CN1712478A - Nanometer multifunctional composite thin-membrane, its production and use - Google Patents

Nanometer multifunctional composite thin-membrane, its production and use Download PDF

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Publication number
CN1712478A
CN1712478A CN 200410047995 CN200410047995A CN1712478A CN 1712478 A CN1712478 A CN 1712478A CN 200410047995 CN200410047995 CN 200410047995 CN 200410047995 A CN200410047995 A CN 200410047995A CN 1712478 A CN1712478 A CN 1712478A
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film
laminated film
feooh
multifunctional nano
nano laminated
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陈运法
谢裕生
叶树峰
吴镇江
张冬海
王奇
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

A multifunctional nanometer composite thin film, its production and use are disclosed. The thin film contains silicone, it is grafted with perfluoro-silicane 0.02-0.1wt% on surface and doped with nanometer iron oxide particle 1-4wt% in network, which is fusiform or needle alpha-FeOOH, beta-FeOOH, alpha-Fe2O3 or gamma-Fe2O3. The process is carried out by hydrolyzing for silane coupling agent and ethyl orthosilicate in water, alcohol and hydrolytic catalyst system, mixing, adding into alcohol, condensing and generating silicone polymer at 30-60 DEG C, adding into nanometer iron oxide particle and fluorosurfactant, reacting, obtaining thin-film sol, forming thin-film sol into film on treated substrate material, drying and curing. It achieves higher anti-aging and mechanical performances.

Description

A kind of multifunctional nano laminated film and its production and use
Technical field
The present invention relates to a kind of laminated film, specifically relate to a kind of antipollution, anti-scratch, ageing-resistant organic-inorganic nano multifunctional composite film, and its production and use.
Background technology
Along with science and technology development, the various section bars that macromolecular material makes are because its good performance has obtained application widely in people's life.But well-known, a subject matter of these macromolecular material finished product is all can produce as time passes at occurring in nature to wear out, and for example the aging meeting of organic polymer material causes that variable color, be full of cracks and mechanical property descend.After the accession to WTO, domestic materials for construction industry standard will be consistent with the new standard that formulated in 2003 in Europe, and this standard was strict to the ageing-resistant performance requirement of macromolecular material section bar.So the ageing-resistant ability of section bar is in urgent need to be improved.
In order to solve the problem of aging of polymer section bar, normally in material, add such as TiO 2, ZnO and so on inorganic nano uvioresistant material, this class bill of material reveals excellent uv absorption property, for example, adds Rutile type Titanium Dioxide in material, can shield a large amount of ultraviolet rays.Or add the UV-531 UV light absorber, and can sponge the energy of ultraviolet that enters material or generation as far as possible, reduce photolysis to resin.But these materials often need import, and cost is too high, are difficult to widespread use industrial; And the photocatalytic activity of himself produces Degradation to section bar and mould material easily.
In addition, the polymer section bar is except having limitation aspect the ageing resistance, its wear resistance, and easily the problem of contaminative is also very outstanding, and existing section bar often easily scratches in transportation, installation process, and is easily contaminated in the use.
Summary of the invention
The objective of the invention is to overcome prior art adds in the raw material of polymer section bar that anti ultraviolet agent improves ageing resistance and the cost that exists is too high, and himself photocatalytic activity easily section bar and mould material are produced the defective of Degradation, thereby provide a kind of antipollution of low cost method preparation, anti-scratch, ageing-resistant organic-inorganic nano multifunctional composite film of adopting, be coated with then and install to the section bar surface, to improve its ageing-resistant performance and mechanical property.
Another object of the present invention is to provide the preparation method of above-mentioned multifunctional nano laminated film.
A further object of the present invention is to provide the purposes of above-mentioned multifunctional nano laminated film.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of organic-inorganic nano multifunctional composite film, it is the polysiloxane film that is coated on substrate surface, exists with cross-linked structure; Surface grafting at cross-linked network has perfluoro silane, accounts for film 0.02～0.1wt%; Be doped with the nanometer iron-series oxide particle of 1～4wt% in network internal.
Described base material comprises synthetic glass, glass, plastics, rubber, pottery and metal.
The thickness of described film is 1～5 μ m.
Described ferrous oxide particle is fusiform or aciculiform, and major axis is that 60～75nm, minor axis are 15～35nm, and the ratio of major and minor axis is 2～4.
Described nanometer iron-series oxide compound is alpha-feooh, β-FeOOH, α-Fe 2O 3Or γ-Fe 2O 3
The invention provides a kind of preparation method of above-mentioned multifunctional nano laminated film, may further comprise the steps:
1) preparation of film colloidal sol:
At 25～60 ℃, with silane coupling agent, water, ethanol by weight 3～12: mix at 1: 1, and add a certain amount of hydrolyst, make the pH value of system, obtain mixture A at 1～5 generation hydrolysis reaction;
At 25～60 ℃, with tetraethoxy, water, ethanol by weight 3～12: mix at 1: 1, and add a certain amount of hydrolyst, make the pH value of system, obtain mixture B at 1～5 generation hydrolysis reaction;
Get an amount of mixture A and B respectively, after 1: 2～6 mixing, the ethanol that weigh add and total amount etc., 30～60 ℃ of stirring reactions 1～2 hour, so that condensation generates siloxane polymer between A, the B, add the nanometer iron-series oxide particle that accounts for siloxane polymer 1～4wt% while stirring, 60～100 ℃ of reactions 2～3 hours, reduce to 30～40 ℃ again, add the fluorochemical surfactant that accounts for siloxane polymer 0.02～0.1wt%, continue to stir 1～3 hour, naturally cool to room temperature, obtain film colloidal sol;
The general formula of described silane coupling agent is: R ' (CH 2) nSi (OR) 3, wherein:
R’＝-CH 3，-NH 2，-SH，-NH(CH 2)NH 2，-CH＝CH 2，-OCHCHOCH 2
R＝-CH 6，-CH 2CH 3
n＝1～16
Described hydrolyst is hydrochloric acid, nitric acid, sulfuric acid, acetic acid or hydrofluoric acid;
Described fluorochemical surfactant general formula is: C xF 2x+1(CH 2) ySiCl 3, x=6～8 wherein, y=2～6;
Described nanometer iron-series oxide particle is alpha-feooh, β-FeOOH, α-Fe 2O 3Or γ-Fe 2O 3, this ferrous oxide particle is fusiform or aciculiform, and major axis is that 60～75nm, minor axis are 15～35nm, and the ratio of major and minor axis is 2～4.
This nanometer iron-series oxide particle also can be according to document 1: Luo Yimin, Huang Kelong etc., the preparation and the sign of nanometer alpha-FeO (OH) fine powder, Journal of Inorganic Materials, 1994,9 (2): 239～243, document 2: go away for some great undertakings Li Dacheng recklessly, PREPARATION OF NANO FERRIC OXIDE method and progress, the Sichuan non-ferrous metal, 2001 (1): the method described in 15～20 makes as follows:
A. nanometer alpha-feooh particulate preparation:
FeSO to 0.2～0.35mol/L 4Add FeSO in the solution 4The dispersion agent of 0.3～0.5wt% of quality, ultrasonic 10～30 minutes, treat that the dispersion agent dissolving finishes, control different precipitation reaction temperature according to precipitation agent is different, take to force feed way, the conduit mouth that is about to precipitation agent places following, parallel with the paddle plane of liquid level, with the paddle spacing be the paddle size half, speed with 1～5mL/min adds precipitation agent, is 4～5 until the pH of system value, obtains blackish green ferrous hydroxide colloidal precipitation; Described dispersion agent is to be selected from silicate, phosphoric acid salt, Citrate trianion, lipid acid, the alcohols one or more; Described precipitation agent is NaOH, KOH, Na 2CO 3, NaHCO 3, NH 3H 2O or CO (NH 2) 2In a kind of.
The tensio-active agent that adds 3～5wt% of Fe amount, ultra-sonic dispersion 10～30 minutes adds oxygenant and carries out oxidizing reaction, until the colloid flavescence; Growing the grain 20～60 minutes heats up then, continues oxidation 3～6 hours at 50 ℃～80 ℃, obtains yellow colloidal mixture; Described tensio-active agent is an anion surfactant, comprising: Sodium dodecylbenzene sulfonate (DBS), Sodium n-caproate (C 6A), Sodium octoate (C 8A), dodecylic acid sodium (C 12A) etc. one or more in; Described oxygenant is air, Potcrate, sodium chlorate, clorox or hydrogen peroxide.
Centrifugation uses deionized water and ethanol repetitive scrubbing filter cake for several times successively, is neutral up to pH value of filtrate; Filter cake is ground 80～180 ℃ of dry down backs, obtain Yellow nanometer alpha-feooh particle, prepared nanometer alpha-feooh is a needle-like, and particle diameter is even, and good dispersity, major axis are that 60～70nm, minor axis are 15～20nm, and the ratio of major and minor axis is 3～4.
B. nanometer β-FeOOH particulate preparation:
Similar with method among a, be in initial reaction liquid, also to add to account for FeSO 4The NaF of quality 0.5～1.5%, KF, KCl or NaCl, what obtain at last is golden yellow nanometer β-FeOOH particle, prepared nanometer β-FeOOH is an aciculiform, particle diameter is even, good dispersity, major axis are that 60～75nm, minor axis are 20～25nm, and the ratio of major and minor axis is 3～4.
C. nanometer α-Fe 2O 3The particulate preparation:
Nanometer alpha-feooh or β-FeOOH particle were calcined 2～5 hours at 450～650 ℃, ground, obtain red nano α-Fe 2O 3Particle, this nanometer α-Fe 2O 3Be fusiform, particle diameter is even, and good dispersity, major axis are that 60～65nm, minor axis are 30～35nm, and the ratio of major and minor axis is 2～3.
D. nanometer γ-Fe 2O 3The particulate preparation:
With nanometer α-Fe 2O 3Particle under nitrogen atmosphere in 350～450 ℃ of calcinings 2～4 hours, then under oxygen atmosphere in 200～250 ℃ of calcinings 1～3 hour, grind, obtain brown nanometer γ-Fe 2O 3Particle, this nanometer γ-Fe 2O 3Be fusiform, particle diameter is even, and good dispersity, major axis are 65～70nm, and minor axis is 30～35nm, and the ratio of major and minor axis is 2～3.
2) application of film and curing:
Take ordinary method that different substrate materials is carried out surperficial pre-treatment, the film colloidal sol that then step 1) is made adopts ordinary method in the substrate surface film forming, after the seasoning,, promptly obtain multifunctional nano laminated film of the present invention 60～120 ℃ of isothermal curings 5～10 hours.
Described base material comprises synthetic glass, glass, plastics, rubber, pottery and metal;
The method of surface pre-treatment comprises uses aqueous detergent and organic solvent that substrate surface is carried out the power flushing, removes dirts such as dust that its surface is stained with, releasing agent, grease; Or the method for employing wiping strong solvent, substrate surface is carried out roughened, make its surface produce weak corrosion, energy enhanced film sticking power; Or 10 centimetres of vertical irradiations of ultraviolet lamp spacing 5～10 minutes, can improve substrate surface polarity, increase sticking power
The method of surface filming comprises and adopts dipping to lift, revolve means such as deposited, brushing or spraying drying.
The invention provides the purposes of above-mentioned multifunctional nano laminated film, this composite membrane is coated in the surface of polymer section bar, can improve its ageing-resistant performance and mechanical property, reaches antipollution, anti-scratch, ageing-resistant purpose.
Multifunctional nano laminated film provided by the invention is that the nanometer iron-series oxide particle of certain crystal formation is introduced the film sol system, be used to improve easy pollution, easily scratch or easily during aged section bar surface, composite membrane by application and curing generation, compared with the prior art, its advantage is:
1) the present invention prepares a series of nanometer iron-series oxide particles with excellent uvioresistant performance based on the wet-chemical oxidation style, and with its film sol system that is doped into tetraethoxy and silane coupling agent formation first, makes multifunctional composite film colloidal sol; This preparation technology is simple, and cost is low, is easy to realize industrialization;
2) multifunctional composite film of the present invention's preparation has improved the hydrophobic self-cleaning property of section bar greatly; improved wear resistance; and give the section bar uvioresistant function, thus improved its ageing-resistant ability, be specially adapted to the protection that commute wears out, easily pollutes and easily abrade the section bar surface.
Description of drawings
Fig. 1 is the different contact angles that scribble multifunctional nano laminated film (1) front and back of the embodiment of the invention 5; Wherein A is for before filming, and B is for after filming;
Fig. 2 is " adding unloaded-depth of indentation " curve of the multifunctional nano laminated film (1) of the embodiment of the invention 5; The laminated film (1) of nanometer alpha-feooh has been introduced in curve 1 representative; The film of nanometer alpha-feooh is not introduced in curve 2 representatives; The blank base material that curve 3 representatives are not filmed;
Fig. 3 is " frictional coefficient-cut " curve of the multifunctional nano laminated film (1) of the embodiment of the invention 5; Wherein, the laminated film (1) of nanometer alpha-feooh has been introduced in curve 1 representative; The film of nanometer alpha-feooh is not introduced in curve 2 representatives; The blank base material that curve 3 representatives are not filmed.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment;
Embodiment 1, the preparation of nanometer alpha-feooh particulate
To 500mL concentration is the FeSO of 0.3mol/L 4Add respectively in the solution and account for FeSO 4The Sodium hexametaphosphate 99 of quality 0.3%, temperature control is at 30 ℃, stirring velocity 500 (r/min), dissolving finishes, adopt to force feed way with the speed of 2mL/min gradually to the sodium hydroxide solution 50mL that wherein adds 3mol/L, get blackish green ferrous hydroxide colloidal precipitation, ultra-sonic dispersion 30min is with 0.15m 3The speed bubbling air oxidation of/h, color from blackish green to pea green again to lead, flavescence soon then, growing the grain is after 30 minutes, adds to account for FeSO 4The Sodium dodecylbenzene sulfonate of 3wt% is warming up to 80 ℃, with 0.5m behind the ultra-sonic dispersion 30min 3The speed bubbling air of/h continues oxidizing reaction 5h, yellow colloidal mixture, centrifugation then, the repetitive scrubbing filter cake be neutral up to pH value, with filter cake drying under 120 ℃ grind after 3 hours Yellow nanometer alpha-feooh particle.This nanometer alpha-feooh is a needle-like, and particle diameter is even, and good dispersity, major axis are that 60～70nm, minor axis are 15～20nm, and the ratio of major and minor axis is 3～4.
Embodiment 2, nanometer β-FeOOH particulate preparation
To 540mL concentration is the FeSO of 0.4mol/L 4Add in the solution and account for FeSO 4The water glass of quality 0.45% and 0.1% sodium-chlor, temperature control is at 35 ℃, stirring velocity 600 (r/min), dissolving finishes, to the aqueous solution of urea 60mL that wherein drips 2mol/L, ultra-sonic dispersion 25min progressively is warmed up to 85 ℃ with the speed of 5mL/min, color is from the blackish green lead that becomes, keep system temperature, take to force feed way, add 10% hydrogen peroxide 10mL oxidation with the speed of 1ml/min gradually, the rapid flavescence of color, adding accounts for FeSO 4The Sodium n-caproate of quality 4wt% stirs, and continues the hydrogen peroxide 90mL with the speed adding 10% of 1ml/min, get yellow colloidal mixture, centrifugation then, repetitive scrubbing filter cake are neutral up to the pH value, with filter cake 100 ℃ grind after dry 2 hours down golden yellow nanometer β-FeOOH particle.This nanometer β-FeOOH is a fusiform, and particle diameter is even, and good dispersity, major axis are that 60～75nm, minor axis are 20～25nm, and the ratio of major and minor axis is 3～4.
Embodiment 3, nanometer α-Fe 2O 3The particulate preparation
With nanometer alpha-feooh particle in 30min, be warming up to 450 ℃ of calcinings grind after 3 hours red nano α-Fe 2O 3Particle.This nanometer α-Fe 2O 3Be fusiform, particle diameter is even, and good dispersity, major axis are that 60～65nm, minor axis are 30～35nm, and the ratio of major and minor axis is 2～3.
Embodiment 4, nanometer γ-Fe 2O 3The particulate preparation
With the nanometer α-Fe that makes 2O 3Particle under nitrogen atmosphere in 400 ℃ the calcining 2 hours, again under oxygen atmosphere in 250 ℃ the calcining 2 hours, grind brown nanometer γ-Fe 2O 3Particle.This nanometer γ-Fe 2O 3Be fusiform, particle diameter is even, and good dispersity, major axis are 65～70nm, and minor axis is 30～35nm, and the ratio of major and minor axis is 2～3.
The preparation of embodiment 5, multifunctional nano laminated film
At 25 ℃, with 65.6g glycidoxypropyltrime,hoxysilane [CH 2OCHCH 2O (CH 2) 3Si (OCH 3) 3] and 10g water, 10g ethanol mix, dropwise add the HCl of 5g 0.02mol/L while stirring, this moment, pH value was 3, continued to get mixture A behind the reaction 2h, and is standby.
At 60 ℃, with 57.8g tetraethoxy [Si (OCH 2CH 3) 4] and 10g water, 10g ethanol mix, dropwise add the HCl of 5g 0.02mol/L while stirring, this moment, pH value was 3, continued to get mixture B behind the reaction 2h, and is standby.
Getting 3g mixture A mixes with 9g mixture B, add 12g ethanol, at 40 ℃ of stirring reaction 1h, add the nanometer alpha-feooh powder granule that 0.10g embodiment 1 makes again, be warming up to 80 ℃ of stirring reaction 3h after the dissolving, be cooled to 40 ℃ then, add the 0.005g silicon fluoride, after continuing to stir 1h, naturally cool to room temperature, get laminated film colloidal sol.
(10 * 10cm), successively use sanitising agent and ethanol carry out power flushing to the surface, remove dirts such as dust that its surface is stained with, releasing agent, grease to get one of PVC plastic basis material; Secondly, use the acetone wiping, substrate surface is carried out roughened, make its surface produce weak corrosion,, do not produce defectives such as finedraw, loss of gloss again after the application simultaneously with enhanced film sticking power; Then, in seasoning, base material is carried out uviolizing, ultraviolet lamp spacing base material 10cm vertical irradiation 10 minutes to improve its surface polarity, increases sticking power.After substrate surface treatment finishes, be placed on the equal glue machine, predetermined film forming rotating speed is 500rpm, and the film forming rotating speed is 1500rpm, and drying at room temperature 35min behind the deposited film of rotation places 70 ℃ of baking ovens, solidifies 10h, obtains multifunctional nano laminated film of the present invention (1).
Adopt Phoenix300 contact angle tester that multifunctional nano laminated film (1) is carried out the hydrophobic performance test, as shown in Figure 1, scribble before and after the multifunctional nano laminated film (1) of the embodiment of the invention 5, hydrophobic angle increases to 110 degree by 30 degree, illustrates that the hydrophobic self-cleaning property of this film greatly improves.
Adopt nano hardness meter (MTS Nano Indenter XP (R) system) that multifunctional nano laminated film (1) is carried out the wear resisting property test.
Hardness before and after the method that adopts nano impress to test is filmed to base material is measured, and the result is: H 1=2.76720E-01 (GPa); H 2=2.33227E-01 (GPa); H 3=1.73523E-01 (GPa).Shown in " adding unloaded-depth of indentation " curve of Fig. 2,, these three various sample, wherein the film (1) that the film colloidal sol of nanometer alpha-feooh makes has been introduced in curve 1 representative; The film of nanometer alpha-feooh is not introduced in curve 2 representatives; The blank base material that curve 3 representatives are not filmed.Can obviously find out from Fig. 2: under the situation of the equal depth of indentation of control (1000nm), big before the load ratio behind the deposited film is filmed, the ability of bearing contact load is stronger, illustrates that the front and back hardness of filming obviously increases; In addition, introduce nanometer alpha-feooh particle rear film hardness and obviously improve, illustrate that alpha-feooh brought into play the distinctive physicals of inorganic particulate, played the effect of raising film hardness.Remaining depth of indentation when the terminal basic reflection of unloading curve unloads, as can be seen from Figure 2, film is little than the base material impression residual degree of depth, and viscous deformation is little, and elastic recovery capability is strong, has the mechanical property of better opposing external force.
Frictional coefficient before and after the method for employing nanometer scratch experiment is filmed to base material is measured.The result is: F 1=0.572; F 2=0.541; F 3=0.488.Shown in " frictional coefficient-scratch depth " curve of Fig. 3, these three various sample, wherein the film (1) that the film colloidal sol of nanometer alpha-feooh makes has been introduced in curve 1 representative; The film of nanometer alpha-feooh is not introduced in curve 2 representatives; The blank base material that curve 3 representatives are not filmed.From Fig. 3, can obviously find out, apply film sample frictional coefficient and become big, in this explanation scratch experiment, under identical positive pressure, increase along with the cut displacement, the horizontal force that applies on the film base material that is applied to becomes big, and greater than not applying film base material, the wear resistance of material opposing cut strengthens behind the promptly deposited film.
By the variation of these nano hardnesses and skin friction coefficient, illustrate that multifunctional nano laminated film provided by the invention (1) has wear resistance, the wear resistance of the back material opposing cut of filming strengthens.
Multifunctional nano laminated film (1) is carried out the ageing resistance test.Entrust national constructional ornamental material quality supervision and test center according to GB/T8814-1998, plastic material is tested in the weathering resistance before and after the application function film, the weathering resistance assay is 2000 hours behind the deposited film, than having improved 50% before the deposited film, after carrying out the weathering resistance test, apply the check sample of film, flavescence gradually in the process accelerated deterioration process of simulating nature, keep original color and apply the film sample, fully demonstrate good weather resistance.
Embodiment 6～19
The method for preparing laminated film (1) according to embodiment 5, kind, content and the reaction conditions that embodiment 6～19 changes film colloidal sol major function components prepared multifunctional nano laminated film (2)～(15) in that PVC section bar surface is corresponding, and it is carried out performance test.Corresponding film colloidal sol function ingredients in preparation serial nano multifunctional composite film (1)～(15) and content thereof are listed in table 1, and corresponding The performance test results is listed in table 2.
The component and the content thereof of table 1, multifunctional nano laminated film (1)～(15)
The film sequence Film colloidal sol main component and content thereof
Silane coupling agent Tetraethoxy Nano particle Fluorine surfactant
??(1) ??CH 2OCHCH 2O(CH 2) 3Si(OCH 3) 3??3g ??9g ??α-FeOOH ??(0.10g) ??C 6F 13(CH 2) 2SiC 13??0.0050g
??(2) ??CH 2OCHCH 2OCH 2Si(OCH 2CH 3) 3??6g ??12g ??α-FeOOH ??(0.10g) ??β-FeOOH ??(0.08g) ??C 6F 13(CH 2) 3SiC 13??0.0036g
??(3) ??CH 2OCHCH 2O(CH 2) 16Si(OCH 3) 3??2g ??12g ??α-FeOOH ??(0.18g) ??β-FeOOH ??(0.18g) ??α-Fe 2O 3??(0.16g) ??C 6F 13(CH 2) 4SiC 13??0.0120g
??(4) ??CH 2＝CH(CH 2) 5Si(OCH 3) 3??3g ??15g ??β-FeOOH ??(0.36g) ??C 6F 13(CH 2) 5SiC 13??0.0108g
??(5) ??CH 2＝CHCH 2Si(OCH 2CH 3) 3??5g ??10g ??α-FeOOH ??(0.05g) ??α-Fe 2O 3??(0.10g) ??C 6F 13(CH 2) 6SiC 13??0.0030g
??(6) ??CH 2＝CH(CH 2) 16Si(OCH 3) 3??3g ??12g ??α-FeOOH ??(0.15g) ??β-FeOOH ??(0.25g) ??γ-Fe 2O 3??(0.10g) ??C 7F 15(CH 2) 2SiC 13??0.0120g
??(7) ??NH 2CH 2NH(CH 2) 7Si(OCH 3) 3??3g ??9g ??α-Fe 2O 3??(0.15g) ??C 7F 15(CH 2) 3SiC 13??0.0120g
??(8) ??NH 2CH 2NHCH 2Si(OCH 2CH 3) 3??4g ??8g ??α-FeOOH ??(0.05g) ??γ-Fe 2O 3??(0.07g) ??C 7F 15(CH 2) 4SiC 13??0.0024g
??(9) ??NH 2CH 2NH(CH 2) 16Si(OCH 3) 3??2g ??12g ??α-FeOOH ??(0.25g) ??α-Fe 2O 3??(0.25g) ??γ-Fe 2O 3??(0.10g) ??C 7F 15(CH 2) 5SiC 13??0.0120g
??(10) ??SH(CH 2) 9Si(OCH 3) 3??4g ??8g ??γ-Fe 2O 3??(0.10g) ??C 7F 15(CH 2) 6SiC 13??0.0020g
??(11) ??SHCH 2Si(OCH 2CH 3) 3??6g ??12g ??β-FeOOH ??(0.08g) ??γ-Fe 2O 3??(0.10g) ??C 8F 11(CH 2) 2SiC 13??0.0036g
??(12) ??SH(CH 2) 16Si(OCH 3) 3??3g ??18g ??α-Fe 2O 3??(0.48g) ??γ-Fe 2O 3??(0.30g) ??C 8F 11(CH 2) 3SiC 13??0.0180g
??(13) ??NH 2(CH 2) 11Si(OCH 3) 3??3g ??9g ??β-FeOOH ??(0.05g) ??α-Fe 2O 3??(0.15g) ??γ-Fe 2O 3??(0.15g) ??C 8F 11(CH 2) 4SiC 13??0.009g
??(14) ??NH 2CH 2Si(OCH 2CH 3) 3??4g ??8g ??β-FeOOH ??(0.06g) ??α-Fe 2O 3??(0.06g) ??C 8F 11(CH 2) 5SiC 13??0.0024g
??(15) ??NH 2(CH 2) 16Si(OCH 3) 3??4g ??24g ??α-FeOOH ??(0.06g) ??β-FeOOH ??(0.06g) ??α-Fe 2O 3??(0.35g) ??γ-Fe 2O 3??(0.30g) ??C 8F 11(CH 2) 6SiC 13??0.025g
The performance test of table 2, multifunctional nano laminated film (1)～(15)
The film sequence Film performance test
Hydrophobic angle (°) Nano hardness (Gpa) Frictional coefficient The anti-aging time (h)
??(1) ??110 ??2.76720E-01 ??0.572 ??2000
??(2) ??113 ??2.54781E-01 ??0.578 ??2100
??(3) ??128 ??2.32154E-01 ??0.601 ??2050
??(4) ??110 ??3.01418E-01 ??0.498 ??2000
??(5) ??112 ??2.74156E-01 ??0.502 ??2050
??(6) ??124 ??3.21544E-01 ??0.591 ??2100
??(7) ??120 ??2.98977E-01 ??0.564 ??2000
??(8) ??115 ??2.54786E-01 ??0.551 ??2050
??(9) ??111 ??2.52214E-01 ??0.501 ??2050
??(10) ??108 ??2.50245E-01 ??0.491 ??2000
??(11) ??122 ??2.87954E-01 ??0.584 ??2100
??(12) ??127 ??2.75486E-01 ??0.596 ??2000
??(13) ??115 ??2.52147E-01 ??0.549 ??2050
??(14) ??119 ??2.63251E-01 ??0.550 ??2100
??(15) ??109 ??2.49787E-01 ??0.512 ??2150
By the data of table 2 as can be seen, multifunctional nano laminated film provided by the invention has hydrophobic self-cleaning performance, and hardness and wear resisting property all are higher than the PVC section bar, and have excellent anti ultraviolet ability, be coated on PVC section bar surface energy and improve section bar antipollution, anti-scratch and ageing-resistant performance greatly.

Claims (10)

1, a kind of multifunctional nano laminated film, it is for being the film of main component with the crosslinked polysiloxane; Surface grafting at cross-linked network has perfluoro silane, and its content is 0.02～0.1wt%; Be doped with the nanometer iron-series oxide particle of 1～4wt% in network internal.
2, multifunctional nano laminated film as claimed in claim 1 is characterized in that, described nanometer iron-series oxide compound is alpha-feooh, β-FeOOH, α-Fe 2O 3Or γ-Fe 2O 3
3, multifunctional nano laminated film as claimed in claim 1 or 2 is characterized in that, described nanometer iron-series oxide compound is fusiform or aciculiform, and major axis is that 60～75nm, minor axis are 15～35nm, and the ratio of major and minor axis is 2～4 particle.
4, multifunctional nano laminated film as claimed in claim 1 is characterized in that, the thickness of described film is 1～5 μ m.
5, the preparation method of the described multifunctional nano laminated film of a kind of claim 1 may further comprise the steps:
1) preparation of film colloidal sol:
At 25～60 ℃, with silane coupling agent, water, ethanol by weight 3～12: mix at 1: 1, and add a certain amount of hydrolyst, make the pH value of system, obtain mixture A at 1～5 generation hydrolysis reaction;
At 25～60 ℃, with tetraethoxy, water, ethanol by weight 3～12: mix at 1: 1, and add a certain amount of hydrolyst, make the pH value of system, obtain mixture B at 1～5 generation hydrolysis reaction;
Get an amount of mixture A and B respectively, after 1: 2～6 mixing, the ethanol that weigh add and total amount etc., 30～60 ℃ of stirring reactions 1～2 hour, so that condensation generates siloxane polymer between A, the B, add the nanometer iron-series oxide particle that accounts for siloxane polymer 1～4wt% while stirring, 60～100 ℃ of reactions 2～3 hours, reduce to 30～40 ℃ again, add the fluorochemical surfactant that accounts for siloxane polymer 0.02～0.1wt%, continue to stir 1～3 hour, naturally cool to room temperature, obtain film colloidal sol;
2) application of film and curing:
Take ordinary method that different substrate materials is carried out surperficial pre-treatment, the film colloidal sol that then step 1) is made adopts ordinary method in the substrate surface film forming, after the seasoning,, obtain multifunctional nano laminated film of the present invention 60～120 ℃ of isothermal curings 5～10 hours.
6, the preparation method of multifunctional nano laminated film as claimed in claim 5 is characterized in that: the general formula of the silane coupling agent of described step 1) is: R ' (CH 2) nSi (OR) 3, wherein:
R’＝-CH 3，-NH 2，-SH，-NH(CH 2)NH 2，-CH＝CH 2，-OCHCHOCH 2
R＝-CH 3，-CH 2CH 3
n＝1～16。
7, the preparation method of multifunctional nano laminated film as claimed in claim 5 is characterized in that: the hydrolyst of described step 1) is hydrochloric acid, nitric acid, sulfuric acid, acetic acid or hydrofluoric acid.
8, the preparation method of multifunctional nano laminated film as claimed in claim 5 is characterized in that: the nanometer iron-series oxide compound of described step 1) is alpha-feooh, β-FeOOH, α-Fe 2O 3Or γ-Fe 2O 3, this ferrous oxide particle is fusiform or aciculiform, and major axis is that 60～75nm, minor axis are 15～35nm, and the ratio of major and minor axis is 2～4.
9, the preparation method of multifunctional nano laminated film as claimed in claim 5 is characterized in that: the fluorochemical surfactant general formula of described step 1) is: C xF 2x+1(CH 2) ySiCl 3, x=6～8 wherein, y=2～6.
10, the purposes of the described multifunctional nano laminated film of a kind of claim 1, this composite membrane is coated in the surface of polymer section bar, can improve its ageing-resistant performance and mechanical property.
CN 200410047995 2004-06-14 2004-06-14 Nanometer multifunctional composite thin-membrane, its production and use Pending CN1712478A (en)

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CN110026195B (en) * 2019-05-05 2021-09-03 河北师范大学 High-activity alpha-Fe2O3Nanosheet and preparation method and application thereof
CN110452668A (en) * 2019-08-30 2019-11-15 哈尔滨工业大学 A kind of transmission-type radiation refrigeration material, film, preparation method and application
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