CN101312812A - Hybrid manufacturing platform to produce multifunctional polymeric films - Google Patents
Hybrid manufacturing platform to produce multifunctional polymeric films Download PDFInfo
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- CN101312812A CN101312812A CNA2006800433529A CN200680043352A CN101312812A CN 101312812 A CN101312812 A CN 101312812A CN A2006800433529 A CNA2006800433529 A CN A2006800433529A CN 200680043352 A CN200680043352 A CN 200680043352A CN 101312812 A CN101312812 A CN 101312812A
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Abstract
The present invention relates to a method for producing hybrid materials of thin polymer films with single, laminated, complete and/or partially embedded nanofibers to obtain products with unique functional properties. In one embodiment, the present invention involves a method that comprises the combination of two process technologies; a thin film solution casting process (tape casting, solvent casting) and an electrospinning process, in order to produce hybrid materials of thin polymer films with single, laminated, completely and/or partially embedded electrospun nanofibers to obtain products with unique functional properties. In another embodiment of the present invention, fibers and/or nanofibers of a chosen material are spun directly onto substrates of polymer solutions and/or monomers solutions, where such solutions are located on a carrier belt that is electrically and/or ionically conductive.
Description
Invention field
[0001] the present invention relates to the production method of thin polymer film composite material, this thin polymer film composite material have a lamination, fully and/or the nanofiber that is partially submerged into, to obtain product with unique function character.In one embodiment, for produce have a lamination, fully and/or the thin polymer film composite material of the electro spinning nano fiber that is partially submerged into to obtain product with unique function character, the present invention relates to comprise the method for combination film solution casting method (The tape casting, solvent cast) and two kinds of technologies of electrospinning method.In another embodiment of the invention, to the substrate of polymer solution and/or monomer solution, wherein these solution are set on the carrier band of conduction and/or ionic conduction by direct fabrics for the fiber of selected material and/or nanofiber.
Background of invention
[0002] solution casting method of thin polymer film (industrial The tape casting or the tape casting method of being also referred to as) comprise by grooved mould (slot die), scraper (doctor blade) or reverse roll (reverse roll) with solution coat to carrier, remove and to desolvate by applying heat subsequently.Can produce and have extremely inhomogeneity film from the hundreds of micron thickness to several micrometer ranges.Solution casting method provides advantage for not being melted to handle or demonstrate the instable material of fusing at little thickness range.Commercial solution-cast machine is manufactured to surpass 50 years, and has kind of design widely.Commercial solution-cast machine typically comprises the solid cast surface, have the hothouse of the built-in type device of control cast-solution top air stream, adjustable speed carrier driving governor, control hothouse the filtration feed air themperature air heater and in machine, set up heater under the lathe of preferred temperature curve.The ring-type stainless steel band that carrier normally rotates is although other common polymer support or coated paper carriers also are found in commercial Application.This endless steel belt also can comprise heater under the lathe, to heat cast medium from following conduction.By from top air heat with from the combination of following conduction heating cast fluid or segment fluid flow medium, can realize desolvating and/or polymerization is solidified by removing.In single solution-cast machine, variety carrier also is possible.
[0003] can form the liquid of fiber and/or the electrospinning of solution knows---and form at fiber and be also referred to as electrostatic spinning in the industry, and in many patents and general document, described.The electrospinning method is usually included in liquid surface and produces electric field.The electric power that forms produces the atomizing of liquids that is loaded with electric charge.Can under suitable electric potential, attract these charged atomizing of liquids on fuselage (body) or other object.When forcing atomizing of liquids more and more far away towards object, it elongates.When it was advanced away from liquid storage device, therefore its stably dry and sclerosis formed fiber.Can be by this liquid of cooling (that is, this liquid at room temperature normally the situation of solid); Evaporating solvent (for example, by dehydration); Physics causes sclerosis; Perhaps, make that atomizing of liquids is dry and be hardened to fiber by curing mechanism (chemical induction sclerosis).The fiber that is produced by electrospinning is collected on the charged receiver of suitable setting and shifts out from receiver on demand subsequently.
[0004] fiber of being produced by the electrospinning method is used in multiple application, and from for example United States Patent (USP) 4,043,331 and 4,878, No. 908 known, is suitable in the non-woven pad of wound dressing particularly useful in formation.Other medicines use comprise medicine send (referring to, for example No. 2003/0195611, the application of U.S.'s publication); Medicinal facial mask (referring to, WO01/26610 for example); Make infection rate, blood loss reduce to bandage and suture that minimum and final dissolving enters health.Because their the less microcellular structure with high surface area, nanofiber also has promising application in filtration art.For filter submicron from air or water, electro spinning nano fiber is desirable.They have improved filter life and have had better pollutant blocking capability.
Summary of the invention
[0005] the present invention relates to the production method of thin polymer film composite material, this thin polymer film composite material have a lamination (single, laminated), fully and/or the nanofiber that is partially submerged into, to obtain product with unique function character.In one embodiment, in order to produce thin polymer film composite material, the present invention relates to comprise the method for combination film solution casting method (The tape casting, solvent cast) and two kinds of technologies of electrospinning method to obtain product with unique function character with an electro spinning nano fiber lamination, that completely or partially embed.In another embodiment of the invention, to the substrate of polymer solution and/or monomer solution, wherein these solution are set on the carrier band of conduction and/or ionic conduction by direct fabrics for the fiber of selected material and/or nanofiber.
[0006] therefore, a target of the present invention provides on commercial solution-cast machine the method in conjunction with the electrospinning platform, making the thin polymer film of multi-layer compound structure, this thin polymer film comprises solution-cast substrate and embedding and/or is coated on one deck or multilayer electrospinning fibre and/or nanofiber on this basalis.
[0007] another target of the present invention be describe solution how by electrospinning on the cast membrane to produce sandwich construction, in one embodiment, this cast membrane is positioned on the carrier band of commercial solution-cast machine.
[0008] another target of the present invention is to provide possible application for these products.
[0009] the another target of the present invention is to provide continuation method for producing the multilayer film or the first spinning nano fibre net that are proposed in batches.
[0010] in one embodiment, the present invention relates to produce the method for nanofiber-polymer film bond, the method comprising the steps of: (A) produce polymer film, wherein this polymer film can be admitted one deck or multi-layer nano fiber; (B) deposition one deck or multi-layer nano fiber on polymer film.
[0011] in another embodiment, the present invention relates to produce the method for nanofiber-polymer film bond, the method comprising the steps of: (a) produce polymer film, wherein this polymer film can be admitted one deck or multi-layer nano fiber; (b) make polymer film stand at least one thermal treatment zone; (c) deposition one deck or multi-layer nano fiber on polymer film.
The accompanying drawing summary
[0012] Fig. 1 is to produce the explanation of the production equipment of multifunctional polymer film according to one embodiment of the present invention;
[0013] Fig. 2 illustrates two width of cloth views that can unite the electrospinning platform of use with the present invention;
[0014] Fig. 3 (a) and 3 (b) have illustrated other two width of cloth views of another embodiment that can unite the electrospinning platform of use with the present invention;
[0015] Fig. 4 (a) has illustrated the solution-cast machine that does not have the electrospinning part;
[0016] Fig. 4 (b) has illustrated that these solution-cast facility have the electrospinning platform of type that at least two Fig. 2 describe according to the solution-cast machine of the embodiment of Fig. 4 (a);
[0017] Fig. 4 (c) is the zoomed-in view of Fig. 4 (b) dashed circle;
[0018] Fig. 5 (a) has illustrated another embodiment of the solution-cast machine that does not have the electrospinning part;
[0019] Fig. 5 (b) has illustrated the solution-cast machine according to the embodiment of Fig. 5 (a), and these solution-cast facility have the electrospinning platform of at least four Fig. 3 (a) and 3 (b) type of describing;
[0020] Fig. 6 is applied to poly-(amic acid) (PAA) SEM (SEM) image of the PEO on film surface (PEO) nanofiber;
[0021] Fig. 7 is partially embedded into poly-(amic acid) (PAA) SEM (SEM) image of the PEO of film (PEO) nanofiber;
[0022] Fig. 8 is embedded into poly-(amic acid) (PAA) film but be positioned at very SEM (SEM) image near PEO (PEO) nanofiber of surface fully;
[0023] Fig. 9 fully and dearly is embedded into poly-(amic acid) (PAA) dark field optical microscope (OM) image of the PEO of film (PEO) nanofiber;
[0024] Figure 10 fully and dearly is embedded into poly-(amic acid) (PAA) AFM (AFM) image of the PEO of film (PEO) nanofiber; With
[0025] Figure 11 (a) and 11 (b) are poly-(amic acid) (PAA) dark field optical microscope (OM) images of the scratch-off surface of PEO (PEO) nanofiber in the film, wherein Figure 11 (a) is embedded into poly-(amic acid) (PAA) fibre image and Figure 11 (b) be that the surface is applied to poly-(amic acid) (PAA) fibre image of film wherein of film.
Detailed Description Of The Invention
[0026] the present invention relates to the production method of thin polymer film composite material, this thin polymer film composite material have a lamination, fully and/or the nanofiber that is partially submerged into, to obtain product with unique function character.In one embodiment, for produce have a lamination, fully and/or the thin polymer film composite material of the electro spinning nano fiber that is partially submerged into to obtain product with unique function character, the present invention relates to comprise the method for combination film solution casting method (The tape casting, solvent cast) and two kinds of technologies of electrospinning method.In another embodiment of the invention, in polymer solution and/or monomer solution substrate, wherein these solution are set on the carrier band of conduction and/or ionic conduction by direct fabrics for the fiber of selected material and/or nanofiber.
[0027] as used herein, the term nanofiber is meant that having average diameter arrives the interior fiber of about 25,000 nanometers (25 microns) scope in about 1 nanometer.In another embodiment, nanofiber of the present invention is to have average diameter to arrive about 10 in about 1 nanometer, 000 nanometer, perhaps about 1 nanometer is to about 5,000 nanometers, and perhaps about 3 nanometers are to about 3,000 nanometer, perhaps about 7 nanometers are to about 1,000 nanometer, perhaps even the fiber of about 10 nanometers in about 500 nanometer range.In another embodiment, nanofiber of the present invention is to have average diameter less than 25,000 nanometers, perhaps less than 10,000 nanometers, perhaps even less than the fiber of 5,000 nanometers.In another kind of embodiment still, nanofiber of the present invention is to have average diameter less than 3,000 nanometers, perhaps less than about 1,000 nanometer, perhaps even less than the fiber of about 500 nanometers.In addition, should be noted in the discussion above that herein and other place in the literary composition that scope can make up.
[0028] in one embodiment of the invention, for make comprise at the bottom of the liquid-based and be positioned at this liquid level and/or on one deck or the multilayer polymer structure of multilayer spinning fibre and/or spinning nanofiber, above-mentioned two kinds of technology, ie in solution casting and electrospinning are combined.Nanofiber can have the chemical composition identical or different with fluid base layer.In another embodiment, nanofiber can have with basalis in the identical or different chemical composition of solute substance used.In an example, nano-fiber material should be undissolved or have limited solubility at the solvent that is used for the solution-cast basilar memebrane.
[0029] in one embodiment, one deck or multilayer spinning layer segment ground or be fully inserted in forming the fluid media (medium) of fluid base layer.Fluid base layer can have or can not have chemistry with the material of forming electro spinning nano fiber or physics interacts.By various chemistry and/or physical method, strong can easily between cast base material and electrospinning fibre and/or nanofiber, foundation.In one embodiment, base layer material can be the monomer that polymer solution or be easy to is comprised the various polymerization polymerizations of photopolymerization etc.
[0030] in conjunction with above-mentioned two kinds of technology not only for making described multilayer polymer film but also being actual with useful for the electrospinning process is controlled better.The electrospinning set of standard does not comprise the ability of control electrospinning medium (air typically) temperature, pressure and solvent strength usually.Consideration to the health and safety problem is important, because the steam of emitting from electrospinning solution is in case suck and may be dangerous and therefore should be recovered and handle.In addition, reduce the expensive of this method for electrospinning method expansion scale simultaneously to continuous batch production, challenge still exists.The electrospinning method can be eliminated the great majority in these problems with after solution casting method combines.Therefore, exist in conjunction with the needs of the method for these two kinds of technology at least.
[0031] the present invention also makes the possibility that is combined into of above-mentioned technology, has therefore produced the improved control to process conditions in the electrospinning, and this is conceived to better product uniformity and produces in batches in a continuous manner.
[0032] as described in above this paper, in one embodiment, the present invention relates to the production of multilayer polymer film, it comprises the electro spinning nano fiber pantostrat that the solution-cast basalis is identical with one deck or multilayer or different chemical is formed.In another embodiment, the present invention relates to the production of multilayer polymer film, it comprise in solution-casting (with liquid reactions or nonreactive) basalis and the sandwich construction or partially or even wholly embed form or as the electro spinning nano fiber of this basilar memebrane last layer or multilayer pantostrat.
[0033] composite construction that proposes in order to produce, in one embodiment, nanofiber can direct fabrics on the cast polymerization thing solution and/or monomer on the rotation ring-type steel transport tape of solution-cast machine, perhaps can direct fabrics on the conductive support film of this steel transport tape transmission.
[0034] in the embodiment that relates to direct pouring on steel band, the ground connection receiver will be the conductive steel transport tape, and charged liquid is is directly provided and delivered to the transport tape of solution-cast machine from syringe.Implementing a kind of possible equipment 100 of the present invention shows in Fig. 1.
[0035] in the embodiment of Fig. 1, according to one embodiment of the present invention, equipment 100 comprises the polymer solution 102 that is used to cast, and it is comprised in any suitable containers 104.Polymer solution 102 at first is cast on the carrier band 106 that moves of solution-cast equipment 100.Randomly, in order to promote the solvent evaporation, carrier band 106 can be at next step by one or more thermal treatment zone (not shown).By any suitable equipment that local heat can be provided to one or more zone of solution cast polymer, can form the thermal treatment zone.For example, the thermal treatment zone can form heating clamber (for example, being maintained at the little semi-closed box of one or more high temperature).
[0036] then, as Fig. 1 finding, one or more electrospinning platform 108 is based upon on the solution-cast equipment 100, so that one or more nanofibers of spinning are on solution-cast substrate polymer layer and/or film 110.From suitable nano-fiber material 112 spinning nanofiber of the present invention.Finish this process by removing to desolvate from film 114, thereby dry composite material is provided, it comprises the even substrate film layer 110 with electrospinning fibre surface texture 116, and it can for example be collected in extraction place 118.It is unlimited making the chance that forms sandwich construction in this way.If adopt different polymer/solution mixtures to be used for solution-cast and electrospinning, can produce the mixed polymer film that has different layers polymer and form along thickness direction.If use single polymers/solvent mixture in the method, will form the same polymer that multilayer has different shape along film thickness direction, that is, and homogeneous film and fiber top layer.
[0037] the polymer right and wrong of solution-cast conductive (that is, nonconducting on the electricity meaning)---most polymers normally like this may be before all solvents all evaporate, spinning nanofiber on casting membrane of solution if be used for.In an example, this can be by spinning nanofiber realization on the polymer solution of casting before entering the main thermal treatment zone of solution-cast machine.This set-up/process order has guaranteed to accept steel band and has kept conductibility.This also help nanofiber adhere to formerly the layer on.Also may work as film before all solvents all evaporate through in one group of heating clamber, on this casting membrane of solution, apply nanofiber.
[0038], be desirable so have that removable turnover top board is used for combining with the electrospinning process because most of commercial solution-cast machines are designed to the system of complete closed.Portable electrospinning platform can substitute these top boards in any desired place and time.When not expecting electrospinning, and the solution-cast machine is when only being used for casting film, and the electrospinning platform will be removed, and top board is taken back to their original positions.Importantly, in case the electrospinning platform is put into, they should seal machine chamber.
[0039] although the invention is not restricted to only a kind of layout, but the electrospinning platform (for example will typically hold high voltage source, high-precision pressure/evacuated air pump, one or more big capacity hermetic seal spinning head that is connected to pressure/vavuum pump with flexible pipe, syringe), and one or more be used for being provided with the controller of spinning head pressure and vacuum level.In one embodiment, spinning head is positioned on the translation stage (for example, linear actuator (linear actuator)), and this translation stage is positioned on the platform.Lay this nanofiber equably for the width along cast membrane, translation stage makes spinning head move along the width levels of carrier band.In one embodiment, moving horizontally by laser micrometer of translation stage controlled.In one embodiment, the ability of the pressure/vacuum level in the control spinning head is an important factor of the present invention.
[0040] because spinning head with respect to carrier band positioned vertical, solution should be prevented from from syringe needle drippage.This can realize by pressure/vacuum level of adjusting in the spinning head by any suitable control tool in whole process.Therefore, the present invention can comprise that any suitable permission operator controls the control tool of the pressure/vacuum level in one or more spinning head.In one embodiment, this control tool can be manual adjustments or the pressure regulator of regulating (for example, passing through computer control system) automatically.If solution drips from syringe needle, apply vacuum at first to stop this drippage.Then make it not have the drippage spinning by the air pressure that applies q.s to solution.If after initial vacuum, do not apply enough air pressures to solution, a little while after solution will stop spinning because solution since spinning shift out and cause in the syringe of sealing and will produce vacuum.As known to those skilled in the art, under high voltage solution with higher rate-allocation.In such a case, air pressure also should increase.The balance of power (for example, electric power, surface tension, gravity) that acts on solution in the electrospinning process can be conditioned by pressure/vacuum level of regulating in the sealing spinning head, so that this process does not have drippage.
[0041] in one embodiment, platform has vertically (Z-direction) translation capability.This expects, because required separation distance is influenced by the rate of drying of polymer solution between spinning head and the carrier band.As known to those skilled in the art, for different polymer/solvent systems, rate of drying is with difference.The vertical height regulating power of electrospinning platform makes the height between spinning head and the carrier band regulate becomes possibility, and it makes different polymer/solvent systems in the diverse location spinning simultaneously along the length of present device again.In one embodiment, a plurality of spinning heads amount to from 2 to about 1000, can be used to boost productivity.Containing many pins or little single mould capillaceous is connected on pressure and the vavuum pump to prevent that drips of solution from falling.
[0042] Fig. 2 represents to have according to an embodiment of the invention the electrospinning platform example of single nanofiber deposition capability.In the embodiment of Fig. 2, exemplary electrospinning platform 200 is illustrated, and it comprises controller 202, pressure transmitter 204, is used to hold the solution container 208 of the appropriate solution for the treatment of electrospinning, main reservoir 210, pump 212 and high voltage source 214.As the optional view finding of platform among Fig. 2 200, platform 200 bottoms comprise spinning head 216 and translation stage 218.Translation stage 218 makes spinning head 216 with two-dimensional approach motion at least.
[0043] should be noted in the discussion above that the present invention is not limited only to the embodiment that wherein single nanofiber is deposited.More properly, can use the electrospinning platform of ability in the present invention with one or more nanofibers of deposition.Just to illustrative purposes, the electrospinning platform that Fig. 2 represents has open side.In fact, when they in use, all sides of this platform should be closed and should the lock solution casting machine with isolation environment atmosphere.Fig. 3 (a) and 3 (b) illustrate two additional views of another embodiment of electrospinning platform, and it can be used in combination with the present invention.Once more, just to illustrative purposes, the electrospinning platform of Fig. 3 (a) and 3 (b) expression has open side.In fact, when they in use, all sides of this platform should be closed and should the lock solution casting machine with isolation environment atmosphere.
[0044] in order to produce the hybrid multilayer membrane structure, the solution-cast machine provides actual solution and is provided for directly on the carrier band of rotation or produce the platform of nanometer fiber net continuously on the polymer solution of casting.Fig. 4 (a), 4 (b) and 4 (c) are to commercial solution-cast machine and the explanation of use according to the binding pattern of the present invention of a plurality of electrospinning platforms of Fig. 2 embodiment.Fig. 5 (a) and 5 (b) are to commercial solution-cast machine and the explanation of use according to the binding pattern of the present invention of a plurality of electrospinning platforms of Fig. 3 (a) and 3 (b) embodiment.
[0045] have the state-variable of many adjustable solution-cast technologies, it is useful for controlling the electrospinning process better.For example, enter that heter temperature is adjustable under air themperature and the lathe---help to arrange along the temperature of machine length.For electrospinning, the ability of control air themperature is important, because air themperature influences the dry behavior of nanofiber.By improving inlet air temp, may reduce spinning head and accept distance between the carrier band.Fig. 4 (a) has illustrated the solution-cast machine of the parallel air flow design that has above carrier.Other adopts the design of air impingement drying (air impingement drying) or vapor spray also is commercially available.
[0046] another kind of variable is the speed of carrier top air.The increase of air velocity also can be quickened the dry of nanofiber and promote solvent vapour to remove fast from environment.Usually, the solvent vapour in the exhaust is sloughed from exhaust by the exhaust passage and by solvent recovery unit.In addition, all commercial solution-cast machines all are equipped with LEL (lower expolsionlevel (LEL)) inductor.Because present most of electrospinning technology is carried out in open atmosphere and is not met health and/or safety standard, so these supporting capacities of solution-cast technology are important.
[0047] the another kind of advantage of using the solution-cast carrier platform to be used for electrospinning is that adjustable speed carrier drives control.This brings the collecting region locomotivity for the electrospinning process.The solution-cast machine that exists coating industry to use, its length reaches 300ft and can reach from about bearer rate of 100 to about 1000ft/min.The enough height of these speed are so that nanofiber is arranged in rows, and it is important for some application.For these high-speed application, in one embodiment, the conducting polymer film can be used as carrier substrates, and is coated with the nanofiber of arranging.Also may in the high-speed cruising pattern, be coated with extremely thin solution cast polymer top layer with the nanofiber of arranging.In this operational mode, the time of staying will be inadequately before the solvent evaporation on cast-solution the spinning nanofiber.In this case, extremely thin liquid level can be applied on the carrier film, therefore reduces the requirement of the time of staying in the chamber.In another kind of operational mode,---about 2 to 3 microns---of the thickness of dry polymer film allow fiber and/or nanofiber cast in conductive support (steel, perhaps conducting polymer film) with on desciccator diaphragm on spinning.In one embodiment, this band can rotate in a continuous manner, up to the electrospinning layer thickness that reaches expectation.
[0048] the present invention can produce the hybrid films that extremely thin nanofiber strengthens.These films comprise the homogeneous polymer rete, and it is scribbled or wherein embed one deck or multi-layer fiber and/or nanofiber.Yet be not limited thereto, in one embodiment, the thickness of these films can be in the scope from several microns to the hundreds of micron.For example, film constructed in accordance will be used as the solar sail (solar sail) in the spacecraft.
[0049] in addition, the present invention makes it become possibility: by embed the conducting polymer nanofiber in non-conducting polymer film, make non-conducting polymer film have conductibility.
[0050] hybrid films of the present invention comprises that in manufacturing in the hybrid films of the non-porous layer of different polymer and form and nano porous layer also be useful.These materials are useful in following field: the intellectual material of selection chemical reaction, solid carrier catalyst, film load (membranesupported smart materials) and be used for fixing biology and the pharmaceutically active preparation and the film of molecule.Select except wisdom, can produce and show extreme hydrophobicity or hydrophilic surface for material.
[0051] turn back to the fiber that may make the present invention and/or the discussion of nanofibrous structures, by adjusting the material and the state-variable of electrospinning and solution-cast technology, these fibre structures can embed or only exist only in the film surface.In an example, the quantity of solvent and the electrospinning solution that are retained in the target solution layer of casting are important parameters with the electrical potential difference of accepting between target (for example, casting substrate solution layer).If the cast-solution layer mainly is in liquid form, promptly do not have or few solvent evaporates from cast membrane, then under electric field influence, fiber and/or nanofiber overcome the surface tension of solution-cast basilar memebrane and penetrate into the degree that allows to basilar memebrane viscosity in the film.If nanofiber spinning on the solution cast target that discharges its most of solvent, then this fiber and/or nanofiber may not penetrate into basalis and only on basilar memebrane surface or approach the basilar memebrane surface and exist.
[0052] in addition, when solvent when base target solution evaporates, the conductibility of target reduce and since disadvantageous electrical potential conditions nanofiber advance to target and slow down.In some embodiments, determining that along the position of the electrospinning platform of casting process line nanofiber is that to embed or only exist only in aspect the target layer surface of advancing may be important below electrospinning platform (one or more).The control of evaporation also can be used to form gradient-structure, and wherein nanofiber can be positioned in the different depth of base film thickness direction.In an example, by at fiber and/or nanofiber by drying solution cast membrane partly before electrospinning is to the film, this design is possible.
[0053] in an example, use the scraper tool group at the wet spacing (wetclearance) of 100 μ m, the nmp solution of solution-cast polyamic acid (PAA).Many films make manufactured in this way, and PEO (PEO) nanofiber from water by before electrospinning is on the nmp solution cast membrane of polyamic acid (PAA), dry 0 minute, 10 minutes, 20 minutes, 25 minutes, 30 minutes and 40 minutes.The thermal treatment zone of solution-cast machine is set to 60 ℃ and fan and is set to 50% to promote residual solvent to remove.Use the dry film of SEM (SEM) and light microscope (OM) research.The SEM image has the characteristic 3 D outward appearance, and can be used for judging the surface texture of film.If all fibres from the teeth outwards, SEM shows very clear and definite fiber uniformly.If pars fibrosa embeds, SEM shows bright and dark zone of fiber, respectively expression embed a little and in the zone on surface.
[0054] in another example, embed but still very close film surface as fruit fiber, SEM can detect the faint impression of fiber.If nanofiber is embedded in the film deeply, SEM can not detect any fibre image.In this situation, the light microscope that is in transmission mode or details in a play not acted out on stage, but told through dialogues and/or bright field reflective pattern can detect the nanofiber that is embedded in the film.AFM (AFM) is to can be used for characterizing the another kind of characterization tool that embeds fiber.The real-time detection of the solvent strength by solvent in the film of advancing, above mentioned design can easily be adapted to continuous operation, and, under electrospinning platform (one or mores') control, can reach the concentration of expecting in the film by controlling the temperature of carrier from following (conduction) with from top (convection current).This will make continuous nanometer create possibility.
[0055] Fig. 6 is SEM (SEM) image that is applied to PEO (PEO) nanofiber on polyamic acid (PAA) film surface.Particularly, Fig. 6 shows the lip-deep nanofiber of the casting membrane of solution with uniform luminance and contrast that is perfectly clear, and this casting membrane of solution is dry 40 minutes before electrospinning.Fig. 7 is SEM (SEM) image that is partially embedded into the PEO (PEO) in polyamic acid (PAA) film.Particularly, the image of Fig. 7 is presented at the preceding dry 30 minutes lip-deep nanofiber of casting membrane of solution of electrospinning.This fiber remains significantly, shows dark space and the clear zone that is partially submerged into but have.
[0056] Fig. 8 is embedded into polyamic acid (PAA) film fully but rests on SEM (SEM) image of PEO (PEO) nanofiber that is in close proximity to the surface.Particularly, the image of Fig. 8 shows and to embed but still enough to approach the surface fully with by the faint impressions of the detected fiber of SEM.Usually nanofiber can not found in the film surface of dry 0 minute, 10 minutes and 20 minutes before electrospinning.This be because nanofiber not from the teeth outwards but be embedded in the film deeply, and because its to the surface topography sensitivity, SEM can not observe this fiber and/or nanofiber.
[0057] Fig. 9 is dark field optical microscope (OM) image that fully also is embedded into PEO (PEO) nanofiber in polyamic acid (PAA) film deeply, and Figure 10 is AFM (AFM) image that fully also is embedded into PEO (PEO) nanofiber in polyamic acid (PAA) film deeply.On the other hand, OM and AFM have disclosed the existence that embeds fiber respectively, as shown in Figures 9 and 10.
[0058] the assessment nanofiber is that the another kind of method that only is applied to film surface or is embedded into film inside deeply is by making Physical Interference, as in film mantle friction or scraping.The fiber that embeds is not presented at mantle friction or the variation of their positional alignment of scraping back a little.On the other hand, the fiber that is applied to the surface is bothered by such Physical Interference.Figure 11 (a) and 11 (b) be in polyamic acid (PAA) film PEO (PEO) nanofiber by the dark field optical microscope of scratch-off surface (OM) image, wherein Figure 11 (a) is the fibre image that is embedded in polyamic acid (PAA) film, and wherein Figure 11 (b) is the fibre image that the surface is applied to polyamic acid (PAA) film.
[0059] electrospinning solution and accept the intensity that electrical potential difference decision nanofiber between target impacts the base liquid layer.The electrical potential difference that improves between electrospinning solution and base liquid target will promote fiber and/or nanofiber to penetrate into solution layer.On the other hand, nanofiber can gently be arranged on the base liquid target by the electrical potential difference between regulator solution and target.
[0060] for embedding or coated film with nanofiber, the character of cast-solution and electrospinning fibre (viscosity, surface tension etc.) is a kind of governing factor.Depend on surface tension, cast-solution can show the repellence of wetting fiber and therefore resist fiber and penetrate in the film.If use different polymer/solvent mixture to be used for solution-cast and electrospinning, can make the mixed polymer film that has different layers polymer and form along thickness direction.If use single polymers during the course, can form the same polymer that multilayer has different shape along the thickness direction of film, that is, and film and fibre structure uniformly.Yet, the solvent that is used for film casting with selected so that it does not dissolve this fiber.
[0061], can obtain wherein to expect to have the chemistry of the film that embeds nanofiber and the application that physical property is come the control surface frictional property by control owing to the present invention.In another kind is used, can produce electroactive (electro-active) structure, wherein can change nanofiber with respect to the orientation that is embedded into the plane by the electric hand section.This will provide the effective control to material surface character.
[0062] in another kind is used, can form the projection of nanofiber, and this projection possibility/can be used to from the main structure body heat radiation of conductibility (conduction and/or the heat conduction) film that is connected to its embedding.In another kind was used, the application of nanofiber can be used in the film application of wherein expecting some chemical species of Selective Separation.In another kind was used, nanofiber can be fixed in the substrate, and when nanofiber and one or more suitable inorganic or organic compounds were embedded into, are coated with and/or flood, these structures can be used as catalyst.
[0063] in another kind is used, constituting the required film of fuel cell can be by this mixed method production.The proton-conductive films that nanofiber strengthens can help high temperature conductivity problems.The porous character of this film also will help wetting film with and water holding capacity.
[0064] uses the present invention, may be used for forming physics and chemical coating on the solvent cast film of commodity or high-tech application.These films will be very light on weight.
[0065] owing to the present invention, casting membrane of solution can be as the substrate of supporting the electro spinning nano fiber net.This is important for photonic propulsion (photonics) is attached in textile and the clothes.The wearable photon product such as the intelligent textile structure of Fibre Optical Sensor and combination, and will from this technology, be benefited with present decoration of communicating by letter (current communicationapparel) and optical fiber fabric display in the development of various flexible photon Display Techniques.
[0066] the present invention also can be used for producing photon structure and/or is the manufacturing generation modification method of this structure.In a this example, the present invention can be whole or partly be used to produce tiny coil, and this coil is arranged to be manufactured on the structure that useful frequency has negative dispersion (negativedispersion).This useful frequency range can be by the size Selection of regulating winding.One of negative dispersion material and circular polarization photon interact, and opposite circular polarization does not interact.Coil can fully or partly be coated with metal, so that electric conductivity or polarizability to be provided.This coil can drive crooked unstability by the electricity that utilizes the electrospinning jet manufactured.In this situation, the present invention allows to form the substrate of cast sheet form, and the direction support coils that it is can be on sheet useful is promptly in the direction of three-dimensional best angle and distance.
[0067] in another embodiment, the fiber and/or the nanofiber of the present invention's use can pass through other suitable method manufacturing.These methods include, but not limited to wet spinning, dry spinning, melt spinning, gel spinning and gas and spray nanofiber process (NGJ).As top mentioned, electrospinning is particularly suitable for making fiber of the present invention, and this is because it tends to produce the thinnest (i.e. the thinnest Denier) fiber of any preceding method.Electrospinning is at United States Patent (USP) 4,043, described in 331,4,878,908 and 6,753,454, all is incorporated herein with for referencial use with it.
[0068] for producing nanofiber of the present invention, another kind of special effective method comprises that gas sprays nanofiber process (being the NGJ method).Be used for forming the method for fiber and instrument at United States Patent (USP) 6,382 by NGJ, described in 526,6,520,425 and 6,695,992, it all is incorporated herein with for referencial use with it.
[0069] in brief, this method comprises the equipment that has interior pipe and have the coaxial outer tube of side arm that uses.Should fall in from outer tube edges by interior pipe, therefore form thin one-tenth diaphragm area.Polymer melt is sent into by side arm, and fills empty space between interior pipe and the outer tube.The outflow end of pipe touched the effluent air jet flow up to it in polymer melt continued to flow to.The gas jet of impacting bath surface forms molten polymer film, and it advances to the pipe outflow end, in the rapid cloud of nanofibers of this injected formation.
[0070] should be noted in the discussion above that the present invention is not limited only to the combination of polyamic acid (PAA) film and PEO (PEO) nanofiber.More properly, any combination of polymer film and nanofiber can be used, as long as film/nanofiber combination results is used to expect the combining structure of using with proper strength and durability.Other suitable polymers as film forming compound and/or one-tenth fibrillation compound includes, but not limited to nylon, PCL etc.Also may as fibre-forming material be the pottery the organic parent of metal (metal organic precursors toceramics), or the like.
[0071] in another kind of embodiment still, the present invention also allow with one or more chemical reagent, biological cell and organelle, biomolecule and/or therapeutic substance add, huge legendary turtle is closed or be coated with one deck of the present invention or the multi-layer nano fibrage.
[0072] in another kind of embodiment still, the present invention can comprise one deck or multi-layer nano fibrage, and wherein constituting the fibrolaminar nanofiber of one deck or multi-layer nano is beading nanofiber (see figure 9).In this example, any part of nanofiber or even all nanofibers be formed beading.In another embodiment, the some or all of nanofibers that are included in the structure of the present invention are coiled type nanofibers.
[0073] although the present invention is described in detail with particular reference to some embodiment that this paper describes in detail, other embodiment can reach identical result.Change of the present invention and modification will be obvious for those skilled in the art, and this invention is intended to cover in claims all such modification and equivalents.
Claims (20)
1. produce the method for nanofiber-polymer film bond, described method comprises step:
(A) produce polymer film, wherein said one or more layers nanofiber of polymer film receivability;
(B) deposit one or more layers nanofiber on described polymer film.
2. the described method of claim 1, wherein said one deck or multi-layer nano fiber have in the average diameter of 3 nanometers to about 3,000 nanometer range.
3. the described method of claim 1, wherein said one deck or multi-layer nano fiber have in the average diameter of about 7 nanometers to about 1,000 nanometer range.
4. the described method of claim 1, wherein said one deck or multi-layer nano fiber have in the average diameter of about 10 nanometers to about 500 nanometer range.
5. the described method of claim 1, wherein said polymer film is by being formed by any polymer of solution-cast.
6. the described method of claim 5, wherein said polymer film is formed by polyamic acid.
7. the described method of claim 1, wherein said nanofiber is by being formed by any polymer compound of electrospinning.
8. the described method of claim 7, wherein said nanofiber is formed by PEO.
9. the described method of claim 1, wherein said nanofiber is by forming by any polymer compound that the gas injection method becomes nanofiber.
10. the described method of claim 1, to described polymer film, wherein every layer of layers of nanofibers forms separately by one or more different electro-spinning equipment wherein two-layer at least layers of nanofibers by sequential aggradation.
11. produce the method for nanofiber-polymer film bond, described method comprises step:
(a) produce polymer film, wherein said polymer film receivability one deck or multi-layer nano fiber;
(b) make described polymer film stand at least one thermal treatment zone;
(c) deposition one deck or multi-layer nano fiber on described polymer film.
12. the described method of claim 11, wherein said one deck or multi-layer nano fiber have in the average diameter of 3 nanometers to about 3,000 nanometer range.
13. the described method of claim 11, wherein said one deck or multi-layer nano fiber have in the average diameter of about 7 nanometers to about 1,000 nanometer range.
14. the described method of claim 11, wherein said one deck or multi-layer nano fiber have in the average diameter of about 10 nanometers to about 500 nanometer range.
15. the described method of claim 11, wherein said polymer film is by being formed by any polymer of solution-cast.
16. the described method of claim 15, wherein said polymer film is formed by polyamic acid.
17. the described method of claim 11, wherein said nanofiber is by being formed by any polymer compound of electrospinning.
18. the described method of claim 17, wherein said nanofiber is formed by PEO.
19. the described method of claim 11, wherein said nanofiber is by forming by any polymer compound that the gas injection method becomes nanofiber.
20. to described polymer film, wherein every layer of layers of nanofibers forms separately by one or more different electro-spinning equipments by sequential aggradation for the described method of claim 11, wherein two-layer at least layers of nanofibers.
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| US72734705P | 2005-10-17 | 2005-10-17 | |
| US60/727,347 | 2005-10-17 | ||
| US60/786,132 | 2006-03-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104204345A (en) * | 2012-02-13 | 2014-12-10 | 芬欧汇川集团 | Method, system and apparatus for processing fibril cellulose and fibril cellulose material |
| CN105283292A (en) * | 2013-05-30 | 2016-01-27 | 阿克伦大学 | A continuous roll-to-roll process design for vertical alignment of particles using electric field |
| CN105711019A (en) * | 2016-04-29 | 2016-06-29 | 哈尔滨理工大学 | Device and method for molding thermoset liquid insulation material by casting |
| CN106521722A (en) * | 2015-09-15 | 2017-03-22 | 国网智能电网研究院 | Device for fiber blending |
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- 2006-10-17 CN CNA2006800433529A patent/CN101312812A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104204345A (en) * | 2012-02-13 | 2014-12-10 | 芬欧汇川集团 | Method, system and apparatus for processing fibril cellulose and fibril cellulose material |
| CN105283292A (en) * | 2013-05-30 | 2016-01-27 | 阿克伦大学 | A continuous roll-to-roll process design for vertical alignment of particles using electric field |
| CN106521722A (en) * | 2015-09-15 | 2017-03-22 | 国网智能电网研究院 | Device for fiber blending |
| CN105711019A (en) * | 2016-04-29 | 2016-06-29 | 哈尔滨理工大学 | Device and method for molding thermoset liquid insulation material by casting |
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