CN113801591A - Preparation process and construction method of PTFE (polytetrafluoroethylene) -based anti-icing composite film based on radio frequency plasma treatment - Google Patents

Preparation process and construction method of PTFE (polytetrafluoroethylene) -based anti-icing composite film based on radio frequency plasma treatment Download PDF

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CN113801591A
CN113801591A CN202110953425.4A CN202110953425A CN113801591A CN 113801591 A CN113801591 A CN 113801591A CN 202110953425 A CN202110953425 A CN 202110953425A CN 113801591 A CN113801591 A CN 113801591A
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ptfe
film
blade
radio frequency
protective film
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鞠婕
王红卫
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Suzhou Deruiyuan Material Technology Co ltd
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Suzhou Deruiyuan Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245Vinyl resins, e.g. polyvinyl chloride [PVC]
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/123Treatment by wave energy or particle radiation
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    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
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    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03DWIND MOTORS
    • F03D80/00Details, components or accessories not provided for in groups F03D1/00 - F03D17/00
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03DWIND MOTORS
    • F03D80/00Details, components or accessories not provided for in groups F03D1/00 - F03D17/00
    • F03D80/40Ice detection; De-icing means
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18Homopolymers or copolymers of tetrafluoroethylene
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • C09J2427/00Presence of halogenated polymer
    • C09J2427/006Presence of halogenated polymer in the substrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/70Wind energy
    • Y02E10/72Wind turbines with rotation axis in wind direction

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Abstract

The invention discloses a preparation process of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment, which comprises the following steps: s1, coating a layer of protective film on one surface of the PTFE subjected to low-temperature plasma micro-nano etching; s2, performing surface activation treatment on the surface, not covered with the protective film, of the PTFE in the S1, and performing activation or grafting treatment on the surface, not covered with the protective film, of the PTFE by adopting a radio frequency plasma energy supply mode to form a new active group and a new surface activation structural layer; s3, uncovering the protective film with a certain length at the tail end of the PTFE surface covered with the protective film, and performing radio frequency plasma activation treatment; s4, compounding the surface of the PTFE, which is not covered with the protective film, with a surface activation structure layer by using the high-toughness cold bonding adhesive; and S5, covering an isolating film on the cold bonding glue surface. The invention carries out surface activation treatment on the cold bonding glue surface and the etching surface of the composite film, ensures that the adjacent composite films are mutually overlapped with the head and the tail, and prevents the edges or the seams from being frozen.

Description

Preparation process and construction method of PTFE (polytetrafluoroethylene) -based anti-icing composite film based on radio frequency plasma treatment
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a preparation process and a construction method of a PTFE (polytetrafluoroethylene) -based anti-icing composite film based on radio frequency plasma treatment.
Background
Wind power is clean energy with huge resource potential and basically mature technology, becomes the core content for promoting energy transformation and an important way for coping with climate change in China, and is an important measure for implementing ecological priority and green development and an important means for deeply promoting energy production and consumption revolution and promoting atmospheric pollution prevention and treatment in China. The most direct influence of the icing of the wind power blades is the loss of the generated energy and the electric charge income thereof and the safe operation risk of forming a sharing unit.
The anti-icing film is paved on the wind power blade, so that the blade airfoil aerodynamic performance is improved and the blade operation efficiency is improved besides the function of preventing the blade from icing. Meanwhile, the blade is equivalent to a protective coat of the blade, the surface strength of the blade can be enhanced, the integral fixing effect is achieved, the integral bearing capacity of the blade is improved, potential safety hazards such as blade aging and cracking are eliminated, and the erosion resistance of the blade is improved. The whole film of blade surface, the non-staining blade, do not consume the electric energy, do not need to maintain, maintain and carry on special lightning protection design and set up monitored control system, do not constitute to blade operation potential safety hazard or lead to blade to damage, damage.
The conventional PTFE film is a film which is generally accepted to have a good anti-icing effect, but the low surface tension is generally accepted to have strong surface non-adhesiveness and no technical problem of material adhesion. When the etched PTFE film has the surface appearance of the ultra-micro structure, the surface non-adhesiveness is stronger. The wind power blade material is basically a glass fiber reinforced composite material consisting of thermosetting polyester-based materials, has the limitation of the use temperature range of-40-50 ℃, and the PTFE film is not suitable for being paved and adhered with the wind power blade by adopting a welding method. Therefore, innovative design of PTFE films in the prior art is needed to impart better cold-stick properties while achieving good anti-icing function.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a preparation process and a construction method of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation process of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment is characterized by comprising the following steps:
s1, coating a layer of protective film on one surface of the PTFE subjected to low-temperature plasma micro-nano etching;
s2, performing surface activation treatment on the surface, not covered with the protective film, of the PTFE in the S1, adopting a radio frequency plasma energy supply mode, performing activation or grafting treatment on the surface, not covered with the protective film, under a proper working gas condition and process, forming a new active group on the surface, not covered with the protective film, and forming a surface activation structure layer with a nano depth;
s3, uncovering the protective film with a certain length at the tail end of the PTFE surface covered with the protective film in the S2, respectively carrying out radio frequency plasma activation treatment on the tail ends of the PTFE, and forming an active group and a surface activation structure layer with nanometer depth on the surface of the tail ends;
s4, compounding the surface of the PTFE layer which is not covered with the protective film in the S3 with the surface activation structure layer by the high-toughness cold bonding adhesive, wherein active groups on the surface activation structure layer can perform chemical bonding with characteristic groups of the high-toughness cold bonding adhesive, and strong affinity and bonding strength are generated between the high-toughness cold bonding adhesive and the surface activation structure layer;
and S5, covering the cold bonding glue surface in the S4 with an isolating film, and forming a PTFE-based anti-icing composite film.
In a preferred embodiment of the present invention, in S3, the protective films on two ends of the width direction of the PTFE side covered with the protective film in S2 are further uncovered, and the two ends of the PTFE in the width direction are subjected to rf plasma activation in a roll-to-roll manner, so as to form active groups and a surface active structure layer with a nano depth.
In a preferred embodiment of the present invention, in S2, the surface of the PTFE not covered with the protective film is batch processed in a roll-to-roll manner in a low temperature plasma surface activator at a processing speed of 10-15 m/min.
In a preferred embodiment of the present invention, in S2 and S3, the working gas for the surface activation treatment is Ar or O2、NH3Or mixed media of Ar and AAC, the mixed media are quantitatively conveyed through a heat preservation pipeline and a flow controller, and the mixed media are placed in a vacuum closed environment at the temperature of 30-40 ℃ to realize uniform activation modification.
In a preferred embodiment of the present invention, in S4, the components of the high toughness cold bond adhesive include: 20-30 parts of polytetrahydrofuran glycol, 5-10 parts of magnesium hydroxide, 6-8 parts of carbon black, 12-20 parts of phenyl alkyl sulfonate, 2-10 parts of methyl methacrylate, 1-6 parts of sodium dodecyl benzene sulfonate, 3-8 parts of triethyl formate, 4-9 parts of polyamide wax, 1-2 parts of gamma-isocyanate propyl trimethoxy silane and 1-2 parts of dimorpholinyl diethyl ether.
In a preferred embodiment of the present invention, in S1, after the low-temperature plasma micro-nano etching, the PTFE surfaces form a nano-scale and micro-scale ultra-micro structure surface morphology with micro-asperities and aggregated together, and the micro-structure papilla has a nano-structure.
The construction method of the PTFE-based anti-icing composite membrane prepared based on the preparation process comprises the following steps:
a1, pretreatment of the surface of the blade: removing impurities and cleaning the surface of the blade, locally repairing the surface of the blade and carrying out flatness and finish treatment on the surface of the blade by using a handheld polishing machine;
a2, detecting the surface of the blade; the method comprises the steps of checking the surface cleanliness and the flatness and the smoothness of the blade so as to meet the bonding condition of the PTFE-based anti-icing composite film;
a3, spraying of blade surface interface agent: micro air holes on the surface of the blade adhesion base layer are sealed off, and the adhesion strength and tearing strength of the PTFE-based anti-icing composite membrane and the blade are improved;
a4, ice coating film adhesion resistance: cutting and pasting the film at the blade tip part and carrying out surface treatment, winding and pasting the film at the blade tip part and compacting at the lap joint part;
a5, quality acceptance: the film surface has no hollowness, no bubble, no wrinkle, no damage, no deformation, no leakage and no adhesion, no scratch, no crack and no raised edge.
In a preferred embodiment of the present invention, in a4, the method for adhering the blade portion by winding comprises: unfolding the composite film, and transversely winding and bonding the cold bonding adhesive surface of the composite film and the blade while tearing the isolating film; in the process of transverse winding, the boundary of the surface activated structure layers at the two ends of the composite film in the width direction is taken as a reference to ensure that the composite films are mutually lapped in the length direction of the blade,
the surface activation structure layer of the composite film is bonded with the cold bonding adhesive surface of the adjacent composite film to form a double-layer structure;
when the composite films with different lengths are lapped, the cold bonding glue surface at the head end of the next composite film is lapped on the surface at the tail end of the previous composite film; the above operations are repeated.
In a preferred embodiment of the present invention, when the film is applied to the lightning arrester of the blade, the PTFE-based anti-icing composite film is completely adhered to the surface of the lightning arrester, the PTFE-based anti-icing composite film covering the hole of the lightning arrester is cut one by one, and the seam is pressed flat.
In a preferred embodiment of the invention, in the A4, the gas circulation carrying particles and the ion gas flow for eliminating static electricity are ejected from the side surface by the eliminating device in the attaching process.
The invention solves the defects in the background technology, and has the following beneficial effects:
(1) the invention adopts a radio frequency plasma energy supply mode and adopts Ar and O2、NH3Or Ar and AAC are used as working gases, surface activation or grafting treatment can be carried out on the surface of the PTFE cold bonding adhesive surface and the position of the PTFE film where the protective film is uncovered under a proper process condition, new active groups are formed on the surface of the PTFE adhesive applying surface and the position of the PTFE film where the protective film is uncovered, the active groups on the surface of the PTFE adhesive applying surface can be chemically bonded with characteristic groups of the adhesive, strong affinity and bonding strength are generated between the adhesive and the film, and uniform activation modification of the surface is realized by adopting a unique vaporization grafting technology.
(2) The invention aims at the bonding problem of the PTFE composite membrane in the practical construction, and the cold bonding glue surface of the composite membrane and the tail end covered with the protective membrane or the two ends along the width direction are subjected to surface activation to endow adhesiveness, wherein the cold bonding glue surface of the composite membrane and the two ends covered with the protective membrane along the width direction are realized in a roll-to-roll mode, and the surface activation of the tail end covered with the protective membrane is realized by extending a certain length into a portable low-temperature plasma surface activator.
(3) The composite films prepared in the invention are strip-shaped, the composite films are sequentially wound on the blades according to the wing profiles, chord lengths or curvatures of the blades, and the adjacent composite films are mutually overlapped, so that the phenomenon that edges are warped or the seams are frozen when in use is prevented; the head and the tail of each composite film are mutually overlapped, so that firm bonding between the composite films is ensured.
(4) The special high-toughness cold bonding adhesive for the PTFE film, which is developed specially aiming at the performance characteristics, application requirements and use environment of the PTFE film after surface activation, has the excellent characteristics of high cold bonding peeling strength, high tensile elongation at break and impact strength, relatively low hardness, tensile strength and tensile elastic modulus, long ultraviolet aging (yellowing resistance) time, no obvious plastic deformation property, less thermal expansion and cold contraction stress than the elastic limit of the adhesive, capability of keeping the adhesive in a toughness state all the time, high bonding strength and durable bonding peeling force.
(5) The invention sprays gas circulation carrying particles and ion gas flow for eliminating static electricity from the side surface by the eliminating device in the attaching process. This ion air current can eliminate the static when the pad pasting, effectively gets rid of the anti icing complex film of PTFE base and the granule between the blade, guarantees the anti icing complex film of PTFE base and the effect of adhering of blade.
(6) The portable low-temperature plasma surface activator is specially used for carrying out surface activation treatment on the membrane surface of the tail end of a PTFE-based anti-icing composite membrane in an engineering field so as to further improve the free radical energy of the membrane surface at the lap joint part and enable the membrane and glue to form stronger bonding strength, peeling strength and long-term performance and durability of bonding performance. The portable nanometer deep surface activation device has the characteristics of high treatment efficiency, obvious effect, large treatment area selectivity of the portable low-temperature plasma body surface activator and convenience in transportation, installation and use.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts;
FIG. 1 is a flow chart of a process for preparing a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment according to a preferred embodiment of the invention;
fig. 2 is a flow chart of the application of a PTFE-based anti-icing composite membrane of a preferred embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be considered limiting of the scope of the present application. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the invention, the meaning of "a plurality" is two or more unless otherwise specified.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art through specific situations.
As shown in fig. 1, a flow chart of a preparation process of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment according to the present invention is shown. A preparation process of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment is characterized by comprising the following steps:
s1, coating a layer of protective film on one surface of the PTFE subjected to low-temperature plasma micro-nano etching;
s2, performing surface activation treatment on the surface, not covered with the protective film, of the PTFE in the S1, adopting a radio frequency plasma energy supply mode, performing activation or grafting treatment on the surface, not covered with the protective film, under a proper working gas condition and process, forming a new active group on the surface, not covered with the protective film, and forming a surface activation structure layer with a nano depth;
s3, uncovering the protective film at the tail end of the PTFE surface covered with the protective film in the S2, respectively carrying out radio frequency plasma activation treatment on the tail ends of the PTFE, and forming an active group and a surface activation structure layer with nanometer depth on the surface of the tail ends;
s4, compounding the surface of the PTFE layer which is not covered with the protective film in the S3 with the surface activation structure layer by the high-toughness cold bonding adhesive, wherein active groups on the surface activation structure layer can perform chemical bonding with characteristic groups of the high-toughness cold bonding adhesive, and strong affinity and bonding strength are generated between the high-toughness cold bonding adhesive and the surface activation structure layer;
and S5, covering the cold bonding glue surface in the S4 with an isolating film, and forming a PTFE-based anti-icing composite film.
It should be noted that, in the invention, after the low-temperature plasma micro-nano etching, the two surfaces of the PTFE form the surface morphology of the nano-scale and micro-scale ultramicro structures which are micro-uneven and aggregated together, and the mastoid of the micro-structure has the nano-structure, so that the surface of the modified PTFE film has the functional characteristics of no adhesion, high stain resistance, moisture absorption resistance, self-cleaning, ultralow surface tension and the like.
In the invention, S2 and S3 are respectively treated in a low-temperature plasma roll-to-roll film surface activation treatment system and a portable low-temperature plasma surface activator. Wherein, the working gas for surface activation treatment is Ar and O2、NH3Or Ar and AAC, and the mixed medium is quantitatively conveyed through a heat preservation pipeline and a flow controller, andthe mixed medium is placed in a vacuum closed environment at 30-40 ℃ to realize uniform activation modification.
In the low-temperature plasma roll-to-roll film surface activation treatment system, one surface of PTFE, which is not covered with a protective film, is subjected to batch treatment in a low-temperature plasma surface activator in a roll-to-roll mode at a treatment speed of 10-15 m/min in an intermittent manner. The low-temperature plasma surface activator applies a high-frequency electric field to the working gas, and the working gas is ionized under the excitation of the high-frequency electric field and generates plasma.
The portable low-temperature plasma surface activator is specially used for carrying out surface activation treatment on the tail end surface of the PTFE-based anti-icing composite membrane on an engineering site so as to further improve the free radical energy of the membrane surface at the lap joint part and enable the membrane and the glue to form stronger bonding strength, peeling strength and long-term performance and durability of bonding performance. The portable nanometer deep surface activation device has the characteristics of high treatment efficiency, obvious effect, large treatment area selectivity of the portable low-temperature plasma body surface activator and convenience in transportation, installation and use. When the invention is used, the protective film with a certain length at the tail end of one surface of the PTFE coated with the protective film is uncovered, and the tail ends of the PTFE are respectively subjected to radio frequency plasma activation treatment.
The portable low-temperature plasma surface activator has the characteristics of energy conservation and environmental protection, is a novel material preparation technology, can realize precise cleaning, surface activation and surface passivation of the surface of a material and generate specific functional groups on the surface of the material, can be applied to the PTFE-based anti-icing composite membrane, and can also be widely applied to the fields of filter materials, composite materials, high-function membrane materials, medical consumables and the like.
The invention also discloses a method for preparing the surface active structure layer, which comprises the steps of uncovering the protective films at two ends of one surface of PTFE coated with the protective films in the width direction, and carrying out radio frequency plasma activation treatment on the two ends of the PTFE in the width direction in a roll-to-roll mode to form active groups and a surface active structure layer with nano depth. In the winding and attaching process of the composite films and the blades, the overlapping parts of the adjacent composite films are easy to warp due to the non-adhesiveness of the surfaces of the composite films, so that the overlapping parts are easy to gather and freeze, and the anti-icing effect of the composite films is poor. Therefore, the end of each composite film needs to be activated for a certain length and the overlapping part of the adjacent composite films, so as to ensure that the overlapping part is not warped and the head and tail joints are firmly bonded.
The invention provides a high-toughness cold bonding adhesive which comprises the following components: 20-30 parts of polytetrahydrofuran glycol, 5-10 parts of magnesium hydroxide, 6-8 parts of carbon black, 12-20 parts of phenyl alkyl sulfonate, 2-10 parts of methyl methacrylate, 1-6 parts of sodium dodecyl benzene sulfonate, 3-8 parts of triethyl formate, 4-9 parts of polyamide wax, 1-2 parts of gamma-isocyanate propyl trimethoxy silane and 1-2 parts of dimorpholinyl diethyl ether. The special high-toughness cold bonding adhesive for the PTFE film, which is developed specially aiming at the performance characteristics, application requirements and use environment of the PTFE film after surface activation, has the excellent characteristics of high cold bonding peeling strength, high tensile elongation at break and impact strength, relatively low hardness, tensile strength and tensile elastic modulus, long ultraviolet aging (yellowing resistance) time, no obvious plastic deformation property, less thermal expansion and cold contraction stress than the elastic limit of the adhesive, capability of keeping the adhesive in a toughness state all the time, high bonding strength and durable bonding peeling force.
As shown in FIG. 2, the construction method of the PTFE-based anti-icing composite membrane prepared based on the preparation process comprises the following steps:
a1, pretreatment of the surface of the blade: removing impurities and cleaning the surface of the blade, locally repairing the surface of the blade and carrying out flatness and finish treatment on the surface of the blade by using a handheld polishing machine;
a2, detecting the surface of the blade; the method comprises the steps of checking the surface cleanliness and the flatness and the smoothness of the blade so as to meet the bonding condition of the PTFE-based anti-icing composite film;
a3, spraying of blade surface interface agent: micro air holes on the surface of the blade adhesion base layer are sealed off, and the adhesion strength and tearing strength of the PTFE-based anti-icing composite membrane and the blade are improved;
a4, ice coating film adhesion resistance: cutting and pasting the film at the blade tip part and carrying out surface treatment, winding and pasting the film at the blade tip part and compacting at the lap joint part;
a5, quality acceptance: the film surface has no hollowness, no bubble, no wrinkle, no damage, no deformation, no leakage and no adhesion, no scratch, no crack and no raised edge.
The invention discloses a method for winding and bonding blade parts, which comprises the following steps: unfolding the composite film, and transversely winding and bonding the cold bonding adhesive surface of the composite film and the blade while tearing the isolating film; in the process of transverse winding, the boundary of the surface activation structure layers at the two ends of the composite film in the width direction is taken as a reference, the composite films are ensured to be mutually lapped in the length direction of the blade, so that the surface activation structure layers of the composite films are bonded with the cold bonding adhesive surfaces of the adjacent composite films to form a double-layer structure; when the composite films with different lengths are lapped, the cold bonding glue surface at the head end of the next composite film is lapped on the surface at the tail end of the previous composite film; the above operations are repeated.
It should be noted that, when the film is applied to the lightning arrester of the blade, the PTFE-based anti-icing composite film is completely adhered to the surface of the lightning arrester, the PTFE-based anti-icing composite films covering the holes of the lightning arrester are cut one by one, and the seams are flattened. In A4, in the attaching process, a gas circulation carrying particles and an ionic gas flow for eliminating static electricity are sprayed from the side surface through an eliminating device, the ionic gas flow can eliminate the static electricity in the film attaching process, particles between the PTFE-based anti-icing composite film and the blade are effectively removed, and the adhesion effect of the PTFE-based anti-icing composite film and the blade is ensured.
The invention carries out film covering on the blade, and meanwhile, the PTFE-based anti-icing composite film is equivalent to a protective coat of the blade, can enhance the surface strength of the blade, plays a role in integrally fixing, improves the integral bearing capacity of the blade, eliminates potential safety hazards such as blade aging and cracking and the like, and improves the anti-erosion capacity of the blade. The whole film of blade surface, the non-staining blade, do not consume the electric energy, do not need to maintain, maintain and carry on special lightning protection design and set up monitored control system, do not constitute to blade operation potential safety hazard or lead to blade to damage, damage. The film has a self-cleaning function, dust and insect adhering dirt do not exist on the surface of the blade, the blade does not need to be cleaned, and a large amount of cleaning cost can be saved.
Because the PTFE-based anti-icing composite film has high hydrophobicity and cold adhesiveness, the later-period product can popularize the application range of the PTFE-based functional film into more application fields, such as the fields of marine fouling organism adhesion prevention and corrosion prevention of offshore wind power steel pipe piles and offshore platform facilities, anti-icing of high-voltage power transmission and transformation iron towers, anti-icing of cable-stayed bridge inhaul cables and suspension cables, anti-icing of snow, and energy sources such as marine aquaculture net cage and netting materials, communication, ships, industrial automation, ocean engineering and the like.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. A preparation process of a PTFE-based anti-icing composite membrane based on radio frequency plasma treatment is characterized by comprising the following steps:
s1, coating a layer of protective film on one surface of the PTFE subjected to low-temperature plasma micro-nano etching;
s2, performing surface activation treatment on the surface, not covered with the protective film, of the PTFE in the S1, adopting a radio frequency plasma energy supply mode, performing activation or grafting treatment on the surface, not covered with the protective film, under a proper working gas condition and process, forming a new active group on the surface, not covered with the protective film, and forming a surface activation structure layer with a nano depth;
s3, uncovering the protective film with a certain length at the tail end of the PTFE surface covered with the protective film in the S2, respectively carrying out radio frequency plasma activation treatment on the tail ends of the PTFE, and forming an active group and a surface activation structure layer with nanometer depth on the surface of the tail ends;
s4, compounding the surface of the PTFE layer which is not covered with the protective film in the S3 with the surface activation structure layer by the high-toughness cold bonding adhesive, wherein active groups on the surface activation structure layer can perform chemical bonding with characteristic groups of the high-toughness cold bonding adhesive, and strong affinity and bonding strength are generated between the high-toughness cold bonding adhesive and the surface activation structure layer;
and S5, covering the cold bonding glue surface in the S4 with an isolating film, and forming a PTFE-based anti-icing composite film.
2. The preparation process of the PTFE-based anti-icing composite membrane based on the radio frequency plasma treatment according to claim 1, characterized in that: in S3, the protective films on the two ends of the PTFE surface in the width direction covered with the protective film in S2 are also uncovered, and the two ends of the PTFE in the width direction are subjected to radio frequency plasma activation treatment in a roll-to-roll manner to form active groups and a surface activation structure layer with a nano depth.
3. The preparation process of the PTFE-based anti-icing composite membrane based on the radio frequency plasma treatment according to claim 1, characterized in that: in the step S2, the surface of the PTFE film which is not covered with the protective film is batch processed in a low-temperature plasma surface activator in a roll-to-roll mode, and the processing speed is 10-15 m/min.
4. The preparation process of the PTFE-based anti-icing composite membrane based on the radio frequency plasma treatment according to claim 1, characterized in that: in S2 and S3, the working gas for the surface activation treatment is Ar or O2、NH3Or mixed media of Ar and AAC, the mixed media are quantitatively conveyed through a heat preservation pipeline and a flow controller, and the mixed media are placed in a vacuum closed environment at the temperature of 30-40 ℃ to realize uniform activation modification.
5. The preparation process of the PTFE-based anti-icing composite membrane based on the radio frequency plasma treatment according to claim 1, characterized in that: in S4, the high toughness cold bond adhesive comprises: 20-30 parts of polytetrahydrofuran glycol, 5-10 parts of magnesium hydroxide, 6-8 parts of carbon black, 12-20 parts of phenyl alkyl sulfonate, 2-10 parts of methyl methacrylate, 1-6 parts of sodium dodecyl benzene sulfonate, 3-8 parts of triethyl formate, 4-9 parts of polyamide wax, 1-2 parts of gamma-isocyanate propyl trimethoxy silane and 1-2 parts of dimorpholinyl diethyl ether.
6. The preparation process of the PTFE-based anti-icing composite membrane based on the radio frequency plasma treatment according to claim 1, characterized in that: in the step S1, after the low-temperature plasma micro-nano etching, the two surfaces of the PTFE form the surface appearances of nano-scale and micron-scale ultramicro structures which are micro-uneven and aggregated together, and the mastoid of the micro-structure has a nano-structure.
7. The construction method of the PTFE-based anti-icing composite membrane prepared by the preparation process of any one of claims 1 to 6 is characterized by comprising the following steps:
a1, pretreatment of the surface of the blade: removing impurities and cleaning the surface of the blade, locally repairing the surface of the blade and carrying out flatness and finish treatment on the surface of the blade by using a handheld polishing machine;
a2, detecting the surface of the blade; the method comprises the steps of checking the surface cleanliness and the flatness and the smoothness of the blade so as to meet the bonding condition of the PTFE-based anti-icing composite film;
a3, spraying of blade surface interface agent: micro air holes on the surface of the blade adhesion base layer are sealed off, and the adhesion strength and tearing strength of the PTFE-based anti-icing composite membrane and the blade are improved;
a4, ice coating film adhesion resistance: cutting and pasting the film at the blade tip part and carrying out surface treatment, winding and pasting the film at the blade tip part and compacting at the lap joint part;
a5, quality acceptance: the film surface has no hollowness, no bubble, no wrinkle, no damage, no deformation, no leakage and no adhesion, no scratch, no crack and no raised edge.
8. The construction method according to claim 7, wherein:
in a4, a method for using wrap bonding at a blade site, comprising: unfolding the composite film, and transversely winding and bonding the cold bonding adhesive surface of the composite film and the blade while tearing the isolating film; in the process of transverse winding, the boundary of the surface activated structure layers at the two ends of the composite film in the width direction is taken as a reference to ensure that the composite films are mutually lapped in the length direction of the blade,
the surface activation structure layer of the composite film is bonded with the cold bonding adhesive surface of the adjacent composite film to form a double-layer structure;
when the composite films with different lengths are lapped, the cold bonding glue surface at the head end of the next composite film is lapped on the surface at the tail end of the previous composite film; the above operations are repeated.
9. The construction method according to claim 7, wherein: when the film is pasted on the lightning protection lightning arrester of the blade, the PTFE-based anti-icing composite film is completely pasted on the surface of the lightning protection lightning arrester, the PTFE-based anti-icing composite films covering the hole of the lightning protection lightning arrester are cut one by one, and the seam is flattened.
10. The construction method according to claim 7, wherein: in a4, a gas circulation carrying particles and an ion gas flow for eliminating static electricity are ejected from the side by an eliminating device during the attaching process.
CN202110953425.4A 2021-08-19 2021-08-19 Preparation process and construction method of PTFE (polytetrafluoroethylene) -based anti-icing composite film based on radio frequency plasma treatment Pending CN113801591A (en)

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CN112339388A (en) * 2020-11-05 2021-02-09 中国长江三峡集团有限公司 Preparation method and application of PTFE (polytetrafluoroethylene) -based nano functional composite membrane
CN113072905A (en) * 2021-03-26 2021-07-06 河南省锅炉压力容器安全检测研究院 Adhesive composition for protective film, protective film and preparation method of protective film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103945630A (en) * 2014-04-21 2014-07-23 上海交通大学 Barometric pressure air micro-plasma jet device for etching thin polymer film without mask
CN106313812A (en) * 2016-08-15 2017-01-11 吴建华 Preparation method and application of PTFE and polyester-based composite film for preventing wind turbine blades from icing
US20180112107A1 (en) * 2016-10-21 2018-04-26 Tesa Se Plasma treatment for multilayer adhesive bonding element
CN110038445A (en) * 2019-04-08 2019-07-23 同济大学 A kind of hydrophobic membrane hydrophilic modification method
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Application publication date: 20211217