CN102672958B - Preparation method of TiO2 coating type polyurethane (PU) or thermoplastic polyurethane (TPU) film drag reduction micro-groove used for airship skins - Google Patents

Preparation method of TiO2 coating type polyurethane (PU) or thermoplastic polyurethane (TPU) film drag reduction micro-groove used for airship skins Download PDF

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CN102672958B
CN102672958B CN201210168760.4A CN201210168760A CN102672958B CN 102672958 B CN102672958 B CN 102672958B CN 201210168760 A CN201210168760 A CN 201210168760A CN 102672958 B CN102672958 B CN 102672958B
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tio
preparation
tpu film
groove
coating
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CN102672958A (en
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刘宇艳
谭惠丰
马涛
刘振国
刘羽熙
刘少柱
王长国
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Harbin Institute of Technology
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Abstract

The invention provides a preparation method of TiO2 coating type polyurethane (PU) or thermoplastic polyurethane (TPU) film drag reduction micro-groove used for airship skins, relates to the preparation method of airship skin materials, and aims to solve the problems that the existing stratosphere airship skin is poor in weather resisting property, large in resistance, poor in thermal insulation, low in load and large in volume. The method comprises the following steps of preparing TiO2 sol precursor liquid, coating a TiO2 coating on PU or TPU film to be stamped, preparing aluminum template with a groove structure, washing the template and coating a demolding agent; and stamping the template at a temperature of 135-140 DEG C and a speed of 15-20 kg/cm<2>. The prepared TiO2 coating type PU or TPU film drag reduction micro-groove is clear in marks, good in regularity and prominent in damping reduction effect, and plays significant roles in reducing airship volume, improving load and prolonging time in air; and meanwhile, the TiO2 coating can strongly absorb ultraviolet, can shielding atom oxide, reduce harm of ultraviolet to the film, and increase the weather resisting property. The method provided by the invention can be used for preparing airship skin materials.

Description

Airship envelope TiO 2the preparation method of application type PU or the micro-groove of TPU film drag reduction
Technical field
The present invention relates to the preparation method of airship sheath material.
Background technology
Nearly space also can be called near space, near space, and meanwhile, this is highly also the region at stratosphere place, is on the natural phenomena active layers such as wind and rain thunder and lightning, belongs to high safety area.Enter after 21 century, the value of nearly this special dimension of space is more and more subject to the attention of countries in the world, and each military power has been considered as it the frontier of 21st century military struggle one after another.In recent years, caused worldwide common concern using near space dirigible as the application study of communication navigation platform.In the process of development near space dirigible, related key technical problem is the emphasis that various countries endeavour research at present.Because near space dirigible is not low latitude dirigible, many conceptive what develop, as all completely different in low latitude dirigible in the key technologies such as working environment, skin material, the energy, power propelling, many aspects are faced with great challenge.The existing dirigible demonstration test that enters near space for four times, feasibility and the using value of near space airship platform are proved, the problem in science that has proposed many keys in its application process is urgently to be resolved hurrily, wherein, how effectively reducing windage by the micro-groove of design skin-surface is one of key problem of target while realizing the long boat of large-scale near space dirigible.
Be subject to the inspiration of large nature, research is found, can effectively reduce surface of moving object frictional resistance by reasonably laying certain groove at surface of moving object.In recent years, in world wide, rigid face groove drag-reduction effect and drag reduction mechanism are carried out to a certain amount of research, and partly carried out engineering application numerical simulation and experimental verification, and thought that groove drag reduction technology is current optimal surperficial drag reduction method.
At present, although groove drag reduction technology has been applied on aircraft and naval vessels, the research that is aimed at the groove drag reduction of this flexible substrate of covering there is not yet report.Be different from general rigid face high reynolds number aircraft surface groove drag reduction, the flow field near space dirigible surface is mainly thin low velocity gas, has low reynolds number operation characteristic; Meanwhile, near space dirigible is the flexible structure of a quasi-representative, and utricule carries part under effect at wind large deformation very easily occurs, and the groove on utricule surface is also flexible micro-fold, has deformable speciality under Flow Field outside effect, and easy and Flow Field outside is coupled.Large-scale near space dirigible is surrounded and is formed by flexible covering material, and its resistance mainly contains pressure drag and hull skin friction resistance composition.Because dirigible has larger surface area, reduce skin friction resistance and can reduce by a relatively large margin the drag overall of hull.Therefore, the preparation technology of the micro-groove in research skin material surface is most important.
Research about micro-groove preparation method in domestic and foreign literature can be divided into: the methods such as Fine Machinery processing (as microscopic carvings quarters, micro-forging and stamping etc.), laser ablation method, soft lithographic technique and the hot padding method of forming.If the people such as the Zhang Deyuan of BJ University of Aeronautics & Astronautics are taking pretreated sharkskin as micro-masterplate that copies, utilize the soft mould technology in soft carving technology to prepare silicon rubber matter elasticity negative template, taking the graft copolymer of aqueous epoxy resins and polyacrylamide as base material, elasticity negative template is carried out to replica and turn over mould, a kind of composite anti-drag sharkskin that has nanometer long-chain drag reduction interface and micron true to nature groove pattern concurrently that is shaped, but yet there are no pertinent literature report for micro-groove preparation method of flexible thin-film material at present.
Sol-gal process is prepared TiO 2coating is mainly used in photocatalysis and anti-corrosion of metal field, conventional TiO 2preparation technology of coating has sol-gal process, sputtering method, hydro-thermal method, the precipitation method, vapour deposition process etc., and wherein sol-gal process is prepared Ti0 2coating is compared with additive method, has equipment simple, easily large area film, and technological temperature is low, and coating is even, fine and close, and chemical composition is the advantage such as controls easily, is research and widely used a kind of wet chemistry methods at present.But current to TiO 2durability of coating research is relatively less, to the Research on Weatherability of the complicated stratosphere environment of height just still less.
Summary of the invention
The present invention will solve the problem that existing stratospheric airship covering weatherability is poor, resistance is large, thermal insulation is poor, load is low and build is large, and a kind of airship envelope TiO is provided 2the preparation method of application type PU or the micro-groove of TPU film drag reduction.
Airship envelope TiO of the present invention 2the preparation method of application type PU or the micro-groove of TPU film drag reduction carries out according to the following steps:
One, preparation TiO 2precursor sol liquid:
A, take butyl titanate, absolute ethyl alcohol, strong acid, deionized water and glacial acetic acid, wherein the ratio of the amount of substance of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid is 1: 10: 3: 1, and H in the amount of substance of butyl titanate and strong acid +the ratio of amount of substance be 1: (0.6～1); Described strong acid is concentrated hydrochloric acid, red fuming nitric acid (RFNA) or the concentrated sulfuric acid;
B, get two conical flasks, be labeled as A and B, the absolute ethyl alcohol measuring in step a is divided into 3 parts, wherein 2 parts are placed in conical flask A, 1 part is placed in conical flask B, then the glacial acetic acid measuring in step a is joined in conical flask A, under the condition stirring, in conical flask A, add the butyl titanate measuring in step a, stir 20～25min;
C, the strong acid measuring in step a and deionized water are joined in conical flask B, after shaking up, the mixed liquor in conical flask B is transferred in the conical flask A processing through step b, stir after 5～10min, the mixed liquor in conical flask A is transferred in there-necked flask;
D, the there-necked flask in step c is placed in to the water-bath of 40～45 DEG C, stirs 1h, naturally cooling, standing 5～7 days, obtain TiO 2precursor sol liquid;
Two, e, PU or the TPU film of wish impression are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 20～30min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 5～10min, completes the preparation of one deck coating in early stage;
F, the PU or the TPU film that are coated with coating in one deck early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 40～60min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 10～15min, completes the preparation of final coating;
Three, g, employing ultraprecise microfabrication machine tool system process surface and have the Al pallet of " V " type groove structure, described " V " type groove forms and replaces penetrating rill on Al pallet surface, the width s of each rill is 90～110 μ m, and degree of depth h is 90～110 μ m;
H, by acetone ultrasonic cleaning 15～20min for Al pallet prepared in step g, after oven dry, first apply three layers of clean film, then apply three layers of hole sealing agent, finally apply three layers of aqueous release agent, the coating time of every one deck is spaced apart 15～20min;
Four, TiO step 2 being obtained 2the Al pallet that application type PU or TPU film and step 3 obtain is put into 110～115 DEG C of baking oven preheating 15～20min, then Al pallet is fixed on the pressure head of hot stamp machine, on the plummer of hot stamp machine, place quartz glass substrate, by the TiO of preheating 2application type PU or TPU film are laid in quartz glass substrate, fall pressure head, treat Al pallet and TiO 2after application type PU or the contact of TPU film, boost to 15～20kg/cm 2, be that 135～140 DEG C, pressure are 15～20kg/cm in temperature 2condition under, impression 15～20min, stops heating, naturally cooling, and pressurize 2～3h, removes pressure, lifts pressure head, completes airship envelope TiO 2the preparation of application type PU or the micro-groove of TPU film drag reduction.
The hot padding mechanism of thin-film material of the present invention is analyzed as follows:
The hot padding of thin-film material is that the heat flow moulding based on polymer realizes graph copying.When template graphics size is less, when periodically strong, polymer easily shifts completely, and template graphics can copy in polymeric substrates well; When template graphics size is very large, polymer shifts incomplete and inherent lax behavior meeting and occurs various special patterns in patterned area and adjacent domain thereof.Its mechanism can be described as: template is pressed in polymer, polymer under template convex region is pressed in the cavity between adjacent two convex regions, and rise along cavity sidewalls, and the interior original polymer of cavity is owing to being subject to the extruding of two side liquids, distortion can raise up, intersection in two fluid streams forms two contacts, along with the prolongation of impression time, the polymer of both sides constantly pushes in cavity, original polymer constantly compresses rising, last whole cavity is filled, through thermal balance after a while, separate template and substrate, just obtain patterned polymer.Fig. 5 is polymer-filled mechanism schematic diagram in hot padding process, and downward arrow represents that template imposes on the extruding force of film, and arrow upwards represents that substrate imposes on the extruding force of film, and middle arrow represents the flow direction of film under pressure.If larger at moulding process applied pressure, the polymer under template projection flows into after cavity, due to capillary effect, first form small hill one by one, if polymer is enough thick, impression time long enough, small hill can be fused into and be integrated gradually, realizes the filling completely of cavity.
It is simple that the sol-gal process using in the present invention has equipment, easily large area film, technological temperature is low, the advantages such as coating is even, fine and close, consider in application aspect of the present invention does not need high degree of crystallinity (only to need to meet fine and close, even to reach photocatalysis or anti-corrosion of metal performance simultaneously, thinner thickness, finally can be to elemental oxygen and ultraviolet shielded) and the situation of fexible film PU or TPU pyrolytic, the TiO of preparation herein 2coating, without high-temperature calcination processing, is compared calcination processing sol-gal process and is prepared TiO 2coating, coating nerve is lower, crackle is less.And collosol and gel covers 2～3 layers of TiO 2coating, has effectively filled up because ground floor coating and matrix material thermal coefficient of expansion differ the crack defect causing compared with greatly, considers coating preparation process temperature lower, the coating densification that makes, evenly, flawless, to film better protecting effect.
PU or TPU film itself have good ageing-resistant performance, and hot padding is front to PU or TPU thin film coated TiO 2, make a large amount of elemental oxygens of PU or TPU film and stratosphere space isolated, greatly alleviate the oxidation under PU or TPU film ultra-violet radiation condition, simultaneously TiO 2coating itself has more by force and absorbs ultraviolet, has reduced the injury of ultraviolet to PU or TPU film.The prepared TiO of the present invention 2the TiO of application type PU or TPU film 2coating densification, even, flawless, all have good shield effectiveness to elemental oxygen, ultraviolet ray; The TiO of preparation 2the micro-groove rill of application type PU or TPU film drag reduction clearly, regularity is good, drag-reduction effect is outstanding, for further reducing dirigible volume, improve load, the time in sky that extends plays an important role, and is a kind of simple and convenient, direct method of raising PU efficient, with low cost or the resistance to marquis of TPU film, resistance reducing performance.
The present invention is for the preparation of airship sheath material.
Brief description of the drawings
Fig. 1 is airship sheath material structural representation; Wherein 1 represent weathering layer, 2 represent bearing layer, and 3 represent barrier layer, and 4 represent hot sealing layer;
Fig. 2 is thermal imprint process sample assembly figure of the present invention, wherein 5 represents Al pallet, and 6 represent PU or TPU film, and 7 represent quartz glass substrate;
Fig. 3 is Al pallet, PU or TPU film and the quartz glass substrate schematic diagram in hot pressing of the present invention;
Fig. 4 is that hot-forming the obtained surface of the present invention has the PU of " V " type groove or the cross sectional representation of TPU film;
Fig. 5 is polymer-filled mechanism schematic diagram in hot padding process;
Fig. 6 is the photo (top observation) on the prepared Al pallet surface of embodiment mono-;
Fig. 7 is the photo (side observation) on the prepared Al pallet surface of embodiment mono-;
Fig. 8 is the prepared TiO with the micro-groove structure of drag reduction of embodiment mono- 2the photo (top observation) of application type PU film surface;
Fig. 9 is the prepared TiO with the micro-groove structure of drag reduction of embodiment mono- 2the photo (side observation) of application type PU film surface;
Figure 10 is the prepared TiO with the micro-groove structure of drag reduction of embodiment bis- 2the photo (top observation) of application type TPU film surface;
Figure 11 is the prepared TiO with the micro-groove structure of drag reduction of embodiment bis- 2the photo (side observation) of application type TPU film surface;
Figure 12 is the airship envelope TiO that surface that embodiment mono-makes has the micro-groove structure of drag reduction 2the TiO of application type PU film 2the stereoscan photograph of coating surface;
Figure 13 is the airship envelope TiO that surface that embodiment mono-makes has the micro-groove structure of drag reduction 2the TiO of application type PU film 2be coated with the stereoscan photograph of layer cross section;
Figure 14 is the enlarged drawing of Figure 12;
Figure 15 is that surface is coated with TiO 2the ultraviolet of the quartz glass A of coating sees through spectrogram;
Figure 16 is that surface is coated with TiO 2the ultraviolet of the quartz glass B of coating sees through spectrogram;
Figure 17 is three-dimensional model gridding division figure;
Figure 18 is speed of incoming flow while being 10m/s, flows to cross section speed cloud atlas;
Figure 19 is near speed cloud atlas groove;
Figure 20 is smooth plates superficial velocity cloud atlas;
Figure 21 flows to cross section vortex strength degree cloud charts;
Figure 22 is near vortex strength cloud charts groove;
Figure 23 is that near the z of groove is to shear stress.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: present embodiment airship envelope TiO 2the preparation method of application type PU or the micro-groove of TPU film drag reduction carries out according to the following steps:
One, preparation TiO 2precursor sol liquid:
A, take butyl titanate, absolute ethyl alcohol, strong acid, deionized water and glacial acetic acid, wherein the ratio of the amount of substance of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid is 1: 10: 3: 1, and H in the amount of substance of butyl titanate and strong acid +the ratio of amount of substance be 1: (0.6～1); Described strong acid is concentrated hydrochloric acid, red fuming nitric acid (RFNA) or the concentrated sulfuric acid;
B, get two conical flasks, be labeled as A and B, the absolute ethyl alcohol measuring in step a is divided into 3 parts, wherein 2 parts are placed in conical flask A, 1 part is placed in conical flask B, then the glacial acetic acid measuring in step a is joined in conical flask A, under the condition stirring, in conical flask A, add the butyl titanate measuring in step a, stir 20～25min;
C, the strong acid measuring in step a and deionized water are joined in conical flask B, after shaking up, the mixed liquor in conical flask B is transferred in the conical flask A processing through step b, stir after 5～10min, the mixed liquor in conical flask A is transferred in there-necked flask;
D, the there-necked flask in step c is placed in to the water-bath of 40～45 DEG C, stirs 1h, naturally cooling, standing 5～7 days, obtain TiO 2precursor sol liquid;
Two, e, PU or the TPU film of wish impression are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 20～30min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 5～10min, completes the preparation of one deck coating in early stage;
F, the PU or the TPU film that are coated with coating in one deck early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 40～60min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 10～15min, completes the preparation of final coating;
Three, g, employing ultraprecise microfabrication machine tool system process surface and have the Al pallet of " V " type groove structure, described " V " type groove forms and replaces penetrating rill on Al pallet surface, the width s of each rill is 90～110 μ m, and degree of depth h is 90～110 μ m;
H, by acetone ultrasonic cleaning 15～20min for Al pallet prepared in step g, after oven dry, first apply three layers of clean film, then apply three layers of hole sealing agent, finally apply three layers of aqueous release agent, the coating time of every one deck is spaced apart 15～20min;
Four, TiO step 2 being obtained 2the Al pallet that application type PU or TPU film and step 3 obtain is put into 110～115 DEG C of baking oven preheating 15～20min, then Al pallet is fixed on the pressure head of hot stamp machine, on the plummer of hot stamp machine, place quartz glass substrate, by the TiO of preheating 2application type PU or TPU film are laid in quartz glass substrate, fall pressure head, treat Al pallet and TiO 2after application type PU or the contact of TPU film, boost to 15～20kg/cm 2, be that 135～140 DEG C, pressure are 15～20kg/cm in temperature 2condition under, impression 15～20min, stops heating, naturally cooling, and pressurize 2～3h, removes pressure, lifts pressure head, completes airship envelope TiO 2the preparation of application type PU or the micro-groove of TPU film drag reduction.
The Al pallet that surface of the present invention has " V " type groove structure utilizes Harbin Institute of Technology's ultraprecise microfabrication machine tool system to process; What impression instrument adopted is the hot stamp machine that German Suss MicroTechnology company produces.Present embodiment clean film, hole sealing agent and aqueous release agent used is commercially available prod.
It is simple that the sol-gal process using in present embodiment has equipment, easily large area film, technological temperature is low, the advantages such as coating is even, fine and close, consider in application aspect of the present invention does not need high degree of crystallinity (only to need to meet fine and close, even to reach photocatalysis or anti-corrosion of metal performance simultaneously, thinner thickness, finally can be to elemental oxygen and ultraviolet shielded) and the situation of fexible film PU or TPU pyrolytic, the TiO of preparation herein 2coating, without high-temperature calcination processing, is compared calcination processing sol-gal process and is prepared TiO 2coating, coating nerve is lower, crackle is less.And collosol and gel covers 2～3 layers of TiO 2coating, has effectively filled up because ground floor coating and matrix material thermal coefficient of expansion differ the crack defect causing compared with greatly, considers coating preparation process temperature lower, the coating densification that makes, evenly, flawless, to film better protecting effect.
PU or TPU film itself have good ageing-resistant performance, and hot padding is front to PU or TPU thin film coated TiO 2, make a large amount of elemental oxygens of PU or TPU film and stratosphere space isolated, greatly alleviate the oxidation under PU or TPU film ultra-violet radiation condition, simultaneously TiO 2coating itself has more by force and absorbs ultraviolet, has reduced the injury of ultraviolet to PU or TPU film.The prepared TiO of present embodiment 2the TiO of application type PU or TPU film 2coating densification, even, flawless, all have good shield effectiveness to elemental oxygen, ultraviolet ray; The TiO of preparation 2the micro-groove rill of application type PU or TPU film drag reduction clearly, regularity is good, drag-reduction effect is outstanding, for further reducing dirigible volume, improve load, the time in sky that extends plays an important role, and is a kind of simple and convenient, direct method of raising PU efficient, with low cost or the resistance to marquis of TPU film, resistance reducing performance.
Detailed description of the invention two: present embodiment is different from detailed description of the invention one: the mass fraction of concentrated hydrochloric acid described in step a is 37.5%, the mass fraction of red fuming nitric acid (RFNA) is 65%, the mass fraction of the concentrated sulfuric acid is 70%.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is different from detailed description of the invention one or two: the stirring in step b adopts electric mixer, and mixing speed is 150～180r/min.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is different from one of detailed description of the invention one to three: the stirring in step c and steps d adopts electric mixer, and mixing speed is 180～200r/min.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is different from one of detailed description of the invention one to four: in step 2, complete after the preparation of one deck coating in early stage, the PU or the TPU film that are coated with one deck coating in early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, then prepare coating in second layer early stage according to the parameter of step e, finally the PU or the TPU film that are coated with coating in two-layer early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, according to the parameter of step f, complete the preparation of final coating.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is different from one of detailed description of the invention one to five: the thickness of PU described in step e or TPU film is 98～102 μ m.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment is different from one of detailed description of the invention one to six: in step g, the length of Al pallet is 50～52mm, width is 50～52mm, thickness is 5～8mm.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment is different from one of detailed description of the invention one to seven: step 4 is that 136～138 DEG C, pressure are 16～18kg/cm in temperature 2condition under, impression 15～20min.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention nine: present embodiment is different from one of detailed description of the invention one to seven: step 4 is that 135 DEG C, pressure are 15kg/cm in temperature 2condition under, impression 20min.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention ten: present embodiment is different from one of detailed description of the invention one to nine: adopting surface to have the Si template of " V " type groove structure or Ni template substitution tables mask has the Al pallet of " V " type groove structure.Other is identical with one of detailed description of the invention one to nine.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment mono-:
The present embodiment airship envelope TiO 2the preparation method of the micro-groove of application type PU film drag reduction carries out according to the following steps:
One, preparation TiO 2precursor sol liquid:
A, take hydrochloric acid solution, deionized water and glacial acetic acid that butyl titanate, absolute ethyl alcohol, mass fraction are 37.5%, wherein the ratio of the amount of substance of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid is 1: 10: 3: 1, and H in the amount of substance of butyl titanate and hydrochloric acid solution +the ratio of amount of substance be 1: 0.8;
B, get two conical flasks, be labeled as A and B, the absolute ethyl alcohol measuring in step a is divided into 3 parts, wherein 2 parts are placed in conical flask A, and wherein 1 part is placed in conical flask B, then the glacial acetic acid measuring in step a are joined in conical flask A, under the condition stirring, in conical flask A, add the butyl titanate measuring in step a, with the speed of 150r/min, electric stirring 20min;
C, the hydrochloric acid solution measuring in step a and deionized water are joined in conical flask B, after shaking up, the mixed liquor in conical flask B is transferred in the conical flask A processing through step b, with the speed of 200r/min, after electric stirring 10min, the mixed liquor in conical flask A is transferred in there-necked flask;
D, the there-necked flask in step c is placed in to the water-bath of 45 DEG C, with the speed of 200r/min, electric stirring 1h, naturally cooling, leave standstill 7 days, obtain TiO 2precursor sol liquid;
Two, e, the PU film of wish impression is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 30min of 60 DEG C, complete the preparation of one deck coating in early stage; The PU film that is coated with one deck coating in early stage is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 30min of 60 DEG C, complete the preparation of second layer coating in early stage; F, the PU film that is coated with coating in two-layer early stage is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 60min of 60 DEG C, complete the preparation of final coating;
Three, g, employing ultraprecise microfabrication machine tool system process surface and have the Al pallet of " V " type groove structure, described " V " type groove forms and replaces penetrating rill on Al pallet surface, the width s of each rill is 100 μ m, and degree of depth h is 100 μ m; H, by acetone ultrasonic cleaning 15min for Al pallet prepared in step g, after oven dry, first apply three layers of clean film, then apply three layers of hole sealing agent, finally apply three layers of aqueous release agent, the coating time of every one deck is spaced apart 20min;
Four, TiO step 2 being obtained 2the Al pallet that application type PU film and step 3 obtain is put into 115 DEG C of baking oven preheating 15min, then Al pallet is fixed on the pressure head of hot stamp machine, places quartz glass substrate, by the TiO of preheating on the plummer of hot stamp machine 2application type PU film is laid in quartz glass substrate, falls pressure head, after Al pallet contacts with PU film, boosts to 15kg/cm 2, be that 135 DEG C, pressure are 15kg/cm in temperature 2condition under, impression 20min, stops heating, naturally cooling, and pressurize 2h, removes pressure, lifts pressure head, completes airship envelope TiO 2the preparation of the micro-groove of application type PU film drag reduction.
The raw materials used commercially available prod that is of the present embodiment, the product of clean film, hole sealing agent and the production and sales of aqueous release agent Shi Aifabi international trade (Shanghai) Co., Ltd. used in step 2.The present embodiment PU film used is commercially available prod, and thickness is 100 μ m.The length of the Al pallet in the present embodiment is 50mm, and width is 50mm, and thickness is 6mm; The model of Al pallet Al material used is Al-LY12.
Embodiment bis-:
The present embodiment airship envelope TiO 2the preparation method of the micro-groove of application type TPU film drag reduction carries out according to the following steps:
One, preparation TiO 2precursor sol liquid:
A, take hydrochloric acid solution, deionized water and glacial acetic acid that butyl titanate, absolute ethyl alcohol, mass fraction are 37.5%, wherein the ratio of the amount of substance of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid is 1: 10: 3: 1, and H in the amount of substance of butyl titanate and hydrochloric acid solution +the ratio of amount of substance be 1: 0.8;
B, get two conical flasks, be labeled as A and B, the absolute ethyl alcohol measuring in step a is divided into 3 parts, wherein 2 parts are placed in conical flask A, and wherein 1 part is placed in conical flask B, then the glacial acetic acid measuring in step a are joined in conical flask A, under the condition stirring, in conical flask A, add the butyl titanate measuring in step a, with the speed of 150r/min, electric stirring 20min;
C, the hydrochloric acid solution measuring in step a and deionized water are joined in conical flask B, after shaking up, the mixed liquor in conical flask B is transferred in the conical flask A processing through step b, with the speed of 200r/min, after electric stirring 10min, the mixed liquor in conical flask A is transferred in there-necked flask;
D, the there-necked flask in step c is placed in to the water-bath of 45 DEG C, with the speed of 200r/min, electric stirring 1h, naturally cooling, leave standstill 7 days, obtain TiO 2precursor sol liquid;
Two, e, the TPU film of wish impression is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 30min of 60 DEG C, complete the preparation of one deck coating in early stage; The TPU film that is coated with one deck coating in early stage is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 30min of 60 DEG C, complete the preparation of second layer coating in early stage; F, the TPU film that is coated with coating in two-layer early stage is vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 5min, go out with the VELOCITY EXTRACTION of 50cm/min, at the baking oven inner drying 60min of 60 DEG C, complete the preparation of final coating;
Three, g, employing ultraprecise microfabrication machine tool system process surface and have the Al pallet of " V " type groove structure, described " V " type groove forms and replaces penetrating rill on Al pallet surface, the width s of each rill is 100 μ m, and degree of depth h is 100 μ m; H, by acetone ultrasonic cleaning 15min for Al pallet prepared in step g, after oven dry, first apply three layers of clean film, then apply three layers of hole sealing agent, finally apply three layers of aqueous release agent, the coating time of every one deck is spaced apart 20min;
Four, TiO step 2 being obtained 2the Al pallet that application type TPU film and step 3 obtain is put into 115 DEG C of baking oven preheating 15min, then Al pallet is fixed on the pressure head of hot stamp machine, places quartz glass substrate, by the TiO of preheating on the plummer of hot stamp machine 2application type TPU film is laid in quartz glass substrate, falls pressure head, after Al pallet contacts with PU film, boosts to 15kg/cm 2, be that 135 DEG C, pressure are 15kg/cm in temperature 2condition under, impression 20min, stops heating, naturally cooling, and pressurize 2h, removes pressure, lifts pressure head, completes airship envelope TiO 2the preparation of the micro-groove of application type TPU film drag reduction.
The raw materials used commercially available prod that is of the present embodiment, the product of clean film, hole sealing agent and the production and sales of aqueous release agent Shi Aifabi international trade (Shanghai) Co., Ltd. used in step 2.The present embodiment TPU film used is commercially available prod, and thickness is 100 μ m.The length of the Al pallet in the present embodiment is 50mm, and width is 50mm, and thickness is 6mm; The model of Al pallet Al material used is Al-LY12.
Utilize three-dimensional optical microscopic observation system [Keyemce company, digit microscope (digital microscope), model VHX-600] the micro-groove pattern of skin-surface after masterplate and impression is characterized, Fig. 8 is the airship envelope TiO that the prepared surface of embodiment mono-has the micro-groove structure of drag reduction 2the photo (top observation) of application type PU film; Fig. 9 is the airship envelope TiO that the prepared surface of embodiment mono-has the micro-groove structure of drag reduction 2the photo (side observation) of application type PU film; As can be seen from the figure, the rill of PU film surface clearly, mate intact with impression block by groove shape of stripes and size, and three-dimensional appearance is even, and impression effect is better.Figure 10 is the airship envelope TiO that the prepared surface of embodiment bis-has the micro-groove structure of drag reduction 2the photo (top observation) of application type TPU film; Figure 11 is the airship envelope TiO that the prepared surface of embodiment bis-has the micro-groove structure of drag reduction 2the photo (side observation) of application type TPU film; As can be seen from the figure, the rill of TPU film surface clearly, mate intact with impression block by groove shape of stripes and size, and three-dimensional appearance is even, and impression effect is better.
The surface that embodiment mono-is made has the airship envelope TiO of the micro-groove structure of drag reduction 2the TiO of application type PU film 2test scan electron microscopic observation is carried out in coating surface, cross section, and as shown in Figure 12 and Figure 13, Figure 12 is the airship envelope TiO that surface that embodiment mono-makes has the micro-groove structure of drag reduction to result 2the TiO of application type PU film 2the stereoscan photograph of coating surface, Figure 13 is the airship envelope TiO that surface that embodiment mono-makes has the micro-groove structure of drag reduction 2the TiO of application type PU film 2be coated with the stereoscan photograph of layer cross section; As can be seen from the figure, three-layer thin-film thickness is labeled as 1863.84nm, and thickness in monolayer is about 610nm, TiO 2coating densification, evenly, Figure 14 is the enlarged drawing of Figure 12, can find out coating surface have graininess separate out and particle larger, further observe surperficial vast scale SEM and scheme known bulky grain bottom TiO 2uniform particles, particle diameter are close and arrange closely, and the bulky grain shape that part is separated out is probably the surperficial dehydration retraction TiO forming that reunites 2, the TiO that the method is produced generally 2the densification of coating, even, flawless, meet isolation elemental oxygen, absorb ultraviolet ray to TiO 2coating demand.
Ultraviolet shielded measure of merit:
It is pure quartz glass that ultraviolet sees through test (ultraviolet-visible sees through spectral measurement, wave-length coverage 200nm～800nm) blank, transmitance 100%.
Getting two transmitances is 100% pure quartz glass, is labeled as A, B, and quartz glass A is put into TiO prepared by the step 1 of embodiment mono- 2in precursor sol liquid, after dipping 5min, under the condition that is 700W, process at microwave power, every operation 20s, suspends 2s, and accumulative total microwave treatment 10min, obtains surface and be coated with TiO 2the quartz glass A of coating;
Quartz glass B is put into TiO prepared by the step 1 of embodiment mono- 2in precursor sol liquid, after dipping 5min, at the baking oven inner drying 30min of 60 DEG C, obtain surface and be coated with TiO 2the quartz glass B of coating.
Test surfaces applies TiO 2the quartz glass transmitance of coating, result is as shown in Figure 15, Figure 16, and Figure 15 is that surface is coated with TiO 2the ultraviolet of the quartz glass A of coating sees through spectrogram, and Figure 16 is that surface is coated with TiO 2the ultraviolet of the quartz glass B of coating sees through spectrogram, as shown in Figure 15, and TiO after microwave 10min processes 2coating ultraviolet absorption effect is obvious, is more than or equal to 85% at 200～325nm scope rate of absorbing UV, and the absorption of ultraviolet light effectively reduces the direct injury of ultraviolet to PU or TPU film, has promoted its ageing-resistant performance, has extended film service life; Near ultraviolet and visible light wave range absorptivity are in 25% left and right, and the absorption of this wave band has reduced the absorption of near ultraviolet and visible light wave, has improved to a certain extent dirigible effect of heat insulation; As shown in Figure 16, the TiO that 60 DEG C of dry 0.5h of baking oven obtain 2coating ultraviolet absorption effect figure is similar to microwave treatment, all comparatively obvious, be more than or equal to 85% at 200～323nm scope rate of absorbing UV, the absorption of ultraviolet light effectively reduces the direct injury of ultraviolet to PU or TPU film, promote its ageing-resistant performance, extended film service life; Near ultraviolet and visible light wave range absorptivity are in 25% left and right, and the absorption of this wave band has reduced the absorption of near ultraviolet and visible light wave, has improved to a certain extent dirigible effect of heat insulation.
Groove drag reduction numerical simulation:
Grooved surface has two kinds of laying methods be following current to vertical current to, following current is more conducive to drag reduction to groove.Flow field to symmetrical V-groove is analyzed.Model groove height and spacing are 0.1mm, and flow field regions is opened up to 1mm, and flow field flows to as 3mm, grooved surface and platen surface spacing 3mm, and grid is divided and is seen Figure 17.
Flow field entrance is speed entrance, and speed of incoming flow 10m/s exports as free export; Left and right, territory, flow field boundary definition is symmetrical border.Atmospheric density is taken as 0.08803kg/m 3, air viscosity is 1.4126 × 10 -5kg/m × s.Adopt RNG κ-ε tubulence energy equation solution, result is as follows:
Figure 18 is speed of incoming flow while being 10m/s, flows to cross section speed cloud atlas, and the upper end of figure is smooth plates face, and lower end is grooved surface, and Figure 18 shows that flow field wall has obvious boundary layer, and when near wall, the speed in flow field is all smaller; Figure 19 and Figure 20 have provided respectively the speed cloud atlas of groove wall peace wooden partition face, can find out from two figure, there is larger difference in flute surfaces VELOCITY DISTRIBUTION and flat board, outside high-velocity fluid directly flows through from the low velocity fluid on grooved surface surface, has avoided larger area contact plate face and causes energy loss; Meanwhile, channel bottom y direction velocity gradient is less than the velocity gradient at groove spike place, makes whole grooved surface compare platen surface and has less frictional resistance and become possibility;
Figure 21 shows, the platen surface of this example and grooved surface all have whirlpool to produce; Figure 22 has provided near the cloud charts of the vortex strength degree of groove, shows that vortex strength degree is larger near V-type tip, flows more complicated;
Figure 23 shows that shear stress mainly occurs near the tip of V-groove, and this is because velocity gradient is larger than channel bottom to changing along y herein.
Groove drag reduction numerical simulation result shows, the prepared surface of the present invention has drag-reduction effect with PU or the TPU film of micro-groove structure.

Claims (10)

1. airship envelope TiO 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that airship envelope TiO 2the preparation method of application type PU or the micro-groove of TPU film drag reduction carries out according to the following steps:
One, preparation TiO 2precursor sol liquid:
A, take butyl titanate, absolute ethyl alcohol, strong acid, deionized water and glacial acetic acid, wherein the ratio of the amount of substance of butyl titanate, absolute ethyl alcohol, deionized water and glacial acetic acid is 1: 10: 3: 1, and in the amount of substance of butyl titanate and strong acid, the ratio of the amount of substance of H+ is 1: (0.6～1); Described strong acid is concentrated hydrochloric acid, red fuming nitric acid (RFNA) or the concentrated sulfuric acid;
B, get two conical flasks, be labeled as A and B, the absolute ethyl alcohol measuring in step a is divided into 3 parts, wherein 2 parts are placed in conical flask A, 1 part is placed in conical flask B, then the glacial acetic acid measuring in step a is joined in conical flask A, under the condition stirring, in conical flask A, add the butyl titanate measuring in step a, stir 20～25min;
C, the strong acid measuring in step a and deionized water are joined in conical flask B, after shaking up, the mixed liquor in conical flask B is transferred in the conical flask A processing through step b, stir after 5～10min, the mixed liquor in conical flask A is transferred in there-necked flask;
D, the there-necked flask in step c is placed in to the water-bath of 40～45 DEG C, stirs 1h, naturally cooling, standing 5～7 days, obtain TiO 2precursor sol liquid;
Two, e, PU or the TPU film of wish impression are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 20～30min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 5～10min, completes the preparation of one deck coating in early stage;
F, the PU or the TPU film that are coated with coating in one deck early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, after dipping 3～5min, VELOCITY EXTRACTION with 45～55cm/min goes out, at the baking oven inner drying 40～60min of 60～80 DEG C, or under the condition that is 700W at microwave power, carry out microwave treatment, every operation 20～30s, suspends 2～3s, accumulative total is moved 10～15min, completes the preparation of final coating;
Three, g, employing ultraprecise microfabrication machine tool system process surface and have the Al pallet of " V " type groove structure, described " V " type groove forms and replaces penetrating rill on Al pallet surface, the width s of each rill is 90～110 μ m, and degree of depth h is 90～110 μ m;
H, by acetone ultrasonic cleaning 15～20min for Al pallet prepared in step g, after oven dry, first apply three layers of clean film, then apply three layers of hole sealing agent, finally apply three layers of aqueous release agent, the coating time of every one deck is spaced apart 15～20min;
Four, TiO step 2 being obtained 2the Al pallet that application type PU or TPU film and step 3 obtain is put into 110～115 DEG C of baking oven preheating 15～20min, then Al pallet is fixed on the pressure head of hot stamp machine, on the plummer of hot stamp machine, place quartz glass substrate, by the TiO of preheating 2application type PU or TPU film are laid in quartz glass substrate, fall pressure head, treat Al pallet and TiO 2after application type PU or the contact of TPU film, boost to 15～20kg/cm 2, be that 135～140 DEG C, pressure are 15～20kg/cm in temperature 2condition under, impression 15～20min, stops heating, naturally cooling, and pressurize 2～3h, removes pressure, lifts pressure head, completes airship envelope TiO 2the preparation of application type PU or the micro-groove of TPU film drag reduction.
2. airship envelope TiO according to claim 1 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, the mass fraction that it is characterized in that concentrated hydrochloric acid described in step a is 37.5%, the mass fraction of red fuming nitric acid (RFNA) is 65%, the mass fraction of the concentrated sulfuric acid is 70%.
3. airship envelope TiO according to claim 2 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that the stirring in step b adopts electric mixer, and mixing speed is 150～180r/min.
4. airship envelope TiO according to claim 1 and 2 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that the stirring in step c and steps d adopts electric mixer, and mixing speed is 180～200r/min.
5. airship envelope TiO according to claim 4 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that in step 2, completes after the preparation of one deck coating in early stage, and the PU or the TPU film that are coated with one deck coating in early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, then prepare coating in second layer early stage according to the parameter of step e, finally the PU or the TPU film that are coated with coating in two-layer early stage are vertically put into TiO prepared by step 1 2in precursor sol liquid, according to the parameter of step f, complete the preparation of final coating.
6. airship envelope TiO according to claim 5 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, the thickness that it is characterized in that PU described in step e or TPU film is 98～102 μ m.
7. according to the airship envelope TiO described in claim 5 or 6 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, the length that it is characterized in that Al pallet in step g is 50～52mm, and width is 50～52mm, and thickness is 5～8mm.
8. airship envelope TiO according to claim 7 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that step 4 is that 136～138 DEG C, pressure are 16～18kg/cm in temperature 2condition under, impression 15～20min.
9. airship envelope TiO according to claim 7 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, is characterized in that step 4 is that 135 DEG C, pressure are 15kg/cm in temperature 2condition under, impression 20min.
10. airship envelope TiO according to claim 1 2the preparation method of application type PU or the micro-groove of TPU film drag reduction, the Si template that it is characterized in that adopting surface to have " V " type groove structure or Ni template substitution tables mask have the Al pallet of " V " type groove structure.
CN201210168760.4A 2012-05-28 2012-05-28 Preparation method of TiO2 coating type polyurethane (PU) or thermoplastic polyurethane (TPU) film drag reduction micro-groove used for airship skins Expired - Fee Related CN102672958B (en)

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