Background technology
Electrostatic spinning technique is the effective ways preparing polymer nano material, can obtain diameter in tens nanometers to the one dimension fibre of hundreds of nanometer.Compare conventional fibre, nanofiber has higher high porosity and specific area.This makes electrostatic spinning technique obtain investigation and application widely in filtration art.
Common single needle electrospinning device is primarily of parts compositions such as high voltage source, Spinning pumps, spinning syringe needle and collecting boaries.By high voltage source, between spinning syringe needle and collecting board, define high-voltage electrostatic field, the polymer solution droplets at spinning Needle outlet place is under the effect of electrostatic field, and shape can become taper, becomes " taylor cone ".Along with the increase of electric field force, " taylor cone " comes to a point gradually, and after cone-apex angle reaches a critical value, vertex of a cone surface molecular is subject to enough large electric field force to overcome the surface tension of solution, and polymer solution ejects from the vertex of a cone, forms injection stream.Electric field force makes jet stretch thousands of times to millions of times, and the diameter of jet is reduced to several micron to tens nanometers thereupon.Along with solvent evaporates, the fiber of gained is finally distributed on collecting board desultorily, forms nano fiber non-woven fabric.
In the electrospinning process of single needle, spinning efficiency very low (flow velocity of general spinning solution is 0.1-10mL/h), cannot meet the requirement of industrial production to production efficiency.
Publication number is CN1962966(publication date on May 16th, 2007) patent application document disclose a kind of Multi needle electrospinning process, can amplify single needle spinning.Its shortcoming is that spinning efficiency is limited to the quantity of syringe needle, and syringe needle is easily blocked, will cause instability in the industrial production, and extremely difficult cleaning.
Publication number is CN1849418A(publication date on October 18th, 2006) patent application document disclose a kind of columniform axial symmetry spinning electrode, its part immerses spinning solution, spinning electrode with electrostatic field is formed to electrode, rotated around its symmetry axis by this electrode, spinning solution is fed in electrostatic field continuously, reaches the object of continuous spinning.This invention, solves the little and interactive problem of electric field between Multi needle of syringe needle spinning amount well.And the cylindric spinning electrode of this invention needs a larger solution pool, to make cylindrical electrode rotate freely, solution is constantly fed electric field wherein.The shortcoming of this invention is that columniform electrode is in rotary course, old solution remaining after spinning is directly brought into solution pool and new soln mixing, this will greatly affect the Polymer Solution Property of whole solution pool, accelerates the aging of solution in pond, affects spinning quality.Concrete reason is as follows: the old solution after spinning is different from new soln concentration, can affect solution concentration, and the diameter of solution concentration and nanofiber, stuctures and properties is contacted directly after mixing, and the exception of solution concentration will bring the instability of nanofiber product; Old solution contacts with the steam in air, and SOLUTION PROPERTIES changes, then mixes with new soln, can affect spinning quality equally; By electrode polarization, part is aging for old solution, mixes new soln will be made aging with new soln.
Publication number is CN101755079A(publication date is on June 23rd, 2010) patent application document disclose a kind of spinning process applying liquid-phase substrate on cable, introduce in the method the mechanism that liquid-phase substrate applies and remove, compare patent application CN1849418A(publication date on October 18th, 2006) the spinning process of cylinder electrode solve new and old solution and mix the nanofiber product quality problems brought.The deficiency of this invention is that spinning cable used is little because of diameter, and the spinning fields be in electrostatic field is positioned at a part for the upper surface of cable, and this makes spinning fields area too small, causes spinning efficiency lower.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of polymer solution electrostatic spinning assembly, apparatus and method, to solve the too small and problem that spinning efficiency that is that cause is lower of polymer solution electrospinning device spinning fields area.
The present invention first aspect provides a kind of polymer solution electrostatic spinning assembly, comprising:
First electrode and described first electrode the second electrode staggered relatively and the spray body between described first electrode and described second electrode, wherein, described first electrode is plate electrode, and described spray body is used for described first electrode surface spray solution.
Further, described spray body moves in the plane being parallel to described first electrode.
Further, the speed range of described spray body movement in the plane being parallel to described first electrode is 2-30 cel.
Further, described spray body comprises the jet pipe be arranged in parallel and flat board that are positioned near described first electrode side, wherein, the length direction of described jet pipe is parallel to the plane at the first electrode place, the tube wall of described jet pipe has for the opening to described first electrode spray solution, between described flat board and described first electrode surface, there is gap.
Further, the cross section of described jet pipe is circular, oval or polygon.
Further, described opening comprises several nozzles.
Further, described opening comprises several apertures.
Further, described opening is the slit along described jet pipe length direction.
Further, the length of described slit is equal with the length of jet pipe.
Further, described spray body also comprises the scraper for removing solution on described first electrode surface be arranged in parallel with described jet pipe, and described jet pipe is between described flat board and described scraper.
Further, the surface configuration of described first electrode is polygon, and described polygonal size dimension is between 5 ~ 2000 millimeters, or the surface configuration of described first electrode is circular, and the diameter of described circle is between 5 ~ 2000 millimeters.
Further, the material of described first electrode is the nonmetallic materials that metal material, alloy material or surface have the coat of metal.
Further, the material of described spray body is insulating materials.
Second aspect of the present invention provides a kind of polymer solution electrostatic spinning apparatus, comprising:
Power supply, fiber collecting parts, liquid-accumulating container and connect the communication means of liquid-accumulating container and spray body, also comprise at least one filament spinning component, described filament spinning component adopts arbitrary spinning component structure described in the present invention first aspect, described collecting part is between described first electrode and institute's the second electrode.
3rd aspect of the present invention provides a kind of polymer solution electrospinning process, comprising:
To the first electrode surface spray solution, be sprayed on solution on described first electrode surface under the effect of electrostatic field, form fiber, wherein, between described first electrode and the second electrode staggered relatively, form electrostatic field, and described first electrode is plate electrode.
Further, describedly also to comprise after the first electrode surface spray solution,
Strike off the solution be sprayed on described first electrode surface, make it form the uniform solution layer of a layer thickness.
Further, describedly also to comprise before the first electrode surface spray solution, remove the surplus solution on described first electrode surface.
Further, also comprise, collect the fiber formed.
A kind of polymer solution electrostatic spinning assembly provided by the invention, apparatus and method, significantly can improve spinning efficiency.The first electrode wherein in filament spinning component is plate electrode, and its electrode surface is the plane that area is larger.By spray body, polymer solution is sprayed on the surface of the first electrode, this first electrode and place corresponding thereto form spinning fields to after electrode second electrifying electrodes, be sprayed on the spinning under the effect of electrostatic field of the solution on the first electrode surface, form nanofiber.Because the area of the first electrode is comparatively large, so the area of the spinning fields formed is also comparatively large, the technical problem limiting spinning efficiency in prior art because the area of spinning fields is too small can be overcome.
Detailed description of the invention
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment one
Composition graphs 1(1) describe the structure of the polymer solution electrostatic spinning assembly of the embodiment of the present invention one in detail.As shown in Fig. 1 (1), this polymer solution electrostatic spinning assembly comprises the first electrode 01 and described first electrode 01 second electrode 03 staggered relatively and the spray body 02 between described first electrode 01 and described second electrode 03.Wherein, spray body 02 is for the surface spraying polymer solution to the first electrode 01, in order to polymer solution electrostatic spinning has the spinning fields of larger area, it is plate electrode that the present embodiment limits the first electrode 01, the shape of the present embodiment to the second electrode 03 does not limit, it can be cylinder electrode, also can be plate electrode, also can be the electrode of other shape.As long as can make to form electrostatic field between the first electrode 01 and the second electrode 03.The cylinder electrode that second electrode 03 preferably can rotate around symmetry axis, like this can the electrostatic field that formed between the first electrode 01 and the second electrode 03 of disturbance, and the electrostatic field of this disturbance is favourable to initiation spinning.In addition, the material making the first electrode 01 or the second electrode 03 can be the nonmetallic materials that metal, alloy or surface have the coat of metal.
The shape and size of the present embodiment to the first electrode 01 are not construed as limiting.The surface of the first electrode 01 can be the arbitrary shapes such as polygon, circle, ellipse, in order to the relatively uniform polymer foil solution of thickness can be formed on the first electrode surface, surface be the size dimension of polygonal first electrode between 5 ~ 2000 millimeters, surface is that the diameter of circular the first electrode is between 5 ~ 2000 millimeters.It should be noted that, the length of side on described polygonal every bar limit can be equal, also can be unequal.More particularly, when the first electrode is four distortion, it can be long limit and broadside rectangle not etc.This size range can realize the spinning fields of larger area, can ensure that again polymer solution sprays evenly on the first electrode surface.
Described spray body 02 can be fixing, such as, be positioned at the central area of the first electrode 01 and the second electrode 03, in this position to the surface spraying solution of the first electrode 01.But, spray body 02 in fixed position the surface spraying solution to the first electrode 01, there is the problem that spraying is uneven, especially when the surface area of the first electrode 01 is relatively large, the amount of solution meeting opposed central regions being sprayed on the surface edge zone of the first electrode is less.Further, in order to make the thickness of the polymer solution be sprayed on the first electrode surface even, described spray body 02 can move in the plane being parallel to described first electrode 01.When spray solution, spray body 02 from the side of the first electrode 01 with certain speed translation to opposite side.Like this, can ensure that polymer solution sprays evenly on the first electrode surface.Further, according to the kind of polymer solution and the difference of viscosity, the translational speed of spray body 02 controls in the scope of 2 ~ 30 cels.
Owing to being in the atmosphere of electrostatic field when this spray body 02 works, so this spray body 02 can not conduct electricity, this spray body 02 can be made by any one non electrically conductive material.
Further, as shown in Fig. 1 (1) and Fig. 1 (2), Fig. 1 (2) is the schematic diagram 1(1 of the embodiment of the present invention one) A direction view, described spray body 02 can comprise the jet pipe 21 and dull and stereotyped 22 near the first electrode 01 side, this jet pipe 21 and dull and stereotyped 22 opposing parallel settings, and the length direction of described jet pipe 21 is parallel to the plane at the first electrode 01 place, the tube wall of jet pipe 21 have for the opening to the first electrode 01 spray solution, and the direction of this opening is preferably towards the surface of the first electrode 01, solution can be made like this to be sprayed on to greatest extent on the surface of the first electrode 01.When jet pipe comprising multiple opening, the plurality of opening can be positioned on the straight line along its length of jet pipe 21 tube wall, also irregularly can distribute on jet pipe 21 tube wall.
Gap 24 is left between flat board 22 and the first electrode 01 surface, dull and stereotyped 22 are utilized to strike off the solution be sprayed on the first electrode 01 surface, make solution even at the first electrode 01 surface thickness everywhere, owing to there is the gap 24 of certain size between the first electrode 01 surface and dull and stereotyped 22, this gap 24 can control the thickness of the layer of polymer solution be sprayed on the first electrode 01 surface.Be readily appreciated that, this gap 24 size can be the thickness of layer of polymer solution.
The jet pipe that described jet pipe 21 can have any shape, the cross section of this jet pipe can be circular, oval or any polygon.In addition, the opening on this jet pipe 21 can be into several apertures 211 of at least one row, as shown in Figure 2, is sprayed to the surface of the first electrode 01 by polymer solution by this aperture 211 in jet pipe 21.The shape of the present embodiment to aperture 211 is not construed as limiting, and the shape of this aperture 211 can be circular, square or other shape, also can be elongated strip shaped.
In addition, the opening on this jet pipe 21 can be a slit 211 ' running through this jet pipe 21 length direction, as shown in Figure 3.Opening on this jet pipe 21 can also be the sub-slit 211 ' comprising multiple interruption along jet pipe length direction ', as shown in Figure 4.By this slit 211 ' or 211 ' ' by polymer solution from ejection in jet pipe 21, spray on the surface of the first electrode 01.
In addition, the opening of this jet pipe 21 can also be nozzle 211 ' ' opening of ', as shown in Figure 5, and nozzle 211 ' ' ' formula is more conducive to polymer solution and is sprayed on equably on the surface of the first electrode 01.
The filament spinning component that embodiment one provides utilizes dull and stereotyped 22 to be struck off by the polymer solution be sprayed on the first electrode surface, become the uniform polymer solution thin layer of a layer thickness, like this under the effect of high-strength electrostatic field, the polymer foil solution taylor cone that quantity of formation is huge on whole first electrode surface on first electrode 01 surface, between taylor cone, there is repulsive interaction, make taylor cone be uniformly distributed at whole electrode surface and flow among a small circle, form good polymer nanofiber.The spinning cycle is defined as to the solution consumption of the first electrode surface to when cannot maintain normal spinning from polymer solution sprays to the first electrode, in a spinning cycle, spinning process experienced by initiation spinning, normal spinning, cannot maintain normal spinning three phases, and wherein said normal spinning is the state that those skilled in the art is easy to judge.Complete all after dates of a spinning, again to the first electrode surface spraying new soln, be then defined as the beginning in next spinning cycle.
When being in continuous spinning state, the filament spinning component that embodiment one provides is sprayed to the first electrode surface by spray body cannot by the old solution removal of remnants in a upper spinning cycle before new soln, new and old solution is caused to mix, because the old solution of remnants is under the effect of electric field, meeting part is aging, the mixing of new and old like this solution, can affect spinning quality.In order to avoid the mixing of new and old solution, can spraying new soln before, by upper one the spinning cycle remnants old solution removal.
Embodiment two
Fig. 6 is the structural representation of the filament spinning component of the embodiment of the present invention two, the filament spinning component of this filament spinning component and embodiment one has a lot of similarity, for the sake of brevity, the present embodiment only carries out describing emphatically to its difference, the part identical with embodiment one is not described in detail, describes in detail and refer to embodiment one.
See Fig. 6, compared to embodiment one, the spray body 02 of the filament spinning component of the present embodiment also comprises the scraper 23 be arranged in parallel with described jet pipe 21, and this scraper 23 and dull and stereotyped 22 lays respectively at the both sides of jet pipe, in other words, jet pipe 21 is between dull and stereotyped 22 and scraper 23.Scraper 23 can by the solution removal residual a upper spinning cycle, avoid the new soln of spraying and mixing of old solution, can not cause the aging of new soln, compared to the filament spinning component of embodiment one, the filament spinning component that the present embodiment provides more can ensure the quality of spinning.
Based on the filament spinning component of embodiment one or embodiment two, present invention also offers a kind of polymer solution electrostatic spinning apparatus.
Embodiment three
Fig. 7 is the device for spinning schematic diagram of the embodiment of the present invention three.This device for spinning comprises the first electrode 01, second electrode 03, spray body 02, high voltage source 04, fiber collecting parts 05, liquid-accumulating container 06 and is communicated with the communication means 07 of liquid-accumulating container 06 and spray body 02.Wherein, the first electrode 01, second electrode 03 and spray body 02 form filament spinning component, the structure of the filament spinning component that the structure employing embodiment one of this filament spinning component or embodiment two provide.
During spinning, the first electrode 01 is connected the both positive and negative polarity of high voltage source 04 respectively with the second electrode 03, or the first electrode 01 connects one of them electrode and second electrode 03 ground connection of high voltage source, to form high-strength electrostatic field between the first electrode 01 and the second electrode 03.
Fiber collecting parts 05 are between the first electrode 01 and the second electrode 03, under normal circumstances, fiber collecting parts 05 are the parts (as panel) of a surfacing, the fiber 08 generated between the first electrode 01 and the second electrode 03 can be gathered on fiber collecting parts 05, forms one deck fibrage.Wherein, fiber collecting parts 05 along the plane translation at its place, can move to opposite side from the side of spinning fields, collect the fiber 08 of generation.Wherein, the direction of fiber collecting parts 05 movement can be parallel with the direction of spray body 02 movement, can be vertical, also can become unspecified angle.
By communication means 07, liquid-accumulating container 06 being communicated with spray body 02, in order to make to have larger pressure during solution spraying, polymer solution being sprayed smoothly, in communication means 07, a force (forcing) pump can also be installed, be used for increasing the pressure of solution.
Device for spinning provided by the invention, can also comprise the filament spinning component described in multiple (at least two).The spinning fields be made up of multiple filament spinning component, compared to the spinning fields that single filament spinning component forms, its spinning efficiency can significantly improve.Because the device for spinning comprising multiple filament spinning component is substantially identical with the structure of the device for spinning comprising a filament spinning component.The spinning fields that the formation one that is together in parallel by filament spinning component is larger, and then be connected with other parts in device, its connected mode is identical with the connected mode of single filament spinning component.Those skilled in the art, on the basis of embodiment three, are easy to the embodiment of the device for spinning expected containing multiple filament spinning component.For the sake of brevity, no longer the device for spinning containing multiple filament spinning component is described in detail at this.
Based on the device of the polymer solution electrostatic spinning described in embodiment three, present invention also offers a kind of polymer solution electrospinning process.
Embodiment four
Fig. 8 is the flow chart of steps of the method for the present embodiment, and this spinning process comprises the following steps:
S801, to the first electrode surface spray solution:
Adopt the pressure of the supply solution of this area routine that solution is pushed into spray body 02 by liquid-accumulating container 06 via communication means 07, then via jet pipe 21, polymer solution is sprayed at the first electrode 01 on the surface.In order to obtain the comparatively uniform solution layer of thickness on the surface at the first electrode 01, spray body is preferably along the planar movement with the first electrode 01 place.
It should be noted that, generally, polymer solution has larger viscosity, in order to make polymer solution successfully spray from jet pipe, preferably adopts force (forcing) pump to increase the pressure of solution.And when the pressure increase of polymer solution, polymer solution not easily blocks the opening of jet pipe.
S802, strike off the solution be sprayed on described first electrode surface, make it form the uniform solution layer of a layer thickness:
When spray body moves, while jet pipe ejection solution, and then dull and stereotyped 22 can strike off the solution be sprayed on the first electrode surface, makes it form the uniform solution layer of a layer thickness.
S803, solution layer, under the effect of electrostatic field, form fiber:
First electrode and the second electrode are connected to the two poles of the earth of high voltage source, or first electrode 01 connect a wherein electrode and second electrode 03 ground connection of high voltage source, form high-strength electrostatic field between the first electrode and the second electrode, be sprayed on the solution layer on the first electrode surface under the effect of electrostatic field, spinning forms fiber.
Particularly, the occurrence of described power supply and electric power outputting current can see table 1.
S804, by fiber collecting on fiber collecting parts:
Fiber collecting parts 05 between the first electrode 01 and the second electrode 03 pass through spinning fields with certain speed and direction, and the fiber of formation can be collected on these fiber collecting parts 05.Wherein, the direction of fiber collecting parts 05 movement can be parallel with the direction of spray body 02 movement, also can be perpendicular.In addition, the speed of this fiber collecting parts 05 movement is that those skilled in the art select according to required fiber layer thickness, and the speed of speed determines the size of collected nanofiber layer thickness.Be collected in the microstructure of the fiber on fiber collecting parts 05 as shown in Figure 9 and Figure 10.
From Fig. 9 and Figure 10, can find out, the nanofiber diameter that this spinning process obtains can reach 90nm or 500nm.So can infer, the nanofiber that this spinning process obtains can reach the demand of different-diameter.
In order to be well understood to the detailed description of the invention of polymer solution electrospinning process of the present invention.Can see table 1.Table 1 lists the relation in the spray body direction of motion and fiber collecting component movement direction, the shape of opening, spray body gait of march, the size of the first electrode and supply voltage and output current to the impact of spinning efficiency.
Table 1:
In the electrostatic spinning process of reality, jet pipe 21 in the spray body 02 of motion is to while the first electrode 01 surface spraying solution, dull and stereotyped 22 can strike off the solution be sprayed on the first electrode surface, simultaneously, if the first electrode 01 has residual solution on the surface, scraper 23 can remove residual solution.When spray body 02 moves in spinning fields, each parts in spray body 02 comprise jet pipe 21, flat board 22 and scraper 23 and can work simultaneously, and do not need to carry out separately.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.