Ultrafarma surface

 

Describes structured (profiled) surface with Ultratone properties, and how it is obtained. The topography of this surface is characterized by the fact that the relationship between the spatial frequency f of the individual Fourier components and their amplitudes a(f) is determined by the function S:S(log f)=a(f)f, the integral of which is calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3 is at least 0.5 and that the surface is made of a hydrophobic or primarily oleophobic material or have a coating of such hydrophobic or primarily oleophobic material. The technical result of the invention is to enable the testing of different materials with different surface structure on their ultrafine properties, the ability of the claimed ultraformal surface to self-clean and no need for expensive production of a new negative topography required ultraformal surface. 6 N. and 20 C.p. f-crystals, 11 tab., 1 PL.

The present invention relates to ultraformal surface to method E. the only frequency f of the individual Fourier components and their amplitudes a(f) is determined by the function S

the integral of which is calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log (f2/μm-1) = 3 is at least 0.5 and that the surface is made of a hydrophobic or primarily oleophobic material or have a coating of such hydrophobic or primarily oleophobic material.

A distinctive feature of Ultraphobic surfaces is that the wetting angle of a drop of liquid, usually water, on the surface, significantly exceeds 90and the angle of roll does not exceed 10. Ultrafine surface with an edge angle of >150and above the angle of the roll are of great technical importance, since they cannot be wetted, for example, water, as well as oil, dirt particles possess only the smallest adhesion to these surfaces, and these surfaces are self-cleaning. Under the purification means is a surface property, in which sticky particles of dirt or dust can easily be washed off with her flow.

With this in mind, made the EP 476510 A1 describes a method of obtaining ultraformal surface, where on the glass surface applied film of metal oxide, after which the etching process using plasma discharge in argon (ar-plasma). The disadvantage is obtained in this way surfaces is that the boundary angle located at a surface of the droplets is less than 150.

In the patent US 5693236 also described several ways to obtain Ultraphobic surfaces, according to which the surface using appropriate linking cause microneedles from zinc oxide, after which it a different way (for example, plasma treatment) partially bare. Then, in a structured way the surface is applied a coating of water repellent products. However, with this approach, get structured (profiled) surface with boundary angle not exceeding 150.

From the application WO 96/04123 also known methods for producing Ultraphobic surfaces. Under proposed in this application technical solution the profile of the required surface will be in the manufacture of the respective molded articles made of hydrophobic polymers through the use of these order forms, internal powerteam approach inherent disadvantage, consisting in the fact that before the molded product with a desired surface profile, it is necessary to make the negative with this profile. In addition, in the manufacture of the specified form with a reverse imprint there is a possibility of occurrence of defects in the surface, which are then cast from the negative, i.e., obtain a "positive" of the hydrophobic polymer, will adversely affect the surface properties.

Based on the foregoing, the present invention was based on the objective to obtain a surface with Ultratone properties and to develop a method of obtaining such surfaces with boundary contact angle150and preferably with an angle inclining10.

The term "angle roll" in the context of the present description refers to the angle of mostly flat and together with the profiled surface relative to the horizontal at which a stationary drop of water volume of 10 µl with the inclination of the surface begins to slide it under their own gravity.

A special problem in this case, as apparent from the above examples, is that ultrafine properties stand the crystals, and they are in most cases different structure. To date, there is no way that would allow to determine ultrafine properties of surfaces regardless of the material from which they are made. Another object of the invention accordingly is to develop a method by which one could test the surface on their ultrafine properties regardless of the material from which they are made.

This task is solved according to the invention thanks to the profiled accordingly the surface with Ultratone properties, which differs in that it is characterized by topography, in which the integral of a function S

establishing the relationship between the spatial frequency f of the individual components of the Fourier series and their amplitudes a(f), calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3 is at least 0.5, and the surface itself is made of a hydrophobic or primarily oleophobic material or have a coating of such hydrophobic or primarily oleophobic material.

The hydrophobic material predstavlennosti exceeds 90.

Oleophobic material is according to the invention the material, wetting angle which the long-chain n-alkanes, such as n-decane, on a flat, non-profiled surface exceeds 90.

Preferably, the specified integral function (1) exceed 0,6.

It is preferable ultrafarma surface wetting angle which water is at least 150first of all at least 155.

Ultrafamous surface or substrate should consist of metal, plastic, glass or ceramics. Particularly preferred metal selected from the group comprising beryllium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhenium, palladium, silver, cadmium, indium, tin, lanthanum, cerium, prasadi, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, primarily titanium, aluminum, magnesium and Nickel, or an appropriate alloy of the aforementioned metals. Nai is IDE just A1Mg3.

As plastic for ultraphone surface or substrate, it is preferable to use an example or thermoplastics. Duroplast it is advisable to choose primarily from the group comprising diallylphthalate resin, epoxy resin, urea resin, melamine-formaldehyde resin, melamineformaldehyde resin, a phenol-formaldehyde resin, polyimide, silicone resin, unsaturated polyester resin. Thermoplastic advisable to choose primarily from a group comprising thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, politicaland, polyesters, such as PBT or PET, polystyrene, copolymer of styrene, a copolymer of styrene and Acrylonitrile, kouchakzadeh grafted copolymer of styrene, for example a copolymer of Acrylonitrile, butadiene and styrene (ABS), polyamide, polyurethane, polyster, polyvinyl chloride or any mixture of these polymers.

As substrates for surface according to the invention is primarily suitable thermoplastic polymers:

polyolefins, such as polyethylene high and low density, i.e. a density of from 0.91 to 0.97 g/cm3which can be obtained by known die industrielle application, Munchen, published by Hanser Verlag (1983)).

Besides the above-mentioned suitable polypropylene with a molecular weight of from 10000 to 1000000 g/mol, which can be obtained by known methods (see Ullmann, 5th edition, a10, page 615; Houben-Weyl E 20/2, page 722; Ullmann, 4th edition 19, page 95 and later; Kirk-Othmer, 3rd edition, 16, pages 357 and later).

Can also be used copolymers of these olefins or copolymers with other-olefins, such as copolymers of ethylene with butene, hexene and/or octene, a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and ethyl acrylate, a copolymer of ethylene and butyl acrylate, a copolymer of acrylic acid and ethylene, a copolymer of ethylene and vinylcarbazole, block copolymers of ethylene and propylene, a copolymer of ethylene, propylene and diene (Sept), polybutylene, polymethylpentene, polyisobutylene, copolymer of Acrylonitrile and butadiene, polyisoprene, copolymer of methyl and butylene, a copolymer of isoprene and isobutylene.

Methods of obtaining such polymers are described in particular in the following publications: Handbook Kunststoff-Handbuch, volume IV, Munchen, published by Hanser Verlag; Ullmann, 4th edition 19, page 167; Winnacker-Kuchler, 4th edition, 6, pp. 353-367; Elias and Vohwinkel, Neue Polymere Werkstoffe, Munchen, published by Hanser Verlag (1983); Franck and Biederbick, Kunststoff Kompendium, Wurzburg, ed-Vogel Verlag (19 polycarbonates, primarily those based diphenols formula I

in which

And indicates simple link1-C5alkylen,2-C5alkyliden,5-C6cycloalkylation, -S-, -SO2-, -O-, -CO -, or C6-C12Allenby residue, which optionally may be condensed with other containing heteroatoms, aromatic rings,

residues each independently from each other represents C1-C8alkyl,

With6-C10aryl, particularly preferably phenyl, With7-C12aralkyl,

preferably benzyl, halogen, preferably chlorine, bromine,

x is independent from other values, and means 0, 1 or 2 and

p denotes 1 or 0,

or substituted by alkyl dihydroxyphenylalanine formula II

in which

R1and R2independently of one another denote hydrogen, halogen, preferably chlorine or bromine, With1-C8alkyl, C5-C6cycloalkyl,6-C10aryl, preferably phenyl, and C7-C12aralkyl, preferably phenyl-C1-C4alkyl, especially benzyl,

m denotes an integer from 4 to 7, the UGA denote hydrogen or C1-C6alkyl, preferably hydrogen, methyl or ethyl, and

Z represents carbon, provided that at least one atom Z R3and R4simultaneously represent alkyl.

Suitable for use in these purposes diphenolate formula I are, among other things, hydroquinone, resorcinol, 4,4’-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. Preferred as diphenols formula I is 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis(4-hydroxyphenyl)cyclohexane.

For your preferred diphenols formula II include dihydroxydiphenyl-cycloalkanes with 5 and 6 ring C-atoms in the cycloaliphatic residue (m=4 or 5 in formula (II), such as divinely formulas IIA, IIb and IIC

when 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula IIc) is particularly preferred.

Suitable according to the invention, the polycarbonates can be obtained known by branched-chain, namely, more than three functional groups of compounds, for example containing three or more phenolic groups, which in particular include

toropytsin,

4,6-dimethyl-2,4,6-three(4-hydroxyphenyl)heptan-2,

4,6-dimethyl-2,4,6-three(4-hydroxyphenyl)heptane,

1,3,5-three(4-hydroxyphenyl)benzene,

1,1,1-three(4-hydroxyphenyl)ethane,

three-(4-hydroxyphenyl)phenylmethane,

2,2-bis(4,4-bis(4-hydroxyphenyl) cyclohexyl) propane,

2,4-bis(4-hydroxyphenyl)isopropyl)phenol,

2,6-bis(2-hydroxy-5’-methylbenzyl)-4-METHYLPHENOL,

2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane,

ether hexa (4-(4-hydroxyphenylethyl)phenyl)ochoterenai acid,

Tetra(4-hydroxyphenyl)methane,

Tetra(4-(4-hydroxyphenylethyl)phenoxy)methane and

1,4-bis-((4’-,4’-dihydroxydiphenyl)methyl)benzene.

From other trifunctional compounds can be called 2,4-dihydroxybenzoic acid, timesyou acid, trimellitic acid, cyanuric chloride and 3,3-bis(3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindol.

For your preferred polycarbonates along with homopolymerisation bisphenol a include copolycarbonate bisphenol a with up to 15 mol.%, in terms of mol. the total number of diphenols, 2,2-bis(3,5-dibromo-4-hydroxyphenyl) propane.

Used aromatic polycarbonates partially lieferservice known from the literature or can be obtained by known literature methods (extraction of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", published by Interscience Publishers, 1964 and DE-AS 1495626, DE-OS 2232877, DE-OS 2703376, DE-OS 2714544, DE-OS 3000610, DE-OS 3832396; obtaining aromatic poliefirketonov see, for example, DE-OS 3077934).

Aromatic polycarbonates and/or aromatic politicalparty can be obtained, for example, the interaction of diphenols with carbonic acid halides, preferably phosgene, and/or halides of aromatic dicarboxylic acids, preferably with dehalogenating benzylcarbamoyl acid, by the method that uses the interfacial reaction, optionally with the use of agents of an open circuit and, if necessary, using trifunctional or more than trifunctional splitters chain.

As thermoplastics can be used, in addition, styrene copolymers of one or at least two ethylene unsaturated monomers (vinyl monomers), such as styrene,-methylsterol substituted in the nucleus of styrene, Acrylonitrile, Methacrylonitrile, methyl methacrylate, maleic acid anhydride, N-substituted maleinimide and esters of (meth)acrylic acid with 1-18 C-atoms in the alcohol component. These copolymers of solobodan, Thurmer one monomer from the group including styrene,-methylsterol and/or substituted in the nucleus of styrene and at least one monomer from the group comprising Acrylonitrile, Methacrylonitrile, methyl methacrylate, maleic acid anhydride and/or N-substituted maleinimide.

Especially preferred mass ratio of styrene monomers and other vinyl monomers, thermoplastic copolymer, respectively 60-95 wt.% and 40-5 wt.%.

The most preferred copolymers are copolymers of styrene with Acrylonitrile and optionally with methyl methacrylate,-methylstyrene with Acrylonitrile and optionally with methyl methacrylate or copolymers of styrene and-methylstyrene with Acrylonitrile and optionally with methyl methacrylate.

Copolymers of styrene and Acrylonitrile are known and can be obtained by radical polymerization, especially by emulsion, suspension polymerization, polymerization in solution or in bulk. Molecular massthese copolymers (a weighted average determined by the scattering or sedimentation) is preferably from 15,000 to 200,000 g/mol.

Especially the slots, which can be obtained from the corresponding monomers preferably continuous polymerization in bulk or by polymerization in solution at incomplete conversion of the monomers. The proportion of both components as used according to the invention of statistical copolymers of styrene and maleic anhydride can vary within wide limits. The preferred content of maleic anhydride is from 5 to 25 wt.%.

Instead of the styrene polymers may also contain substituted in the nucleus of styrene, such as p-methylsterol, 2,4-dimethylstyrene and other substituted styrene, for example-methylsterol.

Molecular weight (srednekislye molecular mass) copolymers of styrene and maleic anhydride can vary within wide limits. The preferred range of 60,000 to 200,000 g/mol. Preferred characteristic viscosity of these products is from 0.3 to 0.9 (definition in dimethylformamide at 25C; see Hoffmann, Kromer, Kuhn, Polymeranalytik I, Stuttgart (1977), pages 316 and later).

As thermoplastics also acceptable grafted copolymers. This concept in the context of the present description includes having kyuchukov the uh the following monomers, selected from the group comprising chloroprene, butadiene-1,3, isopropane, styrene, Acrylonitrile, ethylene, propylene, vinyl acetate and esters of (meth)acrylic acid with 1-18 C-atoms in the alcohol component, i.e. the copolymers described, for example, in "Methods der Organischen Chemie (Houben-Weyl), volume 14/1, published by Georg Thieme-Verlag, Stuttgart (1961), pp. 393-406, and S. C. Bucknall "Toughened Plastics", published in Appl. Science Publishers, London (1977). Preferred graft copolymers which are partially crosslinked and contains the gel more than 20 wt.%, preferably more than 40 wt.% and above all, more than 60 wt.%.

To preferably apply the grafted copolymers include, among others, copolymers of styrene and/or Acrylonitrile and/or alilovic esters of (meth)acrylic acid grafted on the polybutadienes, copolymers of butadiene and styrene and the acrylate rubbers; i.e., the copolymers described in the application DE-OS 1694173 (patent US 3564077) type; grafted with alkylamino esters of acrylic or methacrylic acid, vinyl acetate, Acrylonitrile, styrene and/or alkylsilane polybutadienes, copolymers of butadiene and styrene or butadiene and Acrylonitrile, polyisobutene or polyisoprene described, for example, in the application DE-OS 2348377 (patent US 3919353).

Especially preferred polymers are, for example ABS plastic, measures can be obtained by known methods, for example, by polymerization in bulk, suspension, emulsion polymerization, or by a combination of polymerization in bulk and suspension polymerization.

As thermoplastic polyamides may be used polyamide 66 (polyhexamethylenediamine) or polyamides, cyclic lactams with 6 to 12 C-atoms, preferably of laurinlactam and particularly preferably-caprolactam, i.e., polyamide 6 (polycaprolactam), or copolyamids with the main components 6 and 66 or mixtures containing as the main component called polyamides. Preferred get activated anionic polymerization of polyamide 6 or received by the activated anionic polymerization of copolyamide, the main component of which is polycaprolactam.

As ceramic materials are oxides, carbides and nitrides of the aforementioned metals, as well as composites of these materials.

The topography of any surface can be described in principle on the basis of the composition composed of the Fourier components of the spatial frequency fxand fyand corresponding to these frequencies, amplitudes a(fx) and a(fy). When thisx=f-1xthe e widely used method for the determination of the so-called spectral power density S2(fxfy). The average power spectral density is proportional to the average value of the squares of all of the amplitudes at the respective spatial frequencies fxand fy. If we are talking about an isotropic surface, the topography of such a surface can be characterized using spectral power density PSD(f) averaged over the polar angle. Power spectral density PSD(f) though is a two-dimensional function of dimension [length]4nevertheless both directions of reference coincide, and therefore can be considered only one of them. This method is similar to the calculation described, for example, in the publication authors C. Ruppe and A. Duparre, Thin Solid Films 288 (1996), page 9, equation (2).

Depending on the used to determine the topography of the method of measuring the value of the spectral power density or receive directly, or the results must be converted into a power spectral density PSD(f) by Fourier-transform data about the height of roughness profile, which determines the surface topography. The technique is similar to the calculation described in the aforementioned publications C. Ruppe and A. Duparre, Thin Solid Films 288 (1996), page 9, which is incorporated into this description in the minute elevations (protrusions and depressions (hollows), height, respectively, the depth of which varies from 0.1 nm to 1 mm Due to such a wide range of values to determine the surface topography at the present time it is impossible with only one measurement method, and therefore to accurately determine the surface topography is necessary to use a combination of three methods of measuring and processing the results. Such measurement methods are:

1) interferometry on the interference of white light (CHD),

2) scanning atomic force microscopy (CACM),

3) scanning tunneling microscopy (STM).

These methods allow us to measure power spectral density PSD(f) in each case locally in relatively narrow rangesf spatial frequencies. Then these values locally specific spectral power density combined into the final (total) power spectral density PSD(f) in the range of spatial frequencies from f=10-3μm-1up to f=103μm-1. The method of this Association locally obtained PSD curves are described, for example, C. Ruppe and A. Duparre in Thin Solid Films 288 (1996), page 10, which publication is hereby incorporated into this description by reference.

Interferometry on the integration is stannah frequenciesf 110-3μm-1up to 1 μm-1while

to plot the measured surface size 11201120 μm measured at a range of spatial frequenciesf 910-4μm-1to 210-1μm-1,

to plot the measured surface size 280280 μm is in the range of spatial frequenciesf 410-3μm-1to 910-1μm-1,

to plot the measured surface size 140140 µm - range spatial frequenciesf 710-3μm-1to 2100μm-1.

During the measurements by this method the height of the roughness profile z(x,y) is determined using an interferometer used for measuring interference in white light, while z denotes the height above some arbitrary datum level z0in the corresponding point of x or y. In more detail the conditions for such research and measurement technique is described in R. J. Reck is discussed below is carried out at a scanning atomic force microscopy, accordingly scanning tunneling microscopy.

Scanning atomic force microscopy (CACM) are used to determine the spectral power density in the range of spatial frequenciesf 110-2μm-1to 1102μm-1and when the measurements by this method, which is widely known in the art, the height of the roughness profile zm,nthe surface is recorded by a scanning atomic force microscope in contact or vibrarion. During the measurements by this method scans different areas (ranges sample) of size LL. based On the scanned areas and the number N of points possible to calculate the minimum, respectively maximum spatial frequency that can be explored on each of the scanned area, thus we have the following condition: fmax=N/2L, respectively, fmin=1/L. Preferably each of the scanned area to use 512 points of measurement, and, thus, on the scanned area 5050 μm measured at a range of spatial frequenciesf 2f 110-1μm-1to 3101μm-1and

on the scanned area size 11 μm - range spatial frequenciesf from 1 μm-1to 3102μm-1.

The height of the roughness profile zm,ndetermine with respect to some arbitrarily chosen baseline z0where m and n are the coordinates of the measurement points in the direction of x, y respectively, which are separated from each other with an equal pitchL. Data on the height of the roughness profile are converted to mean values of spectral power density PSD, using the equations 1 and 2 presented in the publication of C. Ruppe and A. Duparre, Thin Solid Films 288 (1996), page 9.

Scanning tunneling microscopy (STM) are used to determine the spectral power density in the range of spatial frequenciesf 1101μm-1to 1103μm-1and when the measurements by this method, which is widely known in the art, the height is uneven is. When measuring this method also scan different parts of size LL. based On the scanned areas and the number N of points possible to calculate the minimum, respectively maximum spatial frequency that can be explored on each of the scanned area, thus we have the following condition: fmax=N/2L, respectively, fmin=1/L. Preferably each of the scanned area to use 512 points of measurement, and, thus, on the scanned area 0.50.5 µm measurement is carried out in the range of spatial frequenciesf from 2 μm-1to 5102μm-1,

on the scanned area with a size of 0.20.2 μm is in the range of spatial frequenciesf from 5 μm-1to 1103μm-1,

on the scanned area in the range of 0.10.1 ám - range spatial frequenciesf 1101μm-1to 3103μm-1.

The height of the roughness profile zm,ndefine relatively certain about the no x, accordingly y, which are separated from each other with an equal pitchL. Data on the height of the roughness profile are converted to mean values of spectral power density PSD, using the equations 1 and 2 presented in the publication of C. Ruppe and A. Duparre, Thin Solid Films 288 (1996), page 9.

In more detail the conditions for such research and measurement technique CACM and STM are described, for example, S. N. Magonov and M. N. Whangbo, Surface Analysis with STM and AFM, published by VCH, Weinheim (1966), in particular, on pages 47-62.

Obtained by different methods of measurement, respectively, for different scanned areas of the PSD curves unite in the PSD curve(f) in the range of spatial frequencies from 10-3μm-1up to 103μm-1. The specified curve PSD(f) is built on the basis of the received data in accordance with the method described C. Ruppe and A. Duparre in Thin Solid Films 288 (1996), pp. 10-11. In Fig.1-4 in this publication is shown resulting from such merger curves PSD(f) in a double logarithmic, in which log(PSD(f)/nm4) is a function of log(f/µm-1).

The method of determining the spectral power density of the specified type has been known and used for obtaining specifications are also other, ellingham, Washington, USA, Chapter 2, page 29 and forth, and Chapter 4, page 85 and below).

For a more visual confirmation of topography of surfaces, determined in accordance with the invention, on the basis of the spectral power density PSD(f) is calculated dependent on the spatial frequency amplitude a(f) sinusoidal Fourier components. With this purpose, use the formula (4.19) on page 103, and table 2.1 on page 34 and table 2.2 on page 37 of the above publications J. C. Stover, Optical Scattering, 2nd ed. (1995), published by SPIE Press, Bellingham, Washington, USA.

Normalized by the corresponding lengths of the structures=f-1the amplitude a(f) sinusoidal Fourier components are shown in Fig.5-8 as a function of S

the logarithm of the spatial frequency log(f/µm-1).

With the invention it has been unexpectedly found that the surface has a structure in which the integral of the function S(logf)=a(f)f calculated between the lower limit of integration f1/μm-1=-3 and the upper limit of integration f2/μm-1that is more than 0.5, and is made of a hydrophobic material or coated with a hydrophobic material, has ultramobile properties, Blagodat new, an unexpected effect allows largely to accurately determine in advance the possible subsequent technological operations in the manufacture Ultraphobic surfaces. The basic idea is the following: Fig.5-8 on a logarithmic frequency scale, log(f) is shown normalized to the corresponding wavelengths=f1the amplitude of the structures a(f)f for various frequencies f. The value of a(f)f=0.5 means, for example, that the normalized amplitude, i.e., "roughness" is defined for this Fourier component is half the length of the wave=f1. Thus the integral equation (1) reflects the following:

- the average of all normalized amplitudes a(f)f at different frequencies exceed a value of 0.5, in other words, to obtain ultraformal surface averaged over all frequencies, the roughness should be maximum;

- different spatial frequencies with equal weights included in this amount (expressed through log(f)).

Thus, no matter in any range of frequencies are separate roughness.

On this basis, the specialist will be able eticheskikh) particles of the same size will not give the desired effect. To achieve this effect, however, in that case, if you give the surface of the particles of the additional roughness due to smaller structures, using for this purpose, for example, small particles that are deposited on large particles or linked with them, but in any case both particles must not be separated from each other.

It is obvious further that, for example, when making the surface roughness of a drawing of her scratches (krzewina), (for example, by using abrasive particles), it is necessary to take into account the fact that the recesses (cavities) formed in this way should be in turn most rough in the range that does not extend beyond the next order-of-magnitude. Failure to comply with this condition roughening the specified primary recesses will need additional surgery.

Should be noted that the above-described new approach does not imply any limitation on the shape or profile of the recesses, respectively structures roughness. So, in the example where roughening use particles deposited on the surface and form required to obtain ultraformal surface structure, microsubstrates themselves Castoro these particles form on the surface.

The described approach when determining dependent frequency amplitudes of the Fourier components with spectral power density offers among other things a new, not known to date, the opportunity to experience a variety of materials with very different surface structure on their ultrafine properties and accordingly oharakterizovat them.

The object of the present invention is further a method of testing surfaces on their ultrafine properties, which differs from the surface by spraying a thin layer, especially a thickness of from 10 to 100 nm, from precious metals, primarily gold, or GaAs as adhesion promoter, then cover with a layer of auxiliary turuosaga substances, preferably by decantillon, and then analyze the surface topography, primarily using scanning tunneling microscopy, atomic force microscopy and interferometry on the interference of white light in combination, and on the basis of the received data to determine the spatial frequency f of the individual Fourier components and their amplitudes a (f) expressed through the integral of a function S

calculated between the bottom and optionally measure the edge angle, formed by the water being treated in this way surface.

Thanks deposited layer of adhesion promoter (usually gold, with a thickness from 10 to 100 nm) and the choice of homogeneous turuosaga agent is possible regardless of the materials used to explore a variety of materials, the surface of which is suitable for giving her Ultraphobic properties. This is realized by the ability to compare different surface structure.

It is preferable ultrafarma surface, wherein the deposited layer of hydrophobic turuosaga auxiliary agent, especially anionic, cationic, amphoteric or nonionic surface-active compounds.

As a subsidiary turuosaga agent acceptable surface-active compounds with any of molar mass. These compounds are preferably cationic, anionic, amphoteric or nonionic surface-active compounds, see, for example, in the Handbook "Surfactants Europa, A Dictionary of Surface Active Agents available in Europe", edited by Gordon L. Hollis, publishing house of the Royal Society of Chemistry, Cambridge (1995).

As the anionic auxiliary pourouma agents include, for example, alkylsulphonate, parafinalia, reincorporate, sarcosinate, isothionate, taurate and lignocaine.

As cationic auxiliary pourouma agents include, for example, Quaternary alkylammonium compounds and imidazoles.

As amphoteric auxiliary pourouma agents acceptable, among other things, betaine, glycine chelates, propionate and imidazoles.

Among the non-ionic auxiliary pourouma agents include, for example, alkoxylate, alkylamide, esters, aminoxide, alkylpolyglycoside, alkylsulfate and alkylsulfate. In addition to these, you can also use interaction products alkalisation with alkiliruushimi compounds, such as fatty alcohols, fatty amines, fatty acids, phenols, ALKYLPHENOLS, kalkiliya, such as condensates of styrene and phenol, amides, carboxylic acids and resin acids.

Particularly preferred auxiliary pourouma agents, which have from 1 to 100%, most preferably from 60 to 95% of hydrogen atoms substituted by fluorine atoms. As examples of perfluorinated alkylsulfate, the perfluorinated alkyl sulphonates, perfluorinated alkylsulfate, perfluorinated alkylsulfate, perfluorinated alkyl is x auxiliary pourouma agents for applying a hydrophobic coating or as a polymeric hydrophobic material to the surface, it is preferable to use compounds with a molar mass of MWranging from more than 500 to 1,000,000, preferably from 1,000 to 500,000, and particularly preferably from 1500 to 20,000. Such polymeric auxiliary poborowski agents may be nonionic, anionic, cationic or amphoteric compounds. In addition called as polymer auxiliary pourouma agents can be used Homo - and copolymers, grafted polymers, and grafted copolymers, statistical copolymers. The most preferred polymeric auxiliary fourousi agents include copolymers of the type AB, VAV and ABC. In the copolymers of the type AB or VAV AND-chain is a hydrophilic homopolymer or copolymer, and the block is a hydrophobic homopolymer or copolymer or salt.

Especially preferred are anionic polymeric auxiliary pourouma agents, primarily condensation products of aromatic sulphonic acids with formaldehyde and alkylnaphthalenes or derived from formaldehyde, naphthalenesulfonic and/or benzosulfimide, condensation products of optionally substituted phenol with formaldehyde and sodium bisulfite.

Preferred further condensation products, obtained vzaimodei terminal hydroxy groups in sulfopropyl or palefire maleic acid and phthalic acid or succinic acid.

According to another preferred variant as an auxiliary turuosaga agent using one selected from the group comprising esters sulfonterol acid, and alkylbenzenesulfonate. My favorite are sulfated, alkoxysilane fatty acids or their salts. Under alkoxycarbonyl alcohols from fatty acids are meant primarily saturated or unsaturated alcohols from C6-C22fatty acids containing 5-120mm, preferably 6-60 and most preferably 7-30 ethylenoxide links, in particular stearyl alcohol. Sulfated alkoxysilane alcohols from fatty acids presented preferably in the form of salts, especially alkali metal salts or amine salts, preferably in the form of salts diethylamine.

Another object of the invention is a method for ultraphone surface, which differs in that it is made in form of negative, i.e. the form with reverse print with the corresponding required ultraformal surface topography, made from a mixture of plastic and hydrophobic or primarily oleophobic additive, which when cured is deposited in a thin film between the surface of the Fort is liveout of polymer material and then is molded product of the polymer material is applied hydrophobic or primarily oleophobic coating.

Under used in the context of the present description the term "form" refers to any shape that can be produced by casting from polymeric materials or from blends of such materials. The surface shape is designed so that its topography is a reverse imprint, or, in other words, the negative of any desired ultraformal surface.

It is preferable, however, that the topography ultraformal surface corresponded processed by etching, anodized and treated with hot water and water vapor aluminum surface, which is obtained according to the methods described in the application Germany 19860138.7, and it is envisaged that these surfaces should not have any hydrophobic coating. The surface of a core of aluminium processed by electrochemical etching in an acidic medium by anodic oxidation and hot water or steam at temperatures in the range from 50 to 100With and, if necessary, cover with a layer of adhesion promoter.

Depending on the material surface can be formed by pouring or spraying of molten or dissolved thermoplastic, respectively, yet the IKI.

Another object of the present invention is a method of obtaining a surface with Ultratone properties, which differs from that obtained with reverse print (negative) surface profile which corresponds to the desired ultraformal surface is formed using a mixture of plastic and hydrophobic or primarily oleophobic additive, which when cured is deposited in a thin film between the surface of the mold and molded plastics.

According to another preferred variant of the specified form is moulded from a polymeric material and then is molded product of the polymer material is applied hydrophobic or primarily oleophobic coating.

Under used in the context of the present description form meant any form, which may be made by casting from polymeric materials or from blends of such materials. The surface shape is designed so that its topography is a reverse imprint any surface that can be used in the following for structuring (profiling) required ultraformal surface.

Preferably, however, to the topographer water and water vapor aluminum surface, which is obtained according to the methods described in the application Germany 19860138.7, and it is envisaged that these surfaces should not have any hydrophobic coating. The surface of a core of aluminium processed by electrochemical etching in an acidic medium by anodic oxidation and hot water or steam at temperatures in the range from 50 to 100With and, if necessary, cover with a layer of adhesion promoter.

Depending on the material surface can be formed by pouring or spraying of molten or dissolved thermoplastic, respectively, are not yet fully cured thermoplastic. Appropriate technology is well known to a person skilled in the technical field.

Proposed in the invention method is based, as unexpectedly it was found that the surface topography which serves as a "prototype" required ultraformal surface may be formed directly by, and the negative can be reused for the formation of the next Ultraphobic surfaces. This approach eliminates the need for expensive manufacturing every time a new negative topography required ul is about to get ultrafine surface, characterized in that the wetting angle on the surface of a liquid drop155°. The object of the invention in accordance with this are also ultrafine surface obtained by the proposed method.

In the implementation of both variants of the proposed method of molding can be applied plastics from the group of example or thermoplastics. Duroplast it is advisable to choose primarily from the group comprising diallylphthalate resin, epoxy resin, urea resin, melamine-formaldehyde resin, melamineformaldehyde resin, a phenol-formaldehyde resin, polyimide, silicone resin, unsaturated polyester resin. Thermoplastic advisable to choose primarily from a group comprising thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, politicaland, polyesters, such as PBT or PET, polystyrene, copolymer of styrene, a copolymer of styrene and Acrylonitrile, kouchakzadeh grafted copolymer of styrene, for example a copolymer of Acrylonitrile, butadiene and styrene (ABS), polyamide, polyurethane, polyster, polyvinyl chloride or any mixture of these polymers.

As an additive acceptable surface-active compounds with any of molar mass. These compounds are preferably cationic, anionic, amphoteric or nonionic surface-active compounds, see, for example, in the Handbook "Surfactants Europa, A Dictionary of Surface Active Agents available in Europe", edited by Gordon L. Hollis, publishing house of the Royal Society of Chemistry, Cambridge (1995).

As anionic additives include, for example, alkyl sulphates, esterified sulfates, esterified carboxylates, esters of phosphoric acid, sulfosuccinate, sulfosuccinate, parafusulina, reincorporate, sarcosinate, isothionate, taurate and lignocaine.

As cationic additives include, for example, Quaternary alkylammonium compounds and imidazoles.

As amphoteric additives acceptable, among other things, betaine, glycine chelates, propionate and imidazoles.

Among the non-ionic additives include, for example, alkoxylate, alkylamide, esters, aminoxide, alkylpolyglycoside, alkylsulfate and alkylsulfate. In addition to these, m as fatty alcohols, fatty amines, fatty acids, phenols, ALKYLPHENOLS, kalkiliya, such as condensates of styrene and phenol, amides, carboxylic acids and resin acids.

Particularly preferred additives that have from 1 to 100%, most preferably from 60 to 95% of hydrogen atoms substituted by fluorine atoms. As examples of perfluorinated alkylsulfate, the perfluorinated alkyl sulphonates, perfluorinated alkylsulfate, perforated alkylsulfate, perfluorinated alkylphosphonate, perfluorinated alkylphosphonate and perfluorinated carboxylic acids.

As polymer additives for applying a hydrophobic coating or as a polymeric hydrophobic material to the surface, it is preferable to use compounds with a molar mass of MWranging from more than 500 to 1,000,000, preferably from 1,000 to 500,000, and particularly preferably from 1500 to 20,000. Such polymeric additives can be nonionic, anionic, cationic or amphoteric compounds. In addition called as polymer additives can be used Homo - and copolymers, grafted polymers, and grafted copolymers, statistical copolymers. The most preferred polymeric additives include Blocco the emer or copolymer, and the block is a hydrophobic homopolymer or copolymer or salt.

Especially preferred are anionic polymer additives, primarily condensation products of aromatic sulphonic acids with formaldehyde and alkylnaphthalenes or derived from formaldehyde, naphthalenesulfonic and/or benzosulfimide, condensation products of optionally substituted phenol with formaldehyde and sodium bisulfite.

Preferred further condensation products obtained by the interaction Naftalan with alkanols, addition products accelerated and at least partial translation of end hydroxyl groups in sulfopropyl or palefire maleic acid and phthalic acid or succinic acid.

According to another preferred variant as an additive used one selected from the group comprising esters sulfonterol acid, and alkylbenzenesulfonate. My favorite are sulfated, alkoxysilane fatty acids or their salts. Under alkoxycarbonyl alcohols from fatty acids are meant primarily saturated or unsaturated alcohols from C6-C22fatty acids containing 5-120mm, predpone alkoxysilane alcohols from fatty acids presented preferably in the form of salts, first of all alkali metal salts or amine salts, preferably in the form of salts diethylamine.

Because of this technology on the molded product does not need to apply a hydrophobic or oleophobic coating, eliminating the need to conduct envisaged in other cases, the relevant technological operations.

One of the advantages Ultraphobic surfaces according to the invention is their ability to self-purification, the purification may occur while in the rain or when washing any flow of water. Because the surface has ultramobile properties located on the surface of the water droplet roll with it, carrying with them particles of dirt, with only a very weak adhesion to the surface and thus removed from the surface. This purification takes place not only under the action of water and oil.

The object of the invention is also structural material or construction material having ultrafamous surface according to the invention.

Proposed in the invention ultrafarma surface can be used in various fields of technology. The object of the invention in accordance with this JW what you can provide for the hull to reduce friction resistance.

Another possibility of application Ultraphobic surfaces due to the need of processing corresponding to the working surface to prevent adhesion thereto of water to prevent freezing. As examples, the surface of heat exchangers used in refrigeration, or the fuselage of the aircraft.

In addition, the surface according to the invention is suitable for application on facades, roofs, monuments, etc. in order to give them the ability to self-clean.

Another object of the invention is the application of the proposed Ultraphobic surfaces to minimize friction lining of vehicle bodies, the fuselage of the aircraft or ship hulls.

Another object of the invention is the use of Ultraphobic surfaces as capable of self-cleaning coating or cladding of buildings, roofs, Windows, building materials of ceramics, for example, plumbing, appliances, etc.,

The object of the invention is further the use of Ultraphobic surfaces as corrosion-resistant coating of metal products. The object of the invention is also the application of the proposed Ultraphobic surfaces in osimage on transparent glass, first of all, quartz or polymer glass, intended, in particular, for solar panels, vehicles or houses.

Another object of the invention is the use of Ultraphobic surfaces as a coating containers intended for the respective liquids, which, for example, requires a certain way to dispense or serve in these capacities. Have in mind, in particular, cannula, hoses (hoses) or storage containers.

Another object of the invention is a method of obtaining a surface with Ultratone properties based alloy A1Mg3, which is characterized by the fact that this surface is cleaned, processed by etching, is subjected to anodic oxidation, Passepartout in boiling water, if necessary, put on her first deposition, the layer of the noble metal as an adhesion promoter, primarily of gold, with a thickness from 10 to 100 nm, and finally cover with a hydrophobic material, especially anionic, cationic, amphoteric or nonionic surface-active compound as an auxiliary turuosaga agent.

Instead of the integral of a function S

calculated between the lower limit of the integration is 0,5, to determine ultraformal surface equally, you can use the integral of a function F

calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3. For classification of the surface to the discharge surfaces having ultramobile properties, the integral of this function F in the interval of positive values exceed 5. To use such a function F to describe the surface topography has already been proposed in the application DE 19860136.0. However, the advantage associated with the description of the surface topography using equation (1), i.e., using the function S, is that the value of the integral of this function S(logf) is more revealing. This is because specified value is proportional to the normalized amplitude of all Fourier components <a(f)f>, averaged on a logarithmic scale of frequencies in the interval -3log(f/µm-1)3. Thereby found the criterion which must satisfy the received ultrafine surface, can be summarized as follows: defined on a logarithmic scale the image, Fourier amplitude for the "average" frequency should be at least about 8% of the length of the structure.

For comparison of results obtained using both equations (1) and (2), you can refer to the following examples 1-6 and accompanying Fig.10 and 11, which additionally used the function F considered in the application DE 19860136.0.

Below the invention is explained in more detail based on examples with reference to the accompanying drawings on which is shown:

in Fig.1 - curves PSD(f) obtained for the proposed invention Ultraphobic surfaces of examples 1-6,

in Fig.2 - curves PSD(f) obtained for the proposed invention Ultraphobic surfaces of examples 7-9,

in Fig.3 - PSD curves(f) obtained for the proposed invention Ultraphobic surfaces of examples 10-11,

in Fig.4 - curves PSD(f) obtained for the proposed invention Ultraphobic surfaces of examples 12-13,

in Fig.5 - graphs of the frequency-dependent amplitudes a(f) of the Fourier components for the proposed in the invention of the surfaces of examples 1-6,

in Fig.6 - graphs, the frequency-dependent amplitudes a(f) of the Fourier components for the proposed in the invention of the surfaces of examples 7-9,

in Fig.7 - graphics-dependent h is 8 - graphs of the frequency-dependent amplitudes a(f) of the Fourier components for the proposed in the invention of the surfaces of examples 12-13,

in Fig.9 - dependence of contact angles of water drops from the integral of the function S(logf)=a(f)f calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3, for different surfaces of examples 1-13,

in Fig.10 is a graph of the frequency-dependent amplitudes a(f) of the Fourier components of the proposed invention the surfaces of examples 1-6 in the form of the function F(logf), presented in double logarithmic (in accordance with the application DE 19860136.0),

in Fig.11 - dependence of contact angles of water drops from the integral of a function F(logf) calculated in the interval of positive values of the function F between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3, for a variety of surfaces from examples 1-6 (in accordance with the application DE 19860136.0).

Examples

General notes examples

1. Determination of surface topography

To determine the surface topography of the latter was investigated using the scanning tunneling microscope, skanirujushie what make your decision.

When scanning tunneling microscopy used microscope type Nanoscope III by Digital Instruments, Santa Barbara, PCs California, who worked in the constant current mode. The measurements were carried out in air at room temperature with mechanical retractable platinum-iridium tip. While sequentially scanned plots of L2500500 nm2, 200200 nm2and 5050 nm2with the number of points on each plot (N2=512512 when the spacing between these pointsL=N/L.

Data on the height of the roughness profile was counted in the average power spectral density PSD according to equations (1) and (2) from the publication of C. Ruppe and A. Duparre, Thin Solid Films 288 (1996), page 9.

Measurement by scanning atomic force microscopy was performed using a scanning atomic force microscope type DIMENSION 3000 by Digital Instruments, Santa Barbara, USA in continuous mode. The measurements were carried out in air at room temperature. Used silicon tip with a radius of about 10 nm and sequentially scanned plots of L211 μm2that is castke N2=512512 when the spacing between these pointsL=N/L.

When interferometry on the interference of white light used microscope type LEICA DMR, Leica, Wetzlar. When this was investigated plots 140140 μm2, 280280 μm2, 11201120 μm2and 28002800 μm2with the number of points in each section 512512.

Obtained using the above methods of measurement curves PSD (f) were then combined into a single curve PSD(f), which is built in the form of a double logarithmic according to Fig.1-4, with power spectral density PSD division at nm4and the spatial frequency f division μm-1translated into immense value.

The calculation of the frequency-dependent amplitudes a(f)

The frequency-dependent amplitude a(f) was determined on the basis of the PSD curves(f) by the following formula

.

As a constant D, which defines the limits of integration, in which the function PSD(f) is considered as constant, in all the considered cases used a value of D equal to 1.5.

Example 1

Polished finishing rolls plate from A1Mg3size: 3535 mm2and 0.5 mm thick was degreased first distilled chloroform, and then for 20 with in aqueous NaOH (5 g/l) at 50C. thereafter, over 20 were treated by etching in N3RHO4(100 g/l), within 30 washed in distilled water and within 90 conducted with electrochemical etching in a mixture of HCl/H3BO3(4 g/l) at 35With a current density of 120 mA/cm2AC voltage 35 C. After a 30-second rinse in distilled water and 30-second rinse with alkali in aqueous NaOH (5 g/l) repeatedly washed for 30 s in distilled water and then within 90 with anodic oxidation was performed in H2SO4(200 g/l) at 25With a current density of 30 mA/cm2a constant voltage of 50 C. thereafter, over 30 were washed in distilled water for 60 s at 40In Panso3(20 g/l) and then again after 30 seconds in delibrately in this way the plate deposited a layer of gold of a thickness of approximately 50 nm, then this sample is aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated and finally washed with ethanol and dried.

Static wetting angle located at a surface of the water droplet is 167. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 1 in Fig.1.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-l)=3, is 0.81.

Example 2

In this example, the processing plate from A1Mg3and application of a coating was carried out analogously to example 1, however, the difference is that advanced, before sputtering a layer of gold over 20 were etched in 1 M NaOH, then after 30 seconds were washed in distilled water and then in ethanol, and within 1 hour of sleep this surface of the water droplet is 161. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 2 in Fig.1.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.58.

Comparative example 3

In this example, the processing plate from A1Mg3and application of a coating was carried out analogously to example 2, however, differs in that the etching was carried out for 120 s in 1M NaOH.

Static wetting angle located at a surface of a drop of water is 150. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 3 in Fig.1.

The integral of the normalized Foriegner the limit of integration

log(f2/μm-1)=3, is 0.46.

Comparative example 4

In this example, a polycarbonate substrate with a size of 3535 mm2and a thickness of 1 mm was applied for subsequent spraying a layer of aluminium of a thickness of 200 nm. After that, the sample for 30 min were treated in distilled water at 100With, then after 30 seconds were washed in distilled water at room temperature and for 1 h and dried in a drying Cabinet at 80C.

Further processed in this way the sample is deposited a layer of gold of a thickness of approximately 50 nm. Then this sample is aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated and finally washed with ethanol and dried.

Static wetting angle located at a surface of a drop of water is 135. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and received the produced interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0,28.

Comparative example 5

In this example, the polished finishing rolls plate from A1Mg3size: 3535 mm2and 0.5 mm thick was degreased distilled chloroform. After a 30-second rinse in distilled water for 600 with anodic oxidation was performed in H2SO4(200 g/l) at 20With a current density of 10 mA/cm2DC voltage 35 C. and Then washed in distilled water for 1 h and dried at 80With in a drying Cabinet.

Further processed in this way the sample is deposited a layer of gold of a thickness of approximately 50 nm. Then this sample is aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated and finally washed with ethanol and dried.

Static wetting angle located at a surface of the water droplet is 122. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface is obtained measurement data are presented as curve 5 in Fig.1.

The integral of the normalized Fourier amplitude S (log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.14.

Comparative example 6

In this example, a raw polished finishing rolls monocrystalline silicon plate deposited a layer of gold of a thickness of 200 nm on the sample aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated, and then washed with ethanol and dried.

Static wetting angle located at a surface of a drop of water is 115. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data is presented in the form of the curve 6 in Fig.1.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integrirovannaja area 3535 mm2and a thickness of 1 mm was applied for subsequent spraying a layer of aluminium of a thickness of 100 nm. After that, the sample for 3 min were treated in distilled water at 100With, then after 30 seconds were washed in distilled water at room temperature and for 1 h and dried in a drying Cabinet at 80C.

Further processed in this way the sample is deposited a layer of gold of a thickness of approximately 100 nm. Then this sample is aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated and finally washed with ethanol and dried.

Static wetting angle located at a surface of the water droplet is 147. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 1 in Fig.2.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower prerelease 0,39.

Example 8

In this example, the test sample was obtained analogously to example 7, however, differs in that the thickness of the sputtered layer of gold was 50 nm.

Static wetting angle located at a surface of the water droplet is 154. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 2 in Fig.2.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.53.

Comparative example 9

In this example, the polished finishing rolls plate from A1Mg3size: 3535 mm2and 0.5 mm thick was degreased distilled chloroform. Then the sample within 20 were treated with distilled water at 100C. then washed in ethanol for 1 h and dried in a drying Cabinet at 80m for the sample aged for 24 hours immersed in a solution of n-decandiol in ethanol (1 g/l) at room temperature in a closed vessel was coated and finally washed with ethanol and dried.

Static wetting angle located at a surface of a drop of water is 130. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 3 in Fig.2.

The integral of the normalized Fourier amplitude S (log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.15.

Comparative example 10

In this example, on a polished finishing rolls monocrystalline Si (100)-vinyl electrolocation sputtering at a temperature of K sequentially applied layers of the substrate HLHL (H=LaF3L=MgF2). While layers N had a thickness of 100 nm, and the layers L 116 nm. This technology corresponds to the one described in the publication S. Jakobs, A. Duparre, and N. Truckenbrodt, Applied Optics 37, pp. 1180 (1998).

Further processed in this way the sample is deposited a layer of gold of a thickness of approximately 50 nm. Then this sample is aged for 24 h in submerged is involved and finally washed with ethanol and dried.

Static wetting angle located at a surface of a drop of water is 120. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 1 in Fig.3.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.10.

Comparative example 11

In this example, the test sample was obtained analogously to example 10, however, the difference is that when the above-mentioned successive coats instead of (HL)2used (HL)8.

Static wetting angle located at a surface of a drop of water is 130. When the inclination of the surface at <10a drop of water volume of 10 µl roll with it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of the strain Fourier amplitudes S(log f), calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.23.

Example 12

In this example, the test sample was obtained in the same way as described in the unpublished application DE 19935326.3. Cyclo {SiO(CH3) [(CH2)2Si(OH)-(CH3)2}4(denoted in the following as D4-silanol combined with caffeine) was obtained similarly as described in the application DE 19603241.

4.1 g of AEROSIL®812 (company Degussa) was dispersively 28.5 g of 1-methoxy-2-propanol, 5.0 g D4-silanol and 6.5 g of tetraethoxysilane. To this dispersion was added 1.1 g of 0.1 n p-toluenesulfonic acid and the mixture was stirred for 1 h at room temperature. Then, the resulting varnish solution by means of a frame for stretching a film covered glass plate with the formation of the layer of wet film thickness of 120 μm. After evaporation at room temperature the volatile components of the formed coating was utverjdali for 1 h at 130With in a drying Cabinet with air circulation.

Further processed in this way the sample is deposited a layer of gold of a thickness of approximately 50 nm. Then this sample is aged for 24 h in pagri floor and finally washed with ethanol and dried.

Static wetting angle located at a surface of a drop of water is 165. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data are presented as curve 1 in Fig.4.

The integral of the normalized Fourier amplitude S(log f) calculated in the interval between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is to 0.71.

Example 13

In this example, the test sample was obtained analogously to example 12, however, the difference is that instead of 1.1 g of p-toluenesulfonic acid was added 2.3 g Hcl.

Static wetting angle located at a surface of the water droplet is 157. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

The topography of this surface was described and investigated in the same way as described above in section 1. Determination of surface topography", and the obtained measurement data to provide the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration

log(f2/μm-1)=3, is 0.60.

Example 14

Obtaining a reverse print (negative)

In this example, using a polymer solution was obtained reverse print (negative), the employee form to obtain the required ultraformal surface. As this form was used the surface obtained in example 1.

The mold was filled with a 30% solution of polymer in methylene chloride, which was used is a copolymer of polymethylmethacrylate and performancecriteria (-[CH2- (SOON3)CH3]nand -[CH2-C(COOC18F37)CH3]mwhen the ratio n/m=10; 50 wt.%-tion solution in butanone), which results in the stretching of the coating film in the form of a film thickness of approximately 20 μm. After drying at room temperature from a film with a scalpel cut a strip width of 10 mm, with the upper side of the reinforced its bonding an adhesive film and separated from the form.

On the bottom (i.e., initially converted to the form) side of the film deposited a layer of gold of a thickness of about 50 nm. Then the sample aged for 24 h were deposited by sputtering of n-decandiol rooms at the second contact angle being on such a surface, drops of water is 165. When the inclination of the surface at <10a drop of water volume of 10 µl slides down from it.

Example 15

Getting ultraformal surface with reverse print (negative)

In this example, using a polymer solution using negative received the required ultrafamous surface. As such negativity used the surface obtained in example 1.

Stage 1: obtaining a reverse imprint of the employee form to obtain ultraformal surface

The mold was filled with 50 wt.%-s ' solution of the polycarbonate of bisphenol a (Mn=1000) in methylene chloride and using the frame for pulling the film received coverage in the form of a film thickness of approximately 100 microns.

After drying at room temperature of the film was cut with a scalpel strip width of 20 mm, with the upper side of the reinforced its bonding an adhesive film and separated from the form.

On the bottom (i.e., initially converted to the form) side of the film deposited a layer of gold of a thickness of about 50 nm. Then, on this layer of gold sample aged in 24 hours with a few drops of a solution of n-pertrochanteric,,-triptoreline (1 g/l) at p://img.russianpatents.com/chr/945.gif">,-CryptoStream and dried.

Stage 2: Obtaining a reverse imprint required ultraformal surface using a polymer mixture containing an oleophobic polymer as an additive

The mold was filled with a 30% solution of polymer in methylene chloride polystyrene (Mn=15000) and approximately 10 wt.% copolymer of polymethylmethacrylate and performancecriteria (-[CH2- (SOON3)CH3]n- and- (CH2-C(COOC18F37]m-; the ratio n/m=10) to obtain the use of a molding frame cover in the form of a film thickness of about 20 μm. After prolonged drying at room temperature for about 10 h) of the film was cut with a scalpel stripe width of 10 mm, from the upper side thereof strengthened by gluing adhesive tape and separated from the form.

On the bottom (i.e., initially converted to the form) side of the film deposited a layer of gold of a thickness of about 50 nm. Then the sample aged at 24 h was applied by spraying n-decandiol at room temperature in a closed vessel floor, and then washed with ethanol and dried.

Static wetting angle located on the thus obtained surface is s volume of 10 µl slides down from it.

In the table presented in a systematic way the results obtained in the examples according to the invention and in comparative examples.

Clearly it is obvious that when Ultraphobic surfaces, in which the wetting angle located on the surface of the water droplet exceeds 150the integral curve a(f)f=S(log f), calculated between the lower limit of integration log (f1/μm-1) = -3 and the upper limit of integration log (f2/μm-1) = 3, higher than or equal to 0.5. Boundary angle such ultraformal surface obtained with a reverse imprint, as well as regional negative angle exceeds 150.

Claims

1. Structured (profiled) surface with Ultratone properties, characterized in that it has a topography in which the relationship between the spatial frequency f of the individual Fourier components and their amplitudes a(f) is determined by the function S

the integral of which is calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log (f2/μm-1) = service material or have a coating of such hydrophobic or primarily oleophobic material.

2. Ultrafarma surface p. 1, characterized in that the integral of the function S exceeds 0.6.

3. Ultrafarma surface under item 1 or 2, characterized in that it has a wetting angle of at least 150and the angle of roll of less than 10.

4. Ultrafarma surface according to any one of paragraphs.1-3, characterized in that it has a wetting angle of at least 155.

5. Ultrafarma surface according to any one of paragraphs.1-4, characterized in that it is made of metal or plastic.

6. Ultrafarma surface under item 5, wherein the metal is selected from the group comprising beryllium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, aluminum, gallium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhenium, palladium, silver, cadmium, indium, tin, lanthanum, cerium, prasadi, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, primarily titanium, aluminum, magnesium and Nickel, or an appropriate alloy of the aforementioned metals.

7. Ultrafarma surface under item 5, characterized by the lead under item 5, characterized in that the plastic is selected Duroplast or thermoplastic.

9. Ultrafarma surface under item 8, characterized in that Duroplast selected from the group comprising diallylphthalate resin, epoxy resin, urea resin, melamine-formaldehyde resin, melamineformaldehyde resin, a phenol-formaldehyde resin, polyimide, silicone resin, unsaturated polyester resin, and a thermoplastic selected from the group including thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, politicaland, polyesters, such as PBT or PET, polystyrene, copolymer of styrene, a copolymer of styrene and Acrylonitrile, kouchakzadeh grafted copolymer of styrene, for example a copolymer of Acrylonitrile, butadiene and styrene (ABS), polyamide, polyurethane, polyster, polyvinyl chloride or any mixture of these polymers.

10. Ultrafarma surface according to any one of paragraphs.1-9, characterized in that the surface damage layer of hydrophobic auxiliary turuosaga agent, especially anionic, cationic, amphoteric or nonionic surface-active compounds.

11. Construction material or construction Mat, characterized in that it is designed to minimize friction lining of vehicle bodies, the fuselage of the aircraft and ship hulls.

13. Ultrafarma surface according to any one of paragraphs.1-10, characterized in that it is intended for use as capable of self-cleaning coating or cladding of buildings, roofs, Windows, building materials from ceramics, used, for example, plumbing and appliances.

14. Ultrafarma surface according to any one of paragraphs.1-10, characterized in that it is designed for use as a corrosion-resistant coating of metal products.

15. Ultrafarma surface according to any one of paragraphs.1-10, characterized in that it is designed for use as a transparent panel or as a transparent layer on a transparent glass, primarily quartz or polymer glass, primarily for solar panels, vehicles or houses.

16. A method of obtaining a surface with Ultratone properties according to any one of paragraphs.1-10-based alloy lg3, characterized in that the surface is cleaned, processed by etching, is subjected to anodic oxidation, Passepartout in boiling water, when the need is only of gold, thickness from 10 to 100 nm, and finally cover with a hydrophobic material, especially anionic, cationic, amphoteric or nonionic surface-active compound as an auxiliary turuosaga agent.

17. A method of obtaining a surface with Ultratone properties, characterized in that make a shape representing a reverse imprint ultraformal surface with a desired topography, using for this purpose the mixture of plastic material and a hydrophobic or primarily oleophobic additive, which when cured is deposited in a thin film between the surface of the mold and molded product of plastic.

18. A method of obtaining a surface with Ultratone properties, characterized in that ultrafamous surface with a desired structure is formed using plastic, especially Duroplast or thermoplastic, and on the surface of the thus obtained with a reverse imprint of the molded product, if necessary, put a layer of adhesion promoter and then coated with hydrophobic or primarily oleophobic material.

19. The method according to p. 18, characterized in that the polymer used as the hydrophobic polymer, preferably a copolymer of polymethylmethacrylate and from their hydrophobic or oleophobic material.

20. The method according to p. 17 or 18, characterized in that as a form of reverse imprint, respectively, obtained from the inverse of the fingerprint surface with the required structure, use the surface subjected to etching, anodized and treated with hot water with a temperature in the range from 50 to 100With and containing mainly aluminum or aluminum alloy.

21. The method according to p. 17 or 18, characterized in that as a form of reverse imprint, respectively, obtained from the inverse of the fingerprint surface with the required structure, use of a microstructured, anodized, soda and containing mainly aluminum or aluminum alloy surface.

22. The method according to any of paragraphs.17-21, characterized in that the plastic material for forming the surface applied Duroplast or thermoplastic.

23. The method according to p. 22, characterized in that as Duroplast apply one selected from the group comprising diallylphthalate resin, epoxy resin, urea resin, melamine-formaldehyde resin, melamineformaldehyde resin, a phenol-formaldehyde resin, polymid, silicone rubber and the unsaturated polyester with the, Lucaya thermoplastic polyolefin, for example polypropylene or polyethylene, polycarbonate, politicaland, polyesters, such as PBT or PET, polystyrene, copolymer of styrene, a copolymer of styrene and Acrylonitrile, kouchakzadeh grafted copolymer of styrene, for example a copolymer of Acrylonitrile, butadiene and styrene (ABS), polyamide, polyurethane, polyster, polyvinyl chloride or any mixture of these polymers.

25. The method according to any of paragraphs.17-24, characterized in that obtained with a reverse imprint of the surface of the molded product coated with a secondary hydrophobic turuosaga agent, especially anionic, cationic, amphoteric or nonionic surface-active compounds, or the use of such auxiliary pomeroyi agent as an additive to a compatible polymers, which makes the surface hydrophobic properties.

26. Method of test surfaces on their ultrafine properties, characterized in that on the surface, primarily by spraying, put a layer of noble metal or GaAs as a promoter of adhesion, primarily of gold, with a thickness from 10 to 100 nm, then cover with a layer of supporting fo the power of scanning tunneling microscopy, scanning atomic force microscopy and interferometry on the interference of white light in combination, and on the basis of the received measurement data to determine the spatial frequency f and amplitude of their structures and(f), and the integral of a function S

calculated between the lower limit of integration log(f1/μm-1)=-3 and the upper limit of integration log(f2/μm-1)=3.

 

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FIELD: processes for applying fluent materials to surfaces to obtain anti-friction surface with the purpose to reduce hydraulic and aerodynamic friction of vehicle moving in liquid and to reduce friction in friction assemblies of machines and mechanisms working in aqueous medium.

SUBSTANCE: method involves obtaining and applying antifriction coating on vehicle body so that specific coating surface energy along liquid streamlines (streamline surface) has negative gradient.

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EFFECT: increased application properties and strength of the paper, provision of reliable peeling force to paper separation from adhesive layer within wide temperature range, increased quality of composition application due to increased fullness of composition introduction in surface layer of paper web.

13 cl, 2 dwg

FIELD: furnaces.

SUBSTANCE: method comprises securing means of the anchor fastening to the surface, applying the lining material on the surface, solidifying the lining, AND drying the lining at a temperature sufficient to the melting of the coating at the means of anchor fastening. The device for anchor fastening is proposed.

EFFECT: enhanced reliability.

16 cl, 1 tbl, 3 ex

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3 ex

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SUBSTANCE: invention relates to a composition comprising 0.1-4% of mixture of perfluoropolyoxaalkylene carboxylic acids of the general formula: wherein n = 3-50. For preparing colloidal solution of perfluoropolyoxaalkylene acid the composition comprises additionally 1-2% of amidoalcohol of the general formula: wherein n = 0 or 1; m = 1 at q = 1 and m = 2 at q = 0 that is prepared by interaction of dimer and/or trimer of hexafluoropropylene oxide with mono- and/or diethanolamine and water, up to 100. After treatment with the proposed composition surface of solid bodies acquires water-oil-repelling properties and the gluing seam rupture strength is reduced by two orders that accords with strength levels providing by the nearest analog representing a mixture of perfluoropolyoxaalkylene acids in coolants. Invention can be used for decreasing adherence of moldable plastic, crude rubber articles and other polymers to a tool and press-forms.

EFFECT: improved and valuable technical properties of composition.

1 tbl, 2 ex

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