CN102490430B - Method for rapid preparation of polymer multilayer film - Google Patents
Method for rapid preparation of polymer multilayer film Download PDFInfo
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- CN102490430B CN102490430B CN201110360007.0A CN201110360007A CN102490430B CN 102490430 B CN102490430 B CN 102490430B CN 201110360007 A CN201110360007 A CN 201110360007A CN 102490430 B CN102490430 B CN 102490430B
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Abstract
Belonging to the technical field of chemistry and chemical industry production, the invention discloses a method for rapid preparation of a polymer multilayer film. The method can realize rapid preparation of a polymer multilayer film on a planar substrate and a non-planar substrate, and is suitable for industrial production. The method integrates a hypergravity technology and a layer-by-layer self-assembly technology, or in other words, an alternate layered self assembly process is carried out in a hypergravity machine so as to prepare a polymer multilayer film. The method can effectively enhance the preparation speed of a polymer multilayer film without changing the properties of the prepared polymer multilayer film. Being suitable for substrates of different shapes and different materials, the method has strong concentration adaptability, and can realize rapid preparation of a polymer multilayer film under a low concentration. Being suitable for acidic assembling liquids, alkaline assembling liquids and other assembling liquids of different properties, the method of the invention has the characteristics of simple operation process, short operation time, high efficiency, and suitability for industrial production.
Description
Technical field
The invention belongs to chemical production technical field, what relate generally to is a kind of method of rapid preparation of polymer multilayer film, the method can realize the quick preparation of polymer multilayer film in planar substrates and non-planar substrate, and the method is applicable to suitability for industrialized production.
Background technology
In modern technologies growing today, the material of simple function can not meet people's demand, is more and more subject to people's favor with the compound material of multiple improved performance.For many years, compound material has attracted increasing scientific research personnel to be engaged in its research field with its distinctive character.Wherein, at existing material surface assembling one layer of polymeric multilayer film, and make the research with extra character of material, equipment, be subject to gradually more researchers' attention.
Polymer multilayer film is the new way of creating novel substance, acquisition new material, controlled material Surface Physical Chemistry character with molecule aggregate.According to the difference of selected molecule aggregate, can make the different function of green wood material strip of creating.For example: we can prepare one deck and have in solar cell surface the polymer multilayer film of superhydrophobic characteristic, and the solar cell surface of preparation just has self-cleaning function like this; In addition, can also prepare one deck and have at ocean tanker or the hull surface of underwater submarine the polymer multilayer film of superhydrophobic characteristic, will play to hull like this effect of drag reduction, thereby save the consumption to the oils energy; Further, we can also be by silver ion, temperature sensitivity material, and photosensitive molecular, material heat-resisting, resistance to acids and bases is prepared in polymer multilayer film, thereby makes prepared polymer multilayer film with corresponding character.Polymer multilayer film is applicable to multiple material, can comparatively ideally reach the requirement of people to new material, and it is with a wide range of applications, and higher using value.
1991, the fairly simple method of preparing polymer multilayer film was suggested first.Traditional preparation method adopts the mode of alternately soaking substrate in the polyelectrolyte solution with opposite charges, prepares polymer multilayer film thus at substrate surface.The method of soaking due to what adopt, so that traditional preparation method has the selection of substrate is larger restricted, and length consuming time, be not suitable for suitability for industrialized production.In order to improve the shortcoming in traditional preparation method, in the time of recent two decades, scientists has been developed the method for some improvement, for example: spin coating construction from part, spraying construction from part and continuously dynamic construction from part etc., the shortcoming of looking consuming time in traditional assemble method that above modification method has been single improvement.New modification method is still not suitable for suitability for industrialized production.Therefore, develop a kind of industrial method of the quick preparation that can realize polymer multilayer film in planar substrates and non-planar substrate extremely urgent.
Summary of the invention
The object of the invention is to overcome that prior art is high to substrate requirement, preparation process length consuming time and be not suitable for the shortcoming of suitability for industrialized production, and provide one efficient technology of preparing, realized the preparation of polymer multilayer film in planar substrates and non-planar substrate, and the present invention is applicable to suitability for industrialized production.
Can be in planar substrates and non-planar substrate the method for rapid preparation of polymer multilayer film, its feature is: the method is that high-gravity technology is combined with layer-by-layer, in the environment of hypergravity, replaces stratiform self assembling process.
Described hypergravity refers to than terrestrial gravitation acceleration (9.8m/s
2) under much bigger environment, the power that material is suffered.Under hypergravity condition, the molecular diffusion between different sized molecules and interphase mass transfer process are all than faster under conventional gravitational field.Existing research is mainly applied in high-gravity technology in the similar fields such as the preparation of selectively absorption of wastewater treatment, H2S, biooxidation reactions, nanometer grade powder material.The Elevated Gravity of the inventive method is to use hypergravity machine to realize.Wherein the interior filler as rotor by copper mesh, plays the effect of dispersing liquid.The size of substrate, shape depend on the structure of the hypergravity machine of selecting.
Described alternately layered self-packaging refers to substrate is immersed in the polyelectrolyte solution with opposite charges repeatedly, taking active forces such as hydrogen bond, coordinate bond or molecular recognition as motive force, there is the technology of the polymer multilayer film of specific function at substrate surface assembling one deck.
The inventive method goes for the preparation technology taking active forces such as coordinate bond, hydrogen bond, electrostatic interactions as the polymer multilayer film of film forming motive force.
The technical solution adopted for the present invention to solve the technical problems is:
1) quartz plate, silicon chip or polyethylene (be called for short PE) are cleaned, with washed with de-ionized water quartz plate or silicon chip, then dry up with nitrogen;
2) prepare the required solution of constructing primitive with static, hydrogen bond to acceptor, coordinate bond to acceptor: polymine (is called for short to PEI, M
w=1800,99%) be dissolved in the solution that in absolute ethyl alcohol, compound concentration is 0.1mg/ml; The nano zine oxide that is 30% by mass fraction (ZnO) dissolve with ethanol solution is in absolute ethyl alcohol, and compound concentration is the solution of 0.1mg/ml, 0.01mg/ml, 0.005mg/ml respectively; Kayexalate (is called for short to PSS, M
w=70000) be dissolved in deionized water the solution that compound concentration is 1mg/ml; The polydiene propyl-dimethyl ammonium chloride that is 20% by mass fraction (is called for short PDDA, M
w=200000) aqueous solution is diluted in deionized water, and compound concentration is the solution of 1mg/ml, 2mg/ml respectively; Nano-cerium oxide (the CeO that is 12% by 0.5ml mass fraction
2) aqueous solution is diluted in the PDDA aqueous solution of 1mg/ml of 80ml, prepares required PDDA+CeO
2the aqueous solution; Polyacrylic acid (is called for short to PAA, M
w=240000,25%) in dilution deionized water, compound concentration is the solution of 1mg/ml, 2mg/ml respectively; Diazo resin (Mw=2640) is dissolved in deionized water to the solution that compound concentration is 1mg/ml; The hydrochloride of polypropylene amine (is called for short to PAH, M
w=15000) be dissolved in deionized water the solution that compound concentration is 2mg/ml;
3) clean substrate is placed in a kind of above-mentioned solution and soaks 30min, take out with absolute ethyl alcohol or deionized water rinsing, then after drying up with nitrogen, put into the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed; By the Flow-rate adjustment of charging constant flow pump, at 8-42ml/min, the rotational speed regulation of hypergravity machine is at 600-3000rpm;
4) to the above-mentioned solution of another kind that passes into 5s-10min in hypergravity machine, idle running 30s-1min, passing into 1min-2min absolute ethyl alcohol or deionized water cleans, idle running 30s-1min, pass into again the solution using when 5s-10min soaks substrate, idle running 30s-1min, passing into 1min-2min absolute ethyl alcohol or deionized water cleans, idle running 30s-1min, repeat above operation, until quartz plate, in silicon chip or PE surface-assembled after the polymer multilayer film of the required number of plies, stop passing into solution, take out quartz plate, silicon chip or PE, at quartz plate, silicon chip or PE surface make the required number of plies, the polymer multilayer film of thickness and character.
A kind of novel method of preparing polymer multilayer film at substrate surface that involved in the present invention is, this kind of method is that substrate is placed in to hypergravity machine, replaces stratiform self assembling process under the condition of hypergravity.The ultraviolet absorptivity of the every strata compound film to quartz plate, PE surface-assembled in preparation process detects, from result, can find out, every strata compound film has the absorbance of near-sighted equal sizes, this just illustrates that hypergravity assemble method has good stability in the process of preparing polymer multilayer film, can prepare the polymer multilayer film of same thickness for every layer.By AFM, we observe, the concentration of no matter assembling solution is how many, the polymer multilayer film on the quartz plate surface that utilization hypergravity assemble method obtains with immersion assemble method has similar coverage and surface topography, soaks the time that assemble method uses but the time that hypergravity assemble method uses is obviously less than.This is explanation just, and hypergravity assemble method is a kind of method of rapid preparation of polymer multilayer film, and it can prepare the polymer multilayer film with immersion process same nature and thickness in the short period of time.
The present invention, by the research of the character of the preparation process to quartz plate, silicon chip or PE surface aggregate thing multilayer film and the polymer multilayer film to preparation, has confirmed a kind of feasibility of new rapid preparation of polymer multilayer film method.Polymer multilayer film prepared by the present invention can have different functional characters according to the difference of constructing primitive of its selection.For example, because Particle Size of Nanometer ZnO is little, the transparency is high, a kind of novel high function fine inorganic material with excellent ultraviolet radiation absorption function, so, use PEI and nano zine oxide can be widely used in antiultraviolet field as constructing polymer multilayer film prepared by primitive.And, nano zine oxide has fabulous anti-oxidant and resistance to corrosion, high fusing point, good mechanical-electric coupling and the feature of environmental protection, can make the polymer multilayer film of preparation there are many unusual characteristics at aspects such as optics, electricity, magnetics, chemistry, have a wide range of applications aspect numerous at photoelectric device, chemical industry, medicine etc.; In addition, nano-cerium oxide has good chemical stability, at high temperature has good lubricity, so the polymer multilayer film that uses nano-cerium oxide to prepare has certain friction resistant performance.Can find out, the polymer multilayer film that uses the inventive method to prepare has good character, can be widely used in the preparation process of material, equipment surface aggregate thing multilayer film.The method is with a wide range of applications equally preparing the field such as environment-friendly materials, self-cleaning material.
1, the inventive method has the character of rapid-assembling, can effectively promote the preparation speed of polymer multilayer film, and the character of prepared polymer multilayer film does not change;
2, the inventive method is applicable to difform substrate, and according to hypergravity machine model selected in preparation process, the difference of specification, the inventive method can be for the preparation process of planar substrates, non-planar substrate and special substrate surface polymer multilayer film;
3, the inventive method is applicable to the substrate of unlike material, can in the materials such as quartz, glass, silicon chip, prepare polymer multilayer film;
4, the inventive method has stronger concentration adaptive character, under low concentration, the inventive method still can realize the quick preparation of polymer multilayer film, and character and the thickness of the polymer multilayer film of preparing under the character of the polymer multilayer film of preparation and thickness and High Concentration Situation do not have difference;
5, the inventive method goes for multiple assembling solution, and according to the difference of hypergravity machine model selected in preparation process, the inventive method can be applied to the assembling of the heterogeneity assembling liquid such as acid assembling liquid, alkalescence assembling liquid;
6, the inventive method method of operating is simple, and the operating time is short, and efficiency is high;
7, the inventive method is applicable to suitability for industrialized production.
Brief description of the drawings
Fig. 1. the hypergravity machine legend that the present invention selects, 1: liquid-inlet, 2: liquid outlet, 3: filler, 4: rotor, 5: axle, 6: liquid distribution trough, 7: shell;
Fig. 2. process flow diagram flow chart of the present invention, 1: liquid-inlet, 2: liquid outlet;
Fig. 3. the linear relationship research figure of PEI/ZnO polymer multilayer film ultraviolet absorptivity value prepared by the present invention;
Fig. 4. the affect figure of hypergravity machine rotor speed on the PEI/ZnO polymer multilayer film ultraviolet absorptivity value of preparing;
Fig. 5. the affect figure of the flow of charging constant flow pump on the PEI/ZnO polymer multilayer film ultraviolet absorptivity value of preparing;
Fig. 6. under variable concentrations, use the inventive method to measure curve of adsorption kinetics figure, zero: 0.1mg/ml,: 0.01mg/ml, △: 0.005mg/ml; Fig. 7. under variable concentrations condition, use different assemble methods to measure dynamic absorption curve map; (1): 0.1mg/ml (zero: hypergravity,: soak), (2): 0.01mg/ml (zero: hypergravity,: soak), (3): 0.005mg/ml (zero: hypergravity,: soak);
Fig. 8. under variable concentrations condition, use different assemble methods to prepare the atomic force microscopy figure of individual layer PEI/ zinc oxide polymer film;
Fig. 9. the curve of adsorption kinetics figure that uses the inventive method to measure under different rotating speeds condition, zero: 3000rpm,: 2400rpm, △: 1800rpm, ◇: 1200rpm,
600rpm; Figure 10. the saturated adsorption time under different rotating speeds condition and the relation of rotating speed;
Figure 11. PDDA+CeO prepared by the inventive method
2the linear relationship research figure (quartz plate is substrate) of/PSS polymer multilayer film ultraviolet absorptivity value;
Figure 12. PDDA+CeO prepared by the inventive method
2the linear relationship research figure (PE is substrate) of/PSS polymer multilayer film ultraviolet absorptivity value;
Figure 13. the linear relationship research figure of diazo resin/PAA polymer multilayer film ultraviolet absorptivity value prepared by the inventive method;
Figure 14. the linear relationship research figure of PAH/PAA polymer multilayer film ultraviolet absorptivity value prepared by the inventive method.
Detailed description of the invention
Below in conjunction with examples of implementation and accompanying drawing, technical scheme of the present invention is further described:
Embodiment 1:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into respectively nano zine oxide ethanolic solution 1min, idle running 30s, passes into absolute ethyl alcohol 1min, and idle running 30s, takes out the ultraviolet absorptivity that detects quartz plate;
6, the quartz plate of assembling one layer of polymeric film is put into hypergravity machine, pass into PEI ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, then pass into nano zine oxide ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, takes out the ultraviolet absorptivity that detects quartz plate;
7, repeating step 6, until detect 8 strata compound films.
As shown in Figure 3, the ultraviolet absorptivity of PEI/ZnO polymer multilayer film is linear growth to acquired results.Illustrate that constructing primitive can be spread to quartz plate surface, alternately stratiform self assembling process can carry out smoothly, and the inventive method can be used for preparing polymer multilayer film.PEI and nano zine oxide are taking coordinate bond as film forming motive force, and by experimental result, we know that the inventive method can be applied to the preparation technology taking coordinate bond as the polymer multilayer film of film forming motive force.
Embodiment 2:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the rotational speed regulation of hypergravity is at 3000rpm.The quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, then pass into PEI ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, until preparation 5 strata compound films take out the ultraviolet absorptivity that detects quartz plate;
6, the rotating speed that changes hypergravity, is adjusted in respectively 2400rpm, 1800rpm, 1200rpm, 600rpm, the experimentation of repeating step 5.
As shown in Figure 4, in the time that the rotating speed of hypergravity machine is controlled between 600～1800rpm, the ultraviolet absorptivity of 5 strata compound multilayer films shows a rising trend acquired results, and the larger slope of a curve of rotating speed is less; In the time that rotating speed is controlled at 1800～3000rpm, the ultraviolet absorptivity of 5 strata compound multilayer films remains unchanged, and illustrates in the time that rotating speed reaches certain numerical value, within the identical time, constructs primitive and be diffused into substrate surface within the extremely short time, and acceleration is more obvious.
Embodiment 3:
1, silicon chip is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use deionized water cleaning silicon chip, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean silicon chip is placed in the PEI ethanolic solution of 1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the silicon chip soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 1min, idle running 1min, pass into absolute ethyl alcohol 2min, idle running 1min, pass into PEI ethanolic solution 1min, idle running 1min, passes into absolute ethyl alcohol 2min again, idle running 1min, the silicon chip of preparation surface-assembled 10 strata compound multilayer films;
6, the standardized cut of silicon chip surface at gained with tweezers.
Embodiment 4:
1, silicon chip is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use deionized water cleaning silicon chip, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean silicon chip is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the silicon chip soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 1min, idle running 1min, pass into absolute ethyl alcohol 2min, idle running 1min, pass into PEI ethanolic solution 1min, idle running 1min, passes into absolute ethyl alcohol 2min again, idle running 1min, the silicon chip of preparation surface-assembled 10 strata compound multilayer films;
6, the standardized cut of silicon chip surface at gained with tweezers.
Embodiment 5:
1, silicon chip is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use deionized water cleaning silicon chip, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.01mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean silicon chip is placed in the PEI ethanolic solution of 0.01mg/ml and soaks 60min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the silicon chip soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 5min, idle running 1min, pass into absolute ethyl alcohol 2min, idle running 1min, pass into PEI ethanolic solution 5min, idle running 1min, passes into absolute ethyl alcohol 2min again, idle running 1min, the silicon chip of preparation surface-assembled 10 strata compound multilayer films;
6, the standardized cut of silicon chip surface at gained with tweezers.
Embodiment 6:
1, silicon chip is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use deionized water cleaning silicon chip, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.005mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean silicon chip is placed in the PEI ethanolic solution of 0.001mg/ml and soaks 150min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the silicon chip soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 10min, idle running 1min, pass into absolute ethyl alcohol 2min, idle running 1min, pass into PEI ethanolic solution 10min, idle running 1min, passes into absolute ethyl alcohol 2min again, idle running 1min, the silicon chip of preparation surface-assembled 10 strata compound multilayer films;
6, the standardized cut of silicon chip surface at gained with tweezers.
From cut, can find out, assemble one layer of polymeric multilayer film at silicon chip surface, illustrate that the inventive method can be used for the preparation technology of silicon chip surface polymer multilayer film.
Embodiment 7:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 8ml/min; The rotational speed regulation of hypergravity is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To alternately passing into following solution in hypergravity machine: nano zine oxide ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, then pass into PEI ethanolic solution 1min, idle running 30s, pass into absolute ethyl alcohol 1min, idle running 30s, until preparation 5 strata compound films take out the ultraviolet absorptivity that detects quartz plate;
6, the flow that changes charging constant flow pump, is adjusted in respectively 16ml/min, 26ml/min, 34ml/min, the experimentation of repeating step 5.
As shown in Figure 5, in the time that the flow-control of charging constant flow pump is between 0～26ml/min, the ultraviolet absorptivity of 5 strata compound multilayer films is linear growth trend to acquired results; When flow-control is during at 26～42ml/min, the ultraviolet absorptivity of 5 strata compound multilayer films shows a rising trend, but slope much smaller than range of flow the slope between 0～26ml/min.This phenomenon explanation, within the scope of low discharge, flow is larger on the adsorbance impact on quartz plate surface.
Embodiment 8:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into nano zine oxide ethanolic solution 5s, idle running 30s, then pass into absolute ethyl alcohol 1min, and idle running 30s, taking-up quartz plate detects its ultraviolet absorptivity;
6, change the time that passes into nano zine oxide ethanolic solution in hypergravity machine into 10s, 15s, 30s, 45s, 1min, 2min, 5min, repeat step 5.
Embodiment 9:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.01mg/ml; 3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To the nano zine oxide ethanolic solution 30s that passes into 0.01mg/ml in hypergravity machine, idle running 30s, then pass into absolute ethyl alcohol 1min, idle running 30s, takes out quartz plate and detects its ultraviolet absorptivity;
6, change the time of the nano zine oxide ethanolic solution that passes into 0.01mg/ml in hypergravity machine into 1min, 2min, 3min, 4min, 5min, 10min, repeat step 5.
Embodiment 10:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.005mg/ml; 3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To the nano zine oxide ethanolic solution 1min that passes into 0.005mg/ml in hypergravity machine, idle running 30s, then pass into absolute ethyl alcohol 1min, idle running 30s, takes out quartz plate and detects its ultraviolet absorptivity;
6, change the time of the nano zine oxide ethanolic solution that passes into 0.005mg/ml in hypergravity machine into 2min, 3min, 4min, 5min, 6min, 7min, 8min, 10min, repeat step 5.
Measured curve of adsorption kinetics as shown in Figure 6, as can be seen from the figure, uses the inventive method can reach in the short period of time absorption saturated.
Comparative example 1:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the zinc oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 5s in the nano zine oxide ethanolic solution of 0.1mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, detect its ultraviolet absorptivity;
4, change the time of the nano zine oxide ethanolic solution that is immersed in 0.1mg/ml into 10s, 15s, 30s, 45s, 1min, 2min, 3min, 4min, 5min, 10min, repeat step 3.
Comparative example 2:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.01mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 5min in the nano zine oxide ethanolic solution of 0.01mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, detect its ultraviolet absorptivity;
4, change the time of the nano zine oxide ethanolic solution that is immersed in 0.01mg/ml into 10min, 15min, 20min, 25min, 30min, 35min, 40min, 50min, 60min, repeat step 3.
Comparative example 3:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.005mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 20min in the nano zine oxide ethanolic solution of 0.005mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, detect its ultraviolet absorptivity;
4, change the time of the nano zine oxide ethanolic solution that is immersed in 0.005mg/ml into 40min, 60min, 80min, 100min, 120min, 140min, repeat step 3.
As shown in Figure 7, Fig. 7 (1) is under 0.1mg/ml concentration conditions for embodiment experimental result and comparative example experimental result, uses hypergravity assembling simultaneously and soak assemble method the comparison of measuring dynamic absorption curve; Fig. 7 (2) is under 0.01mg/ml concentration conditions, use hypergravity assembling simultaneously and soak assemble method and measure the comparison of dynamic absorption curve, Fig. 7 (3) under 0.005mg/ml concentration conditions, use hypergravity assembling simultaneously and soak assemble method and measure relatively distinguishing of dynamic absorption curve.As can be seen from the figure,, in the time that concentration is 0.1mg/ml, reaches absorption and the saturated time shorten to 45s by 4min; In the time that concentration is 0.01mg/ml, reaches absorption and the saturated time shorten to 3min by 35min; In the time that concentration is 0.005mg/ml, reach absorption and the saturated time shorten to 7min by 100min, this shows, the inventive method can improve greatly soaks the alternately time of stratiform self-assembling technique.
Embodiment 11:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To the nano zine oxide ethanolic solution 5min that passes into 0.1mg/ml in hypergravity machine, idle running 30s, then pass into absolute ethyl alcohol 1min, idle running 30s, takes out quartz plate and under AFM, observes its surface topography and coverage.
Embodiment 12:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.01mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To the nano zine oxide ethanolic solution 5min that passes into 0.01mg/ml in hypergravity machine, idle running 30s, then pass into absolute ethyl alcohol 1min, idle running 30s, takes out quartz plate and under AFM, observes its surface topography and coverage.
Embodiment 13:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.005mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To the nano zine oxide ethanolic solution 10min that passes into 0.005mg/ml in hypergravity machine, idle running 30s, then pass into absolute ethyl alcohol 1min, idle running 30s, takes out quartz plate and under AFM, observes its surface topography and coverage.
Comparative example 4:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 10min in the nano zine oxide ethanolic solution of 0.1mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, under AFM, observe its surface topography and coverage.
Comparative example 5:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.01mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 60min in the nano zine oxide ethanolic solution of 0.01mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, under AFM, observe its surface topography and coverage.
Comparative example 6:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: PEI is dissolved in absolute ethyl alcohol, be mixed with the solution that concentration is 0.1mg/ml, the nano zine oxide ethanolic solution that is 30% by mass fraction is diluted in absolute ethyl alcohol, is mixed with the solution that concentration is 0.005mg/ml;
3, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen.Again the quartz plate soaking is immersed in to 140min in the nano zine oxide ethanolic solution of 0.005mg/ml in PEI ethanolic solution, after taking out quartz plate absolute ethyl alcohol and cleaning, then dries up with nitrogen, under AFM, observe its surface topography and coverage.
The atomic force microscopy obtaining contrasts as shown in the figure, and Fig. 8 (1) is under 0.1mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method; Fig. 8 (2) is under 0.1mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method; Fig. 8 (3) is under 0.01mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method; Fig. 8 (4) is under 0.01mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method; Fig. 8 (5) is under 0.005mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method; Fig. 8 (6) is under 0.005mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method, as can be seen from the figure, the single-layer polymer film tube obtaining under different condition has identical surface topography and coverage, this explanation, the inventive method does not change the character of prepared polymer multilayer film, so use the immersion polymer multilayer film that alternately layered self-packaging can be prepared can use the inventive method to make yet.
Embodiment 14:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 600rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into nano zine oxide ethanolic solution 30s, idle running 30s, then pass into absolute ethyl alcohol 1min, and idle running 30s, taking-up quartz plate detects its ultraviolet absorptivity;
6, change the time that passes into nano zine oxide ethanolic solution in hypergravity machine into 60s, 90s, 120s, 150s, 180s, 200s, 220s, 240s, repeat step 5.
Embodiment 15:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 1200rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into nano zine oxide ethanolic solution 15s, idle running 30s, then pass into absolute ethyl alcohol 1min, and idle running 30s, taking-up quartz plate detects its ultraviolet absorptivity;
6, change the time that passes into nano zine oxide ethanolic solution in hypergravity machine into 30s, 45s, 60s, 75s, 90s, 105s, 120s, 150s, repeat step 5.
Embodiment 16:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and nano zine oxide ethanolic solution: the nano zine oxide ethanolic solution that the solid PEI that is 99% by mass fraction and mass fraction are 30% dissolves respectively and is diluted in absolute ethyl alcohol, the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 1800rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into nano zine oxide ethanolic solution 10s, idle running 30s, then pass into absolute ethyl alcohol 1min, and idle running 30s, taking-up quartz plate detects its ultraviolet absorptivity;
6, change the time that passes into nano zine oxide ethanolic solution in hypergravity machine into 20s, 30s, 40s, 50s, 60s, 70s, 80s, 120s, repeat step 5.
Embodiment 17:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PEI ethanolic solution and zinc oxide ethanolic solution: the nano zine oxide ethanolic solution that is 30% by PEI and mass fraction dissolves respectively and is diluted in absolute ethyl alcohol, and the solution concentration of preparation is 0.1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 3000rpm;
4, clean quartz plate is placed in the PEI ethanolic solution of 0.1mg/ml and soaks 30min, after cleaning with absolute ethyl alcohol, then dry up with nitrogen;
5, the quartz plate soaking in PEI ethanolic solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into nano zine oxide ethanolic solution 5s, idle running 30s, then pass into absolute ethyl alcohol 1min, and idle running 30s, taking-up quartz plate detects its ultraviolet absorptivity;
6, change the time that passes into nano zine oxide ethanolic solution in hypergravity machine into 10s, 15s, 20s, 25s, 30s, 45s, 60s, 120s, repeat step 5.
As shown in Figure 9, as can be seen from the figure, along with the increase of rotating speed, the time of the absorption that reaches capacity shortens measured curve of adsorption kinetics.Saturated adsorption time under different rotating speeds and the relation of rotating speed as shown in figure 10, can significantly be observed out from figure, and rotating speed is larger, and saturated adsorption time is shorter, and the degree that saturated adsorption time changes with rotating speed is larger.So while preparing polymer multilayer film, under the condition of larger rotating speed, can shorten the time that passes into assembling solution.This experimental result also to Fig. 4 made explanation: Fig. 4 select built-up time be 1min, in the time that hypergravity machine rotating speed is 600-1200rpm, the absorption on quartz plate surface does not reach capacity, and adsorbance can increase along with the increase of rotating speed; In the time that hypergravity machine rotating speed is 1800-3000rpm, it is saturated that the quartz plate surface under any rotating speed reaches absorption, so the absorbance on 5 double-deck quartz plate surfaces of assembling does not change.
Embodiment 18:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare the required PSS aqueous solution, the PDDA aqueous solution and PDDA+CeO2 solution: the PDDA aqueous solution that is 20% by PSS and mass fraction dissolves respectively and is diluted in deionized water, the solution concentration of preparation is 1mg/ml, the nano-cerium oxide aqueous solution that is 12% by 0.5ml mass fraction is diluted in the PDDA aqueous solution of 1mg/ml of 80ml, prepares the required PDDA+CeO2 aqueous solution;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PDDA aqueous solution of 1mg/ml and soaks 30min, with after washed with de-ionized water, then dry up with nitrogen; The quartz plate soaking in the PDDA aqueous solution is inserted in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into PSS solution 1min, idle running 30s, passes into deionized water 1min, and idle running 30s carries out substrate modification;
5, in hypergravity machine, pass into PDDA+CeO2 aqueous solution 2min, idle running 30s, pass into deionized water 1min, idle running 30s, passes into PSS aqueous solution 1min, idle running 30s, pass into deionized water 1min, idle running 30s, the polymer multilayer film that preparation surface-assembled is 5 layers, taking-up quartz plate detects its ultraviolet absorptivity;
6, the experiment of repeating step 5, until 30 bilayers of quartz plate surface-assembled.
Experimental result as shown in figure 11, PSS and PDDA+CeO2 can replace stratiform self assembling process smoothly on quartz plate surface.PSS and PDDA+CeO2 be taking electrostatic interaction and coordinate bond as film forming motive force, and by experimental result, we know that the inventive method can be applied to taking electrostatic interaction and coordinate bond in the preparation technology of the polymer multilayer film of film forming motive force.
Embodiment 19:
1, by alternately ultrasonic cleaning four times in deionized water and ethanol of PE, each ultrasonic 5min, finally with drying up with nitrogen after deionized water rinsing;
2, prepare the required PSS aqueous solution, the PDDA aqueous solution and PDDA+CeO2 solution: the PDDA aqueous solution that the solid PSS that is 100% by mass fraction and mass fraction are 20% dissolves respectively and is diluted in deionized water, the solution concentration of preparation is 1mg/ml, the nano-cerium oxide aqueous solution that is 12% by 0.5ml mass fraction is diluted in the PDDA aqueous solution of 1mg/ml of 80ml, prepares the required PDDA+CeO2 aqueous solution;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean PE is placed in the PDDA aqueous solution of 1mg/ml and soaks 30min, with after washed with de-ionized water, then dry up with nitrogen; The PE soaking in the PDDA aqueous solution is fixed in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.In hypergravity machine, pass into PSS solution 1min, idle running 30s, passes into deionized water 1min, and idle running 30s carries out substrate modification;
5, in hypergravity machine, pass into PDDA+CeO2 aqueous solution 2min, idle running 30s, passes into deionized water 1min, idle running 30s, pass into PSS aqueous solution 1min, idle running 30s, passes into deionized water 1min, idle running 30s, the polymer multilayer film that preparation surface-assembled is 5 layers, taking-up PE detects its ultraviolet absorptivity;
6, the experiment of repeating step 7, until 25 bilayers of quartz plate surface-assembled.
Experimental result as shown in figure 12, PE is soft substrate, and can there is nonplanar torsion in assembling, PSS and PDDA+CeO2 can replace stratiform self assembling process smoothly on PE surface, illustrate that the inventive method not only can be applied to the preparation of plane polymer multilayer film, and can be applied to the preparation of non-planar substrate surface aggregate thing multilayer film, have advantages of and be applicable to multiple substrate.
Embodiment 20:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare required PAA solution and diazo resin solution: the PAA aqueous solution that is 25% by mass fraction and diazo resin dilute respectively and be dissolved in deionized water, the solution concentration of preparation is 1mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is immersed in the mixed solution of hydrogen peroxide and glacial acetic acid, in quartz plate finishing, has become sulfonic group;
5, the quartz plate soaking in mixed solution is fixed in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To passing into following solution in hypergravity machine: diazo resin aqueous solution 1min, idle running 30s, passes into deionized water 1min, and idle running 30s, passes into PAA aqueous solution 1min, and idle running 30s, passes into deionized water 1min, and idle running 30s takes out quartz plate and detects its ultraviolet absorptivity;
6, repeating step 6, until preparation 10 strata compound films.
Experimental result as shown in figure 13, the ultraviolet absorptivity of diazo resin/PAA polymer multilayer film is linear growth.Diazo resin and PAA be taking electrostatic interaction and hydrogen bond as film forming motive force, and by experimental result, we know that the inventive method can be applied to the preparation technology taking electrostatic interaction and hydrogen bond as the polymer multilayer film of film forming motive force.
Embodiment 21:
1, quartz plate is immersed in the mixed solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 7: 3) of 98% concentrated sulfuric acid and 30% hydrogen peroxide and cleans to without till Bubble formation, use washed with de-ionized water quartz plate, then dry up with nitrogen;
2, prepare the required PAH aqueous solution, the PAA aqueous solution: the PAA aqueous solution that is 25% by mass fraction and PAH dilute respectively and be dissolved in deionized water, the solution concentration of preparation is 2mg/ml;
3, by the Flow-rate adjustment of charging constant flow pump at 42ml/min, the rotational speed regulation of hypergravity machine is at 2400rpm;
4, clean quartz plate is placed in the PAH aqueous solution of 2mg/ml and soaks 30min, with after washed with de-ionized water, then dry up with nitrogen
5, the quartz plate soaking in the PAH aqueous solution is fixed in the draw-in groove of hypergravity machine rotor, then rotor is put into hypergravity machine, hypergravity machine is installed.To passing into following solution in hypergravity machine: PAA aqueous solution 1min, idle running 30s, passes into deionized water 1min, and idle running 30s takes out quartz plate and detects its ultraviolet absorptivity;
6, the quartz plate of assembling one layer of polymeric film is put into hypergravity machine, pass into PAH aqueous solution 1min, idle running 30s, passes into deionized water 1min, idle running 30s, then pass into PAA aqueous solution 1min, idle running 30s, pass into deionized water 1min, idle running 30s, takes out the ultraviolet absorptivity that detects quartz plate;
7, the experiment of repeating step 6, until 9 bilayers of quartz plate surface-assembled.Experimental result as shown in figure 14.Under soaking conditions, the alternately stratiform assembling process of PAH and PAA is exponential increase, the PAH/PAA polymer multilayer film that uses the inventive method to prepare is also exponential increase, explanation thus, the inventive method is simple raising prepares the speed of polymer multilayer film, and do not change the physical property of preparation process, so that the inventive method has is stronger stable.
The illustraton of model of the hypergravity machine that the inventive method is selected is shown in Fig. 1, the process flow diagram flow chart of the inventive method is shown in Fig. 2, Fig. 3 is shown in the linear relationship research of PEI/ zinc oxide polymer multilayer film ultraviolet absorptivity value prepared by utilization the inventive method, while using the inventive method to prepare polymer multilayer film, Fig. 4 is shown in the impact of the PEI/ZnO polymer multilayer film of hypergravity machine rotating speed on preparation, while using the inventive method to prepare polymer multilayer film, Fig. 5 is shown in the impact of the PEI/ZnO polymer multilayer film of the flow of charging constant flow pump on preparation, the curve of adsorption kinetics that uses the inventive method to measure under variable concentrations is shown in Fig. 6 (zero: 0.1mg/ml,: 0.01mg/ml, △: 0.005mg/ml), under variable concentrations condition, that uses dynamic absorption curve that hypergravity assemble method measures relatively sees Fig. 7 (1): 0.1mg/ml (zero: hypergravity,: soak), (2): 0.01mg/ml (zero: hypergravity,: soak), (3): 0.005mg/ml (zero: hypergravity,: soak), under 0.1mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method is shown in Fig. 8 (1), under 0.1mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method is shown in Fig. 8 (2), under 0.01mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method is shown in Fig. 8 (3), under 0.01mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method is shown in Fig. 8 (4), under 0.005mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization hypergravity assemble method is shown in Fig. 8 (5), under 0.005mg/ml concentration conditions, the atomic force microscopy of single-layer polymer film tube prepared by utilization immersion assemble method is shown in Fig. 8 (6).Use curve of adsorption kinetics under the different rotating speeds condition that records of the inventive method see Fig. 9 (zero: 3000rpm,: 2400rpm, △: 1800rpm, ◇: 1200rpm,
600rpm); Saturated adsorption time under the different rotating speeds condition that utilization the inventive method records and the relation of rotating speed are shown in Figure 10; Use the PDDA+CeO of hypergravity assemble method in the preparation of quartz plate surface
2figure 11 is shown in the linear relationship research of/PSS polymer multilayer film ultraviolet absorptivity value; Use the PDDA+CeO of hypergravity assemble method in the preparation of PE surface
2figure 12 is shown in the linear relationship research of/PSS polymer multilayer film ultraviolet absorptivity value; Use the linear relationship research of diazo resin/PAA polymer multilayer film ultraviolet absorptivity value of hypergravity assemble method surface preparation to see Figure 13; Figure 14 is shown in the linear relationship research of PAH/PAA polymer multilayer film ultraviolet absorptivity value prepared by utilization hypergravity assemble method.
Claims (1)
1. can be in planar substrates and non-planar substrate the method for rapid preparation of polymer multilayer film, its feature is that step is as follows:
1) quartz plate, silicon chip or polyethylene are cleaned, with washed with de-ionized water quartz plate, silicon chip or polyethylene, then dry up with nitrogen;
2) prepare required solution: it is the solution of 1-0.005 mg/ml that polymine is dissolved in to compound concentration in absolute ethyl alcohol; The nano zine oxide dissolve with ethanol solution that is 30% by mass fraction is in absolute ethyl alcohol, and compound concentration is the solution of 1-0.005 mg/ml; Kayexalate is dissolved in deionized water, and compound concentration is the solution of 1 mg/ml; Polydiene propyl-dimethyl ammonium aqueous chloride solution is diluted in respectively in deionized water, and compound concentration is the solution of 1 mg/ml-2 mg/ml; The nano-cerium oxide aqueous solution is diluted in the PDDA aqueous solution of 1 mg/ml, prepares required PDDA+CeO
2the aqueous solution; Polyacrylic acid is diluted in deionized water, and compound concentration is the solution of 1-2 mg/ml; Diazo resin is dissolved in deionized water, and compound concentration is the solution of 1 mg/ml; The hydrochloride of polypropylene amine is dissolved in deionized water, and compound concentration is the solution of 2 mg/ml;
3) clean substrate is placed in a kind of above-mentioned solution and soaks 30 min, take out with absolute ethyl alcohol or deionized water rinsing, then after drying up with nitrogen, put into the draw-in groove of hypergravity machine rotor; Rotor is put into hypergravity machine, hypergravity machine is installed; By the Flow-rate adjustment of charging constant flow pump, at 8-42 ml/min, the rotational speed regulation of hypergravity machine is at 600-3000 rpm;
4) to the above-mentioned solution of another kind that passes into 5 s-10 min in hypergravity machine, 30 s-1 min dally, passing into 1 min-2 min absolute ethyl alcohol or deionized water cleans, 30 s-1 min dally, pass into again the solution using when 5 s-10 min soak substrate, 30 s-1 min dally, pass into absolute ethyl alcohol or deionized water is cleaned, 30 s-1 min dally, repeat above operation, until quartz plate, after the polymer multilayer film of silicon chip or the upper required number of plies of polyethylene surface assembling, stop passing into solution, take out quartz plate, silicon chip or polyethylene, at quartz plate, silicon chip or polyethylene surface make the required number of plies, the polymer multilayer film of thickness and character.
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| CN1857918A (en) * | 2006-05-30 | 2006-11-08 | 浙江大学 | Method for preparing high obstruction self assembling multilayer composite film |
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| US6033774A (en) * | 1994-12-14 | 2000-03-07 | Northwestern University | Self-assembled superlattices and waveguides prepared for use therewith |
| CN1857918A (en) * | 2006-05-30 | 2006-11-08 | 浙江大学 | Method for preparing high obstruction self assembling multilayer composite film |
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| 超重力条件下交替层状自组装制备聚合物多层膜;马兰馨、石峰;《2011年全国高分子学术论坛报告会》;20110924;第442页 * |
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