CN103757744A - Hydrogel antifouling fiber, preparation method thereof and preparation method of implanted type high-strength hydrogel antiflouling coating layer - Google Patents
Hydrogel antifouling fiber, preparation method thereof and preparation method of implanted type high-strength hydrogel antiflouling coating layer Download PDFInfo
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- CN103757744A CN103757744A CN201410035518.9A CN201410035518A CN103757744A CN 103757744 A CN103757744 A CN 103757744A CN 201410035518 A CN201410035518 A CN 201410035518A CN 103757744 A CN103757744 A CN 103757744A
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Abstract
The invention discloses a hydrogel antifouling fiber, a preparation method of hydrogel antifouling fiber and a preparation method of an implanted type high-strength hydrogel antiflouling coating layer, and relates to antiflouling materials, preparation methods of the antiflouling materials, and preparation methods of vessel antifouling coating layers, for mainly solving the technical problems that the conventional PVA (Polyvinyl Acetate) fiber implanted type vessel antiflouling coating layer is poor in antifouling effect and short in service life. The hydrogel antifouling fiber disclosed by the invention is a fiber with a core-shell structure, the shell layer of the fiber is made of polyacrylamide, and the core layer is made of carbon nano tube modified polyacrylamide. The preparation method comprises the following steps: 1, preparing polyacrylamide hydrogel, 2, preparing a core layer spinning dope, 3, preparing a shell layer spinning dope, 4, spinning by using a wet method to obtain the hydrogel antifouling fiber. The preparation of the antifouling coating layer comprises the following steps: spraying implantation gel onto a substrate, further implanting the hydrogel antifouling fiber into the substrate through a high-pressure static implantation technique, and drying to obtain the implanted type high-strength hydrogel antifouling coating layer. The coating layer is not changed when being soaked in seawater or industrial water for 6 months, so that the coating layer can be applied to vessel antifouling.
Description
Technical field
The present invention relates to the preparation method of anti-fouling material, its preparation method and marine antifouling coating.
Background technology
Ocean macro-organism, microorganism and plant can apposition growth on naval vessel, be immersed in and close on the facility in the middle of harbour seawater and utilize seawater as the surface of all facilities of ocean such as cooling power generating equipment, marine biofouling brings inconvenience and great economic loss to boats and ships and other marine facility.It can accelerate the corrosion of hull on the one hand, the service life of shortening boats and ships etc.; The bottom that sticks on the other hand hull increases dynamics resistance, reduces naval vessel mobility, thereby reduces ship's speed and increase fuel consumption.According to statistics, when marine biofouling rate is 5%, the resistance of boats and ships is just equivalent to 2 times of clean surface, and fuel consumption increases by 10%.Therefore, solve biological attachment and there is huge economic benefit.The biological attachment that solves at present boats and ships adopts antifouling paint, and the biological attachment that solves Treatment of Industrial Water adopts adds bactericide, the copper adding in antifouling paint, the serious Marine Pollution of organotin, and bactericide also forms the pollution to environment.Hydrogel material immersion rear surface forms water film, there is splendid low-friction coefficient characteristic, there is the glutinous sliding characteristic quite similar with marine organisms Skin mucus layers such as dolphins, and, this slime layer elastic modelling quantity is extremely low, in current water, show dynamic flexible, working in coordination with fluff structures on it exists under the condition that flows solid boundary slip and carries out cyclic fluctuation at micro/nano-scale, at seawater, relatively flow velocity ratio hour, also can get rid of and stick biology, reach automatically cleaning effect, utilize hydrogel coating to realize long-acting and anti-fouling object and obtained people and show great attention to.Chinese Marine University combines the physical blending thing (COP) of polyacrylamide and organic siliconresin and polymer (PAS) with Qingdao Haiyang corrosion and protection technology national defence key lab, add respectively and in organic siliconresin, make coating, simulate shagreen slime layer state, there is certain anti-fouling effect.The research of Jiang Lei seminar of the Chinese Academy of Sciences finds that the bionical hydrogel surface of fish-skin with micro-nano hierarchy has super fuel shedding quality, and expectation has excellent antifouling property.The poor adhesive force of bionical hydrogel material above, intensity is low.In the structure of the similar dolphin epidermis of the Master's thesis < < micro-structural of the Wei Huan of Harbin Engineering University in 2012 and bionic coating antifouling property thereof research > >, disclose and take epoxy resin varnish as coated substrate, by by virgin pp alcohol (PVA) fiber and SiO
2the implantation of modified PVA fiber, has prepared the super hydrophilic nonpolluting coating system with dolphin epidermal structure, and the feature of this coating is the problem that can solve hydrogel coating poor adhesive force.But because mechanical strength after the water suction of PVA aquagel fibre significantly reduces, coating life is only 3 months, can not realize long-acting and anti-fouling object, and SiO
2modified PVA composite fibre intensity improves but hydrophilicity declines, and has had a strong impact on the performance of antifouling property.
Summary of the invention
The present invention will solve the existing anti-fouling effect with PVA fiber embedded type marine antifouling coating short technical problem in poor and service life, and the preparation method of a kind of aquogel soil resistant fibre, its preparation method and embedded type high intensity hydrogel nonpolluting coating is provided.
A kind of aquogel soil resistant fibre of the present invention is the fiber with core shell structure, and its shell is polyacrylamide, and sandwich layer is the polyacrylamide of CNT (CNT) modification.
The external diameter of this aquogel soil resistant fibre is 20～60 μ m, and the thickness of shell is 10～30 μ m.
The water absorption rate of this aquogel soil resistant fibre is 50%～300%.
Above-mentioned a kind of aquogel soil resistant fibre preparation method carries out according to the following steps:
One, prepare PAHG: by water and the volume ratio of dimethyl sulfoxide (DMSO), be first that 1:2～2.5 mix water with dimethyl sulfoxide (DMSO), obtain double solvents; The mass ratio of pressing again acrylamide and double solvents is (2～3): 1, acrylamide is joined in double solvents, and be warming up to 45 ℃～50 ℃ and stir 2～2.5h, obtain PAHG;
Two, prepare sandwich layer spinning solution: by the mass concentration of polyacrylamide solution, be 10%～20% to take polyacrylamide solution and deionized water, polyacrylamide solution is added in deionized water, mix, obtain sandwich layer spinning solution;
Three, prepare shell spinning solution: by the mass concentration of polyacrylamide solution be 7%～10%, the mass concentration of CNT is 0.5%～1% to take polyacrylamide solution, CNT and deionized water; First the CNT taking is joined in fluorine carbon wetting dispersing agent, after dispersed with stirring 2～2.5h, then add anti-settling agent, stir 0.5～1h, obtain carbon nanotube dispersed slurry; Again the polyacrylamide solution taking and carbon nanotube dispersed slurry are joined in the deionized water taking, mix, obtain shell spinning solution;
Wherein in carbon nanotube dispersed slurry, the mass percentage concentration of CNT is 10%～15%, and the mass percentage concentration of anti-settling agent is 0.03～0.05%;
Four, wet spinning: shell spinning solution prepared by sandwich layer spinning solution prepared by step 2 and step 3 joins in coaxial device for spinning, sandwich layer spinning solution is extruded by coaxial spinning-nozzle with shell spinning solution simultaneously, after coagulating bath is solidified, obtain aquogel soil resistant fibre.
Wherein the anti-settling agent described in step 3 is BYK-405 anti-settling agent or BYK-425 anti-settling agent;
Coagulating bath described in step 4 is 20% Na
2sO
4solution;
The schematic diagram of the coaxial device for spinning described in step 4 is as shown in Figure 1:
Coaxial device for spinning is by coaxial spinning-nozzle, shell material extruder hopper, shell material extruder cylinder, shell material extruder screw, core material extruder hopper, core material extruder cylinder and core material extruder screw form, shell spinning solution joins in shell material extruder hopper, fall into shell material extruder cylinder, shell material extruder screw through rotating is carried again, enters into the shell solution cavity of coaxial spinning-nozzle by shell solution entrance; Sandwich layer spinning solution joins in core material extruder hopper simultaneously, falls into core material extruder cylinder, then the conveying of the core material extruder screw through rotating, and enters in the sandwich layer solution cavity of coaxial spinning-nozzle by sandwich layer solution entrance; Sandwich layer solution is through the ejection of sandwich layer taphole, and shell solution, through the ejection of shell taphole, obtains the silk of nucleocapsid structure simultaneously.
This coaxial spinning-nozzle, the in-built sandwich layer spinning solution of sandwich layer solution cavity, at the in-built shell spinning solution of shell solution cavity, this coaxial spinning-nozzle has guaranteed that sandwich layer spinning solution did not contact before arriving spinneret orifice mutually with shell spinning solution, thereby can spin coaxial composite fibre.
Utilize above-mentioned aquogel soil resistant fibre to prepare the method for embedded type high intensity hydrogel nonpolluting coating, carry out according to the following steps:
One, by the mass ratio of epoxy resin adhesive and acetone, be 1:(1～1.5) by epoxy resin adhesive with after acetone diluted, obtain implantation adhesive, by implantation adhesive spraying, on matrix, thickness is 100～200 μ m;
Two, aquogel soil resistant fibre is cut into the staple fibre that length is 1.0～1.5mm, utilize static implantation machine, at high-pressure electrostatic, be under the condition of 5～100,000 volts, the matrix surface static implantation 15～25s that scribbles implantation adhesive in step 1, then dry, obtain embedded type high intensity hydrogel nonpolluting coating;
Advantage of the present invention is as follows:
Acrylamide is very easily polymerization at normal temperatures, what the present invention adopted water and dimethyl sulfoxide (DMSO) is that 1:2～2.5 mixed liquor is as solvent by volume, it in temperature, is polymerisation under the condition of 45 ℃～50 ℃, the molecular weight of the polyacrylamide resin obtaining is even, for polymer melt, the water absorption rate 60%～80% of this polyacrylamide, largest deformation rate 70%～90%; Compressive strength 10～14MPa;
The sandwich layer of aquogel soil resistant fibre prepared by the present invention is with CNT modification PAAm, has improved the intensity of fiber, and the PAAm of shell has super water-wet behavior.Guaranteed that embedded type nonpolluting coating has good antifouling properties and longer service life.
Embedded type high intensity hydrogel nonpolluting coating of the present invention is that super hydrophilic fibers is utilized to high-pressure electrostatic implant plate surface, by epoxy adhesive bonding, form upright fine hair array structure, can on surface of steel plate protective coating, implement, its advantage is: (1) fiber has certain flexibility can make coating in seawater, be rendered as Dynamic Water membrane stage, marine microalgae adheres to difficulty, has improved antifouling property; (2) preparation technology of coating is simple and materials safety is nontoxic, meets environmental requirement, and the large-scale surface construction that relates to extra large structure such as applicable naval vessel and underwater facility; (3) to implant organic coating inner for aquagel fibre root, solved the problem of hydrogel layer poor adhesive force, can be in seawater scouring, the temperature difference the severe marine environment of complexity such as large and alternation of wetting and drying use for a long time; (4) can be combined with the organic nonpolluting coating of existing high-performance the existing anticorrosion and antifouling technology of high efficiency composition.The wet film coefficient of friction of embedded type high intensity hydrogel nonpolluting coating of the present invention is 0.01～0.02, in water body environment, can make fouling organism remove under less shearing force effect, in this embedded type high intensity hydrogel nonpolluting coating (1) seawater, soak 6 months unchanged; (2) in industry water, soak 6 months unchanged; (3) 3.5%NaCl, 75 ℃/144h is unchanged; (4) 12.5%NaOH room temperature/60d is unchanged; (5) implantation film percentage elongation 50%～300%, water absorption rate is 50%～300%.Coating antifouling property is more satisfactory, can meet related industries application.
Accompanying drawing explanation
Fig. 1 is the structural representation of coaxial melt spinning device in the specific embodiment six; In figure, 1 is coaxial spinning-nozzle, and 2 is shell material extruder hopper, and 3 is shell material extruder cylinder, and 4 is shell material extruder screw, and 5 is core material extruder hopper, and 6 is core material extruder cylinder, and 7 is core material extruder screw;
Fig. 2 is coaxial spinning-nozzle 1 structural representation of coaxial melt spinning device in the specific embodiment six; 1-1 is shell solution entrance, and 1-2 is shell solution cavity, and 1-3 is sandwich layer solution entrance, and 1-4 is sandwich layer solution cavity; 1-5 is that sandwich layer taphole, 1-6 are shell taphole;
Fig. 3 is the upward view of the coaxial spinning-nozzle 1 of coaxial melt spinning device in the specific embodiment six; 1-5 is that sandwich layer taphole, 1-6 are shell taphole;
Fig. 4 is the transmission electron microscope photo of the aquogel soil resistant fibre of example 1 preparation;
Fig. 5 be example 1 preparation be the stereoscan photograph on embedded type high intensity hydrogel nonpolluting coating surface.
Fig. 6 is that the micro-algae of traditional nonpolluting coating surface marine adheres to pattern SEM photo.
Fig. 7 is the SEM photo that the micro-algae of embedded type high intensity hydrogel nonpolluting coating surface marine of example 1 preparation adheres to.
The specific embodiment
The specific embodiment one: a kind of aquogel soil resistant fibre of present embodiment has the fiber of core shell structure, its shell is polyacrylamide, sandwich layer is the polyacrylamide of CNT (CNT) modification.
The specific embodiment two: present embodiment is different from the specific embodiment one is that the external diameter of this aquogel soil resistant fibre is 20～60 μ m, and the thickness of shell is 10～30 μ m.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one to three is that the water absorption rate of this aquogel soil resistant fibre is 50%～300%.Other is identical with the specific embodiment one.
The specific embodiment four: a kind of aquogel soil resistant fibre preparation method described in the specific embodiment one, carries out according to the following steps:
One, prepare PAHG: by water and the volume ratio of dimethyl sulfoxide (DMSO), be first that 1:2～2.5 mix water with dimethyl sulfoxide (DMSO), obtain double solvents; The mass ratio of pressing again acrylamide and double solvents is (2～3): 1, acrylamide is joined in double solvents, and be warming up to 45 ℃～50 ℃ and stir 2～2.5h, obtain PAHG;
Two, prepare sandwich layer spinning solution: by the mass concentration of polyacrylamide solution, be 10%～20% to take polyacrylamide solution and deionized water, polyacrylamide solution is added in deionized water, mix, obtain sandwich layer spinning solution;
Three, prepare shell spinning solution: by the mass concentration of polyacrylamide solution be 7%～10%, the mass concentration of CNT is 0.5%～1% to take polyacrylamide solution, CNT and deionized water; First the CNT taking is joined in fluorine carbon wetting dispersing agent, after dispersed with stirring 2～2.5h, then add anti-settling agent, stir 0.5～1h, obtain carbon nanotube dispersed slurry; Again the polyacrylamide solution taking and carbon nanotube dispersed slurry are joined in the deionized water taking, mix, obtain shell spinning solution;
Four, wet spinning: shell spinning solution prepared by sandwich layer spinning solution prepared by step 2 and step 3 joins in coaxial device for spinning, sandwich layer spinning solution is extruded by coaxial spinning-nozzle with shell spinning solution simultaneously, after coagulating bath is solidified, obtain aquogel soil resistant fibre.
The specific embodiment five: present embodiment is different from the specific embodiment four be in step 3 in carbon nanotube dispersed slurry the mass percentage concentration of CNT be 10%～15%, the mass percentage concentration of anti-settling agent is 0.03～0.05%.Other is identical with the specific embodiment four.
The specific embodiment six: what present embodiment was different from the specific embodiment four or five is that the anti-settling agent described in step 3 is BYK-405 anti-settling agent or BYK-425 anti-settling agent.Other is identical with the specific embodiment four or five.
The specific embodiment seven: what present embodiment was different from one of specific embodiment four to six is that the coagulating bath described in step 4 is that mass concentration is 20%～25% Na
2sO
4solution.Other is identical with one of specific embodiment four to six.
The specific embodiment eight: what (referring to accompanying drawing 1,2 and 3) present embodiment was different from one of specific embodiment four to seven is that the coaxial device for spinning described in step 4 comprises coaxial spinning-nozzle 1, shell material extruder hopper 2, shell material extruder cylinder 3, shell material extruder screw 4, core material extruder hopper 5, core material extruder cylinder 6 and core material extruder screw 7; Shell material extruder screw 4 is arranged in shell material extruder cylinder 3, shell material extruder hopper 2 is arranged on one end of shell material extruder cylinder 3, at the other end of shell material extruder cylinder 3, by shell solution entrance 1-1, is communicated with the shell solution cavity 1-2 of coaxial spinning-nozzle 1; Core material extruder screw 7 is arranged in core material extruder cylinder 6, core material extruder hopper 5, be arranged on one end of core material extruder cylinder 6, the other end of core material extruder cylinder 6 is communicated with the sandwich layer solution cavity 1-4 of coaxial spinning-nozzle 1 by sandwich layer solution entrance 1-3.Other is identical with one of specific embodiment four to seven.
The operation principle of the wet spinning of the coaxial device for spinning of present embodiment: shell spinning solution joins in shell material extruder hopper 2, fall into shell material extruder cylinder 3, shell material extruder screw through rotating 4 is carried again, enters into the shell solution cavity 1-2 of coaxial spinning-nozzle 1 by shell solution entrance 1-1; Sandwich layer spinning solution joins in core material extruder hopper 5 simultaneously, falls into core material extruder cylinder 6, then 7 conveyings of the core material extruder screw through rotating, and enters in the sandwich layer solution cavity 1-4 of coaxial spinning-nozzle 1 by sandwich layer solution entrance 1-3; Sandwich layer solution is through sandwich layer taphole 1-5 ejection, and shell solution, through shell taphole 1-6 ejection, obtains the silk of nucleocapsid structure simultaneously.
In the coaxial spinning-nozzle 1 of coaxial device for spinning, the in-built sandwich layer spinning solution of sandwich layer solution cavity 1-4, at the in-built shell spinning solution of shell solution cavity 1-2, this sleeve has guaranteed that sandwich layer spinning solution did not contact before arriving spinneret orifice mutually with shell spinning solution, thereby can spin coaxial composite fibre.
The specific embodiment nine: utilize aquogel soil resistant fibre described in the specific embodiment one to prepare the method for embedded type high intensity hydrogel nonpolluting coating, carry out according to the following steps:
One, by the mass ratio of epoxy resin adhesive and acetone, be 1:(1～1.5) by epoxy resin adhesive with after acetone diluted, obtain implantation adhesive, by implantation adhesive spraying, on matrix, thickness is 100～200 μ m;
Two, aquogel soil resistant fibre is cut into the staple fibre that length is 1.0～1.5mm, utilize static implantation machine, at high-pressure electrostatic, be under the condition of 5～100,000 volts, the matrix surface static implantation 15～25s that scribbles implantation adhesive in step 1, then dry, obtain embedded type high intensity hydrogel nonpolluting coating;
The specific embodiment ten: present embodiment is different from the specific embodiment seven is that the density of aquogel soil resistant fibre is 7～10/mm
2.Other is identical with the specific embodiment seven.
The specific embodiment 11: present embodiment is different from the specific embodiment seven or eight is that matrix described in step 1 is steel plate or the steel plate that is coated with corrosion-inhibiting coating.Other is identical with the specific embodiment seven or eight.
The specific embodiment 12: what present embodiment was different from one of specific embodiment seven to nine is that the baking temperature described in step 2 is 20～30 ℃, and be 24～48h drying time.Other is identical with one of specific embodiment seven to nine.
With following case verification beneficial effect of the present invention:
Example 1: a kind of aquogel soil resistant fibre preparation method of this example carries out according to the following steps:
One, prepare polyacrylamide resin solution: by water and the volume ratio of dimethyl sulfoxide (DMSO), be first that 3:7 mixes water with dimethyl sulfoxide (DMSO), obtain double solvents; By the mass ratio of acrylamide and double solvents, be 1:0.5 again, acrylamide is joined in double solvents, be warming up to 45 ℃ and stir 2h, obtain polyacrylamide resin solution;
Two, prepare sandwich layer spinning solution: by the mass concentration of polyacrylamide solution, be 10% to take polyacrylamide solution and deionized water, polyacrylamide solution is added in deionized water, mix, obtain sandwich layer spinning solution;
Three, prepare shell spinning solution: by the mass concentration of polyacrylamide solution be 10%, the mass concentration of CNT is 1% to take polyacrylamide solution, CNT and deionized water; First the CNT taking is joined in fluorine carbon wetting dispersing agent, after dispersed with stirring 2h, then add anti-settling agent BYK-405, continue to stir 0.5h, obtain carbon nanotube dispersed slurry; Again the polyacrylamide solution taking and carbon nanotube dispersed slurry are joined in the deionized water taking, mix, obtain shell spinning solution; Wherein in carbon nanotube dispersed slurry, the mass percentage concentration of CNT is 10%, and the mass percentage concentration of anti-settling agent BYK-405 is 0.5%;
Four, wet spinning: shell spinning solution prepared by sandwich layer spinning solution prepared by step 2 and step 3 joins in coaxial device for spinning, it is 20% Na that sandwich layer spinning solution and shell spinning solution are expressed into mass percentage concentration by spinneret orifice simultaneously
2sO
4after solidifying in solution, obtain aquogel soil resistant fibre.
Coaxial device for spinning described in (referring to accompanying drawing 1,2 and 3) step 4 is by coaxial spinning-nozzle 1, shell material extruder hopper 2, shell material extruder cylinder 3, and shell material extruder screw 4, core material extruder hopper 5, core material extruder cylinder 6 and core material extruder screw 7 form; Shell material extruder screw 4 is arranged in shell material extruder cylinder 3, shell material extruder hopper 2 is arranged on one end of shell material extruder cylinder 3, at the other end of shell material extruder cylinder 3, by shell solution entrance 1-1, is communicated with the shell solution cavity 1-2 of coaxial spinning-nozzle 1; Core material extruder screw 7 is arranged in core material extruder cylinder 6, core material extruder hopper 5, be arranged on one end of core material extruder cylinder 6, the other end of core material extruder cylinder 6 is communicated with the sandwich layer solution cavity 1-4 of coaxial spinning-nozzle 1 by sandwich layer solution entrance 1-3.Shell spinning solution joins in shell material extruder hopper 2, sandwich layer spinning solution joins core material extruder hopper 5, through extruder screw extruding, be transported to respectively in shell solution cavity 1-2 and sandwich layer solution cavity 1-4, and through it, through taphole, spray respectively, after solidifying, form the silk of nucleocapsid structure. simultaneously
The water absorption rate 80% of polyacrylamide prepared by this example 1 step 1, largest deformation rate 90%, compressive strength 12MPa.
The stereoscan photograph of the aquogel soil resistant fibre of this example 1 preparation as shown in Figure 4, as can be seen from Figure 4, aquogel soil resistant fibre has core shell structure, its shell consists of polyacrylamide, sandwich layer consists of the polyacrylamide of CNT (CNT) modification, wherein the external diameter of aquagel fibre is 57 μ m, and the thickness of shell is 25 μ m; The water absorption rate of the aquogel soil resistant fibre of this example 1 preparation is 50% after tested.
The aquogel soil resistant fibre that utilizes example 1 to prepare is prepared the method for the super hydrophilic nonpolluting coating of embedded type high strength, carries out according to the following steps:
One, by the mass ratio of epoxy resin adhesive and acetone, be 1:1, epoxy resin adhesive, with after acetone diluted, obtained to implantation adhesive, then by implantation adhesive spraying on steel plate, the thickness of implantation adhesive is 200 μ m;
Wherein epoxy resins adhesive is room temperature curing epoxy adhesive, epoxy resin is A component, polyamide 66 curing agent is B component, in A component, add the defoamer that accounts for A constituent mass 0.5%, stir after 5min, add B component, stir 5min, standing 10min froth breaking, obtains epoxy resin adhesive;
Two, the aquogel soil resistant fibre of example 1 preparation being trimmed to length is 1.5mm, utilize electrostatic flocking machine, at high-pressure electrostatic, be under the condition of 100,000 volts, the surface of steel plate flocking 15s that scribbles implantation adhesive in step 1, then in temperature, be dry 24h under the condition of 25 ℃, obtain embedded type high intensity hydrogel nonpolluting coating;
The percentage elongation 200% of the embedded type high intensity hydrogel nonpolluting coating of the present embodiment 1 preparation, water absorption rate is 50%; Wet film coefficient of friction is 0.01.
As shown in Figure 5, as can be seen from Figure 5, aquogel soil resistant fibre fine hair is uprightly implanted matrix surface to the stereoscan photograph of the embedded type high intensity hydrogel nonpolluting coating of this example 1 preparation.The density of aquogel soil resistant fibre is 9/mm
2.
Embedded type high intensity hydrogel nonpolluting coating prepared by this example 1 and traditional organosilicon low-surface-energy nonpolluting coating are put into seawater simultaneously and are soaked 6 months, then take out coating surface pattern scanning electron microscopic observation, Fig. 6 is the stereoscan photograph on traditional nonpolluting coating surface, on traditional nonpolluting coating surface, have as can be seen from Figure 6 the little crescent rhombus of a large amount of spindles marine microalgae to adhere to, little crescent rhombus marine microalgae is stacked layer by layer.Fig. 7 is the SEM photo that the micro-algae of embedded type high intensity hydrogel nonpolluting coating surface marine of test 1 preparation adheres to, as can be seen from Figure 7, at coating surface, only there is the little Nitzschia closterium minutissima of a small amount of spindle to adhere to, can not form complete biomembrane, its reason is that the flexible aquogel soil resistant fibre that stands upright on coating surface makes coating in seawater, be rendered as Dynamic Water membrane stage, under the shear action of seawater, marine microalgae adheres to difficulty, has improved antifouling property.
The embedded type high intensity hydrogel nonpolluting coating of this example 1 preparation is placed in cooling tower, utilizes in industry water and soak 6 months, find, after 6 months, coating surface inanimate object adheres to, and surface is unchanged.
In the salt solution that is 3.5% by the NaCl mass concentration that temperature is 75 ℃ by the embedded type high intensity hydrogel nonpolluting coating of this example 1 preparation, soak 144 hours, after taking out, find, coating is unchanged.The embedded type high intensity hydrogel nonpolluting coating that 1 preparation of this example is described has good anti-fouling effect, can be used in commercial Application.
Claims (10)
1. an aquogel soil resistant fibre, is characterized in that this aquogel soil resistant fibre is the fiber with core shell structure, and its shell is polyacrylamide, the polyacrylamide that sandwich layer is carbon nano-tube modification.
2. a kind of aquogel soil resistant fibre according to claim 1, the external diameter that it is characterized in that this aquogel soil resistant fibre is 20～60 μ m, the thickness of shell is 10～30 μ m.
3. a kind of aquogel soil resistant fibre according to claim 1 and 2, the water absorption rate that it is characterized in that aquogel soil resistant fibre is 50%～300%.
4. the method for preparation a kind of aquogel soil resistant fibre claimed in claim 1, is characterized in that the method carries out according to the following steps:
One, prepare PAHG: by water and the volume ratio of dimethyl sulfoxide (DMSO), be first that 1:2～2.5 mix water with dimethyl sulfoxide (DMSO), obtain double solvents; The mass ratio of pressing again acrylamide and double solvents is (2～3): 1, acrylamide is joined in double solvents, and be warming up to 45 ℃～50 ℃ and stir 2～2.5h, obtain PAHG;
Two, prepare sandwich layer spinning solution: by the mass concentration of polyacrylamide solution, be 10%～20% to take polyacrylamide solution and deionized water, polyacrylamide solution is added in deionized water, mix, obtain sandwich layer spinning solution;
Three, prepare shell spinning solution: by the mass concentration of polyacrylamide solution be 7%～10%, the mass concentration of CNT is 0.5%～1% to take polyacrylamide solution, CNT and deionized water; First the CNT taking is joined in fluorine carbon wetting dispersing agent, after dispersed with stirring 2～2.5h, then add anti-settling agent, stir 0.5～1h, obtain carbon nanotube dispersed slurry; Again the polyacrylamide solution taking and carbon nanotube dispersed slurry are joined in the deionized water taking, mix, obtain shell spinning solution;
Four, wet spinning: shell spinning solution prepared by sandwich layer spinning solution prepared by step 2 and step 3 joins in coaxial device for spinning, sandwich layer spinning solution is extruded by coaxial spinning-nozzle with shell spinning solution simultaneously, after coagulating bath is solidified, obtain aquogel soil resistant fibre.
5. the preparation method of a kind of aquogel soil resistant fibre according to claim 4, is characterized in that in step 3 in carbon nanotube dispersed slurry that the mass percentage concentration of CNT is 10%～15%, and the mass percentage concentration of anti-settling agent is 0.03～0.05%.
6. according to the preparation method of a kind of aquogel soil resistant fibre described in claim 4 or 5, it is characterized in that the coagulating bath described in step 4 is that mass concentration is 20%～25% Na
2sO
4solution.
7. according to the preparation method of a kind of aquogel soil resistant fibre described in claim 4 or 5, it is characterized in that the coaxial device for spinning described in step 4 comprises coaxial spinning-nozzle (1), shell material extruder hopper (2), shell material extruder cylinder (3), shell material extruder screw (4), core material extruder hopper (5), core material extruder cylinder (6) and core material extruder screw (7); Shell material extruder screw (4) is arranged in shell material extruder cylinder (3), shell material extruder hopper (2) is arranged on one end of shell material extruder cylinder (3), and the other end of shell material extruder cylinder (3) is communicated with the shell solution cavity (1-2) of coaxial spinning-nozzle (1) by shell solution entrance (1-1); Core material extruder screw (7) is arranged in core material extruder cylinder (6), core material extruder hopper (5) is arranged on one end of core material extruder cylinder (6), and the other end of core material extruder cylinder (6) is communicated with the sandwich layer solution cavity (1-4) of coaxial spinning-nozzle (1) by sandwich layer solution entrance (1-3).
8. utilize aquogel soil resistant fibre described in claim 1 to prepare the method for embedded type high intensity hydrogel nonpolluting coating, it is characterized in that the method carries out according to the following steps:
One, by the mass ratio of epoxy resin adhesive and acetone, be 1:(1～1.5) by epoxy resin adhesive with after acetone diluted, obtain implantation adhesive, by implantation adhesive spraying, on matrix, thickness is 100～200 μ m;
Two, aquogel soil resistant fibre is cut into the staple fibre that length is 1.0～1.5mm, utilize static implantation machine, at high-pressure electrostatic, be under the condition of 5～100,000 volts, the matrix surface static implantation 15～25s that scribbles implantation adhesive in step 1, then dry, obtain embedded type high intensity hydrogel nonpolluting coating.
9. the method for preparing embedded type high intensity hydrogel nonpolluting coating according to claim 8, the density that it is characterized in that aquogel soil resistant fibre is 7～10/mm
2.
10. the method for preparing embedded type high intensity hydrogel nonpolluting coating according to claim 8 or claim 9, is characterized in that the matrix described in step 1 is steel plate or the steel plate that is coated with corrosion-inhibiting coating.
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| CN104031275A (en) * | 2014-06-03 | 2014-09-10 | 哈尔滨工程大学 | Method for preparing clay modified polyvinyl alcohol antifouling hydrogel |
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| US10675609B2 (en) | 2016-03-02 | 2020-06-09 | Nike, Inc. | Articles with soil-shedding performance |
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| US11001031B2 (en) | 2017-10-19 | 2021-05-11 | Nike, Inc. | Composite materials, methods of making, methods of use, and articles incorporating the composite materials |
| US11130309B2 (en) | 2017-10-19 | 2021-09-28 | Nike, Inc. | Color change materials, methods of making, methods of use, and articles incorporating the color change materials |
| CN109267177A (en) * | 2018-09-03 | 2019-01-25 | 浙江理工大学 | A kind of conductive hydrogel fiber and preparation method thereof with self-healing properties |
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| CN110747551B (en) * | 2019-11-01 | 2021-12-28 | 南开大学 | Hydrogel fiber of artificial spider silk and preparation method thereof |
| CN110747551A (en) * | 2019-11-01 | 2020-02-04 | 南开大学 | Hydrogel fiber of artificial spider silk and preparation method thereof |
| US11975517B2 (en) | 2021-08-24 | 2024-05-07 | Nike, Inc. | Color change materials, methods of making, methods of use, and articles incorporating the color change materials |
| CN113679166A (en) * | 2021-08-31 | 2021-11-23 | 深圳市丰和信新材料有限公司 | Making process of cosmetic brush filaments |
| CN116082895A (en) * | 2022-11-28 | 2023-05-09 | 北京航空航天大学 | Flexible fiber array coating and preparation method and application thereof |
| CN116082895B (en) * | 2022-11-28 | 2024-04-19 | 北京航空航天大学 | Flexible fiber array coating and preparation method and application thereof |
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