CN110331384A

CN110331384A - A kind of flexible membrane surface treatment method and gas injection apparatus

Info

Publication number: CN110331384A
Application number: CN201910691286.5A
Authority: CN
Inventors: 赵超; 郭鸿晨; 许淘元; 李瑞斌; 贾培军; 陈静升; 崔东旭
Original assignee: Shaanxi Coal and Chemical Technology Institute Co Ltd
Current assignee: Shaanxi Coal and Chemical Technology Institute Co Ltd
Priority date: 2019-07-29
Filing date: 2019-07-29
Publication date: 2019-10-15
Anticipated expiration: 2039-07-29
Also published as: CN110331384B

Abstract

The invention discloses a kind of flexible membrane surface treatment method and gas injection apparatus, processing method includes: to provide the tractive force of traction flexible membrane movement；The first gas thin layer for spraying to flexible membrane first surface is provided；First gas thin layer includes that face gas blanket is isolated in at least first air guiding layer of two-way first, first buffering area gas blanket and first gas；For first buffering area gas blanket between the first air guiding layer of two-way first, face gas blanket is isolated in the surrounding of the first first air guiding layer and first buffering area gas blanket for being isolated from the outside in first gas；The first gas recovery layer of reversed flexible membrane first surface is provided, the first gas recovery layer is by the flowing pressure difference movement of gas for forming gas occluding to the first first air guiding layer, first buffering area gas blanket and first gas isolation face gas blanket；Gas recovery layer is the working gas of recycling.The present invention realizes that the processing of technical grade flexible macromolecule polymer continuous surface, especially mass production encapsulate continuous processing work capacity.

Description

A kind of flexible membrane surface treatment method and gas injection apparatus

Technical field

The invention belongs to technical field of material surface treatment, it is related to a kind of flexible membrane surface treatment method and gas injection dress It sets.

Background technique

Technique for atomic layer deposition using reactant molecule orderly alternately transport, surface from it is restricted growth, step-by-step movement surface Modes and the mechanism such as covering control the gas-phase chemical reaction of body surface, to realize that film is raw in nanometer/sub-nanometer scale The accurate control of long rate.Currently, in the application for needing to prepare ultra-thin, high uniformity and the fabulous various thin-film materials of shape-retaining ability In, technique for atomic layer deposition has irreplaceable status.Just because of this, technique for atomic layer deposition has a wide range of applications neck Domain.According to incompletely statistics, exponentially increases in the past ten years for the application of technique for atomic layer deposition, and current this method is It is widely used in semiconductor and related industry, such as: integrated circuit, sensor, III-V device, micro-/nano electromechanical systems manufacture Industry, optical device and photoelectric project, antirust wear-resistant material and renewable energy application (such as: solar energy).Other are large-scale Using including anti-corrosion, energy storage and production (such as: advanced thin films battery and fuel cell), flexible electronic moisture or gas Seal coating, the biocompatible coating for Medical Devices and implant, Water warfare, advanced lighting apparatus (such as: LED), ecological packaging material, decorative paint, glass anti-cracking layer, water-repellent paint etc..

NCAP is the abbreviated form of Nano-Encapsulation.NCAP technology (NCAP Technology) is special needle The general name that the developed multiple technologies of flexible macromolecule polymeric film material (i.e. " flexible membrane ") surface encapsulation application are integrated.Envelope The high-performance barrier to multiple gases (especially aqueous vapor and oxygen) that dress then refers in particular to be done for flexible membrane is handled.NCAP technology It is gas phase process for treating surface, its essence is table/interfaces of flexible film material under gas phase condition and internal physiochemical to react.

However how gas phase is carried out to technical grade flexible macromolecule polymer (or other plane hard/soft materials) surface Surface realizes material surface continuity, rapid processing, is urgent problem.

Summary of the invention

In order to solve the problems existing in the prior art, the present invention provides a kind of flexible membrane surface treatment method and gas injection dress It sets, which possesses core function required by technical grade flexible macromolecule polymer surfaces processing technique Can, it can satisfy the technique, engineering and system requirements of NCAP technology, realize material surface continuity, rapid processing.

To reach above several purposes, the following technical solution is employed is achieved by the present invention:

A kind of flexible membrane surface treatment method, comprising the following steps:

The tractive force of traction flexible membrane movement is provided；

The first gas thin layer for spraying to flexible membrane first surface is provided；First gas thin layer includes at least the first guide of two-way Face gas blanket is isolated in gas-bearing formation, first buffering area gas blanket and first gas；First buffering area gas blanket is in the first guide of two-way Between gas-bearing formation, first gas is isolated face gas blanket and is used for and the external world in the surrounding of the first first air guiding layer and first buffering area gas blanket Isolation；Wherein, the first first air guiding layer is the mixing gas of working gas and reactant molecule, for flexible membrane table/interface Physical-chemical reaction；First buffering area gas blanket and first gas isolation face gas blanket are working gas；Working gas is Inert gas；

The first gas recovery layer of reversed flexible membrane first surface is provided, the first gas recovery layer relies on the flowing pressure of gas The movement of power difference is for forming gas resistance to the first first air guiding layer, first buffering area gas blanket and first gas isolation face gas blanket It is disconnected；The first gas recovery layer is the working gas of recycling.

Preferably, further includes:

The second gas thin layer for spraying to flexible membrane second surface is provided；Second gas thin layer includes at least the second guide of two-way Face gas blanket is isolated in gas-bearing formation, second buffering area gas blanket and second gas；Second buffering area gas blanket is in the second guide of two-way Between gas-bearing formation, second gas is isolated face gas blanket and is used for and the external world in the surrounding of the second first air guiding layer and second buffering area gas blanket Isolation；

Second gas recovery layer of reversed flexible membrane second surface is provided, the second gas recovery layer to the second first air guiding layer, Second buffering area gas blanket and second gas isolation face gas blanket form gas occluding.

Preferably, the thickness of first gas thin layer and second gas thin layer is less than 200 μm.

Preferably, first gas thin layer and second gas coating interior reactant molecule is uniformly distributed and interior point pressure It is identical.

Preferably, first gas thin layer and second gas thin layer enable in the intermediate contactless clamping of flexible membrane with And keep the flatness of flexible film surface.

Preferably, the reactant molecule undergoes three regions in flowing gas and is finally transported to flexible film surface Surface Physical Chemistry reaction occurs, three regions are respectively laminar convection area, Convention diffusion area and diffusion region；

Laminar convection area is flowing gas in the conveying parallel direction with flexible membrane, keeps speed when injection, reaction Object molecule is transported by convection action；Convention diffusion area is the aerodynamics boundary layer that flowing gas enters flexible film surface After reduce speed now, reactant molecule is transported by the collective effect of convection current and diffusion；Diffusion region is in nearly flexible film surface, gas Body flow velocity is reduced until body surface flow velocity is reduced to zero, and reactant molecule is finally transported to body surface by diffusion.

Preferably, reactant molecule transporting in flowing gas, adsorption and growth will be carried out by following equation:

Laminar convection area transports

Convention diffusion area transports

Diffusion region transports

Surface reaction mechanism

Wherein, c: reactant molecule number density；

T: time variable；

X: along flexible membrane transmission direction space variable；

U: reactant molecule is along flexible membrane transmission direction velocity component；

P_e: P é clet number demarcates the relative intensity of convection current and diffusion；

Q_NCAP: NCAP transmission exhausts parameter, is derived from adsorption, with diffusion region thickness, flexible film surface energy and surface Topological structure is related, Q_NCAP∝σh^-1/2E_Aθ^2/3, wherein σ represents flexible film surface viscosity, and h is that aerodynamic boundary layer is thick Degree, E_AEnergy is driven for adsorption, θ represents flexible membrane initial surface capture position topological structure coefficient；

P_NCAP: NCAP process control parameter is defined asWherein η represents initial table Probability is reacted in face, and inert polymer is about 0.53, and surface-active polymer and living polymer are about 0.9, k_BFor Bohr Hereby graceful Changshu, T are reaction temperature, E_aFor surface reaction activity, v_thFor the hot movement speed of reactant molecule, H is encapsulation thickness Degree, D are reactant molecule and the intermolecular diffusion coefficient of working gas；

ξ: total surface reaction probabilities, related with molecular scattering section and total molecular number, in flexible film surface, ξ is usually set It is scheduled in 0.55~0.85 range；

Ф: NCAP encapsulating film surface coverage.

Preferably, when handling inert polymer, P_NCAPValue is 30-50, Q_NCAPControl is 0.68 or so；In processing table When the living polymer of face, P_NCAPValue is 155-270, Q_NCAPControl takes 0.53；When handling living polymer, P_NCAPValue is 300-500, Q_NCAPValue 0.35.

A kind of gas injection apparatus, comprising:

Conveying device, for providing the tractive force of traction flexible membrane movement；

And first spray head, for providing the first gas thin layer for spraying to flexible membrane first surface, first gas thin layer includes At least face gas blanket is isolated in the first air guiding layer of two-way first, first buffering area gas blanket and first gas；The first spray head packet It includes:

Sprayer body, for providing support；

Encapsulation work face, the encapsulation work face are arranged on sprayer body surface, and encapsulation work face and flexible film surface It is oppositely arranged；With multiple along the gas vent linearly arranged, gas vent is used in the first table of flexible membrane in the encapsulation work face Face forms first gas thin layer；The gas vent includes:

First air guide gas vent；For providing the first first air guiding layer；First air guide gas vent has two column, and two arrange first air guide exhaust Hole provides two kinds of reaction gas respectively；

Buffering exhaust hole, buffering exhaust hole are connect with the second road admission line for providing first buffering area gas blanket；

Gas barrier gas vent, gas barrier gas vent is connected with third road admission line is isolated for providing first gas Face gas blanket；Wherein, first buffering area gas blanket is between the first air guiding layer of two-way first, and face gas blanket is isolated the in first gas The surrounding of one first air guiding layer and first buffering area gas blanket is for being isolated from the outside；Wherein, the first first air guiding layer is working gas With the mixing gas of reactant molecule, for flexible membrane table/interface physical-chemical reaction；First buffering area gas blanket and It is working gas that face gas blanket, which is isolated, in first gas；Working gas is inert gas；

And the periphery of first air guide gas vent is arranged in gas accumulator tank, gas accumulator tank, for providing reversed flexible membrane The first gas recovery layer on one surface, the first gas recovery layer is by the flowing pressure difference movement of gas for the first first air guide Layer, first buffering area gas blanket and first gas isolation face gas blanket form gas occluding；The first gas recovery layer For the working gas of recycling.

Preferably, further includes:

Second spray head, for providing the second gas thin layer for spraying to flexible membrane second surface.

Preferably, include: on the encapsulation work face

First air guide workspace peripheral groove is arranged at least two first air guide workspaces, the gas accumulator tank；First air guide Gas vent on workspace is first air guide gas vent, and the injection direction of first air guide gas vent is vertical with the conveying direction of flexible membrane, For providing the reaction gas with flexible membrane table/interface physical-chemical reaction being made of reactant molecule and working gas；

Buffer area, for setting buffers between two neighboring first air guide workspace, the gas vent on buffer area is buffering row Stomata, buffering exhaust hole are used to provide the working gas of the two first air guide workspace reaction gas in interval；

Gas barrier face, gas barrier face are arranged along the edge in encapsulation work face, and the gas vent on gas barrier face is gas Body separated exhaust hole, gas barrier gas vent is for encapsulation work face to be isolated with perimeter.

Preferably, exhaust buffering concave surface is provided with around the outlet of each gas vent；The concave panel of exhaust buffering concave surface Opening diameter meet formula (P/2P₀)≤d/h, the P in formula are sprinkler design operating air pressure, P₀For standard pressure, d is spill The opening diameter in face, h are gas vent and fluid control plane datum level distance, and fluid control plane is encapsulation work face and gas barrier Common physical plane.

Preferably, the gas vent is arranged satisfaction on corresponding region: adjacent gas vent along straight line arrangement or Adjacent gas vent is staggered；

When gas vent is along lineal layout, the distance between exhaust bore dia, the total length for being vented pore size distribution and gas vent are full Sufficient relational expression: (P₁/P₀)(D/h₁)≤L/d₁；Wherein, P₁For the gas pressure in encapsulation region, P₀For standard pressure, D is gas vent Diameter, h₁It is encapsulation work face at a distance from flexible membrane, L is the total length for being vented pore size distribution, d₁For the distance between gas vent；

Identical when number is with along lineal layout when gas vent is staggered, staggeredly distance ≈ (W-8)/3, wherein W is exhaust Distributed areas width where hole.

Preferably, it is connected between adjacent gas vent by setting air slot, the air slot between two gas vents is in expansion Open type arrangement；One or two air slot is set between adjacent gas vent, and two air slots are symmetrical with the connecting line of gas vent；

The air slot is spliced in circular arc type or by arc line type；Arc line type air slot stitching portion passes through direct crosspoint Connection；The maximum radian of camber line is located at gas vent, and maximum radian is greater than the circumference arc of two gas vents of connection.

Preferably, gas closed circulation system system is arranged inside sprayer body comprising is used for transport gas Air return system and gas handling system；

Gas vent is connect for forming first gas thin layer in flexible membrane first surface with the gas handling system；

The end of gas accumulator tank connect the first recycling gas for providing reversed flexible membrane first surface with air return system Body layer.

Preferably, the air return system includes:

Return-air duct, return-air duct are arranged inside sprayer body；

And return-air is connected pipeline, return-air is connected pipeline one end and is connected to return-air duct, and the return-air duct other end is connected to gas and returns Receive slot；

The gas handling system includes:

Admission line, admission line are arranged inside sprayer body；

And linking pipeline, linking pipeline are connected to admission line, each linking pipeline connects a gas vent.

Preferably, admission line junction is provided with a miniature adjusting cavity, which is tapered cylinder shape portion Part；The design requirement of miniature adjusting cavity is arctan (d₀-d₃)/2L<arctan(200/R_e), wherein d₀It is straight in admission line Diameter, d₃For main air-channel system pipeline interior diameter, L is the length of miniature adjusting cavity, R_eGas Reynolds is inputted for spray head admission line Number.

Compared with prior art, the invention has the following advantages:

Flexible membrane surface treatment method of the present invention by mobile flexible film surface spray first air guiding layer and flexible membrane table/ The physical-chemical reaction at interface, first air guiding layer are the mixing gas of working gas and reactant molecule, pass through buffer area gas blanket Two pilot gas are isolated, outside air is isolated by gas barrier face gas blanket；Gas recovery layer relies on the flowing pressure of gas The movement of power difference is for forming gas occluding to first air guiding layer, buffer area gas blanket and gas barrier face gas blanket；When continuous spray Gas jet out is formed between flexible membrane and injection apparatus exit facet has adjustable pressure and temperature and the number density of molecule is equal When even gas thin layer, gas locking circulating system must lean on the flowing pressure difference of gas to keep on the go, and then to flexible film surface It carries out continuity and handles operation.

The gas injection apparatus covers flexible membrane by conveying device and sprinkler composition, drive flexible membrane horizontal movement, spray head On flexible film surface area to be processed, interval forms encapsulation region between spray head and flexible membrane；The encapsulation work face of spray head, it is described Encapsulation work face be oppositely arranged with flexible film surface area to be processed, for working gas and reaction gas to be delivered to encapsulation Area simultaneously forms encapsulated layer on flexible film surface area to be processed.The gas closed circulation system system of gas injection apparatus must lean on gas Flowing pressure difference keep on the go, and allow to be arranged in entire gas flow path flexible membrane and injection apparatus exit facet it Between gas thin layer section pressure be higher than standard pressure.Realize the processing of technical grade flexible macromolecule polymer continuous surface, especially Mass production under the conditions of normal pressure gas phase encapsulates continuous processing work capacity.

Detailed description of the invention

Fig. 1 is flexible membrane surface treatment method encapsulated layer aerodynamics distribution map of the present invention；

Fig. 2 is flexible membrane surface treatment method encapsulated layer molecular transport model of the present invention；

Fig. 3 is material surface processing gas injection apparatus schematic diagram；

Fig. 4 is nozzle structure schematic diagram；

Fig. 5 is the structural schematic diagram in encapsulation work face；

Fig. 6 is the gas vent distribution map in encapsulation work face；

Fig. 7 is inside exhaust ports structural schematic diagram；

Fig. 8 is exhaust buffering concave panel schematic diagram；

Fig. 9 is gas vent distribution schematic diagram (linear type)；

Figure 10 is gas vent distribution schematic diagram (staggered)；

Figure 11 is air slot schematic diagram；

Figure 12 is one schematic diagram of air guide groove shape；

Figure 13 is two schematic diagram of air guide groove shape

Figure 14 is the construction profile schematic diagram of sprayer body；

Figure 15 is complex function face schematic diagram；

Figure 16 is nozzle structure schematic diagram arranged up and down；

Figure 17 is that multiple spray heads are arranged side by side structural schematic diagram；

Figure 18 is the multiple spray head arragement construction schematic diagrames connected by connector；

Figure 19 is spray head air inlet side schematic diagram；

Figure 20 is spray head return side schematic diagram；

Figure 21 is electricity/gas/Mechanical course face side schematic diagram；

Figure 22 is electricity/gas/Mechanical course face other side schematic diagram；

Figure 23 is spray head admission line (first air guide 1/2, buffer area, gas barrier face) schematic diagram；

Figure 24 is spray head return-air duct design diagram；

Figure 25 is spray head internal pipeline total distributed schematic diagram；

Figure 26 is spray head inside micro chamber schematic diagram.

Specific embodiment

To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.

The present invention provides a kind of flexible membrane surface treatment methods, comprising the following steps:

The tractive force of traction flexible membrane movement is provided；

Further include: the second gas thin layer for spraying to flexible membrane second surface is provided；Second gas thin layer includes at least two-way Face gas blanket is isolated in second first air guiding layer, second buffering area gas blanket and second gas；Second buffering area gas blanket is in two-way Between second first air guiding layer, second gas is isolated face gas blanket and is used in the surrounding of the second first air guiding layer and second buffering area gas blanket In being isolated from the outside；

Being formed by encapsulated layer at work is that the Complex Flows gas for having multiple functions mixes body, such as Fig. 1 institute Show.For gas distribution, the gas blanket formed after the discharge of first 1 gas vent of air guide in encapsulated layer comprising first air guide 1 (is defined as First 1 gas blanket of air guide), first air guide 2 formed after the discharge of first 2 gas vent of air guide gas blanket (being defined as first 2 gas blanket of air guide), The gas blanket (being defined as buffer area gas blanket) and gas barrier face gas that buffering gas is formed after buffering gas gas vent discharge Layer.Gas occluding is formed by by the gas accumulator tank of spray head between each gas blanket, it is ensured that first air guide 1, buffering gas, first air guide 2, separation gas does not mix mutually respectively in encapsulated layer.

Although respectively completing independent function, 1 gas blanket of first air guide, 2 gas blanket of first air guide, buffering of encapsulated layer are constituted Area's gas blanket, gas barrier face gas blanket and gas partition be as a whole a complete air sky mechanics thin layer simultaneously And it is blended with the boundary layer of material surface.Complete its internal gas flow of aerodynamics thin layer is all satisfied laminar flow item Part；Meanwhile internal-response object molecule is uniformly distributed and internal pressure each point is identical.

In summary encapsulated layer be one containing it is multiple can independent control local from system and all independences is in harmony from being in harmony body System can be used as the aerodynamics thin layer (thickness of thin layer is generally less than 200 μm) an of cooperation again.

Into the various gases of NCAP spray head, it is formed by after the aerodynamics component adjustment of special designing in spray head Encapsulated layer, which meets, stablizes (not changing over time) viscous compressible Newtonian fluid condition.Its integrated air dynamics meets viscosity can Press environment described in Navier-Stokes equation.In addition, encapsulated layer and two aerodynamic boundary layers are closely related, one A physical plane positioned at where encapsulation work face+gas barrier face, another is located at flexible film surface.Gas in encapsulated layer Meet environment described in Prandtl equation in two aerodynamic boundary layers.In above-mentioned encapsulated layer and boundary layer Thus gas molecule mass transport is then set in Boltzmann equation control range.Aerodynamics environment in encapsulated layer Establishment is the theoretical basis that subsequent NCAP governing equation is established.

NCAP encapsulates related storeroom physical chemistry interaction and may be summarized to be: nothing under multiple step format gaseous environment Machine/organic/polymer interpolymer interaction.

Organic-metal molecules 1 are sent by spray head to 1 workspace of first air guide in encapsulation work face, with the flexible membrane of process below Surface reacts；Organic-metal molecules 2 are sent by spray head to 2 workspace of first air guide in encapsulation work face, and by below Flexible film surface reacts.It is responsible for stablizing the intermediate state of reaction 1 and table is remained in reaction 1 in the buffer area in encapsulation work face The by-product in face is purged.When more spray heads connect work, the above process encapsulates index required for being constantly repeated up to Reach.This mode is similar to atomic layer deposition reactive mode, except that can partially be mixed with organic metal in organic-metal molecules 1 Molecule 2 or other organic-metal molecules similarly can partially be mixed with organic-metal molecules 1 or other organic in organic-metal molecules 2 Metallic molecule.This purpose is the functional group in order to form different sizes and function, and it is made to exist with high molecular polymer base chain Polymer surfaces and internal formation hydridization and crosslinking, reach excellent and controllable packaging effect.

The encapsulating material molecule and interpolymer interaction mechanism of flexible membrane surface treatment method of the present invention are as follows:

Flexible macromolecule polymer can be divided into three kinds when implementing NCAP encapsulation operation according to the property of itself base chain Situation: i.e. inert polymer (surface and internal without any reactive group, and reactant molecule not with polymer matrix chain/side chain React), surface-active polymer (there are reactive group, such as a hydroxyl, amido in surface, but reactant molecule not with polymer Base chain/side chain reacts), (reactant molecule reacts living polymer with polymer matrix chain/side chain, such as Louis Acid-base function principle).

(1) inert polymer

The encapsulation of inert polymer mainly comprises the processes of reactant molecule 1 and enters flexible membrane by diffusion and process of osmosis Table/interface can be varied according to 1 concentration of reactant molecule of flexible environmental microbes, capture.Reactant molecule 2 passes through Same process enters flexible membrane table/interface.By repeatedly recycling (flexible membrane passes through multiple spray heads), until reactant molecule 1 and 2 assemble enough quantity in flexible membrane surface and interface, and following reaction object molecule 1 and 2 has an opportunity to meet concurrent biochemical anti- It answers, generates encapsulating film seed, seed can generate covalently key connection with high molecular polymer base chain.With being continuously increased for seed, Reuniting effect can be generated between them, and then in flexible membrane table/interface area connection film forming, is formed organic/inorganic/polymer and mixed Junctional area.Then, will start to gradually form complete encapsulating film in junctional area.Once fine and close encapsulated layer is formed, it will stop The further infiltration of reactant molecule.

The more coarse flexible membrane in surface helps to capture more reactant molecules, to generate comparatively dense encapsulation Film.Higher temperature facilitates the diffusion of captured molecule, to increase the thickness of junctional area, it helps forms fine and close envelope Fill film.Dissolubility facilitates the infiltration of molecule, and reactant molecule identical with polymer matrix strand polarity can be easier to penetrate into soft Property film inside, inside flexible membrane deeper inside construct encapsulated layer, thus be also beneficial to promoted packaging effect.

According to the above analysis, packaging technology control needs: pre-treatment generates more surface roughness (such as Corona work Skill), higher package temperature, higher encapsulated layer gas pressure, slower flexible membrane conveying speed, slower air-flow in buffer area, Power stretches, is mixed into increase in type and size and buffer area of the mixing injection of reactant molecule 1 and 2 to increase encapsulation group Reactant molecule captures the accessory molecule of density, such as O₂Molecule.

(2) surface-active polymer

Shape that the encapsulation of surface-active polymer mainly comprises the processes of reactant molecule 1 and surface active function group reacts At intermediate state, then react to form encapsulating film with reactant molecule 2.Once encapsulated layer is formed, it will stop reactant molecule Further infiltration.Then, encapsulating film can constantly become thicker finer and close with the increase of the spray head number of flexible membrane process. This process class need to be in conventional atom layer deposition process.This class process will form relatively thin and taken turns due to the presence of surface functional group The junctional area of wide clearly encapsulated layer and flexible membrane.

Packaging technology control needs: pre-treatment generates more surface functional group (such as corona treatment), early period Lower package temperature is conducive to slow down the formation of surface barrier layer, later period higher package temperature be conducive to fine and close encapsulating film formed, The mixing injection of reactant molecule 1 and 2 is to increase the type and size, higher encapsulated layer gas pressure and tension that encapsulate group It stretches.

(3) living polymer

The encapsulation of living polymer mainly comprise the processes of reactant molecule 1 and 2 can react to each other to be formed encapsulating film seed and by Seed gradually agglomerates into encapsulating film.Meanwhile reactant 1 and 2 can react with polymer matrix chain/side chain, form hybrid state, And original base chain is disconnected, cause the further infiltration of reactant molecule 1 and 2.It in such cases, can be by controlling technological parameter Come adjust reactant molecule infiltration, reaction product and polymer matrix chain/crosslinking of side chain, the formation of encapsulating film and they Relative scale.Excellent encapsulation performance may be implemented in each process proportion of balance optimizing.

Packaging technology control needs: biggish temperature regulating range, the adjustment of biggish flexible membrane conveying speed, higher encapsulation Layer gas pressure and tension force stretching.

The reaction mechanism is as follows for the molecular transport of flexible membrane surface treatment method of the present invention and surface:

As indicated with 2, under conditions of fluid boundary layers do not separate, reactant molecule undergoes three regions simultaneously final defeated It transports to body surface and Surface Physical Chemistry reaction occurs.Three regions are respectively defined as laminar convection area, i.e., flowing gas is at certain (parallel with the conveying direction of flexible membrane) on one determining direction to have larger speed and flow speed stability, reactant molecule is mainly by right Stream effect is transported；Convention diffusion area, i.e. gas reduce speed now after entering the aerodynamics boundary layer of flexible film surface, expand Scattered effect becomes significantly, and reactant molecule is transported by the collective effect of convection current and diffusion at this time；Diffusion region, i.e., in nearly object Surface, gas flow rate are further decreased until body surface flow velocity is reduced to zero, and at this time based on diffusion, reactant molecule is most Body surface is transported to by diffusion eventually.

The formation of Convention diffusion area and diffusion region is originated from the aerodynamics viscosity of flexible film surface and to gas molecule Absorption.With adsorption and the process deposited is that adsorption process is moved back on surface.Fluid control plane also to gas molecule have absorption and Move back suction-operated.In sprinkler design, fluid control plane is reduced as far as possible to the suction-operated of gas molecule and is increased simultaneously It moves back suction-operated to gas molecule.And then to implement reverse design to flexible film surface, that is, increase flexible film surface to gas Simultaneously reducing it moves back suction-operated to gas molecule simultaneously for the suction-operated of body molecule.The means that can be implemented include rough surface Spend control, table/interfacial activity molecular radical control, in aerodynamic boundary layer thickness control, encapsulated layer gas pressure control, Gas flow rate control, surface temperature and temperature gradient control, encapsulated layer thickness control, flexible membrane surface tension transition in encapsulated layer And (wherein flexible membrane surface tension transition and the control of flexible membrane conveying speed are seen below continuous for flexible membrane conveying speed control etc. NCAP technology illustrates the conveying of 3- flexible membrane and control system).

Corresponding to above-mentioned Step transmission mode, the surface nanoscale that NCAP is controlled encapsulates related reactant molecule Transporting in flowing gas, adsorption and growth will be carried out by following equation:

C: reactant molecule number density；

T: time variable；

X: along flexible membrane transmission direction space variable；

Q_NCAP: NCAP transmission exhausts parameter, is derived from adsorption, with diffusion region thickness, flexible film surface energy and surface Topological structure is closely related, Q_NCAP∝σh^-1/2E_Aθ^2/3, wherein σ represents flexible film surface viscosity, and h is aerodynamics boundary Thickness degree, E_AEnergy is driven for adsorption, θ represents flexible membrane initial surface capture position topological structure coefficient；

P_NCAP: NCAP process control parameter is defined asWherein η represents initial table Probability is reacted in face, and inert polymer is about 0.53, and surface-active polymer and living polymer are about 0.9, k_BFor Bohr Hereby graceful Changshu, T are reaction temperature, E_aFor surface reaction activity, v_thFor the hot movement speed of reactant molecule, H is encapsulation thickness Degree, D are reactant molecule and the intermolecular diffusion coefficient of working gas.

Ф: NCAP encapsulating film surface coverage；

Above-mentioned formula 1-4 disclose surface reaction mechanism show, Q_NCAPWith P_NCAPIt is anti-to will lead to two kinds of completely different surfaces Form is answered, one is the direction successive reaction with air-flow, another is that tendency is reacted since entire flexible film surface, and It is unrelated with the direction of air-flow.In actual operation, according to different substrate material characteristics, by controlling Q_NCAPWith P_NCAPTo reach Excellent packaging effect.Pass through flexible membrane surface pretreatment (Corona processing, corona treatment etc., prebake etc.), encapsulation Pressure P is adjusted in layer, temperature T is adjusted, encapsulation layer thickness H is adjusted etc., adjustable Q_NCAPAnd P_NCAPValue.It is poly- in processing inertia When closing object, P_NCAPValue is between 30-50, Q_NCAPControl is 0.68 or so；When handling surface-active polymer, P_NCAPValue Between 155-270, Q_NCAPControl is 0.53 or so；When handling living polymer, P_NCAPValue is between 300-500, Q_NCAP Control is 0.35 or so.

Above-mentioned encapsulation is occurred in the gaseous environment of flowing.Gas in encapsulated layer is not static, is one Kind flow equilibrium state, gas jet are ejected into flexible film surface and flow to gas accumulator tank along surface.Encapsulation work environment is wanted It asks:

(1) gas jet of gas vent discharge forms uniform air film when touching flexible film surface at once, that is, encapsulates Layer；

(2) reactant molecule density must be uniformly distributed in encapsulated layer；

(3) gas film pressure can require to adjust according to packaging technology；

(4) air film temperature can require to adjust according to packaging technology；

(5) fluid will not generate turbulence effect in encapsulated layer；

(6) encapsulated layer and flexible membrane surface aerodynamic boundary layer will have a stable transition, and reactant molecule is to flexibility The process that film surface transports will not by Turbulent Flow Effects, and only by surface react driving；

(7) aerodynamic boundary layer of spray head enclosure working face is as thin as possible, to reduce reaction in encapsulation work face A possibility that generation；

(8) during gas flow gas accumulator tank, the by-product of upstream does not interfere with the surface reaction in downstream, Flexible film surface or internal absorption position will not be occupied in advance；

(9) the aerodynamics environment (such as pressure and flow velocity etc.) of gas has biggish redundancy in encapsulated layer, can be with It is voluntarily adjusted according to the fluctuation of whole system.

The design and processing, the pre-treatment of flexible membrane, the design of air-channel system, flexible membrane that NCAP encapsulation technology passes through spray head Above-mentioned NCAP encapsulation work requirement, such as the following table 1 are realized in design, packaging technology and design of control parameter of drive technology etc. It is shown；

Table 1

Flexible membrane surface treatment method to realize the present invention, the present invention also provides a kind of surface treatment gas sprays of flexible membrane Injection device, the flexible membrane are surface-treated gas injection apparatus and cover flexible film surface area to be processed.Each flexible film surface Processing gas injection apparatus all should be an independent gas locking circulating system, that is, have independent exhaust and gas-returning devices, Gas exchanges are not carried out with the external world.Simultaneously, flexible membrane surface treatment gas injection apparatus must be set containing special gas manipulation Meter, the gas jet for allowing to be sprayed is formed between flexible membrane and injection apparatus exit facet has adjustable pressure and temperature Degree and the uniform gas thin layer of the number density of molecule；And it is further opposed above and below two flexible membrane surface treatment gas injection apparatus In application, can not only carry out double treatment to flexible membrane, (double treatment can be directed to same function, can also be directed to different function Can), and uniform gas thin layer also will form to the contactless not damaged clamping of in-between flexible membrane and holding flexible membrane The flatness on surface.The gas locking circulating system of flexible membrane surface treatment gas injection apparatus must lean on the flowing pressure of gas poor It keeps on the go, and allows that gas thin layer section between flexible membrane and injection apparatus exit facet is being arranged in entire gas flow path Pressure be higher than standard pressure.

Above-mentioned requirements possess flexible membrane surface treatment gas injection apparatus at technical grade flexible macromolecule polymer surfaces Core function required by reason technology has continuous processing work capacity (such as roll-to-roll system under the conditions of normal pressure gas phase Journey).

Flexible membrane surface treatment gas injection apparatus is one and handles researched and developed dress for a variety of flexible membrane surface vapors It sets.For the technique, engineering and system requirements for meeting NCAP technology, flexible membrane be surface-treated gas injection apparatus it is specific design and Function description will be provided by this specification.

As shown in figure 3, material surface processing gas injection apparatus is the end of NCAP package system reactant molecule transmission, Also it is responsible for the foundation of global context when table/surface physics chemical reaction occurs simultaneously.

As shown in figure 4, work/reaction gas jet stream that spray head is sprayed forms NCAP technique between spray head and flexible membrane Implement area, and the final implementation and control of all overall situation/local variables of NCAP system are all completed inside the process implementing area.This Invention also provides a kind of material surface processing gas injection apparatus for realizing above-mentioned flexible membrane surface treatment method, comprising:

Conveying device, for providing the traction tractive force that flexible membrane 200 moves；

Sprayer body, for providing support；

Encapsulation work face 105, the described setting of encapsulation work face 105 on sprayer body surface, and encapsulation work face 105 with it is soft Property 200 surface of film is oppositely arranged；The encapsulation work face 105 has multiple along the gas vent 1052 linearly arranged, gas vent 1052 for forming first gas thin layer in 200 first surface of flexible membrane；The gas vent 1052 includes:

First air guide gas vent 1052a；For providing the first first air guiding layer；First air guide gas vent 1052a has two column, two column First air guide gas vent 1052a provides two kinds of reaction gas respectively；

Buffering exhaust hole 1052b, buffering exhaust hole 1052b are connect with the second road admission line for providing first buffering area Gas blanket；

Gas barrier gas vent 1052c, gas barrier gas vent 1052c are connect for providing the with third road admission line One gas barrier face gas blanket；Wherein, for first buffering area gas blanket between the first air guiding layer of two-way first, face is isolated in first gas Gas blanket is in the surrounding of the first first air guiding layer and first buffering area gas blanket for being isolated from the outside；Wherein, the first first air guiding layer The mixing gas of working gas and reactant molecule, for flexible membrane table/interface physical-chemical reaction；First buffering area Gas blanket and first gas isolation face gas blanket are working gas；Working gas is inert gas；

And gas accumulator tank 1055, the periphery of first air guide gas vent 1052a is arranged in gas accumulator tank 1055, for providing First gas recovery layer of reversed flexible membrane first surface, the first gas recovery layer are used for by the flowing pressure difference movement of gas Gas occluding is formed to the first first air guiding layer, first buffering area gas blanket and first gas isolation face gas blanket；Described One gas recovery layer is the working gas of recycling.

It further include second spray head, for providing the second gas thin layer for spraying to flexible membrane second surface.Second spray head and the The structure of one spray head is identical.

Include: on the encapsulation work face 105

At least two first air guide workspaces 1054, the gas accumulator tank 1055 is arranged around first air guide workspace 1054 Groove；Gas vent on first air guide workspace 1054 is first air guide gas vent 1052a, the injection side of first air guide gas vent 1052a To vertical with the conveying direction of flexible membrane 200, for provide be made of reactant molecule and working gas with flexible membrane table/boundary The reaction gas of the physical-chemical reaction in face；

Buffer area 1053, the setting of buffer area 1053 is between two neighboring first air guide workspace 1054, on buffer area 1053 Gas vent be buffering exhaust hole 1052b, buffering exhaust hole 1052b is reacted for providing the first air guide workspaces 1054 in two, interval The working gas of gas；

Gas barrier face 1051, gas barrier face 1051 are arranged along the edge in encapsulation work face 105, gas barrier face 1051 On gas vent be gas barrier gas vent 1052c, gas barrier gas vent 1052c is used for encapsulation work face 105 and external Zone isolation.

Wherein, interval forms encapsulation region 300 between spray head 100 and material to be processed 200；The spray head 100 includes:

The main gas circuit gas handling system of NCAP, the main gas circuit gas handling system of NCAP is arranged inside spray head 100, for importing work gas Body and reaction gas；

Encapsulation work face 105, the encapsulation work face 105 is opposite with material 200 surface area to be processed to be processed to be set It sets, for working gas and reaction gas to be delivered to encapsulation region 300 and the shape on the area to be processed of 200 surface of material to be processed At encapsulated layer 400.

Spray head is the end of NCAP package system reactant molecule transmission, while being also responsible for table/surface physics chemical reaction The foundation of global context when generation.

The work that spray head is sprayed/reaction gas jet stream forms the encapsulation region NCAP between spray head and flexible membrane, and NCAP The final implementation and control of all overall situation/local variables of system are all completed inside the encapsulation region.

Wherein, material 200 (can be hard or soft material, such as flexible membrane) to be processed.What nozzle component to be realized Function includes:

Work/reaction gas is transported and is distributed, i.e. the foundation of the encapsulation region NCAP；NCAP packaging technology parameter implements and control It makes (temperature, pressure, throughput etc.)；Aerodynamics controls in the encapsulation region NCAP, such as work/reaction gas is in flexible membrane table In face of flowing and spreading, laminar flow and turbulent flow regulation etc.；The conveying of auxiliary flexible film, such as the flatness of control flexible membrane, flexible membrane are defeated The application of contactless aid, flexible membrane conveying auxiliary pneumatic thrust when sending；It is recovery operation/reaction gas, excess reactant, anti- Answer by-product；Insulation package area and exterior space；Realize the double surface treatments of flexible membrane.

Wherein, NCAP spray head shape is designed as cuboid (containing square), and it is to be processed that area must cover flexible film surface Region.Its 6 outer surfaces by technique and the system integration needs fall into 5 types, respectively " encapsulation work face ", " complex function face ", " electricity/gas/Mechanical course face ", " more spray head combination interfaces " and " gas barrier face ", wherein encapsulation work face and gas every It is located in same physical plane from face.Long side in spray head length must be parallel with the breadth of flexible membrane.Flexible membrane breadth is fixed Justice is the side vertical with flexible membrane conveying direction.

Shown in Fig. 4, nozzle structure schematic diagram, encapsulation work face is responsible for working gas and reaction gas being delivered to encapsulation region (realization is constructed by encapsulation work face and flexible membrane aid in the encapsulation region NCAP in encapsulation region, that is, Fig. 3), and formed in encapsulation region Stable aerodynamics environment is constructed and regulates and controls table/surface physics chemical reaction environment, the conveying of auxiliary flexible film, recycling Work/reaction gas and excess reactant molecule, byproduct of reaction etc..

It is responsible for integrated additional functions and stablizes group in spray head, such as temperature control modules, mechanical strength in complex function face Part, spray head constant temperature suit, the module even for other surface treatment functions, such as compact plasma (orifice) gas generating means Deng.

Relevant control node is contained in electricity/gas/Mechanical course face, for the intake and exhaust control of spray head work/reaction gas System, the reality of monitoring/feedback of spray head working condition, the application and adjustment and spray head Mechanical course function of packaging technology parameter It is existing.

It is mutually stably connected with integral production line when more spray head combination interfaces are used for a large amount of spray head work in combination, with Realize mass production capabilities.

The structure in encapsulation work face is as shown in Figure 5.Entire encapsulation work face is rectangle (comprising square).Wherein, " envelope Dress working face " is defined as " processing boundary line " with the intersection of " more spray heads combine interface ".Handle the length and flexibility of end line The breadth in film surface region processed is equal.The side vertical with processing end line is defined as " isolation boundary on encapsulation work face Line ", be isolated the length of end line by specific sprinkler design process requirement and mechanical/thermal stability determine.

As shown in fig. 6, along the conveying direction of flexible membrane, encapsulation work face is divided into workspace, delays according to NCAP packaging technology Rush the 3 partial function area such as area and gas accumulator tank.Workspace is further divided into 2 workspace of first 1 workspace of air guide and first air guide (first air guide 1 is working gas respectively with the mixing gas of vapor-phase reactant molecule 1 and 2 with first air guide 2, and working gas is then pure The high purity inert gas of degree >=99.999%, such as high pure nitrogen or high-purity argon gas etc.), it is mainly responsible for first air guide 1,2 and flexibility Film table/interface physical-chemical reaction is responsible for flexibility between first 1 workspace of air guide of buffer arrangements and first 2 workspace of air guide The cleaning of the stabilization and reaction intermediate by-products of reaction intermediate state between the first reaction of air guide 1,2 of film surface.Gas recycling Slot be responsible for all gas balance recycling (i.e. gas recovery while auxiliary encapsulation region in pressure be uniformly distributed).

Preferred embodiment, spray head 100 are cuboid, and the top surface or bottom surface of spray head 100 are encapsulation work face 105.It is described Encapsulation work face 105 include:

First air guide workspace 1054, first air guide workspace 1054 is vertical with the conveying direction of material 200 to be processed, for mentioning For the reaction gas with flexible membrane table/interface physical-chemical reaction；

Buffer area 1053, the setting of buffer area 1053 is between two neighboring first air guide workspace 1054, for providing interval The working gas of two 1054 reaction gas of first air guide workspace；

Gas barrier face 1051, gas barrier face 1051 are arranged along the edge in encapsulation work face 105, are used for encapsulation work Face 105 is isolated with perimeter；

And gas vent 1052, the end of gas vent 1052 connect the main gas circuit gas handling system of NCAP.

As shown in Fig. 5 and 4, preferred embodiment, gas vent 1052 includes:

First air guide gas vent 1052a；First air guide gas vent 1052a is connect for providing by reactant with admission line all the way The reaction gas of molecule and working gas composition；First air guide gas vent 1052a has two column, and two arrange first air guide gas vent 1052a Two kinds of reaction gas are provided respectively；The gas accumulator tank 1055 is arranged around first air guide gas vent 1052a；

Buffering exhaust hole 1052b, buffering exhaust hole 1052b connect with the second road admission line and mention for spraying working gas The reaction gas of first air guide gas vent 1052a is arranged for interval two；

And gas barrier gas vent 1052c, gas barrier gas vent 1052c are connect with third road admission line for spraying First air guide gas vent 1052a is isolated working gas with perimeter.

As shown in fig. 7, containing specially designed and distribution gas vent in workspace, buffer area and gas barrier face.Institute The gas for having gas vent to be discharged is as a whole, therefore, to assure that can control flexible film surface has equal or close to rigid Property material surface processing when surface flatness, i.e. the gas jet of gas vent is when constructing encapsulation region, it is ensured that flexible membrane is not Any entirety or local deformation can be generated；Or more precisely, the relaxation time that any entirety or local deformation generate is less than The time that flexible membrane surface gas pressure whole machine balancing reaches.Therefore, NCAP spray head enclosure working face will guarantee in encapsulation region Gas forms pressure unanimously and the gas blanket of internal-response gas molecula number even density in entire flexible film surface, and the gas While the formation of body layer is that the gas sprayed in spray head touches flexible film surface.

In the uniform encapsulated layer of pressure of formation, uniform pressure value is higher than standard atmospheric pressure and barometric gradient variation is small In 5%.In addition, the effect of pressure also resides in offer table/surface physics in encapsulated layer other than guaranteeing flexible membrane surface flatness Pressure condition needed for chemical reaction, it is ensured that main system gas circuit flow direction, and auxiliary clamping when flexible membrane conveying is provided.

See that Fig. 7, gas vent 1052 include the datum hole 1052-3 and crystalline material 1052-2 being embedded in datum hole 1052-3, The crystalline material 1052-2 has exhaust outlet 1052-1.The datum hole 1052-3 is opened in the center of concave panel.It is brilliant Body material 1052-2 is ruby material, and datum hole 1052-3 punctures formation using laser on ruby material.Crystalline material 1052-2 is fixed on encapsulating face using high temperature resistant connection glue 1052-3 sealing.In order to eliminate temperature and mechanical deformation to gas vent The influence of size and meet excellent physics stability, gas vent uses high rigidity crystalline material, such as ruby material.

In vent section, encapsulation work face is concave, is defined as " exhaust buffering concave panel ", as shown in Figure 8.Each row Exhaust buffering concave surface 1052d is provided with around the outlet of stomata 1052；Exhaust buffering its design formula of concave surface 1052d are as follows: (P/ 2P0)≤d/h, wherein P is sprinkler design operating air pressure, and P0 is standard pressure, and d is the opening diameter of concave panel, and h is gas vent Apart from fluid control plane datum level distance, exhaust outlet is located at the center of concave panel.The effect of concave panel is to further speed up gas In being uniformly distributed for flexible film surface；Meanwhile reducing direct impact of the gas vent gas jet to underface flexibility diaphragm area.

As shown in Figure 9 and Figure 10, when gas vent is along one-dimensional lineal layout, the encapsulation with uniform pressure that can be formed Layer is determined by following empirical equation: (P/P0) (D/h)≤L/d, wherein P is the gas pressure in encapsulation region, and P0 is Standard Gases Pressure, D are exhaust bore dia, and h is encapsulation work identity distance with a distance from flexible membrane, and L is the total length of one-dimensional exhaust pore size distribution, and d is The distance between equally distributed gas vent.The applicable condition of this formula is the rectangular area that width is no more than 8 centimetres, that is, is covered Rectangular area be 8L centimetres 2.Implement when design processing by the maximum working pressure (MWP) that encapsulated layer is carried.When width is more than 8 lis Rice and when less than 16 centimetres, gas vent invariable number but is staggered, and staggeredly distance is ≈ (W-8)/3, and wherein W is distributed areas Width is shown in Figure 10.

As shown in Figure 11 to 13, air slot is connected with gas vent.The purpose of air slot design is to touch flexibility in gas Before film, certain gas along flexible film surface is formed in encapsulated layer for elder generation and is distributed, the wink for reducing gas vent is facilitated When air-flow pulse.Air slot can further make entire flexible membrane keep excellent surface flatness.

The design of NCAP spray head air slot includes the air slot by gas vent and the place function of being formed by air slot Certain interconnection of all gas vents in area, such as the concatenation between adjacent air slot can be implemented by gas vent, shown in Figure 11； Or the interconnection for directly intersecting to form all gas vents between air slot can be further increased, as shown in figure 12.It is such to set Meter requires air slot in arc line shaped, and the maximum radian of camber line is located at gas vent, and maximum radian is greater than nearest two exhausts of connection The radian of hole circumference.Preferably, the air slot 1056 is straight line or curve, is arranged one between adjacent gas vent 1052 Or two air slots 1056, two air slots 1056 are symmetrical about the connecting line of gas vent 1052.

It is connected between adjacent gas vent 1052 by setting air slot 1056, the air slot between two gas vents 1052 1056 arrange in expanding；One or two air slot 1056, two air slots 1056 are set between adjacent gas vent 1052 It is symmetrical with the connecting line of gas vent 1052.As shown in figure 13, air slot 1056 is spliced in circular arc type or by arc line type；Camber line Type air slot stitching portion is connected to by direct crosspoint 1056a；The maximum radian of camber line is located at gas vent 1052, and maximum arc Degree is greater than the circumference arc of two gas vents 1052 of connection.

As shown in figure 11, air slot: the purpose of air slot design is to obtain the encapsulated layer of more uniform distribution, is especially existed Along the direction of flexible film surface.It in actual operation, is not each each row in order to reduce difficulty of processing and reduce process time Stomata all must be equipped with air slot, and can selectively apply air slot.As shown in Figure 11~Figure 13, first air guide 1/2 works Area and buffer area have air slot.Air slot is the circular trough for connecting two neighboring gas vent center.The cross section of air slot is Rectangle, circle, triangle or trapezoidal.Air slot 1056 is straight line or curve, is arranged one between adjacent gas vent 1052 A or two air slots 1056, two air slots 1056 are symmetrical about the connecting line of gas vent 1052.

The function that designing above may be implemented includes: to penetrate gas jet firstly, can use by the air slot of gas vent Rapidly to gas vent surrounding expanding while gas vent is discharged, provided by this method to the outgoing gas jet of each gas vent Buffering, to lower the impact force for being directly toward flexible membrane；Secondly, connecting the air slot design of all gas vents makes all exhausts Hole can rush flexible membrane to help further to reduce single gas vent by partly as a bigger gas vent It hits to act on and play and encapsulated layer uniformity is preferably controlled.

There is the encirclement of gas accumulator tank around first 1 workspace of air guide, first 2 workspace of air guide and buffer area, such as Fig. 5 and figure Shown in 6.Gas accumulator tank is responsible for making each spray head form a self-enclosed system all gas recycling in encapsulation work face System.First air guide 1, first air guide 2 are separately recovered.The end of gas accumulator tank connects the main air-channel system of NCAP.The width of accumulator tank is not More than 5mm, depth is no more than 3mm, generates local pressure fluctuation to prevent pressure drop.Usual gas accumulator tank passes through NCAP Main air-channel system is connected with powerful vacuum pump, and by the self regulating charactoristic of pump, the pressure further adjusted in encapsulated layer is flat Weighing apparatus.

Preferred embodiment is provided with around first air guide workspace 1054 and buffer area 1053 for the flat of all gas Weigh the gas accumulator tank 1055 recycled；The end of gas accumulator tank 1055 is connected with the main gas circuit air return system of NCAP.

It is arranged along straight line on the first air guide workspace 1054 of gas vent 1052, buffer area 1053 and gas barrier face 1051 Cloth is connected between adjacent gas vent 1052 by air slot 1056 on same straight line.

The face opposite with encapsulation work face 105 of spray head 100 as shown in figure 14 is complex function face 101.Complex function face 101 Stablize component 1012 and plasma generating means 1011 including adiabatic module 1013, mechanical strength.

As shown in figure 15, the construction profile schematic diagram of sprayer body, spray head are the technology controlling and process for realizing NCAP itself, need reality The multiple functions such as existing temperature control, insulation, pressure adjusting.At the same time, NCAP spray head, which is also devised to future, can carry a variety of gas The functional component of phase surface processing technique.For example, as shown in figure 15, structural strengthening component can be when jet size span be larger When the processing boundary line in encapsulation work face is longer, the structural deformation that self gravity generates is eliminated；Adiabatic module can completely cut off spray head It is relatively changed with extraneous heat, to guarantee that the technique in encapsulation work face requires temperature.The design of NCAP spray head must guarantee in spray head Portion contains biggish freedom and flexibility and arranges space, according to the functional requirement of extension, allows to load other functions from complex function face Module so that NCAP spray head can carry more techniques in following application, such as compact shown in Figure 15 etc. from Daughter generation module can make spray head have both ITO using required surface treatment capabilities.

Wherein, encapsulated layer is the gas blanket between encapsulation work face and flexible film surface, and thickness is the encapsulation of spray head Vertical range between working face and flexible film surface, is denoted as H.Encapsulated layer thickness plays particularly significant in NCAP packaging technology Effect, including distribution of the reactant molecule in encapsulated layer, transporting from gas vent to flexible film surface and encapsulated layer sheet The air dynamic behaviour of body all has close relationship with encapsulated layer thickness.

The gas jet that gas vent is discharged has to just could be formed with effect by the blocking feedback of flexible film surface Encapsulated layer and the recycling for forming gas.The regulation of encapsulated layer thickness is as follows: spray head is each spray by the way of working in pairs " electricity/gas/Mechanical course face " of head all can respectively extend a two spray head spacing adjusting devices at both ends, as shown in figure 15.Pass through Connection lead screw in regulating device, opens the gap between two spray heads, while being put into the gasket of precise thickness to realize encapsulation The accurate adjusting of thickness degree.Regulating mechanism shown in Figure 15, can also further connect motor or cylinder pushes, big to realize Automatic adjustment when amount spray head works together.

As shown in figure 18, electricity/gas/Mechanical course face is responsible for spray head and is integrated with pass electronic control, gas control and mechanical The integrated and installation of control unit.Such as electricity/gas/Mechanical course face -1 that Figure 18 shows, the intake channel interface containing spray head thereon 1058d GI1-GI5, heating module storehouse T1-T4, technological parameter is read and control interface S1-S2；While electricity shown in Figure 19/ Gas/Mechanical course face -2, thereon the return air path interface 1059a GO1-GO2 containing spray head, heating module storehouse T1-T4, technique Parameter is read and control interface S1-S2.Electricity/gas/Mechanical course face Integrated design is NCAP technique integrated automation control, The assembling of NCAP system modular and dilatation and daily maintenance and maintenance provide great convenience.

The side of spray head 100 is electricity/gas/Mechanical course face 102.Electricity/gas/Mechanical course the face 102 includes air inlet Face and deflation area, air inlet face include intake channel interface 1058d, heating module storehouse and technological parameter reading and control interface S1- S2；Deflation area includes return air path interface 1059a, heating module storehouse and technological parameter reading and control interface；Intake channel connects Mouth 1058d is connect with the main gas circuit gas handling system of NCAP, and return air path interface 1059a is connect with air return system.

As shown in figure 16, when mass production encapsulates, more spray heads is needed to combine to form pipeline system operation.At this point, each spray head Between connection will become extremely important.More spray head combination interfaces play the role of being guaranteed when more spray heads work side by side Spray head connects the encapsulation work face of all spray heads later in the same plane.Firstly, to guarantee more spray head combination ranks when processing Junction is exactly perpendicularly to adjacent encapsulation work face, electricity/gas/Mechanical course face and complex function face；Secondly, more spray head combinations The flatness of interface will be within 5 μm to reduce Interconnection error；Again, the rigidity prevented between more spray head combination interfaces connects It connects.Overall package working face directly can be guaranteed by the self-balancing effect between gravity and encapsulated layer itself buoyant gas Flatness, as shown in figure 16, the spacing of more spray heads combination interface of adjacent two spray head are no more than 1mm, this mode requires each The processing of spray head will ensure the high-precision accurate size error of size less than 10 μm, and spray head all surface keeps absolute upright； Meanwhile the carrying platform of spray head also requires the depth of parallelism and plane flatness≤10 μm of height, includes mechanical and thermal stability；? A large amount of spray heads connect more than 50 spray heads when cooperating, in addition to the self-balancing between gravity and encapsulated layer itself buoyant gas is made Except, it is also necessary to guarantee the flatness of overall package working face, such as more spray heads combination rank by other supplementary means Flexible connection between junction, as shown in figure 16.The face vertical with 200 conveying direction of material to be processed of spray head 100 is interface 104, interface 104 between multiple spray heads for connecting.

As shown in Figure 19 and Figure 25, spray head interior conduit is divided into two classes, and a kind of pipeline is admission line, is used for encapsulation work Gas vent in face and gas barrier face is connected with the upstream portion of the main air-channel system of NCAP, and design, which is necessary to ensure that, reaches institute There is the gas of gas vent to reach the number density of molecule in encapsulated layer uniformly and the requirement of stable gas pressure；Another kind of pipeline is muffler Road, for gas accumulator tank to be connected with the downstream part of the main air-channel system of NCAP, design, which needs to meet to carry, reacts secondary Rapid effective discharge of product and excess reactant molecular efforts gas, while the stable air dynamics ring of encapsulated layer is not influenced Border.

In Figure 19 and Figure 21,5 admission line openings are located at electricity/gas/Mechanical course face inlet end, label GI1- GI5.Respectively correspond: GI1- gas barrier face admission line, the air guide 1 of GI2- elder generation or 2 workspace admission lines, the buffer area GI3- into Feed channel, the air guide 1 of GI4- elder generation or 2 workspace admission lines, GI5- gas barrier face admission line.In fig. 8,2 exhaust pipes Road opening is located at electricity/gas/Mechanical course face exhaust end, label GO1, GO2.Each 1 gas barrier face of correspondence, an elder generation respectively The discharge of air guide workspace 1 or 2 and about 50% buffer area gas.The design of admission line and exhaust pipe meets condition: Σ The straight feed channel diameter in exhaust pipe diameter < 0.1, to guarantee spray head tail gas molecule containing excess reactant and byproduct of reaction etc. Effectively discharge rapidly.

Air inlet face includes five intake channel interface 1058d；Deflation area includes two return air path interface 1059a；Air inlet Access interface 1058d respectively with the gas vent 1052 on first air guide workspace 1054, buffer area 1053 and gas barrier face 1051 Connection, return air path interface 1059a are connect with gas accumulator tank 1055.

Wherein, an admission line, each air inlet pipe are respectively contained in first air guide 1,2 workspaces, buffer area, gas barrier face All gas vents in functional areas where road can be connected in series to it.Each gas vent can be connected by a linking pipeline It is connected to admission line, the effect for being connected pipeline is to further increase the pressure of gas vent outgoing air-flow and prevent near exit portal Turbulent flow/backflow phenomenon.Its Sizing requirements is (d1-d2)/2H > 0.1.As shown in figure 24, wherein d1 is in linking pipeline Diameter, d2 are exhaust bore dia, and H is linking duct length.Air inlet pipe interior diameter is typically designed as the Σ of d0 > 10 (d2), i.e. air inlet Pipeline interior diameter is greater than 10 times that all exhaust bore dias in the functional areas of place are added summation.Its purpose is to guarantee abundance Air inflow, so that other gas vents will not be impacted by making the exhaust of each gas vent, to guarantee the air of encapsulated layer Dynamic stability.

Wherein, the main gas circuit air return system of NCAP includes: return-air duct 1059, and return-air duct 1059 is arranged in spray head 100 Portion；Return-air is connected pipeline 1057a, and return-air linking one end pipeline 1057a is connected to return-air duct 1059, and return-air duct 1059 is another End connection gas accumulator tank 1055.

The main gas circuit gas handling system of the NCAP includes: admission line 1058, and admission line 1058 is arranged in spray head 100 Portion；And linking pipeline 1057, linking pipeline 1057 are connected to admission line 1058, each linking pipeline 1057 connects an exhaust Hole 1052.

In the junction of admission line and the main air-channel system of NCAP, since caliber changes to greatly from the main air-channel system of small NCAP NCAP spray head admission line, in order to prevent in the turbulent flow reflux of junction and in order to reduce going out for turbulent flow in spray head admission line It is existing, a miniature adjusting cavity can be connected between admission line and the main gas circuit of system.The miniature adjusting cavity is designed as a taper Cylinder-like part, as shown in figure 26.Its design requirement is arctan (d1-d2)/2L < arctan (200/Re), and wherein d1 is spray Head admission line interior diameter, d2 are the main air-channel system pipeline interior diameter of NCAP, and L is the length of miniature adjusting cavity along fluid flowing side To Re is that spray head admission line inputs gas Reynolds number.

As shown in figure 25, return-air duct is connected with the gas accumulator tank in encapsulation work face.In order to keep gas to recycle Balance, gas accumulator tank connection tube symmetrical in encapsulation work face both ends symmetrical openings connection return-air duct, Figure 26. For the processing respectively of tail gas, first 1 workspace of air guide is separately connected different return-airs from the gas accumulator tank of 2 workspace of first air guide Pipeline.Air inlet and return-air duct inside each spray head constitute one together with gas vent, gas accumulator tank and linking pipeline A organic whole gas return path.The interior diameter design principle of exhaust pipe is that the area summation of all exhaust pipe cross sections is wanted Less than the 10% of the area summation of all admission line cross sections, i.e. Σ S arrange < 0.1 Σ S into.The purpose is in the body that can not calm the anger Under the premise of mass flux is constant, increase the gas flow rate of exhaust pipe by the difference in areas of admission line and exhaust pipe, To guarantee rapid effective discharge that spray head tail gas contains excess reactant molecule and byproduct of reaction etc..Exhaust pipe would generally It is connected with powerful vacuum pump or other gas extraction arrangements, prevents to go out in spray head to further ensure that the smooth discharge of air-flow Penetrate the backflow phenomenon at end.NCAP technology has the real-time trimming system of total system pressure specially researched and developed, and cooperates gas extraction arrangement Realize that any gas flow optimized node of total system includes the connecting node of NCAP spray head discharge line Yu the main gas circuit downstream part NCAP Zero reflux, can subsequent technology explanation in be discussed in detail with reference to NCAP encapsulation technology illustrate -2: aerodynamics assist in synchronization Pressure commutation instants system.

Although specific embodiments of the present invention are described in conjunction with attached drawing above, the invention is not limited to upper The specific embodiment stated, above-mentioned specific embodiment are only schematical, directiveness rather than restrictive.This The those of ordinary skill in field under the enlightenment of this specification, in the feelings for not departing from scope of the claimed protection of the invention Under condition, a variety of forms can also be made, these belong to the column of protection of the invention.

Claims

1. a kind of flexible membrane surface treatment method, which comprises the following steps:

The tractive force of traction flexible membrane movement is provided；

The first gas thin layer for spraying to flexible membrane first surface is provided；First gas thin layer includes at least first air guide of two-way first Face gas blanket is isolated in layer, first buffering area gas blanket and first gas；First buffering area gas blanket is in the first air guide of two-way first Between layer, first gas be isolated face gas blanket the surrounding of the first first air guiding layer and first buffering area gas blanket be used for the external world every From；Wherein, the first first air guiding layer is the mixing gas of working gas and reactant molecule, for flexible membrane table/interface object Physicochemical reaction；First buffering area gas blanket and first gas isolation face gas blanket are working gas；Working gas is lazy Property gas；

The first gas recovery layer of reversed flexible membrane first surface is provided, the first gas recovery layer is poor by the flowing pressure of gas Movement is for forming gas occluding to the first first air guiding layer, first buffering area gas blanket and first gas isolation face gas blanket； The first gas recovery layer is the working gas of recycling.

2. flexible membrane surface treatment method according to claim 1, which is characterized in that further include:

The second gas thin layer for spraying to flexible membrane second surface is provided；Second gas thin layer includes at least first air guide of two-way second Face gas blanket is isolated in layer, second buffering area gas blanket and second gas；Second buffering area gas blanket is in the first air guide of two-way second Between layer, second gas be isolated face gas blanket the surrounding of the second first air guiding layer and second buffering area gas blanket be used for the external world every From；

The second gas recovery layer of reversed flexible membrane second surface is provided, the second gas recovery layer is to the second first air guiding layer, second Buffer area gas blanket and second gas isolation face gas blanket form gas occluding.

3. flexible membrane surface treatment method according to claim 2, which is characterized in that first gas thin layer and second gas The thickness of thin layer is less than 200 μm.

4. flexible membrane surface treatment method according to claim 2, which is characterized in that first gas thin layer and second gas Coating interior reactant molecule is uniformly distributed and interior point pressure is identical.

5. flexible membrane surface treatment method according to claim 2, which is characterized in that first gas thin layer and second gas Thin layer enables in the contactless flatness for clamping and keeping flexible film surface of intermediate flexible membrane.

6. flexible membrane surface treatment method according to claim 1 or 2, which is characterized in that the reactant molecule exists Three regions are undergone in flowing gas and are finally transported to flexible film surface, and Surface Physical Chemistry reaction, three regions difference occur For laminar convection area, Convention diffusion area and diffusion region；

Laminar convection area is flowing gas in the conveying parallel direction with flexible membrane, keeps speed when injection, reactant point Son is transported by convection action；Convention diffusion area is opened after flowing gas enters the aerodynamics boundary layer of flexible film surface Begin to slow down, reactant molecule is transported by the collective effect of convection current and diffusion；Diffusion region is in nearly flexible film surface, gas stream Speed is reduced until body surface flow velocity is reduced to zero, and reactant molecule is finally transported to body surface by diffusion.

7. flexible membrane surface treatment method according to claim 6, which is characterized in that

Reactant molecule transporting in flowing gas, adsorption and growth will be carried out by following equation:

Wherein, c: reactant molecule number density；

T: time variable；

X: along flexible membrane transmission direction space variable；

Q_NCAP: NCAP transmission exhausts parameter, is derived from adsorption, with diffusion region thickness, flexible film surface energy and surface topology knot Structure is related, Q_NCAP∝σh^-1/2E_Aθ^2/3, wherein σ represents flexible film surface viscosity, and h is aerodynamic boundary layer thickness, E_A Energy is driven for adsorption, θ represents flexible membrane initial surface capture position topological structure coefficient；

P_NCAP: NCAP process control parameter is defined asWherein η represents initial surface reaction Probability, inert polymer are about 0.53, and surface-active polymer and living polymer are about 0.9, k_BIt is normal for Boltzmann Ripe, T is reaction temperature, E_aFor surface reaction activity, v_thFor the hot movement speed of reactant molecule, H is encapsulated layer thickness, and D is Reactant molecule and the intermolecular diffusion coefficient of working gas；

ξ: total surface reaction probabilities, related with molecular scattering section and total molecular number, in flexible film surface, ξ is usually set at In 0.55~0.85 range；

Ф: NCAP encapsulating film surface coverage.

8. flexible membrane surface treatment method according to claim 7, which is characterized in that when handling inert polymer, P_NCAP Value is 30-50, Q_NCAPControl is 0.68 or so；When handling surface-active polymer, P_NCAPValue is 155-270, Q_NCAPControl Produce 0.53；When handling living polymer, P_NCAPValue is 300-500, Q_NCAPValue 0.35.

9. a kind of gas injection apparatus characterized by comprising

Conveying device, for providing the tractive force of traction flexible membrane (200) movement；

And first spray head, for providing the first gas thin layer for spraying to flexible membrane first surface, first gas thin layer includes at least Face gas blanket is isolated in the first air guiding layer of two-way first, first buffering area gas blanket and first gas；The first spray head includes:

Sprayer body, for providing support；

Encapsulation work face (105), described encapsulation work face (105) setting on sprayer body surface, and encapsulation work face (105) with Flexible membrane (200) surface is oppositely arranged；The encapsulation work face (105) has multiple along the gas vent linearly arranged (1052), gas vent (1052) is used to form first gas thin layer in flexible membrane (200) first surface；The gas vent (1052) include:

First air guide gas vent (1052a)；For providing the first first air guiding layer；First air guide gas vent (1052a) has two column, two column First air guide gas vent (1052a) provides two kinds of reaction gas respectively；

Buffering exhaust hole (1052b), buffering exhaust hole (1052b) are connect with the second road admission line for providing first buffering area Gas blanket；

Gas barrier gas vent (1052c), gas barrier gas vent (1052c) are connect for providing the with third road admission line One gas barrier face gas blanket；Wherein, for first buffering area gas blanket between the first air guiding layer of two-way first, face is isolated in first gas Gas blanket is in the surrounding of the first first air guiding layer and first buffering area gas blanket for being isolated from the outside；Wherein, the first first air guiding layer The mixing gas of working gas and reactant molecule, for flexible membrane table/interface physical-chemical reaction；First buffering area Gas blanket and first gas isolation face gas blanket are working gas；Working gas is inert gas；

And gas accumulator tank (1055), the periphery of first air guide gas vent (1052a) is arranged in gas accumulator tank (1055), for mentioning For the first gas recovery layer of reversed flexible membrane first surface, the first gas recovery layer is moved by the flowing pressure difference of gas and is used In to the first first air guiding layer, first buffering area gas blanket and first gas isolation face gas blanket formation gas occluding；Described First gas recovery layer is the working gas of recycling.

10. gas injection apparatus according to claim 9, which is characterized in that further include:

11. gas injection apparatus according to claim 9 or 10, which is characterized in that on the encapsulation work face (105) Include:

First air guide workspace (1054) week is arranged at least two first air guide workspaces (1054), the gas accumulator tank (1055) Enclose groove；Gas vent on first air guide workspace (1054) is first air guide gas vent (1052a), first air guide gas vent (1052a) Injection direction it is vertical with the conveying direction of flexible membrane (200), for provide be made of reactant molecule and working gas with The reaction gas of flexible membrane table/interface physical-chemical reaction；

Buffer area (1053), buffer area (1053) setting is between two neighboring first air guide workspace (1054), buffer area (1053) gas vent on is buffering exhaust hole (1052b), and buffering exhaust hole (1052b) is for providing two, interval first air guide work Make the working gas of area (1054) reaction gas；

Gas barrier face (1051), gas barrier face (1051) are arranged along the edge of encapsulation work face (105), gas barrier face (1051) gas vent on is gas barrier gas vent (1052c), and gas barrier gas vent (1052c) is used for encapsulation work face (105) it is isolated with perimeter.

12. gas injection apparatus according to claim 9 or 10, which is characterized in that the outlet of each gas vent (1052) Surrounding is provided with exhaust buffering concave surface (1052d)；The opening diameter of the concave panel of exhaust buffering concave surface (1052d) meets formula (P/2P₀)≤d/h, the P in formula are sprinkler design operating air pressure, P₀For standard pressure, d is the opening diameter of concave panel, and h is row Stomata and fluid control plane datum level distance, fluid control plane are encapsulation work face and the common physical plane of gas barrier.

13. gas injection apparatus according to claim 9 or 10, which is characterized in that the gas vent (1052) is right Arrange and meet on the region answered: adjacent gas vent (1052) is arranged along straight line or adjacent gas vent (1052) staggered row Cloth；

When gas vent is along lineal layout, the distance between exhaust bore dia, the total length for being vented pore size distribution and gas vent, which meet, to be closed It is formula: (P₁/P₀)(D/h₁)≤L/d₁；Wherein, P₁For the gas pressure in encapsulation region, P₀For standard pressure, D is that gas vent is straight Diameter, h₁It is encapsulation work face at a distance from flexible membrane, L is the total length for being vented pore size distribution, d₁For the distance between gas vent；

Identical when number is with along lineal layout when gas vent is staggered, staggeredly distance ≈ (W-8)/3, wherein W is gas vent institute In distributed areas width.

14. gas injection apparatus according to claim 9 or 10, which is characterized in that between adjacent gas vent (1052) It is connected by setting air slot (1056), the air slot (1056) between two gas vents (1052) is arranged in expanding；It is adjacent Gas vent (1052) between one or two air slot (1056) is set, two air slots (1056) are with gas vent (1052) Connecting line is symmetrical；

The air slot (1056) is spliced in circular arc type or by arc line type；Arc line type air slot stitching portion is by directly intersecting Point (1056a) connection；The maximum radian of camber line is located at gas vent (1052), and maximum radian is greater than two gas vents of connection (1052) circumference arc.

15. gas injection apparatus according to claim 9 or 10, which is characterized in that it further include gas closed circulation system system, The gas closed circulation system system is arranged inside sprayer body comprising air return system and air inlet for transport gas System；

Gas vent (1052) is connect for forming first gas thin layer in flexible membrane (200) first surface with the gas handling system；

The end of gas accumulator tank (1055) connect the first recycling for providing reversed flexible membrane first surface with air return system Gas blanket.

16. gas injection apparatus according to claim 15, which is characterized in that the air return system includes:

Return-air duct (1059), return-air duct (1059) are arranged inside sprayer body；

And return-air linking pipeline (1057a), return-air are connected pipeline one end (1057a) connection return-air duct (1059), return-air duct (1059) other end connection gas accumulator tank (1055)；

The gas handling system includes:

Admission line (1058), admission line (1058) are arranged inside sprayer body；

And linking pipeline (1057), linking pipeline (1057) are connected to admission line (1058), each linking pipeline (1057) is even Connect a gas vent (1052).

17. material surface according to claim 16 handles injection apparatus, which is characterized in that admission line (1058) connection Place is provided with a miniature adjusting cavity (1058-1), which is tapered cylinder shape component；Miniature adjusting The design requirement of chamber (1058-1) is arctan (d₀-d₃)/2L<arctan(200/R_e), wherein d₀For admission line interior diameter, d₃ For main air-channel system pipeline interior diameter, L is the length of miniature adjusting cavity, R_eGas Reynolds number is inputted for spray head admission line.