodiment is specific to cylindrical matrix, but uses any matrix and fiber and/or particulate in the solution, can be easy to be generalized to the product of Any shape.

Figure 12 represents the structure of the cylindrical pattern of invention fluid purification product.

Figure 13 represents the flat pattern of invention fluid purification product.

Figure 14 is an optical microscope image, and it shows almost uniform bacterium (dyeing) covering of the solution that is untreated among embodiment 1#, the sample #1.

Figure 15 is an optical microscope image, and it shows the bacterium in groups (dyeing) on the CNT in the nanotube Treatment Solution among embodiment 1#, the sample #2.

Figure 16 is SEM (SEM) image, and it shows and not to have a bacterium that has the normal cell wall under the nanotube situation from embodiment #1, sample #1.

Figure 17 is the SEM image, and it shows diffusion and the bacteria cell wall that damages, and described bacterium and nanotube (among embodiment #1, the sample #2) interact, and it hints that this interaction can damage bacterial cell.

Figure 18 is the schematic depositing device that is used for forming the nanometer net on cylindrical matrix.

Figure 19 is the figure that shows the cylindrical fluid purified product of assembling.

Figure 20 is the photograph of test desalter.

Figure 21 is the schematic diagram of air film testing equipment.

Figure 22 is the SEM microphoto of the CNT/glass fibre nanometer net of self assembly.

Detailed Description Of The Invention

One side of the present disclosure is provided for removing the product of pollutant from fluid. " fluid " means and comprises liquid Or gas. " pollutant " means at least a unnecessary or unwanted composition, molecule or the organic matter in the fluid. " removal " (or its arbitrary form) is understood that to mean with at least a following mechanism to be destroyed, changes or divide From pollutant: granularity is got rid of, absorbs, is absorbed, chemistry or biological interaction or reaction. " chemistry or living The interaction of thing or reaction " be understood that to mean by method and pollutant chemistry or biology and mutually do With, described method causes described pollutant can not cause infringement. Such example is reduction, oxidation, chemistry The physical damage of sex change, microorganism, biomolecule, picked-up and embedding.

" granularity " is by many class declarations, for example by having in a large number the particulate of specific dimensions. Described method is logical Often measure by microscopy, such as by calibrated light microscope, by calibrated polyphenyl second Alkene pearl (polystyrene beads), by calibrated scanning probe microscopy SEM or The optical near-field microscope. Measure the method for size described herein at Walter C.McCrone ' s etc., The Particle Atlas, (An encyclopedia of techniques for small particle identification), Vol.I, instruction among the Principles and Techniques, Ed.2 (Ann Arbor Science Pub.), its quilt Include in this paper as a reference.

The non-limiting example of the liquid that can purify with product described herein comprises water, food, biological stream Body, oil and byproduct thereof, non-petroleum fuel, medicine, organic and inorganic solvent, and hydrogen, oxygen, nitrogen and The liquid form of carbon dioxide, as being used in propellant or the commercial Application.

Can be comprised by the non-limiting example with the food of this product treatment animal byproducts (such as egg and milk), Fruit juice, alcohol with Nonalcoholic beverage, natural and synthetic syrup, and be used for the cooking or food industry In natural and synthetic oil [such as olive oil, peanut oil, caul-fat (sunflower, safflower), vegetable oil or Derived from zoogenous oil (being butter, lard)] or its any combination. As an embodiment, sulfurous Hydrochlorate often is added in the wine to prevent variable color and to help anticorrosion. But sulphite causes that health asks Topic also should be avoided. An aspect of of the present present invention can comprise according to the preparation target removes sulphite, makes the wine worker Industry is benefited from purification method described herein.

Can usually can be derived from animal, the mankind, plant with the biofluid that product described herein purifies, Or comprise the fluid nutrient medium of the cultivation processed for biotechnology or drug products/growth. An enforcement side In the formula, the biofluid that can be cleaned comprises blood (or blood component), serum and milk. Be used for medicine Biologic product in the product often is very unsettled and is difficult to sterilize by routine techniques. Little microorganism is (all Such as mycoplasma and virus) removal can not realize by conventional filtration. The carbon nanometer net product of invention can be used The destruction that does not cause haemocyanin in removing virus, described haemocyanin exists also in the biologic product of being everlasting Be required. In the embodiment, the physics and chemistry characteristic of nanometer net can be controlled to medicine was produced The pollutant that forms in the journey can be removed.

In another embodiment, the product of invention can be used for the sterilization of oil product. A significant pollution Problem is the growth of hiding of bacterium in the oil or derivatives thereof between the storage life, and this especially becomes asking of aviation fuel Topic. Fuel can be seriously polluted and finally destroy in the existence of above-mentioned bacterium. Therefore, in the fluid purification field The major domain of concern be cleaning bacteria from natural and/or synthetic oil product. Natural and/or synthetic That oil and byproduct thereof comprise is aviation, automobile, sea-freight, fuel locomotive and rocket, industry and Machinery oil and lubricating oil and heating oil and gas.

Another substantial pollution problem of oil product is some metal of high sulphur content and excessive levels, and significant example is plumbous.Statutory regulation forbids that sulphur and the lead concentration in the hydrocarbon fuels (being used for internal combustion engine) surpasses specified quantitative (MLC-greatest contamination level).Therefore, need a kind of product from oil, to remove the particular chemical pollutant and do not add other unnecessary compositions.In one embodiment, product described herein can be used to from hydrocarbon or such as removing sulphur and/or special metal in the other types fuel of using the fuel cell such as gas.

Because many aforementioned contaminants can spread in air, need a kind of product to be used for Purge gas.Therefore, another aspect of the present invention comprise purify air with remove any before the method for listed pollutant.But use the non-limiting example of product cleaned gas described herein to comprise one or more gases, it is selected from air or from the discharge gas of the vehicles, chimney, chimney or cigarette.When being used to purify air, product can adopt flat form to be provided for the more high surface area of air stream.The additional benefits that such flat form provides is to be easy to be cut into the suitable shape that is used for the design of various filters, such as being used for those of breathing mask and HVAC system.Following gas that can be processed according to the disclosure (such as being washed with Purge gas or from discharge gas their being removed) comprises argon gas, acetylene, nitrogen, nitrous oxide, helium, hydrogen, oxygen, ammonia, carbon monoxide, carbon dioxide, propane, butane, natural gas, ethene, chlorine or any aforesaid mixture, such as air, nitric oxide be used for the gas of submerged applications, such as helium/oxygen mixture.

What should be noted in addition, is that in fact those that can be identified as pollutant in a kind of fluid is used may be required products in the Another Application.For example, pollutant can contain precious metal or useful drug products.Therefore, it may be useful in the embodiment, separating, keep and collect pollutant rather than only remove and destroy them.The ability that can separate " catch and discharge " required pollutant of useful pollutant or some byproduct of reaction can be by regulating zeta potential and/or utilizing the nanoelectronic technology control of nanometer net product, as described in more detail below.

The application of product described herein comprises (immune construction project (Immune Building Project), army's purposes, refuse are remedied) and the place of medical (for example operating room, clean air and mask) of (for example solvent recovery, reagent purify), the government of (environment filtrations), the industry of family's (for example, the water and air of family expenses filter), amusement.

CNT has two kinds of forms usually: single wall and Duo Bi.SWCN comprises one of these tubular constructions, and interconnective hexagon like this is arranged in rows each other.Fig. 1 describes SWCN.In the embodiment, the normally about 1-2nm of the diameter of these SWCNs, be similar to human DNA (～2nm), and common length range is from hundreds of nanometers to many microns.Multi-walled carbon nano-tubes comprises many concentric shells of these tubular structures.They can have the diameter of tens nanometers, and can have hundreds of meters length at the most in theory.

Yet optionally, nanometer net described herein can comprise connected to one another or be connected to the CNT of other material.Adhering to and/or connecting in the nanometer net is that to be used in nano level result, its non-limiting example be Van der Waals (Van der Waals) power, covalently bound, ion connection, geometrical constraint, static, magnetic, electromagnetism or Casimir active force or its combination to masterpiece.

The disclosure also relates to by contaminated fluid is contacted and the method for bodies for purifying fluids with nanometer net in the product described herein.In the embodiment, the method of bodies for purifying fluids comprises makes fluid contact with the nanometer net, wherein CNT is present in the nanometer net reducing the concentration of at least a pollutant in the fluid with enough quantity, described fluid and nanometer net or contacted by the interaction zone of nanometer net manufacturing.As used herein, " be reduced by at least a kind of pollutant levels " and mean at least a pollutant is reduced to level under the described pollutant level of untreated fluid, under greatest contamination thing level (MLC), this level is limited by the industrial requirements of the particular fluid quality standard after the invention product treatment by suitable management organization or management.

An aspect of the present disclosure relates to the purposes of the CNT with the nanostructured carbocyclic ring volute tubulose or non-tubular shape.Normally single wall, many walls or its combination of these CNTs, and can adopt various structures.For example, be used for that structure that the CNT of the disclosure can have is selected from horn shape, helical form, multiply helical form, spring-like, dendroid, tree-shaped, spider nano tube structure, nanotube Y-connects and the bamboo structure.Some of the above shape are defined in M.S.Dresselhaus more specifically, G.Dresselhaus, andP.Avouris, eds.Carbon Nanotubes:Synthesis, Structure, Properties, andApplications, Topics in Applied Physics.80.2000, Springer-Verlag; With " A ChemicalRoute to Carbon Nanoscrolls, Lisa M.Viculis, Julia J.Mack, and Richard B.Kaner; Science, 28 February 2003; In 299, the two is included in this paper as a reference.

An aspect of disclosed product, most of CNT is twisted by crystal defect, so that they present stronger purifying property than unwrung CNT." crystal defect " refers to the position in the tube wall of CNT, has lattice deformation at least one carbocyclic ring herein.

" lattice deformation " means any deformation of the CNT atomic lattice that forms the tubular piece structure.As illustrated in fig. 2, lattice deformation can comprise owing to any atomic substitutions of inelastic deformation or have 5 and/or 7 members' carbochain or the sp of carbon atom key ²The interaction of the chemistry after hybridization changes.Such defective or distortion can cause the natural torsion in the CNT.

Phrase " presents stronger purifying property " and means the improvement that the nanometer net is represented structural intergrity, its porosity, its porosity distribution, its conductivity, its fluid flow impedance, geometrical constraint or its any combination to structural material, and this result is the removal that strengthens pollutant.For example, stronger purifying property can be since separately the improvement of CNT with more effective absorption or absorption characteristic.In addition, many more defectives are present in the CNT, and many more sites exist and are used to connect the chemical functional group.In the embodiment, increase the performance that the number of functional groups that is present in the nanometer net should improve products obtained therefrom.

The processing of CNT

In the disclosure, CNT can also stand chemistry and/or chemistry and/or the physical property of physical treatment to change them.These processing are done usually so that products obtained therefrom can be presented on the stronger purifying property on the meaning defined above.

In the embodiment, CNT can chemically or with physical method be handled in order to realize at least a following effect: remove pollutant, add defective or connect functional group to defect sites and/or nanotube surface.

This paper, " chemistry or physical treatment " mean with time of acid, solvent or oxidizer treatment abundance removing unnecessary composition, such as amorphous carbon, oxide or the trace accessory substance that forms by the carbon nanotube architecture method.

The chemically treated embodiment of second type is exposed to the time of one section abundance of oxidant to produce the defect concentration on the carbon nano tube surface with CNT.

The chemically treated embodiment of the 3rd type connects to have required zeta potential (as Johnson, P.R., Fundamentals of Fluid Filtration, 2nd Edition, 1998, Tall Oaks Publishing Inc., middle definition, it is by being included in this paper as a reference) the particular functional group.This will fully act on the zeta potential of regulating CNT or isoelectric point (zeta potential is the pH at zero place) to remove the required pollutant of particular group from particular fluid.

In another embodiment, CNT comprise with the effective dose that helps from fluid to remove and/or change pollutant be connected thereto or be positioned at wherein atom, ion, molecule or bunch.

CNT described herein can also be processed changing their characteristic, and the pollutant that can be removed and/or change in the fluid.For example, in the embodiment, CNT is chemically handled with oxidant, and described oxidant is selected from but is not limited to contain the gas of aerobic, nitric acid, sulfuric acid, hydrogen peroxide, potassium permanganate and combination thereof.The CNT of oxidized dose processing can provide unique character, or according to fluid flow, nanotube in the deposits fluid disperses, or from the contact (perspective) (for example, having functionalized especially ability) of functionalization.

As be used for this paper, " functionalized " (or its any translation) refer to have the atom that is connected to the surface or bunch CNT, it can change the nanotube character such as zeta potential etc.Functionalization is implemented by using chemical technology to change carbon nano tube surface usually, and described technology comprises wet-chemical or steam, gas or plasma chemistry and microwave assistant chemical technology, and utilizes surface chemistry to connect material to carbon nano tube surface.These methods are used to " activation " CNT, and it is defined as destroying at least one C-C or C-heteroatomic bond, therefore are provided for molecule or bunch surface that is connected thereto.As shown in Figure 3, functionalized CNT comprises the chemical group such as surfaces such as exterior side wall that is connected to CNT, such as carboxyl.In addition, the functionalization of nanotube can produce by the rapid method of multistep, and functional group is added continuously to nanotube to obtain specific, required functionalized nanotube in the described method.

Functionalized carbon nanotubes can comprise non-uniform composition and/or functional group densities, and described functional group comprises across the type of the functional group of carbon nano tube surface or kind.Similarly, functionalized carbon nanotubes can comprise the basic functional group gradient uniformly across carbon nano tube surface.For example, can there be or many different functional groups types (being hydroxyl, carboxyl, acid amides, amine, polyamines and/or other chemical functional groups) and/or functionalization density along a nanotube length or within nanotube is collected.

In addition, the nanometer net can also or apply or its combination and functionaliseding with zeta potential and/or crosslinked ability that changes them and the strainability that therefore improves the nanometer net with chemical group, decoration (decortions) such as other compositions such as fiber and/or nano particle.

The non-limiting example of implementing the rapid functionalization of specific multistep is to allow the zeta potential of CNT controlled and improve the ability that they remove virus.CNT refluxes in acid blend.Yet, not being subjected to the restriction of any theory, the such method that is that is worth believing increases the quantity of defective on the nanotube surface, increases to be connected to the carboxyl functional group of defective locations, and/or changes the zeta potential of nanotube owing to the negative electrical charge of carboxyl functional group in the water.

Can in the nitrogen atmosphere, in thionyl (two) solutions of chlorine, reflux after the carboxy-functionalized nanotube.Yet, not being subjected to the restriction of any theory, this carboxyl functional group that act as connection before that is that is worth believing is converted into acid chloride functional groups.Subsequently, the functionalized nanotube of these acyl chlorides refluxes in ethylenediamine solution in the nitrogen atmosphere once more.Be this and the amido on the diamines end that has acid chloride functional groups that are worth believing react, therefore by being that an amido of diamines makes acid chloride functional groups be converted into 2-aminoethyl functional group with the chlorine atomic substitutions.The termination that has the nanotube functionalization of amido will give the positive charge of the nanotube in the water, give its positive or less negative zeta potential.The aforementioned nanometer net equipment of constructing with this type nanometer net that will make can be used for catching by Van der Waals force and/or electrostatic force by the electronegative pollutant (such as anion, some molecule and virion) of specific target, causes from the pollutant current they being removed.

In another embodiment, CNT can also be used to the high surface molecular skeleton, is used to comprise the functional group of organic and/or inorganic acceptors or natural or bionic the cell structure and the supporting of [comprising bacterium, nanometer bacteria and extremophilic bacterium] are provided.The bacterium example (comprising the image of receiving bacterium in carbonate sediment and the rock) of receiving can see below with reference to, it is included in this paper as a reference.R.L.Folk，J.Sediment.Petrol.63：990-999(1993)，R.H.Sillitoe，R.L?Folk?and?N.Saric，Science272：1153-1155(1996)。Organic and/or inorganic acceptors optionally target is removed specific pollutants from fluid stream.By active pollutant on the natural or bionic cell of nanotube supporting the biology that consumption, metabolism, neutralization and/or biology-mineralising (bio-mineralize) is specific.For example, have the specified microorganisms that is connected to nanotube, it can reduce the toxicity of oil slick.

Another aspect of the present invention, CNT, carbon nano-tube material or any its assembly can be used radiation treatment.Radiation can be selected from but be not limited to be exposed to electromagnetic radiation and/or at least a be selected from electronics, radionuclide, ion, particulate, bunch, the particulate of molecule or its any combination.As previously mentioned, radiation should be mapped to following effective dose on the CNT: 1) destroy at least one carbon-to-carbon or carbon-heteroatom bond; 2) implement between nanotube-nanotube, nanotube crosslinked to other nanometer net compositions or nanotube to matrix; 3) carrying out particle implants; 4) improve the chemical treatment of CNT, or its any combination.Radiation can cause the difference dosage (for example because the difference penetrance of radiation) of nanotube, and it causes the defect sturcture heterogeneous in the nano tube structure.The variation of this functional group by being connected to CNT can be used to provide change of properties.

CNT described herein can also or flood to realize some beneficial property with the material requested filling.Term " filling " or " dipping " can exchange use, and relate to the partially filled at least CNT with desired substance.The material that is filled or is impregnated in the CNT can improve the strainability of nanometer net and/or its application of target once more specifically usually.Non-limiting example is by increasing nanotube the affinity of specific pollutants to be improved filtration.For example, be used to remove electronegative pollutant as fruit product, such as the arsenic complex compound in the water, CNT at first floods with the electropositive material.Fig. 4 has illustrated the CNT of filling with material.

In addition, can remove pollutant or increase other Performance Characteristicses from fluid by being modified with the perhaps multiple particle coating of material layer or one or decoration helping according to CNT of the present disclosure, such as mechanical strength, volume conductivity or on-mechanical characteristic.Be different from functionalized carbon nanotubes, the CNT that applies or decorate covers with the perhaps multiple particle of material layer and/or, be different from functional group, it needn't be connected to nanotube by chemistry, and its surf zone that fully covers nanotube is to improve the strainability of nanometer net.

The CNT that is used for product described herein can also mix component to help removing pollutant from fluid.As " mixing " CNT that is used for this paper is meant that it is not the ion or the atom of carbon that rolling crystal structure of hexagonal carbon exists.As illustrated in fig. 5, at least one carbon that the CNT that mixes means in the hexagonal rings is replaced by non-carbon atom.

In another embodiment, as described herein CNT can by bunch or atom or micel decorate." decoration " is meant the CNT that part applies as used herein." bunch " mean by any chemistry or physical connection and connect at least two atoms or molecule.

Bunch can present the character of quantum dot, it causes photostable, harmonious colours, as to have wide absorption spectrum and narrow radiation peak nanocrystal.What comprise quantum dot bunch can comprise metal, nonmetal and combination.These connected bunch subsequently can be by photoactivation to remove, to make the pollutant inactivation and/or to destroy pollutant.Quantum dot is a material grains, and its interpolation or removal so little so that electronics can be detected, and changes its character in some useful modes.In the embodiment, quantum dot is the semiconductor crystal that has several nanometer diameters, is also referred to as nanocrystal, because its effect of small size is similar to the potential well that electronics is limited to several nano-area in three dimensions.

Molecule maybe can comprise inorganic compound, and described compound contains and is selected from following at least one metallic atom: lithium, sodium, magnesium, aluminium, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, rhodium, palladium, silver, indium, tin, caesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, bismuth and be selected from following at least one non-metallic atom: hydrogen, boron, carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, antimony, iodine and combination thereof.

Molecule or bunch can also comprise the organic compound that contains at least a protein, described protein comprises natural polymer, it mainly is made up of following: amino acid, carbohydrate, polymer, aromatic series or the aliphatic alcohol that connects by peptide bond, and nucleic acid or non-nucleic acid, and such as RNA and DNA.

The non-limiting example of organic compound can comprise and is selected from following at least one chemical group: carboxyl, amine, aromatic hydrocarbons, nitrile, acid amides, hydro carbons, alkene, alkynes, alcohol, ether, ester, aldehyde, ketone, polyamide, poly-amphipathic compound, diazol, slaine, pyrenyl, thiol base, thioether, sulfydryl, monosilane and combination thereof.

Aforementioned listed polymerization, pottery, the same material that comprises with material biology metal can be filled, functionalized or carbon nano-tube coating.What shown is, if deliberately make the surperficial defectiveness of CNT, above-mentioned material can be easy to be connected or replace in CNT more.

Be included in the fiber in the nanotube

Nanotube described herein can also comprise the fiber that act as maintenance CNT dispersion (or coming off) in processing procedure.Such fiber can be the integral part that sacrifice property (further remove from structure in the processing procedure, such as by chemistry or heat treatment) maybe can remain the equipment of finishing.Usually the diameter range that has of these fibers is from 1nm to 1mm, such as from 10nm to 100 μ m.

As be used for this paper, and term " fiber " means the object of length L and diameter D, and so L is greater than D, and wherein D is a diameter of a circle, and the cross section of fiber is inscribed within this circumference.For example, selected length-width ratio L/D (or form factor) scope, for example from 2 to 10 ⁹, such as from 5 to 10 ⁷, and further such as 5 to 10 ⁶

The fiber that can be used in the composition described herein can be that synthesize or natural inorganic or organic fiber.They can be short or long, and are independent or organized, for example braiding, hollow or solid.According to the specific purposes of expection, they can have Any shape, and can for example have the cross section of circle or polygon (square, hexagon or octagon).

The length range that fiber has is for example from 10nm to 10m, such as from 20nm to 1cm.Their cross section can be at diameter range for example within the circle from 1nm to 1mm.

Fiber can be those that are used for that fabric makes, and Tathagata is from biological mineralising or biopolymerization effect, the cellulose fibre that extracts such as silk fiber, cotton fiber, wool fiber, flax fiber, feather fiber, from for example timber, beans or algae.

Medical fibre also can be used for the disclosure.For example, can comprise by resorbent synthetic fibers: from those of glycolic acid and caprolactone preparation; Can resorbent synthetic fibers type the copolymer that is lactic acid and glycolic acid; And poly-terephthaldehyde's ester fiber.Such as non-can being used by resorbent fiber such as stainless steel screw threads.

Described fiber can be selected from:

(a) at least a polymeric material, it is selected from list or multicomponent polymer, (is Kevlar such as nylon, acrylic acid (polymer), methacrylic acid (polymer), epoxy resin, silicon rubber, synthetic rubber, polypropylene, polyethylene, polyurethane, polystyrene, Merlon, aromatic series polyamide ^And Nomex ^), polychloroprene, terephthalic acids polybutester, poly-to phylene terephthalic acids acid amides (poly-paraphyleneterephtalamide), poly-(to phenylene terephthalic acids acid amides) (poly (p-phenyleneterephtalamide)) and polyester, ester, ketone (polyester ester ketone), polyester [for example, poly-(terephthalic acids vinyl acetate) is such as Dacron ^], polytetrafluoroethylene (PTFE) (is Teflon ^), polyvinyl chloride, polyvinyl acetate, viton fluorubber fluoroelastomer, polymethyl methacrylate (be Plexiglass ^) and polyacrylonitrile (be Orion ^) and combination;

(b) at least aly be selected from following ceramic material: boron carbide, borazon, spinelle, garnet, lanthanum fluoride, calcirm-fluoride, carborundum, carbon and allotrope thereof, silica, glass, quartz, silicon nitride, aluminium oxide, aluminium nitride, aluminium hydroxide, hafnium boride, thorium oxide, cordierite, mullite, ferrite, sapphire, saponite, titanium carbide, titanium nitride, titanium boride, zirconium carbide, zirconium boride, zirconium nitride and combination thereof.

(c) at least aly be selected from following metal material: aluminium, boron, copper, cobalt, gold, platinum, palladium, silicon, steel, titanium, rhodium, iridium, indium, iron, gallium, germanium, tin, tungsten, niobium, magnesium, manganese, molybdenum, nickel, silver, zirconium, yttrium, their oxide, hydride, hydroxide and alloy thereof.

(d) at least aly be selected from following biomaterial or derivatives thereof: cotton, cellulose, wool, silk and feather and combination thereof; And

(e) at least aly be selected from following CNT: the CNT of single wall, double-walled or many walls, its have receive horn shape, receive helical form, receive spring-like, dendroid, tree-shaped, the nano tube structure of spider, nanotube Y-connects and the nested or non-nested structure of bamboo structure or multiply spiral;

(f) at least a metal oxide or metal hydroxides receives lead.For example, metal oxide is received the preparation of lead and can be reached time from 30 minutes to 2 hours scopes by plain conductor and oxygen one being same as be heated in the reaction vessel from the temperature of 230-1000 ℃ of scope.Make any aforementioned metal as raw material, will grow by using macroscopical rank lead nm-class conducting wire.It can be from the 1-100 nanometer that the gained metal oxide is received the diameter dimension scope of lead, such as diameter 1-50 nanometer, comprises diameter 2-5 nanometer.Swiped so that coarse surface structure to be provided so that the purifying property of better nanotube adhesion in the nanometer net and reinforcement product becomes possibility in a useful aspect of the method, the surface of substrate lead.The lead of receiving of these metal oxides or metal hydroxides also can obtain from goods providers.

The matrix that is used for equipment

In the embodiment, described product comprises the porous supporting substrate that uses the differential pressure method to come deposition of carbon nanotubes.The porous supporting substrate can be any form that is suitable for the products obtained therefrom shape, such as bulk, pipe (or cylinder), thin slice or reel, and can comprise the material that is selected from pottery, carbon, metal, metal alloy or plastics or its combination.In the embodiment, matrix comprises braiding or non-woven fibrous material.

In addition, when matrix adopted sheet form, matrix can be the thin slice on flat or plane or with fold form (Fig. 6).Selecteed pleated forms increases the surface area that the nanometer net is exposed to contaminated-fluid.

In the embodiment, matrix is cylinder material, and the nanometer net is placed thereon.In the method, in continuous or semi-continuous mode, can be by a series of depositions and other processing position reels by scrolling.

In another embodiment, wherein said nanometer net is produced by rolling method, and it can be used to twine to form filter medium, as describing among Fig. 7 around hollow, perforated cylinder, bulk or other supporting structures.

In another embodiment, perforated tubular matrix comprises material with carbon element, such as active carbon (bulk or fiber), its outer surface coated with CNT described herein.

In another embodiment, the set (as above-mentioned manufacturing) of lead received of metal oxide/hydroxide can also be used as the matrix of using the pressure reduction sedimentation to come deposition of carbon nanotubes.Gained receive lead carbon nanotube net can or can be not by with heat, with mechanical means or chemically handle and strengthen structural intergrity and/or improve the product purifying property.Chemical treatment can comprise that usefulness chemical group, metal, pottery, plastics or polymer are next functionalized, apply or modify gained nanometer net.In addition, these chemical treatments can so be finished, so that their nanometer net product is with the reaction chemically or physically of pollutant or do so that they are destroyed, modify, fix, remove or separate mutually.

In other embodiments, in the pressure reduction sedimentation process used porous supporting substrate can be sacrifice property or in deposition process only interim use be similar to nanometer net in the method for paper process with formation.

Other forms of expression of equipment

Another embodiment of product comprises many nanometers stratum reticulare, and its each layer can be specifically, and independently, regulates with the specific distribution of removing pollutant or other performance characteristics of improving product by its zeta potential or other modes.Phrase " other modes " means the special properties that the nanometer stratum reticulare is adjusted in expression, such as its porosity rate, and pollutant compatibility [for example, the functionalization of nanometer net composition, special pollutant acceptor] or intensity (for example, used connection or crosslinking agent).

In another embodiment, the nanometer net contains adhesive (such as polyvinyl alcohol), and it act as the strainability that improves product.Before the nanometer web frame formed, such adhesive can be introduced into the suspension that contains CNT and other nanometer net compositions.

In another embodiment, can form the nanometer net by self-assembling method." self assembly " means nanometer net composition oneself and is arranged as final nanometer web frame.This is by selecting functional group, surface charge distribution, composition or dispersant character or its any combination, and the constraint with how much electricity, magnetic by controlling, chemistry realizes.For example, their electrical property is controlled in the adjusting that the surface charge of nanometer net composition distributes, and it determines successively how they are arranged as the structure of assemble nanometer net.This self assembly can be any form that produces the structural framing of the enhancing in the nanometer net, and it has improved removal characteristic, porous, resistance, fluid flow impedance, strength characteristics or its combination.

In addition, above self assembly can be by " guiding " by applying external field.This impressed field is with consistent the acting on of character of arbitrary or all nanometer net compositions and/or fluid, and it is gained nanometer net that the composition in the fluid is suspended to guide their self assembly.For example, in the nanometer net formation process, the suspension that contains the some or all of compositions of nanometer net can be subjected to electromagnetic stimulation and arrange and/or weave with the enhance fluid purifying property to realize required composition.

Do not wish to be bound by any theory, the nanometer net described herein that is that is worth believing forms unique nanometer observation (nanoscopic) interaction zone, and it at first attracts to modify then or separate microorganism or other pathogens of flowing from fluid with chemistry and physical force.For example, what be worth believing is in the fluid disinfection process that microorganism contacts with the nanometer net, and it makes the power of gathering be applied to microorganism.These power at first attract, cause then and adhere to and/or cell modification.Possible is that this kind modification comprises the destruction cell membrane or causes the interior detail cellular damage, therefore makes microorganism or their fecundity inactivation and/or destruction.By this way, fluids for sterilization effectively with regard to microorganism.Usually the size range of microorganism is that the 1-5 micron is long, and like this greater than such as at least 100 times of nanostructureds such as CNT.The known example of these microorganisms comprises that Escherichia coli, comma bacillus (Vibrio cholera), salmonella typhi, will congratulate (family name) dysentery bacillus, Cryptosporidium parvum, giardia intestinalis, Entamoeba histolytica and many other microorganisms.Comprise polio, hepatitis A, rotavirus, enterovirus and a lot of other virus by water-borne viral example.The example of chemical reagent includes, but is not limited to iron, heavy metal, Insecticides (tech) ﹠ Herbicides (tech), organic and inorganic toxin, and microbial toxin (such as causing those of botulism).

Because big size difference, the power on the nanoscopic level can be applied in, and they are than stronger on the order of magnitude based on those of microcosmic or macroscopical technology.Give the mode of laser with intensity by the light that is similar to focusing, the power of focusing is given the attraction intensity and/or the destroy microorganisms of nanoscale (nanoscale).Therefore, the power of the machinery of large level and electricity or too small so that to no effect, or energy very dense, (machinery and the power of electricity) can be used to effectively or remove efficiently or destroy microorganisms on the nanoscale.

In this nanometer range (nano-regime), it is believed that the mechanism that can adsorb destroy microorganisms then can be independently or consistent each other acting on.The non-limiting example of above-mentioned mechanism comprises:

By infiltration of power machinery and/or the wearing and tearing cell membrane that focuses on;

Shock wave, it causes outer damage and/or interior detail cellular damage to the cell membrane of DNA, RNA, protein, organelle official rank and transmission passage;

Around the bubble cavitation erosion from seismic wave in the liquid of CNT, it destroys eucaryotic cell structure;

Electromagnetism, static and/or Van der Waals force, it is caught and the fixed biologically pollutant;

By near the hydrogen bond the electromotive force effect destruction nanostructured, the destruction that causes cell membrane and/or DNA;

Owing to attract spontaneous H in the water ⁺Specific nanotube functionalization, around the environment acidifying of nanostructured, its damaging cells wall and/or DNA.

Because usually the pressure of the projecting fluid of osmotic pressure in the microbial cell is supposed non-physiological conditions and since cell inclusion from high-pressure spray to low pressure, or even the slight damage of pair cell wall can cause integral body to be broken.In addition, can damage at least a breeding of microorganism or the ability of host cells infected, present it and can not cause infection the abundant destruction of virus or microbial cell DNA.

The nanoelectronic fluid purification

According to the disclosure, the other method of fluid purification is also based on nanometer net product.In this case, apply static or electromagnetic field on the net with the control fluid purification in nanometer.Be very similar to the performance of electrostatic separation equipment, apply the pollutant that to remove nanoscale (nanoscale) across the electromotive force of nanometer net.In addition, the method can be made by reversing and be used for the polishing filter product.

In addition, whole nanometer net can stimulate with dynamic electromagnetic field, and described magnetic field will stimulate the vibrations of nanometer net wide cut when suitably being adjusted.These vibrations not only can have microbial destruction effect but also can induced ultrasonic ripple automated cleaning effect.Thus, the effectiveness of invention product is to adopt the advantage of high strength, high rigidity (big Young's modulus), high conductance and the piezoelectric property of nanotube.

Therefore, use, apply the electromagnetic field that more generalizes and to give the purifying property that fluid surpasses prior art for some.For example, in the situation of two conductive nano stratum reticulares, apply the magnetic field (Fig. 8) between the electric current generation nanometer stratum reticulare.This can be conditioned to catch all charged particles from fluid stream.

The liquid desalination

According to the disclosure, the liquid desalination process also is based on described nanometer net product.Be trusted as that can enough described nanometer net products to make a mechanism of liquid desalination be to apply differential voltage between two or more nanometer nethike embranes.In the case, a nanometer nethike embrane carries positive charge, another film negative electrical charge.The electromotive force that applies causes that cation moves towards electronegative film, and then anion moves towards positively charged that.Because the high surface area (1000m of CNT ²/ gram), use differential voltage across the nanometer nethike embrane and produce very high capacitance apparatus, thereby produce effective, compact, reversible ion isolation zone (being ion trap).

The desalination unit can comprise the conductibility nanometer net parallel layers of two or more supportings, and described layer is electrically insulated from each other.Described two or more layers can be charged with the pattern of static or activity.In the static schema, for example, the nanometer stratum reticulare can be reversed charging to produce the salt trap between them.In the active pattern, have four or more multi-layered equipment, for example four phase signals will be applied to the multi-layer nano web frame, so that four phase places of signal are applied to four continuous nanometer stratum reticulares.Repeat this pattern (Fig. 9) every four nanometer stratum reticulares.By this way, the electric charge on each nanometer stratum reticulare can stride across the equipment index in time and in succession from positive to neutrality to negative to neutrality.Finish the equipment inner capacitor of the reality that will produce electronically, move on time in succession, it can cause that salt ion is moving on by the different direction of the direction of equipment with current.Concentrated salt solution will also can have groove at the salt mouth of a river of equipment in the end accumulation of real capacitor, and fresh water will be by described equipment simultaneously.

In fact, because the polarization property of hydrone, the ion in the aqueous solution makes their electric charge by the hydrone cloud protection of surrounding them, and it is described to the debye atmosphere among Figure 10.Because this hydrone cloud is carried with ion when ion moves, it act as effective mass and the ionic radius that increases ion.Therefore, the AC signal of higher frequency (with respect to the required frequency of inducing ion isolation) can apply across the rete in the desalter.The purpose of this higher frequency signal is that the debye atmosphere of protection effects of ion is disintegrated.As the result that this hydrone shell comes off, ion is rendered as littler and lighter and handier and can has the fluid that moves through of littler impedance.The efficient that has improved desalter in this respect of invention.

In addition, desalter described herein can be designed to utilize the biological removal characteristic of aforesaid nanometer web frame to purify gained fresh water.

Biomembranous prevention

According to an aspect of the present disclosure because the adhering to and grow of contaminative microorganism, to biomembrane form the surface of sensitivity can coated layer of nanomaterial to prevent or to adhere to or such as the growth subsequently of undesirable constituents such as mould, bacterium.The non-limiting example of above-mentioned nano material comprises composition or the compound (such as iodine resin, silver, aluminium oxide, aluminium hydroxide or triclosan) with antibacterial properties, and they are connected to described surface or are positioned at CNT or are connected to any other nanometer net means.

By the removable pollutant type of the present invention

Use disclosed product, can include, but is not limited to following biologic product by the non-limiting example of removed pollutant from fluid: pathogenic microorganism [such as virus (for example, smallpox and hepatitis), bacterium (for example, anthrax, typhus, cholera), cystozygote, gemma (natural with weaponized armsization), mould, fungi, coliform, and enterozoon], biomolecule (for example, DNA, RNA) and other pathogen [such as prion and nanometer bacteria (natural and synthetic the two)].

" prion " is defined as little infective, the proteinaceous particle that has, and its opposing is by the deactivation of the step of modification of nucleic acids and most other protein.The two all is easy to infection protein enzyme infectious agent disease [BSE of ox (BSE or rabid ox disease) or people's creutzfeldt-Jacob disease (CJD)] human and animal.

" nanometer bacteria " is the nanoscale bacterium, and recently some of them are assumed to be and not only cause biomineralization in the people but also in animal.It also is assumed to be nanometer bacteria and can works in the formation of the heart disease of kidney stone, some forms and senile dementia (Alzheimer disease).In addition, nanometer bacteria is also doubted to causing the chemical reaction in unnecessary biomineralization and/or some industrial technologies.

Use disclosed product, can be from fluid other non-limiting examples of removed pollutant include, but is not limited to poisonous, dangerous or carcinogenic chemicals, it comprises nature and synthetic organic molecule (such as toxin, endotoxin, protein, enzyme, pesticide and herbicide), inorganic pollution (such as heavy metal, fertilizer, inorganic toxic material) and ion (particle that disseminates such as the salt in the seawater or charged air).

The application that bodies for purifying fluids is particularly purified waste water comprises drinking water, flushing, medical treatment and industrial.For example, be used for industrial treatment as deionized water source, it includes, but is not limited to the semiconductor manufacturing, general chemistry industry and laboratory applications are electroplated, reached to metal.

More particularly, use product described herein, can from fluid, removed chemical compound be the removal of target atom or molecule, described atom or molecule comprise at least a atom or the ion that is selected from following composition: antimony, arsenic, aluminium, selenium, hydrogen, lithium, boron, carbon, oxygen, calcium, magnesium, sulphur, chlorine, niobium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, bromine, strontium, zirconium, yttrium, molybdenum, rhodium, palladium, iodine, silver, cadmium, indium, caesium, tin, barium, lanthanum, tantalum, beryllium, copper, fluoride, mercury, tungsten, iridium, hafnium, rhenium, osmium, platinum, gold, mercury, thallium, plumbous, bismuth, polonium, radon, radium, thorium, uranium, plutonium, radon and combination thereof.

The vague generalization structure of invention

Another aspect of the present disclosure relates to the method for making the nanometer net materials, and described material will be used to remove from fluid in the product that pollutant uses, and such nanometer net materials comprises functionalized CNT.Make the nanometer net commonsense method comprise that to make CNT functionalized and handle glass fibre, this fiber finally is used for the cylindrical product that Figure 11 describes.But noticeablely be that following method can be used to describe the assembling of Any shape product, wherein, before the deposition CNT with or do not mix with added substance.For example, in following method schematic diagram, " glass fibre of processing " described in the step 2 will replace with another material simply, described material is selected from any described herein, and the matrix of describing in the step 4 will be easy to be changed to any required material and shape from " cylindrical carbon piece ", such as the plain weave matrix when being used for air cleaning facility.

The example of the gained equipment of the nanometer web filter of mentioning before comprising is shown in Figure 12 and 13.For example, Figure 12 is the side perspective view of product, it comprise the nanometer net that has CNT on it or the active carbon hollow tube.In this embodiment, the fluid of pollution flows through the outer wall of pipe, and the fluid that purifies leaves described equipment from hollow tube inside.Figure 13 is the schematic diagram of flat or straight cleaning equipment.

1. preparation functionalized carbon nanotubes

One of method that is used for preparing functionalized carbon nanotubes generally includes the CNT initial stage ultrasonic wave that can commercially buy in solution and handles.Above-mentioned CNT comprises the pulvis of the multi-walled carbon nano-tubes of being made by any chemical method, described method such as chemical vapor deposition (CVD) drying box method, it has purity＞95% of basic weight amount usually, and characteristic size is the length of 500nm-50 μ m, diameter such as 10-20 μ m and 2-200nm.

Therefore, ultrasonic wave handle subsequently or simultaneously, in acid, handle CNT, described acid is selected from but is not limited to, nitric acid, sulfuric acid, hydrochloric acid and/or hydrofluoric acid or its combination.These acid can be used alone with the washing CNT, or are used in combination with various.For example, in the embodiment, CNT at first washs in nitric acid, washs in hydrofluoric acid afterwards.In another embodiment, after being washed in nitric acid, in sulfuric acid, washs CNT.

Carry out acid elution removing such as amorphous carbon or catalyst granules and can disturb their any pollutant of supporting etc. of nanotube surface chemistry, and the functional group's (for example, such as carboxyl) that produces is connected to the defective locations on the carbon nano tube surface.

This functionalization is also for CNT provides hydrophily, and this is considered to improve the strainability of products obtained therefrom.So CNT must be through last distilled water rinsing, and is suspended in the suitable dispersant, such as distilled water or alcohol, described alcohol such as ethanol or isopropyl alcohol.In the embodiment, ultrasonic wave is handled, is stirred and heat and runs through this functionalization method use to keep suitably dispersion when purifying.

2. the fiber for preparing metal oxide treated

In the embodiment, the method that manufacturing is used for the nanometer net of described product comprises that aforementioned functionalized carbon nanotubes is handled (apply or decorate) with metal oxide (such as iron oxide) or metal hydroxides (such as iron hydroxide) fiber mixes, as disclosed herein.Prepare glass fibre that above-mentioned metal oxide or metal hydroxides handle and can comprise and mixing mutually with glass fibre that can commercial purchase that this glass fibre is such as having the fiber of diameter range from 0.2 μ m-5 μ m containing the metal oxide of solution or metal hydroxides.

In the embodiment, described method comprises glass fibre and distilled water and colloidal metal oxide or metal hydroxide solutions is stirred the time that is enough to handle described glass fibre that reaches.Processed afterwards fiber can be dry in drying box.

3. supending

The composition that is used to make suspension comprises functionalized carbon nanotubes solution and the fiber of handling with the metal oxide or the metal hydroxides of preceding method preparation.For the component part of supending, at first functionalized carbon nanotubes is scattered in such as in the suitable medium such as water or ethanol by giving birth to handle.In the suitable medium such as water or ethanol etc., the glass fibre of metal oxide or hydroxide treatment is scattered in the container respectively again.Afterwards, the decentralized photo of these separation is mixed to form the suspension of the fiber of functionalized carbon nanotubes and metal oxide or metal hydroxides processing.

In the embodiment, the structure of final nanometer net can comprise the different layers of the glass fibre that functionalized carbon nanotubes and metal oxide or metal hydroxides are handled.These different layers are formed with the different suspension of handling the glass fibre manufacturing by the CNT from different proportion.

4. carbon nanometer net deposits

The step that is used to deposit the mixture of functionalized carbon nanotubes/processing fiber includes, but is not limited to the metal oxide or the metal hydroxides coating of any fiber disclosed herein.For example, the nanometer net can be used differential pressure to deposit or directly assemble and make by the mixture of CNT/processing fiber.In the embodiment, deposition process uses the differential pressure across matrix to deposit on the carbon block base matter with the suspension of functionalized carbon nanotubes/metal being handled fiber.In this embodiment, be that the substrate block internal pressure is lower across matrix applied pressure difference.This differential pressure is ordered about the fluid that contains suspension and is flow through matrix, and therefore deposition of carbon nanotubes/mixture of glass fibers on the matrix outer surface forms the nanometer net.

5. product assembling

After the nanometer net was dried, the matrix of coating was capped with porous protection sheet and rough plastic net with protection nanometer net materials.Be connected also sealed nano network edge sealing after the top cover of end in case the fluid stopping body surrounds the nanometer net.Be incorporated in the shell after this assembly, this shell is sealed to be formed for removing the product of pollutant from fluid.Externally the embodiment of the above-mentioned filter assemblies final, that contain the nanometer net in the plastic housing is shown in Figure 19 before.

Measure the method for effect

Use definite microbial technique described herein, proved that carbon nanometer web filter can remove more than the bacterial pollutant (E.coli) of 7 logarithm levels (log) with more than the substitute that is used for viral agent (MS 2 bacteriophages) of 4 logarithm levels (log).These removal abilities exceed (the Guidance Manual forCompliance with the Filtration and Disinfection Requirements for Public WaterSystems Using Surface Water by US-EPA, U.S.Environmental Protection Agency, March 1991) appointment to removal of bacteria and recommend the requirement of viral removal level.The independence test of invention product has confirmed that described product satisfies the basic standard that water purifies that is used for of the U.S..

Adopt bacterium such as use such as the E.coli of above-outlined and virus and carry out multiple testing preparing on the sample such as the method for viruses such as MS 2 bacteriophages.Is male special, single strand RNA virus as MS 2 bacteriophages of substitute at assessment apparatus usually in to the virus removal ability of drinking water, has diameter and the icosahedron shape of 0.025 μ m.Even MS 2 bacteriophages are not human pathogens, its size and dimension is similar to other water-borne virus, such as poliomyelitis and hepatitis viruse.

Being used for testing E.coli bacterium and MS 2 bacteriophages in all following examples meets and observes usually from the scheme of the removal of water: the standard operating procedure that (i) is used for MS 2 bacteriophage breeding/countings.Margolin, Aaron, 2001, University of New Hampshire, Durham and (ii) be used for water and standard method that waste water is checked, 20 ^ThEdition, Standard Methods, 1998, APHA, AWWA, WEF, Washington, DC, it is included in this paper as a reference.

Use above-described these methods, and, observe the strong adhesive force between bacterium and the CNT as illustrating in following examples.For example, especially when being disperseed in the ultrasonic wave processing procedure, bacterial adhesion is to carbon nano tube surface.Be worth identical the adhering to that is E.coli suspension believed, when its nanometer net by disclosed CNT, take place.

In addition, observe the evidence that the bacterial cell wall integrity can partly be damaged because of the interaction with carbon nanometer net.For example, exist under the CNT situation described herein, the image table that the Electron Microscopy of bacterium shows reveal bacterium shell/cell membrane some obviously penetrate.After extended period (24 hours), some that are caused by the afterbody in the cell membrane integral body (breech) are broken significantly, because the difference of osmotic pressure between cell interior and the outside, it causes cell membrane heavy damage and bacterium to be decomposed.But in case contact with CNT, the destruction of this cell integrality becomes obviously immediately, as observed by the optical microscopy in the phase microscope.

In addition, the destruction of some cells has been confirmed in test, as proving by a spot of at least free bacteria DNA of existence and protein in the filtrate.But contact the most of bacterial cell in back is kept perfectly immediately with nanotube.Remove bacterium effectively from flow out logistics even proved the nanometer net product of invention, nanotube destroys the ability of bacterial cell and does not establish as yet, even if it might property.

In addition, by other tests of invention product, can from water and air, be removed such as those aforesaid other pollutants (comprising metal, salt, organic pollution, endotoxin).

Invention will be further explained by following non-limiting embodiment, and described embodiment means the construed as limiting of invention.

Embodiment #1-E.coli and CNT interact

The interaction of research E.coli bacterial cultures and CNT is to measure the effect that CNT was connected to and made subsequently bacterial cell deactivation or destruction.In addition, this research will provide understanding in depth the effective mechanism of invention nanometer purified product.The sample that is untreated sample and mixes with CNT that described step will contain bacterial cultures compares.Described optics and the atomic force microscopy of relatively will using finished under high power amplification situation.

The preparation of E.coli suspension

, biocycle (can commercial buy) aseptic by using shifts out a domain and rebuilds raw material [from American Type Culture Collection (ATCC) original seed culture ATCC#25922], and it can draw striped on the commercial BAP of buying.In 36 ℃ of hatchings 12-18 hour, shift out and check purity after this ware from incubator.

Use sterilized bio ring (can commercially buy), domain hatching culture be moved out of and place 10ml aseptic can the commercial tryptic soy fluid nutrient medium of buying (Remel catalog number (Cat.No.) No.07228).Afterwards, in 37 ℃ of growths 18 hours, centrifugation subsequently also suspended to be similar to 5 * 10 in the formation water purification E.coli in gained trypticase-soybean fluid nutrient medium ⁹The concentrated bacterial cultures of CFU (cfu)/ml.

CNT functionalization with nitric acid

CNT is handled to remove pollutant (such as amorphous carbon or catalyst particle and can disturb their support of nanotube surface chemistry) with salpeter solution, increases the quantity of crystalline defect sites in the nanotube and the carboxyl chemical group is connected to these defect sites.This functionalization also provides water-wet behavior for CNT.

By the CNT that 250mg is purified, the cone nitric acid of cumulative volume 35ml is mixed in the centrifuge tube, fully vibration and handled 10 minutes with whole power ultrasonics in Cole Parmer 8851 ultrasonication machines and carry out described processing in 50 ℃ of water-baths.2, the 500rpm centrifugation drains supernatant subsequently until supernatant clarification (6-10 minute) after nitric acid/carbon nanotube mixture.Described nitric acid treatment is repeated, but has 20 minutes ultrasonic waves to handle.By washing in the distilled water that they is suspended in the 35ml cumulative volume, ultrasonic wave is handled 10 minutes (as above) to the CNT of nitric acid treatment subsequently, and centrifugal (as above) drains supernatant subsequently.Such washing is repeated to be at least 5.5 (～3-4 time) until pH that each ultrasonic wave was handled 5 minutes.

The preparation test solution

The E.coli suspension for preparing according to above general introduction is divided into two equal portions afterwards.Be untreated the preparation of solution (test solution #1) by one of E.coli suspension of separating with distilled water diluting to obtain～2 * 10 ⁹The E.coli concentration of cfu/ml (dilution in 2: 5).Another solution (test solution #2) prepares by the E.coli suspension that the functionalized nanotube of interpolation 25mg separates to another.This solution subsequently with distilled water diluting with obtain with test solution #1 in identical E.coli concentration.This dilution result is that the CNT concentration among the test solution #2 is 625ppm.

The two handled test solution #1 and #2 3 minutes with Branson-2510 ultrasonic disruption device ultrasonic wave simultaneously.In can the commercial centrifuge of buying, reach 2 minutes forming pellet after these test solutions, and drain supernatant, stay the 1ml of supernatant back with the 2500rpm centrifugation.The pellet of test solution #1 and #2 is used to make two following samples (#1 and #2) subsequently.

Preparation sample #1: carbon nanotubes not

Sample #1 by with one not the test solution of carbon nanotubes (test solution #1) place commercially available glass slide (American Scientific Products, little slide, common, catalogue M6145, size 75 * 25mm is with the sulfuric acid cleaning and with the distilled water washing) upward and in 4 ℃ of coolings 19 hours prepare.After the cooling, Veeco Dimension 3100 scanning probe systems of use penetration type carry out atomic force microscopy (AFM) analysis and study sample.

Sample #1 is also pushed up (by the naked light that is exposed to of short duration) with poststaining (with Gram crystal violet dyestuff), with after washing by thermosetting.Use the Olympus light microscope to carry out light microscopy in 1000 * multiplication factor and under immersion oil.Make digital picture with Olympus DP10 CCD.

The preparation of sample #2: CNT is handled

Sample #2 prepares by a CNT/E.coli test solution (test solution #2) is positioned on the aforesaid glass slide.Described sample is by heat fixation, dyeing, and carries out light microscopy, as above for sample #1.Be placed in 4 ℃ after the sample #2 and reach 19 hours in the refrigerating box, after this time, it is moved out of and carries out AFM and analyze (as previously discussed), as for sample #1.Sample 2# is sent back to refrigerating box and is reached 24 hours again, carries out light microscopy after this time once more.

The microscopic analysis result

Sample #1 (suspension that does not have CNT) shows that the E.coli bacterial cell is uniformly distributed on the whole surface of slide (Figure 14).Image shows that also bacterium has well-defined edge, and its enlightenment bacterial cell is complete.After in refrigerating box, storing 2 days with drying regime, do not find the variation of their shapes.

The result of test solution (sample #2) sample of handling from CNT is presented at that bacterium grows thickly on the CNT (Figure 15).When excessive dyeing most of nanotube when slide is washed is removed.The bacterial concentration that is observed is in the border of CNT.

For the sample that does not have CNT (sample #1), there are a large amount of bacterial cells separately to appear on the whole slide, for the sample that has CNT (sample #2), bacterial cell is not present in most of slide.As shown in Figure 15, any bacterium that comes across in one situation of back closely squeezes around CNT, and this shows that CNT is caught and fixation of bacteria.

Sample 1# explanation E.coli closely is crowded together.As shown in Figure 16, Normocellular bacterial cell has the border of clear-cut.The reducing of size of bacterium and packed bulk density sees afm image before the heat treatment of sample #1 and neutralizes in the optical imagery after the heat treatment of this sample.

Sample #2 shows near some cells the nanotube, and the border of E.coli cell membrane is diffusion and/or damages.In fact, after nanotube mixed, some E.coli cells decomposed more than identification point.The existence of some diffusion E.coli fragments also sees near the nanotube.

The E.coli ultrasonic wave handle and CNT in distilled water when functionalized, described twenty percent divides gathering.This is considered to owing to act on nano level electrostatic force and Fan Dehuali.For measurement range, observedly be that all bacteriums in the suspension contact and are attached with nanotube.Free never again E.coli among the solution #2.The ability that is connected to and makes bacterium to fix that this proof dispersed carbon nano tube is firm.

When being recorded, the decomposition of E.coli cell comes across after the direct contact nanometer pipe of cell.The result is, these bacterial cells are rendered as the border of the clear-cut that loses them, and the inclusion of their inside is rendered as from cell and sheds.For example, scanning electron micrograph (SEM) image of the bacterial cell of Figure 17 demonstration is emergent and interaction CNT.

In the cell that is affected, after 3 hours this process begin be recorded, and inner inclusion sheds after 22 hours, so far is difficult to differentiate cell shape.

Mix with carbon nano-tube solution in the height activity bacterial fluorescence pseudomonad (Pseudomonas flourescens) that reaches 12 hours that in Nutrient broth (from Difco Laboratory), grows under the room temperature.Observe under dark-field microscope, we observe movable bacterium and float near the CNT of gathering and drawn in wherein, and firmly are connected to the carbon nano-tube fibre of exposure.In 5 minutes of contact, the whole surface coverage of CNT agglutinator has hundreds of intact bacterial, and they are obviously firmly connected because they look is struggled but can not leave.These bacteriums have lost all energies and become complete hard in 30 seconds that just contact with carbon nano-tube fibre.This shows that careful dispersed carbon nano tube fiber is connected to and makes the fixing ability of a large amount of bacteriums fast.This has established the basis of the effect of carbon nano-tube fibre aspect the removal microorganism.

Embodiment 2: cylindrical purified product

The structure of cylindrical purified product:

The preparation of the glass fibre that iron hydroxide is handled

Prepare the solution of 23.5 liters of distilled water and 9.62ml 10N NaOH (NaOH) and stirred 1 hour.Addition is the ferric trichloride (FeCI of 16.66 grams ₃6 H ₂O) also stirring until reaching final pH is～2.2 (～24 hours).200 gram glass fibres (Johns-Mansville) of the size of diameter 100-500nm and length 300-500 μ m are added to this solution and continue to stir does not have iron (～3 hours) until solution.With the described solution of distilled water diluting to obtain the glass fibre concentration of 10 grams per liters.

The preparation of deposition suspension

The glass fibre that uses functionalized carbon nanotubes solution and handle as the iron hydroxide of preparation before above-mentioned comes supending.Component part for supending, the water-bath that 5g functionalized carbon nanotubes (by nitric acid washing step described in embodiment #1 carboxylation) is suspended in 1 premium on currency and places the room temperature of Cole Parmer 8851 ultrasonic disruption devices, and handled 20 minutes with whole power ultrasonics.Four liters of distilled water are added in that ultrasonic wave is handled, functionalized carbon nanotubes/aqueous mixtures to produce the concentration of every 1ml water 1mg functionalized carbon nanotubes.The glass fibre solution that approximate 100ml Fe modifies is placed in separately in the container and with distilled water diluting to 1 liter.This mixture in the agitator of buying mixed 5 minutes.

In order to mix the first deposition suspension, the functionalized carbon nanotubes (above description) of 600ml suspension is added to the glass fibre solution (5: 8 CNT/ glass of weight ratio) of 960ml.This mixture is diluted to 4 liters by the distilled water that adds capacity quantity, and is handled 10 minutes by ultrasonic wave with whole power with Branson type 900B probe ultrasonic disruption device.

The deposition of carbon nanometer net

Deposit to by mixture and to realize final nanometer web frame on the carbon block base matter one deck functionalized carbon nanotubes/iron hydroxide coated glass fibers.

The step that is used for depositing functionalized carbon nanotubes/iron hydroxide coating or modifying the mixture of glass schematically is shown in Figure 18.To the perforation footstalk, make filter assemblies by filling cylindrical carbon piece.Fill deposit cavity with CNT/glass fibre suspension (ratio 5: 8).This filter assemblies is connected to the vacuum pipe of guiding Franklin Electronics Varian TriScroll vavuum pump, is dipped into afterwards in the deposit cavity that is full of.The vavuum pump that is connected to filter assemblies is opened, and whole suspension are drawn out of depositing nano net on its outer surface by carbon filter matrix under vacuum.After the deposition, the filter assemblies of deposition shifts out from deposit cavity, remains connected to vavuum pump, and the nanometer web filter assembly of deposition had been arranged in the nitrogen atmosphere in 50 ℃ the drying box under the vacuum dry 1-2 hour.

Zu Zhuan filter product comprises the carbon filter nuclear at center fully, and it applies with functionalized carbon nanotubes nanometer net and is covered by the porous protectiveness paper that is fixed in a certain position with cylindric plastic wire.Be wrapped top and nanometer network edge of this filter cylinder is sealed in case the fluid stopping body surrounds the nanometer net, and places shell to produce finished product (Figure 19).

The effect of cylindrical purified product

Carry out the cleaning test of columniform invention product in contaminant water with E.coli bacterial cultures [obtaining] from American Type Culture Collection (ATCC).

Carry out bacteria test by challenging the nanometer net of making according to present embodiment (embodiment 2) with the challenge fluid of rebuilding E.coli original seed culture ATCC#25922.This challenge fluid is rebuild raw material and draw striped on commercially available BAP by using sterilized bio ring (can commercially buy) to shift out a domain.In 36 ℃ of hatchings 12-18 hour, shift out this culture and check purity from incubator afterwards after this ware.

Use sterilized bio ring (can commercially buy), domain hatching culture be moved out of and place 10ml aseptic can the commercial tryptic soy fluid nutrient medium of buying (Remel catalog number (Cat.No.) No.07228).Afterwards, E.coli grows 18 hours to form approximate 1 * 10 in 37 ℃ in gained trypticase-soybean fluid nutrient medium ⁹The culture of CFU (cfu)/ml.The 1ml sample of this original seed culture is added in the 100ml water and tests to be used for challenge, so diluted concentration is to approximate 1 * 10 ⁷Cfu/ml.So this gained challenge water is by cylindrical purified product.

Test according to " being used for the standard method that water and waste water are checked " cited above.When challenge fluid when passing the nanometer net of invention, established greater than 6 logarithm levels (＞99.99995%) to uniformity according to the such scheme result of the test and to have removed greater than the E.coli bacterium of 7 logarithm levels (＞99.999995%).The clearance that these result of the tests are set up surpasses the EPA drinking water standard (above reference) that is used for removing from water bacterium.The EPA standard code is removed the E.coli bacterium of 6 logarithm levels (＞99.99995%) to reach drinking water.Logarithm clearance (log removal) by the bigger E.coli bacterium of finishing in the above-mentioned test, pass nanometer net according to the E.coli bacterium challenge suspension that has higher concentration of above-mentioned preparation by solution and reach to improve and purify known bacterial concentration (i.e. challenge).The clearance greater than 7 logarithm levels (＞99.999995%) has been determined in above-mentioned test with higher concentration.The independent experiment of nanometer net uses the testing procedure of describing in the present embodiment, makes the barrier layer of this material as E.coli.In addition, independently laboratory results shows that (kluyvera terrigena (Klebsiella terrigena) and Brevindomonas) removed, this has confirmed that described material is the general barrier layer to bacterium for different tests bacterium more than 6 logarithm levels.

Embodiment 3: the structure of straight purified product

Be similar to embodiment 2, by by can the commercial purifying carbon nanometre tube of buying and polypropylene fabric matrix nonwoven, fusion make straight nanometer net.Initial, the functionalized carbon nanotubes of 100g (by as the washing of the nitric acid described among the embodiment #1 and carboxylation) so add to 400ml can the commercial pure isopropyl alcohol of buying in and in " Branson 900B ultrasonic generator ", handle until CNT and suitably disperseed (about 10 minutes) with 80% power ultrasonic.By adding 2 liters of further diluted mixture things of isopropyl alcohol, so that the cumulative volume of gained mixture is 2.4 liters.This diluted mixture thing is handled by ultrasonic wave and is reached 10 minutes again.

Next, the glass nano-fibre that 800mg can the commercial 200nm diameter of buying can handled 10 minutes by homogeneity processing with whole power in the commercial agitator of buying in the commercial pure isopropyl alcohol of buying in 500ml.Afterwards, can dilute the mixture that homogeneity processing is handled by the commercial pure isopropyl alcohol of buying by adding additional 1 liter.

Merge the mixture of CNT and glass nano-fibre, so the isopropyl alcohol of interpolation capacity (Q.S.) quantity is to obtain 4 liters.Reached 15 minute with 80% power by the ultrasonic wave processing with " Branson 900B ultrasonic generator " after these 4 liters of solution, it causes the carbon nanotube material evenly to disperse.

After whole 4 liters of solution by can commercial 5 microns nonwoven fusion activated carbon felts buying under 1 atmospheric differential pressure, being drawn glass fibre nanometer net with deposition of carbon nanotubes/processing.Gained nanometer net shifted out and is allowed in 50 ° drying box dry 2 hours from assembly parts.

Heat-melt adhesive square nanometer net/the matrix membrane that gained is straight that uses NSF to be obedient to is adhered in the side of straight shell.So half of this shell closely cooperates and the counter pair that is adhered to it with sealing.Being shown among Figure 13 of the structural representation of gained equipment.

The effect test of straight purified product

A) water-chemical analysis of E.coli pollution

Filtrate chemical analysis results from E.coli challenge test is below described, as on straight nanometer net purified product, carrying out of describing among the embodiment 2 according to the present embodiment manufacturing.This embodiment provides evidence for the E.coli bacterium of having destroyed some quantity of passing invention nanometer net.The evidence that this pollutant (E.coli bacterium) part is damaged is by existing DNA of bacteria and protein to establish in challenge filtrate.

According to embodiment 2 in the test that throws down the gauntlet of identical step, except the composition of challenge solution be～1 * ₁₀Outside the E.coli of 8cfu/ml.100ml (altogether～1 * 10 altogether ¹⁰Cfu) this challenge solution is drawn by the differential pressure of carbon nanometer net/host material use～0.25psi.By being passed, E.coli challenge filtrate can obtain contrasting filtrate by commercial 0.45 micron the millipore filter of buying.Test challenge filtrate does not concentrate.After the gained filtrate of described contrast and challenge with can the commercial spectrum spectrometer analysis of buying to determine existing of protein and DNA.But, show the DNA of 40 μ g/ml and the protein of 0.5mg/ml with filtrate analysis that can the commercial spectrum spectrometer of buying.The protein of these levels and DNA concentration in non-concentrated challenge filtrate be 6 times greater than by filter the contrast test material that obtains by millipore filter.These concentration have confirmed that at least some parts of the E.coli that adds are destroyed by the nanometer net.

B) water of MS-2 phage virus pollution

The water test that the straight nanometer net product of making according to present embodiment (embodiment 3) pollutes with the MS-2 phage virus, use and above reach the step of describing in " Standard Operating Procedure for MS-2 BacteriophagePropagation/Enumeration; Margolin; Aaron; 2001, An EPA Reference Protocol. ".The MS-2 phage virus is generally used in the assessment into the disposal ability of the film of the design of Drinking Water (NSF 1998).Adopt the above scheme to carry out to the pressurization challenge of present embodiment with the 100ml challenge solution.Those steps preparations of enumerating more than the MS-2 bacteriophage challenge material basis.

In this test, 80 (80) films that comprise the carbon nanotube structural material of making according to present embodiment (embodiment 3) are challenged.The water that used challenge material is polluted by the MS-2 phage virus, concentration approximate 5 * 10 ⁶Plaque forming unit (pfu)/ml.

80 units of test, 50 units reach 5 logarithm levels (99.999%) or remove greater than the MS-2 of 5 logarithm levels (＞99.9995%).Remaining 30 units shows and removes 4 logarithm levels (99.99%) or greater than the MS-2 of 4 logarithm levels (＞99.995%).Yet the EPA standard recommendation is removed the MS-2 bacteriophage of 4 logarithm levels to arrive drinking water, and being of being worth believing can be realized better sensitiveness (higher logarithm clearance) by the logarithm level challenge of the higher MS-2 of challenge.Bigger logarithm clearance by the MS-2 bacteriophage that reached in the above-mentioned test, the carbon nanotube net of making according to present embodiment (embodiment 3) by challenge improve purification with the MS-2 bacteriophage challenge suspension of the higher concentration made as previously discussed.Independent experiment according to the carbon nanometer net product of present embodiment (embodiment 3) is established the barrier layer of this material as the MS-2 bacteriophage.

C) water of arsenic (As) pollution

Make straight filtering product according to present embodiment (embodiment 3) in order to the water of arsenic contamination.In this test, contain～150ppb (1,000,000,000/... part) the 100ml aqueous solution of arsenic passes the carbon nanometer net of making according to present embodiment (embodiment 3).Analyze the sample that arsenic is handled water according to EPA method #SM 183113B.The analysis confirmation arsenic level of challenge filtrate has reduced 86% ± 5%; After the arsenic processing water by challenge, when passing through the carbon nanometer net materials of invention.

D) the airborne vehicle fuel of germ contamination

According to the straight purified product that present embodiment (embodiment 3) is made the jet propulsion fuel that pollutes is tested.Jet propulsion fuel (JP8) sample that pollutes obtains from 33,000 gallons storage tank, and it is positioned at United States Air Force Research facility at the Wright Patterson Air Forcebase.After the collection, described sample is cultivated and is found on trypticase-soybean fluid nutrient medium and contains three bacterioids: the kind of the kind of two Bacillus and a Micrococcus.This sample is separated in each two container of 2 liters.Two containers all present two different layers, and jet propulsion fuel is at the top, and water is in the bottom.Container A contains the grown layer of severe contamination at the interface place of water and fuel room.Container B only is shown as light contamination.The bacterium of challenge test obtains from the fuel of container B and the interface of water.

Fuel/water/bacterium by thermal agitation challenge test reaches 1 minute finishes homogeneity processing and handles, thereafter, the pressure reduction of use～1.5psi makes the challenge mixture of fuel/water/bacterium of 200ml pass CNT, the nano structural material of making according to present embodiment (embodiment 3).

The challenge filtrate sample of fuel/water/bacterium is allowed to be separated into its fuel-water composition, and four test samples are from each composition.Each test sample applies on agar.Sample is hatched to analyze the growth of bacterium at 37 ℃ then, reaches sample and is hatched to analyze the growth of mould in room temperature.After the hatching sample reaches 24 and 48 hours, on (microscope is used) test plate of challenge filtrate, do not observe the growth of the culture of bacterium or mould.The check sample hatching was rendered as the vigorous bacterium and the growth of mold colony after 24 and 48 hours.The carbon nanometer net that results verification is made according to present embodiment (embodiment 3) is the barrier layer of bacterium in the fuel, because it has finished the removal above bacterium in the fuel of testing program detectable limit and mould.

Embodiment #4: the flat purified product of using the rapid functionalization of multistep

By CNT and 0.5oz/yd nonwoven, fusion that can the commercial purifying of buying ²Carbon element thin paper matrix make straight nanometer net equipment.The formation of this equipment is utilized nanometer net self-assembly method as defined above.Specific electropositive or elecrtonegativity official can be used to realize this self-assembly by parts.Making CNT functionalized with amido, will be electropositive (positive zeta potential) when it causes them in being scattered in water.Bunch coming the ambetti fiber with iron hydroxide, will be electronegative when this causes them in being scattered in water.As shown in Figure 22, when two suspension are combined, because the electrical forces nanotube twines around glass fibre.

Beginning, the 36N sulfuric acid of the CNT of 20g and 400ml 60% and the nitric acid of 40%15.8N refluxed 30 minutes in 110 ℃.Adding carboxyl functional group is known to CNT.These carboxy-functionalized nanotubes are filtered in distilled water, wash, and are dry in 100 ℃ drying box afterwards.So the drying nano pipe is suspended in 500ml thionyl (two) chlorine and in 60 ℃ and was handled 20 hours by ultrasonic wave.Thionyl (two) chlorine is distillated, and uses vavuum pump that the CNT sample is dewatered.The nanotube of dehydration is suspended in the ethylenediamine of 500ml and in the nitrogen atmosphere and was handled 20 hours by ultrasonic wave in 60 ℃.Ethylenediamine is distillated, and sample repeats filtration, rinsing until reaching nature pH with the salt acid elution of 0.1M with distilled water.After the amine-functionalized CNT of rinsing in 100 ℃ drying box dry 24 hours.

The mixture of the glass fibre of the amine-functionalized CNT of fusion 360g and the processing of 960g, the distilled water that adds capacity (Q.S.) quantity afterwards is to obtain 4 liters.Reached 15 minute with 80% power by the ultrasonic wave processing with " Branson 900B ultrasonic generator " after these 4 liters of solution, it causes CNT/glass fibre nano material evenly to be disperseed.

By can the commercial non-weaving of buying, the 0.5oz/yd of fusion ²The carbon element thin paper, under～1 atmospheric differential pressure, draw the glass fibre nanometer net of CNT/processing of whole 4 liters of solution with the deposition self-assembly.Gained nanometer net shifted out and is allowed to 50 ℃ drying box dry 2 hours from assembly parts.

The measure of merit of straight purified product

The straight cleaning equipment that the glass fibre that uses amine-functionalized CNT and iron hydroxide to modify constitutes in present embodiment (embodiment #4) in carries out the biological removal test, as the middle description of the effect test of embodiment #3 [test is E.coli and b a)) MS-2 bacteriophage].These tests have illustrated that the nanometer net product of self-assembly has reached bacterium and the viral removal ability that surpasses 8 logarithm levels and 7 logarithm levels respectively.

Embodiment 5: the fluid desalination

64 layers of straight nanometer net equipment are made by following: functionalized carbon nanotubes that can the commercial purification of buying; The diameter of measuring is that 100-500nm and length are the glass fibre of 300-500 μ m; Have 20 in the distilled water, 0.0125% (basic weight amount) poly-vinyl alcohol solution of 000g molecular weight; 1.5oz/yard cellulose filter paper as insulator; Nonwoven, fusion, 0.5oz/yard ²Conductibility carbon element thin paper matrix; Implant the conductibility of silver and the epoxy resin of insulating properties; The non-conducting shell of plastics; With across each mutually the conductibility nanometer stratum reticulare of adjacency pair be provided with the power supply of 1.5V DC.

Beginning, functionalized nanotube of 25mg (by as the nitric acid washing step carboxylation described among the embodiment #1) and 50mg glass fibre (above description) are suspended in 4 liters of distilled water, and it contains the polyvinyl alcohol just like concentration 0.0125% listed above.Use IKA UltraTurrax T18 submergence agitator stirred 3 minutes with 3 speed.

0.5oz/yard in one 5.5 " * 5.5 " ²On 5 " * 5 " area of carbon element thin paper, the pressure reduction of usefulness～1psi deposits this CNT/glass fibre suspension.The nanometer net sheet of 5 " * 5 " cuts four 2 thus " disk of diameter, thus finish 64 layers 2 " 4 layers of diameter equipment (32 of 64 layers is conductive, other be insulating properties).

Use the conductive epoxy resin of filling silver that electric lead is connected to each conductibility nanometer stratum reticulare.All conductibility nanometer stratum reticulares are sandwiched between the insulating barrier and superpose these " interlayers ", and electric lead is in the axial direction by (～11.25 ° of the lead rotations on the upper and lower layer) equally at interval.Electric lead tied and the wall by plastic casing is passed to power supply and whole assembly sealed (embodiment of 16 conducting shell models of desalter prototype is shown in Figure 20).

Do not apply electric charge or stimulation, carry out statically-retained test by 1 liter 1 ‰ saline solution (1 ‰=1g salt/1000g water) is flow through described equipment.The filtrates tested salt content, and it is found and has～loss of the salt of 13mg.Therefore the invention equipment in the static models (promptly not having electronic stimulation) reduces by～13% salinity.This minimizing adds up to every gram CNT removal 0.42 gram salt in the invention equipment.

Carry out dynamic retention test, wherein the difference dc voltage of 4.0mV is applied to each layer (the nanometer stratum reticulare of promptly compiling even number is a positively charged, and the nanometer stratum reticulare of volume odd number is electronegative) of 16 pairs of adjacent conductibility nanometer stratum reticulares.The salt challenge solution that 1g sodium chloride is dissolved in the 1000ml distilled water is used to testing equipment efficient.Through described equipment once, the salt of removal 1.6%.This clearance equals every gram CNT 0.52 gram salt.This expression surpasses the salt of the increase by 23% of static device removes, and shows even salt ion that very faint voltage also strengthens in the aqueous solution is removed, thereby has illustrated and receive-removal effect of electricity.When increasing dc voltage and applying the AC signal that destroys the debye atmosphere, the salt of finishing further enhancing is definitely removed.

Embodiment #6: air film

Use functionalized carbon nanotubes (carboxylation by the washing of nitric acid described in the embodiment #1) the straight air film filter of formation.Described method be suspended in these functionalized nanotubes of 25mg in the 25ml distilled water and in the ultrasonic disruption device of room-temperature water bath, Branson 900B type ultrasonic wave handled 10 minutes.After this solution with distilled water diluting to 4 liter and add polyvinyl alcohol so that obtain the polyvinyl alcohol of concentration 0.125% (basic weight amount).Be provided with 3 with suspension mixing 3 minutes with UltraTurrax T18 basis submergence agitator in speed then.Use differential pressure be～the differential pressure filtration method of 1psi, form the nanometer net by on 5 " * 5 " area of the porous polymeric matrix of 5.25 " * 5.25 " square plate, depositing.

The effect test of air film product:

On described film, carry out the biological removal test to determine its effect.From two 2.5 of quadrangular membrane cuttings " disk, and be fixed between two flat metal rings of 2 " ID, 2.5 " OD.Disk is used to measure the pressure differential that is used for the film product facility curve to flow velocity, and another is used to biology and removes test.Be fixed in 2 by filtering disk " carry out the biological removal test in the cylindrical air channel (in Figure 21, schematically illustrating) of ID; it can test the capture rate of the bacterial spore of bacillus subtilis; described bacillus subtilis is the substitute of accepting extensively that is used for biologic product; but be not human pathogen, this makes it is safe for laboratory test.

Test requirements document discharges bacterial spore in filtering the disk upstream and catching the segment of the filter in that the fluid that passes the testing equipment downstream end is filled, the all-glass sampler by atomizer.The control setting that experimentizes retains with the gemma of evaluation experimental device.In this biological test, we have realized that the gemma that surpasses the bacillus subtilis of 3 logarithm levels is removed.In addition, we can determine that the removal of biologic product does not rely on the removal of abiotic particle and the air flow impedance of filter.

Except as otherwise noted, all numerals of quantity that are used for the expression composition, reaction condition or the like of specification and claims are understood that to revise by term " about " in all cases.Therefore, unless point out on the contrary, the digital parameters that is set forth in following specification and the appended claims is similar to, and it can change according to the desirable characteristics of seeking to obtain by the present invention.

By considering specification and invention disclosed herein practice, other embodiments of invention are conspicuous for those skilled in the art.It means, and specification and embodiment only be considered to imitate, and the true scope of invention and purport are indicated by the following book that what is claimed is.

Claims

1. one kind is used for from the product of fluid removal pollutant, described product comprises CNT, at least one described CNT comprise be attached on it or be positioned at wherein at least one molecule or bunch, wherein said CNT with enough make with described product fluid in contact in the amount that reduces of pollutant levels be present in the described product.

2. product as claimed in claim 1 also comprises carinate or pliable and tough porous supporting substrate.

3. product as claimed in claim 2, wherein said porous supporting substrate comprises and is selected from following group material: pottery, carbon or based on the material of carbon, metal or alloy, nonmetal and plastics, and fibrous material, described fibrous material is braiding or non-woven, or its any combination.

4. product as claimed in claim 1, wherein said CNT is a form with the nanometer net of assembling, CNT is connected to or is attached to other CNTs, fiber, particle described in the described nanometer net, or its any combination.

5. product as claimed in claim 1, wherein at least one molecule or bunch comprise inorganic compound, described inorganic compound contains and is selected from following at least one metallic atom: lithium, sodium, magnesium, aluminium, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, rhodium, palladium, silver, indium, tin, caesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, bismuth and be selected from following at least one non-metallic atom: hydrogen, boron, carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, antimony, iodine and combination thereof.

6. product as claimed in claim 1, wherein said bunch comprises quantum dot.

7. product as claimed in claim 1, wherein at least one molecule or bunch include organic compounds, described organic compound comprises one or more protein, carbohydrate, polymer, aromatic series or aliphatic alcohol and nucleic acid.

8. product as claimed in claim 1, wherein cluster comprises at least a microorganism, histocyte, bacterium or nanometer bacteria at least.

9. product as claimed in claim 1, wherein at least one molecule or bunch include organic compounds, described organic compound comprise and are selected from one or more following chemical groups: carboxyl, amine, aromatic hydrocarbons, nitrile, acid amides, hydro carbons, alkene, alkynes, alcohol, ether, ester, aldehyde, ketone, polyamide, poly-amphipathic compound, diazol, slaine, pyrenyl, thiol base, thioether, sulfydryl, monosilane and combination thereof.

10. product as claimed in claim 4, the nanometer net of wherein said assembling comprises CNT and glass fibre.

11. product as claimed in claim 1, wherein most of described CNT are scattered in and are free of attachment to or are attached to other CNTs, fiber or particle.

12. as claim 4 or 11 described products, wherein said fiber is selected from:

(a) polymeric material, it is selected from list or multicomponent polymer, and described polymer is selected from nylon, acrylic acid, methacrylic acid, epoxy resin, silicon rubber, polypropylene, polyethylene, Merlon, aromatic series polyamide, polychloroprene, terephthalic acids polybutester, poly-to phylene terephthalic acids acid amides, poly-(to phenylene terephthalic acids acid amides) and polyester, ester, ketone, polyester, polytetrafluoroethylene (PTFE), polyvinyl chloride, polyvinyl acetate, viton fluorubber, polymethyl methacrylate, polyacrylonitrile and combination thereof;

(b) ceramic material, it is selected from boron carbide, borazon, boron oxide, spinelle, garnet, lanthanum fluoride, calcirm-fluoride, carborundum, carbon and allotrope thereof, glass, quartz, aluminium oxide, aluminium nitride, aluminium hydroxide, zirconia, zirconium carbide, zirconium boride, zirconium nitride hafnium boride, thorium oxide, yttria, magnesia, cordierite, mullite, silicon nitride, ferrite, sapphire, saponite, titanium carbide, titanium nitride, titanium dioxide, titanium boride and combination thereof;

(c) at least a metal material, it is selected from aluminium, boron, copper, cobalt, gold, platinum, palladium, silicon, steel, iridium, indium, iron, rhodium, palladium, gallium, germanium, tin, titanium, tungsten, nickel, niobium, magnesium, manganese, molybdenum, silver, zirconium, yttrium, their oxide, hydride, hydroxide and alloy thereof;

(d) at least a biomaterial or derivatives thereof, the cellulose fibre that it is selected from silk fiber, cotton fiber, wool fiber, flax fiber, feather fiber, extracts from timber, beans or algae;

(e) at least a CNT, it is selected from the CNT of single wall, double-walled or many walls, and the Y-that described CNT has nano tube structure, the nanotube of nanometer-horn shape, nanometer-helical form, nanometer-spring-like, dendroid, tree-shaped, spider connects, and bamboo structure or multiply spiral; With

(f) nm-class conducting wire of at least a metal oxide or metal hydroxides.

13. as claim 4 or 11 described products, wherein said fiber has the diameter of scope from 1nm to 1cm, and has from 2 to 10 ⁹Length-width ratio (length/diameter).

14. product as claimed in claim 1, wherein at least one CNT is selected from the CNT of single wall, double-walled or many walls, and described CNT has nested or non-nested structure, bamboo structure, multiply spiral, the nested spiral of multiply or the nested spiral that the Y-of nano tube structure, the nanotube of nanometer-horn shape, nanometer-helical form, nanometer-spring-like, dendroid, tree-shaped, spider connects.

15. product as claimed in claim 1, wherein said pollutant comprise one or more kind bacteriums, virus, cystozygote, gemma, mould, coliform, parasite, pollen and fungi.

16. product as claimed in claim 15, wherein said bacterium comprises anthrax, typhus or cholera, and described virus comprises smallpox and hepatitis.

17. product as claimed in claim 1, wherein said pollutant comprise the one or more biomolecule that are selected from DNA, RNA and natural organic molecule.

18. product as claimed in claim 1, wherein said pollutant comprises one or more compounds, and described compound is selected from natural and synthetic organic molecule, inorganic pollution, medicine and ion.

19. product as claimed in claim 18, wherein said natural and synthetic organic molecule is selected from toxin, endotoxin, protein, enzyme, pesticide and herbicide, described inorganic pollution is selected from heavy metal, cleaning agent, fertilizer, inorganic toxic material, described medicine is selected from medicine, solvent, preparation, and described ion is selected from the particle that salt in the seawater and air disseminate.

20. product as claimed in claim 1, wherein at least a pollutant comprises and is selected from following at least one atom or ion: antimony, arsenic, aluminium, selenium, hydrogen, lithium, boron, carbon, oxygen, calcium, magnesium, sulphur, chlorine, niobium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, bromine, strontium, yttrium, zirconium, molybdenum, rhodium, palladium, iodine, silver, cadmium, indium, tin, caesium, barium, lanthanum, tantalum, beryllium, copper, fluoride, mercury, tungsten, iridium, hafnium, rhenium, osmium, platinum, gold, mercury, thallium, lead, bismuth, polonium, radon, radium, thorium, uranium, plutonium and radon.

21. product as claimed in claim 1, wherein said fluid comprises:

(a) liquid, it is selected from water, oil and byproduct thereof, biofluid, food, alcoholic beverage and medicine; Or

(b) gas, it is selected from air, industrial gasses and from the cigarette of the vehicles, chimney, chimney or cigarette, wherein said industrial gasses comprise argon gas, nitrogen, helium, ammonia and carbon dioxide.

22. product as claimed in claim 1 further comprises a plurality of different carbon nanotube layers, wherein each layer reduces the amount of different pollutants.

23. product as claimed in claim 1 also comprises a plurality of different carbon nanotube layers, wherein has voltage difference between at least two described layers.

24. product as claimed in claim 23, wherein or AC voltage, or at least one described carbon nanotube layer of being applied to of dc voltage or its combination is with the removal that helps pollutant, separation, fixing and/or destroy.

25. product as claimed in claim 24, wherein said voltage comprises AC voltage, and frequency that it has and amplitude signal are enough to destroy the described debye atmosphere around at least one charged contaminants in the described fluid.

26. product as claimed in claim 25, wherein said charged contaminants are the ions that comprises the salt in seawater and the salt water.

27. product as claimed in claim 25, wherein said ion comprises sodium, chloride, potassium, calcium, magnesium, sulfate, heavy carbonate, manganese, iron, copper, mercury, gold, silver, platinum, lead, arsenic, uranium and palladium.

28. product as claimed in claim 25, wherein said charged contaminants are the ions that sees in fresh water, waste water and the outflow stream.

29. product as claimed in claim 26, wherein said a plurality of layers at least one are enough to make water to remove freshen, and at least one other layers are enough to remove, separate, fix and/or destroy other pollutants.

30. product as claimed in claim 29, wherein said other pollutants comprise one or more pathogen, virus, microbial organisms, DNA, RNA, natural organic molecule, mould, fungi, natural and synthetic toxin, heavy metal, endotoxin, protein, prion and enzyme.

31. product as claimed in claim 29, wherein said other pollutants comprise and are selected from following at least one atom or ion: antimony, arsenic, aluminium, selenium, hydrogen, lithium, boron, carbon, oxygen, sodium, calcium, magnesium, sulphur, chlorine, niobium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, bromine, strontium, yttrium, zirconium, molybdenum, rhodium, palladium, iodine, silver, cadmium, indium, tin, caesium, tungsten, iridium, hafnium, rhenium, osmium, platinum, gold, mercury, thallium, lead, polonium, radon, radium, thorium, uranium and plutonium.

32. product as claimed in claim 1, wherein said fluid is a water.

33. product as claimed in claim 1, wherein said fluid comprises air.

34. product as claimed in claim 1 also comprises at least a fiber that is selected from glass, quartz, aluminium oxide and aluminium hydroxide.

35. a method that reduces amount of pollutants described in the fluid, described method comprises:

(a) fluid is contacted with the product that comprises CNT, most of described CNTs comprise be attached on it or be positioned at wherein at least one molecule or bunch, wherein said CNT with enough make with described product fluid in contact in the amount that reduces of pollutant levels be present in the described product, and

(b) from fluid, remove at least a pollutant.

36. method as claimed in claim 35, wherein said product comprise a plurality of different layers of described CNT.

37. method as claimed in claim 35, wherein each described a plurality of different layers reduce the quantity of different pollutants.

38. method as claimed in claim 35 also comprises a plurality of different layers of CNT, wherein has voltage difference between at least two described layers.

39. method as claimed in claim 38, wherein AC voltage, dc voltage or its combination are applied to described removal, separation, the fixing and/or destruction of at least one described layer to help pollutant of CNT.

40. product as claimed in claim 39, wherein said voltage comprises AC voltage, and frequency that it has and amplitude signal are enough to destroy the debye atmosphere around at least one charged contaminants in the described fluid.

41. product as claimed in claim 39, wherein said dc voltage difference are from greater than 0.0 to 200kV scope.

42. product as claimed in claim 39, the peak-to-peak amplitude of wherein said AC voltage are from greater than 0.0 to 200kV scope.

43. product as claimed in claim 39, wherein said AC frequency be in 1.0 millihertzs in the described scope of 1.0 megahertzes.

44. method as claimed in claim 40, wherein said charged contaminants are the ions that comprises the salt in seawater and the salt water.

45. method as claimed in claim 35, wherein said ion comprises sodium, chloride, potassium, calcium, magnesium, sulfate, heavy carbonate, manganese, iron, copper, mercury, gold, silver, platinum, lead, arsenic, uranium and palladium.

46. method as claimed in claim 45, wherein said charged contaminants are the ions that sees in fresh water, waste water and the outflow stream.

47. method as claimed in claim 35, wherein said fluid comprises salt solution, and described a plurality of layers at least one be enough to make water to remove freshen, and at least one other layers be enough to remove, separate, fixing and/or destroy other pollutants in the described salt solution.

48. method as claimed in claim 47, wherein said other pollutants comprise one or more pathogen, virus, microbial organisms, DNA, RNA, natural organic molecule, mould, fungi, natural and synthetic toxin, heavy metal, endotoxin, protein, prion and enzyme.

49. method as claimed in claim 47, wherein said other pollutants comprise and are selected from following at least one atom or ion: antimony, arsenic, aluminium, selenium, hydrogen, lithium, boron, carbon, oxygen, sodium, calcium, magnesium, sulphur, chlorine, niobium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, bromine, strontium, yttrium, zirconium, molybdenum, rhodium, palladium, iodine, silver, cadmium, indium, tin, caesium, tungsten, iridium, hafnium, rhenium, osmium, platinum, gold, mercury, thallium, lead, polonium, radon, radium, thorium, uranium and plutonium.

50. method as claimed in claim 35, wherein said fluid is a water.

51. method as claimed in claim 35, wherein said fluid comprises air.

52. method as claimed in claim 35 also comprises at least a fiber that is selected from glass or aluminium oxide.

53. a method for preparing the nanometer net materials that comprises CNT, described method comprises:

(a) handle described CNT by the processing that described CNT is exposed at least one chemistry, radiation or machinery;

(b) the described CNT of rinsing at least a solvent of moisture in being selected from, inorganic and organic solvent;

(c) by described CNT is formed carbon nano tube suspension with being selected from moisture, at least a solvent inorganic and organic solvent, described suspension optionally contains fiber, particle or its combination; And

(d) in the nanometer stratum reticulare of the described suspension of deposition on the porous matrix with formation CNT on described porous matrix.

54. method as claimed in claim 53, wherein said chemical treatment comprise that with oxidizer treatment described radiation treatment comprises microwave, electron beam and heat treated at least a, it is at least a that described mechanical treatment comprises that ultrasonic wave is handled and stirred.

55. method as claimed in claim 53, wherein the described processing of (a) is the amount that enough forms defective, and at least one functional group that described CNT comprises is connected at least one described defective or arrives the non-blemish surface of described CNT.

56. method as claimed in claim 53, wherein the sense chemical group is the amount of enough regulating the described zeta potential of described gained functionalized carbon nanotubes to the described connection of described CNT.

57. method as claimed in claim 53, wherein said CNT is many walls, and has length and scope the diameter from 1 to 300nm of scope from 0.1 μ m to 100mm.

58. method as claimed in claim 54, wherein said oxidant comprises and is selected from following one or more oxidants: nitric acid, sulfuric acid, hydrochloric acid or hydrofluoric acid, potassium permanganate, hydrogen peroxide or its combination, it is the amount that enough at least one functional group is connected to described carbon nano tube surface.

59. method as claimed in claim 58, wherein at least one functional group comprises carboxyl.

60. method as claimed in claim 58, wherein at least one functional group comprises amine or polyamines group.

61. method as claimed in claim 53, wherein said at least a solvent comprises water, alcohol or its combination.

62. method as claimed in claim 53, wherein said suspension is deposited by the differential pressure sedimentation.

63. method as claimed in claim 53, wherein said suspension are deposited on the matrix based on carbon.

64. method as claimed in claim 55 comprises also forming at least one additional suspension that the functionalized carbon nanotubes that described additional suspension has is different from described first suspension to the ratio of fiber.

65. as the described method of claim 64, comprise at least two alternating layers that form the nanometer net, wherein one deck is formed by described first suspension at least, and at least one extra play is formed by described additional suspension.

66. method as claimed in claim 53, wherein said porous supporting substrate comprise sheet or block of material and the fibrous material that is selected from pottery, carbon, metal and plastics, described fibrous material is braiding or non-woven.

67. method as claimed in claim 53, wherein at least one molecule or bunch comprise that inorganic compound, described inorganic compound comprise and be selected from following at least one atom: aluminium, selenium, hydrogen, lithium, boron, carbon, oxygen, calcium, magnesium, sulphur, chlorine, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, rhodium, palladium, iodine, silver, indium, tin, caesium, barium, lanthanum, tantalum, tungsten, iridium, hafnium, rhenium, osmium, platinum, gold, mercury, thallium, bismuth.

68. method as claimed in claim 53, wherein said bunch comprises quantum dot.

69. method as claimed in claim 53, wherein at least one molecule or bunch include organic compounds, described organic compound contain one or more protein, carbohydrate, polymer, aromatic series or aliphatic alcohol, and nuclear or non-nuclear.

70. method as claimed in claim 53, wherein at least one molecule or bunch include organic compounds, described organic compound contain and are selected from following one or more chemical groups: carboxyl, amine, aromatic hydrocarbons, nitrile, acid amides, hydro carbons, alkene, alkynes, alcohol, ether, ester, aldehyde, ketone, polyamide, poly-amphipathic compound, diazol, slaine, pyrenyl, thiol base, thioether, sulfydryl, monosilane and combination thereof.

71. method as claimed in claim 53, wherein said fiber is selected from:

(a) at least a polymeric material, it is selected from list or multicomponent polymer, and described polymer is selected from nylon, acrylic acid (polymer), methacrylic acid (polymer), epoxy resin, silicon rubber, polypropylene, polyethylene, polyurethanes, polystyrene, Merlon, the aromatic series polyamide, polychloroprene, the terephthalic acids polybutester, poly-to phylene terephthalic acids acid amides, poly-(to phenylene terephthalic acids acid amides) and polyester, ester, ketone, polyester, polytetrafluoroethylene (PTFE), polyvinyl chloride, polyvinyl acetate, the viton fluorubber, polymethyl methacrylate, polyacrylonitrile and combination thereof;

(b) at least a ceramic material, it is selected from boron carbide, borazon, boron oxide, spinelle, garnet, lanthanum fluoride, calcirm-fluoride, glass, quartz, carborundum, silicon nitride, carbon and allotrope thereof, aluminium oxide, aluminium hydroxide, aluminium nitride, zirconia, zirconium carbide, hafnium boride, thorium oxide, yttria, mangano-manganic oxide, manganous hydroxide, magnesia, magnesium hydroxide, cordierite, mullite, ferrite, sapphire, saponite, titanium carbide, titanium nitride, titanium boride, zirconium boride, zirconium nitride and combination thereof;

(c) at least a metal material, it is selected from aluminium, boron, copper, cobalt, gold, platinum, palladium, silicon, steel, titanium, rhodium, iridium, indium, iron, palladium, gallium, germanium, tin, tungsten, niobium, manganese, magnesium, molybdenum, nickel, silver, zirconium, yttrium and its oxide, hydroxide and/or alloy; And

(d) at least a biomaterial or derivatives thereof, it is selected from cotton, cellulose, wool, silk and feather and combination thereof.

72. method as claimed in claim 53, wherein the described metal in the glass fibre of described washing or modification comprises iron hydroxide.

73. method as claimed in claim 53, wherein said fiber comprise the glass fibre that metal, metal oxide or metal hydroxides apply or modify, the diameter range that described glass fibre has is from 0.1 μ m-5 μ m.

74. method as claimed in claim 55, wherein said CNT functionalised with the zeta potential of regulating them so that control their attraction to other CNTs, particle, fiber or its combination.