EP1855787B1 - Method and device for producing and recycling nanoemulsions and for processing part surfaces by means thereof - Google Patents

Abstract

The invention relates to a device comprising a tubular circuit provided with at least one pump (9), a vacuum chamber (1) for processing the surfaces of parts placed therein, an actuation device (10), high voltage electrodes and a high frequency coil comprising a separate generator provided with a frequency converter for producing an electric field. The inventive device also comprises a transversal resonator for producing an aerosol and injection nozzles for spraying said aerosol into the vacuum chamber (1). The emulsion crosses the actuation device (10) in which electric and electromagnetic fields of 1-10000 volts, whose superimposed frequencies ranging from 10 Hz to 1 GHz are produced by a high-voltage electrode and the high frequency electromagnetic coil with the aid of the generator. By superimpose in the fields, a potential Zeta variation generates the transformation of a microemulsion into a nanoemulsion for processing part surfaces.

Description

The invention relates to a method and a device in the form of an electromechanical device, with which microemulsions can be converted into nanoemulsions, and this process controlled in different phases, so that in a vacuum chamber by a multi-phase process, a surface treatment of substances is possible, especially an optimal Be and delamination of organic and inorganic solids. The emulsions are then recycled again.

A microemulsion is a thermodynamically stable, isotropic, low viscosity mixture consisting of a hydrophilic and a lipophilic component. The hydrophilic character of a substance is determined by its ability to dissolve in water. (Opposite: hydrophobic = water repellent). Lipophilic characterizes the property of compounds or groups of molecules to easily dissolve in fats, fat-like substances and oils, or to themselves serve as solvents for such substances, whereas lipophobic (fat-repelling) substances have the opposite effect. The electrical and electromagnetic system of the device presented here causes changes in the diffuse interface of a so-called star bilayer on the particles within the emulsions. This star bilayer is composed of a rigid and a diffuse layer. According to the theory of Otto Stern (1888-1969), Nobel laureate in physics, builds due to the charge distribution a potential that decreases linearly in the rigid layer and exponentially in the diffused layer. For the functional effect at the diffuse interface, the respective zeta potential of an emulsion is decisive, which describes the stability of a microemulsion or a single micelle. The zeta potential is a measure of the repulsion or attraction between particles and a micelle is a colloid particle, which is composed of numerous smaller single molecules.

In electrical insulation of high-frequency-carrying lines or in high-frequency fields insulation standing to keep the losses as small as possible. It uses materials that produce as low as possible active power in their fields in such fields and thus lead to low losses. Conversely, microemulsions are chosen in such a way that the highest possible losses and thus desired changes occur in their interior, ie on the micelle surfaces. It thus has a possibility of being able to control and regulate the structure of the micelles, so that they assume kinetic states which enable delamination and coating of materials in the molecular range. A system for such purposes uses a continuous process, which allows activation with the least possible use of energy. With the aid of the method, it is additionally possible to combine the medium to be treated with the different charges in a vacuum chamber, with the result that charge compensation, ie conversion of the microemulsion into a nanoemulsion, takes place close to the surface of the material to be treated. The closest prior art results from the US Pat. No. 5,152,923 ,

The object of the present invention is to provide a device for the surface treatment of parts by means of recyclable nanoemulsions, as well as to provide a method for the production and application of the nanoemulsions in a multiphase interfacial treatment and for the recycling of the nanoemulsions.

This object is achieved by a method for producing, applying and recycling nanoemulsions and for the surface treatment of parts by means of the same, in which one such Nanoemulsion is produced by first an emulsion with micelles of any size flows through an activation device in which of a high-frequency electrode and electromagnetic high-frequency coil by means of generators generated electric and electromagnetic fields are superimposed and resonances are generated by means of selectable voltages, frequencies and phase shifts, so due to the Change of the particle bilayers, which causes a change in the zeta potential, a microemulsion becomes a nanoemulsion, after which the surface of parts are treated in a vacuum chamber, which is then recycled in the recycling system and then reused.

The object is further achieved by a device for generating, applying and recycling nanoemulsions and for the surface treatment of parts by the same, consisting of a pipe circuit with at least one pump for conveying an emulsion in a circuit, this pipe circuit containing a vacuum chamber for surface treatment of therein Parts, wherein the tube circuit passes through an activation device, as well as a high-voltage coil and a high-frequency coil with separate generator with frequency converter for generating an electric field, whereby separate fields for converting a microemulsion into a nanoemulsion can be generated, and the device further comprises a transversal Resonator for generating an aerosol includes, and injector nozzles for spraying the aerosol / nanoemulsion mixture in the vacuum chamber.

Figur 1:

Die Vorrichtung in einer Ansicht von hinten gesehen;

Figur 2:

Die Vorrichtung in einer Ansicht von vorne gesehen, mit entfernter Frontseiten-Abdeckung;

Figur 3:

Aktivierungseinrichtung mit einem Pumpenausgang und einem Transversal-Resonator;

Figur 4:

Einen Querschnitt durch das Rezyklierungssystem;

Figur 5-10:

Die verschiedenen Phasen einer Entschichtung mittels Nanoemulsion schematisch und stark vergrössert dargestellt.

In the drawings, an example device is shown with its essential components in various views and will be described below with reference to these drawings and the method operated therewith will be explained. The physical processes in the course of the stripping process are explained on the basis of schematic, greatly enlarged illustrations.
It shows:

FIG. 1:

The device seen in a view from behind;

FIG. 2:

The device in a view seen from the front, with the front cover removed;

FIG. 3:

Activation device with a pump output and a transversal resonator;

FIG. 4:

A cross section through the recycling system;

Figure 5-10:

The different phases of decoating by means of nanoemulsion are shown schematically and greatly enlarged.

In order to be able to better describe and understand the device and the method operated with it, a brief digression about microemulsions is first given here: These microemulsions can be constructed purely organic or aqueous organic. In the purely organic microemulsion, a carrier liquid is used which consists of one or more types of molecules. In the case of aqueous microemulsions, by contrast, the carrier liquid consists of water.

The carrier liquid is now added to various surface-active substances, that is to say substances which enter into physically-based bonds with their surface in conjunction with another substance. These substances form in the carrier liquid by self-organization so-called micelles. Depending on the task, surface-active substances which form monomolecular or bimolecular micelles are also used. Such surfactants are soluble organic compounds which lower the interfacial tension. They have at least one hydrophobic moiety and one hydrophilic moiety. A prerequisite for the stability and the molecular self-organization of the treatment liquid is that the molecular surfactants are not soluble in the carrier liquid. Enzymes are used to adjust and adjust the interfacial kinetics at the bilayers of nanoparticles.

• Anionische Stoffe
• Kationische Stoffe
• Nichtiogene Stoffe
• Amphotere Stoffe

Anionische oberflächenaktive Stoffe sind in der Lage, Mizellen mit einer negativen Ladung zu bilden. Kationische oberflächenaktive Stoffe sind in der Lage, Mizellen mit einer positiven Ladung zu bilden. Nichtiogene oberflächenaktive Stoffe sind in der Lage, Mizellen mit einer Null-Ladung zu bilden. Amphotere oberflächenaktive Stoffe sind in der Lage, Mizellen mit einer negativen oder positiven Ladung zu bilden. Bei all diesen Stoffen ist die Ladungsstärke vom Zetapotential abhängig. Die Ladungsart wird durch elektrische und magnetische Kräfte bestimmt, welche an der Systemgrenzfläche wirksam sind.For the formation of organic and aqueous microemulsions, various surfactants and surfactants are available. These can be roughly divided into:

• Anionic substances
• Cationic substances
• Non-organic substances
• Amphoteric substances

Anionic surfactants are able to form micelles with a negative charge. Cationic surfactants are able to form micelles with a positive charge. Non-organic surfactants are able to form micelles with a zero charge. Amphoteric surfactants are able to form micelles with a negative or positive charge. For all these substances, the charge strength depends on the zeta potential. The charge type is determined by electrical and magnetic forces acting at the system interface.

The amphoteric-active substances are used in stripping and coating systems where very short conversion times are required. For this reason, these substances are particularly well suited for the present process. With the presented device they can be reloaded with the help of the magnetic and electrical phase control in fractions of seconds. The charge possibilities range between negative (anionic), zero potential (neutral) and positive (cationic). By means of suitable resonances, the zeta potential on a star double layer can be controlled and regulated independently of the chemical potential with this device and the method operated therewith. Zeta potential settings from -15 to +15 are possible.

• Enzyme
• Organische und anorganische Nanopartikel
• Lins- und rechtsdrehende Terpene

Die Enzyme sind in der Lage, die Energieverhältnisse von Mizellen, Nanopartikeln und links- und rechtsdrehenden Molekülen zu steuern. Im Normalfall wirken sie als Katalysatoren, die die Reaktionsenergie zwischen zwei Systemen verkleinern. In der Mikroemulsion werden die Enzyme nicht verbraucht. Nanopartikel die kleiner als 20 nm gross sind, sind sehr reaktionsfreudig und in der Lage, hohe Energieschranken zu durchbrechen. In der Mikroemulsion sind sie wichtig für die selbstorganisierte Reaktion in den einzelnen Phasen der Be- und/oder Entschichtungsverfahren. Die links- und rechtsdrehenden Moleküle (vorwiegend Terpene) sind verantwortlich für die Bildung, Vergrösserung und Stabilisierung der Mikrokapillaren, auf welche später noch genauer eingegangen wird.Other substances used in microemulsions are:

• enzymes
• Organic and inorganic nanoparticles
• Lens and dextrorotatory terpenes

The enzymes are able to control the energy ratios of micelles, nanoparticles and left- and right-handed molecules. Normally, they act as Catalysts that reduce the reaction energy between two systems. In the microemulsion the enzymes are not consumed. Nanoparticles smaller than 20 nm are very reactive and able to break high energy barriers. In the microemulsion, they are important for the self-assembled reaction in the individual phases of the coating and / or stripping processes. The left- and right-handed molecules (predominantly terpenes) are responsible for the formation, enlargement and stabilization of the microcapillaries, which will be discussed in more detail later.

ε₀

elektrische Feldkonstante (ε₀ = 8.854·10^-12AsV^-1m^-1)

ε_r

Dielektrizitätszahl (relative Dielektrizitätskonstante)

E

elektrische Feldstärke

The electrical properties of micelles are in some analogy to the kinetic properties. Since the micelles have almost no electron conductivity in contrast to the metals, the electrical properties depend to a great extent, as do the mechanical properties, on the mobility of the molecular components of the micelles. Characteristic of these properties is the relative permittivity ε _r . One calls ε _r the "Relative Dielectricity". The magnitude of the dielectric constant of an insulating material is determined by the strength of the polarization. It is dimensionless but depends on the material as well as the temperature and the frequency. At the surface of the micelles, under the influence of an electric field, so-called polarization charges are generated which influence. By influence is meant the separation of charges of a conducting body under the influence of the electrical forces exerted by external charges. The dielectric polarization is the proportion of the shift flux density attributable to the dielectric. The size of the dielectric polarization P is given by the relationship: $$P={\epsilon }_0\cdot e\cdot \left({\epsilon }_r-1\right)$$

ε ₀

electric field constant (ε ₀ = 8,854 · 10 ^-12 AsV ^-1 m ^-1 )

ε _r

Dielectric constant (relative dielectric constant)

e

electric field strength

wobei p = Volumengehalt.
So ergibt sich beispielsweise für Lufteinschlüsse (Schaum, Fliesszonen, etc.) mit ε_r,Luft ≈ 1 : $${\epsilon }_{\mathit{eff}}={\epsilon }_{\mathit{Matrix}}\left(1-3p\cdot \frac{{\epsilon }_{\mathit{Matrix}}-1}{2\cdot {\epsilon }_{\mathit{Matrix}}+1}\right)$$

und bei Metalleinschlüssen mit ε _r,Metall ≈ ∞: $${\epsilon }_{\mathit{eff}}={\epsilon }_{\mathit{Matrix}}\left(1+3p\right)$$

It can be deduced from the equation (1) that the more pronounced the polar behavior and thus the P of a substance, the greater the dielectric constant. If there is only one shift polarization, then the dielectric constant is small. kick but in addition to the displacement polarization additionally an orientation polarization, so the dielectric constant is greater. It can then reach values of 4 to 100. If there is a spontaneous polarization, even peak values of up to 100,000 can be achieved as the dielectric constant. But what exactly is the polarization? Real bodies consist of the same number of positive and negative electrical charges on which an applied electric field exerts kinetic forces. Positive charges are accelerated in the field direction, negative against the field direction. Micelles have virtually no free-moving charge carriers. The charges are bound to carriers (atoms, molecule segments). Thus, they can only be displaced elastically by a measure proportional to the field strength. The emphases of positive and negative charges no longer coincide with each other; electric dipoles form. In electron polarization, the outer field causes a deformation of the electron shell of the atoms. It occurs in nonpolar substances. In pure electron polarization, ε _r = n ² (n = optical refractive index). It also practically does not change with the frequency, it decreases with the temperature, because as a result of the thermal expansion, the number of polarizable particles becomes smaller. Since only the molecules used to make micelles themselves or parts of them are "permanent dipoles", they can be aligned in electric fields, giving rise to macroscopic polarization, which is higher for polar surfactants than for nonpolar ones. The polarization components are also differently movable according to the different mechanisms. Since in micelles the permanent dipoles are relatively large groups, they can only follow relatively low frequencies. Of considerable practical interest is the question of the influence of color pigments on the relative dielectric constant. The most important mixing rule is calculated approximately from the sum of the dipole moments of the color pigments and that of the carrier matrix on the total charge density: $${\epsilon }_{\mathit{eff}}={\epsilon }_{\mathit{matrix}}\left(1-3p\cdot \frac{{\epsilon }_{\mathit{matrix}}-{\epsilon }_{r.\mathit{<figure-callout\; id="2"\; label="pigment"\; filenames="imgf0001.png"\; state="\{\{state\}\}">pigment</figure-callout>}}}{2\cdot {\epsilon }_{\mathit{matrix}}+{\epsilon }_{r.\mathit{pigment}}}\right)$$

where p = volume content.
For example, for air inclusions (foam, flow zones, etc.) with ε _{r, air} ≈ 1 results: $${\epsilon }_{\mathit{eff}}={\epsilon }_{\mathit{matrix}}\left(1-3p\cdot \frac{{\epsilon }_{\mathit{matrix}}-1}{2\cdot {\mathrm{<figure-callout\; id="1"\; label="\epsilon \; matrix\; +"\; filenames="imgf0001.png,imgf0002.png"\; state="\{\{state\}\}">\epsilon \; </figure-callout>}}_{\mathit{matrix}}+1}\right)$$

and for metal inclusions with ε _{r, metal} ≈ ∞: $${\epsilon }_{\mathit{eff}}={\epsilon }_{\mathit{matrix}}\left(1+3p\right)$$

• Entfernung von nassen und angetrockneten Druckfarben
• Entfernung von ein- und zweikomponentigen Farben
• Entfernung von Kunststoffbeschichtungen
• Entfernung von industriellen Schmutzschichten
• usw.

Die Beschichtungen dienen der

• Veränderung der Leitfähigkeit von Kunststoffoberflächen
• Veränderung der Oberflächenenergie von Kunststoffoberflächen, z.B. Epilamisierung, Verbesserung der Gleiteigenschaft, etc. • Auftragung funktioneller Nanoschichten auf Festkörper
• usw.

The presented process can be used in conjunction with a microemulsion in various applications. It works for nanoscale coatings and decoating. The decovers serve for example the

• Removal of wet and dried inks
• Removal of one- and two-component colors
• Removal of plastic coatings
• Removal of industrial dirt layers
• etc.

The coatings serve the

• Change in the conductivity of plastic surfaces
• Change in the surface energy of plastic surfaces, eg epilamization, improvement of the sliding properties, etc. • Application of functional nanosheets on solid bodies
• etc.

The aim of the process is to convert a microemulsion into a nanoemulsion in the activation device and to generate active electrical interface bilayers in the molecular, and in the atomic, region by means of the phase resonator by electromagnetic fields on the solid particles of the nanoemulsion. Electrical bilayers are known to be responsible for many physical kinetic phenomena such as electro-osmosis, electrophoresis, flow potentials, and sedimentation potentials. The electric kinetic forces that act on electrically charged particles in a liquid are called Colombian forces. For the function of the named method, which can be used for film formation and layer removal on solids, different at the bilayers Systems generated by electrical and high-frequency high-voltage fields electrokinetic changes. For this purpose, a gas mixture is admitted into the activation device. This results in a part of the nanoemulsion an aerosol, which is sprayed together with the remaining nanoemulsion with the rotating injector nozzles of the transversal resonator in the vacuum chamber. In the vacuum chamber, the rotating transverse resonator generates a parabolic, asymmetric, transversely superimposed rotation field. The double layers of the sprayed particles react in this field and form functional resonances in the individual process phases. For the coating and Entschichtungsverfahren various functional single or multi-phase processes are used.

A decisive role for the multiphase process is, inter alia, the influence of the composition of the microemulsion used as well as the program-controlled reaction technique in the activation device or in the phase resonator. In the individual phases with the phase resonator selective active and high-energy centers are formed with electro-kinetic charges, with which the structure of the organic layer to be replaced is changed. In these active centers, the molecules, enzymes and nanoparticle interface atoms are dissolved and effective, intermolecular forces are generated in the organic layer. This results in different interactions between the layer molecules, which are described in greater detail in the four phases of the multiphase decoating system. A special feature of this method is the self-assembly of nanoparticles, which is formed by the adsorption of ions and by self-dissociation. Nanoparticles that are in this state can lead to system instabilities in contact with ionic interfaces. This effect is effective in the phase 4 described below when removing larger layer agglomerations. Another effect used in the process of Phase 1 described below is the generation of matter waves which form a network of split capillaries in the organic layer. From the formation phenomenon of electrons and neutrons we know that material particles have properties of matter waves if the molecular force constants are very large (extension of the Maxwell equation law of the translation energy). in the In contrast to the electromagnetic waves or protons, in matter waves the propagation velocity is different from the particle velocity. When a particle beam is generated by an infinitely long wave, the momentum of the particle is uniquely determined by the wavelength. However, the place that occupies or passes through a particle at a particular time is completely indeterminate. In order to at least approximately identify the location of a particle entering the organic layer, it is necessary to use a wave packet. Such a wave packet is created by superposition of numerous wave trains, in which the wavelength and the amplitude are selected so that interference occurs. Using a wave packet, which is used in Phase 3 described below, the uncertainty of the local location of the particles can be narrowed. However, this is only possible at the expense of sharpness in the indication of the momentum. The wave nature of material particles therefore brings a fundamental blurring of the simultaneous indication of the location and momentum of a particle (uncertainty principle, physicist Werner Heisenberg, 1927).

A specific application example of the use of such nanoemulsions is the cleaning of tampon printing utensils. For this purpose, a device is used which in FIG. 1 shown from behind. It is made of chrome steel and has a vacuum chamber 1 accessible from above, into which a treatment basket 2 with two handle bars 3 can be inserted. To be cleaned utensils, that is in the example presented tampon printing Clischees are placed in this basket 2 and then introduced into the vacuum chamber 1. Instead of the treatment basket 2 is often used only a grid for receiving the cleaning material. The vacuum chamber can be closed with a cover 4, which is fastened thereto by means of hinges on the upper side of the device. The operator stands on the front side of the device, ie on the side facing away from the image here. The lid is thus, starting from the closed state, swung forwards and forms afterwards a storage area for the to be lifted from the vacuum chamber treatment basket 2 or the items to be cleaned. In addition to the vacuum chamber 1 can be seen a recycling system 5, in which the microemulsion is freed from the color, as will be described in more detail later. At the back of the device is an opening 6 for the exhaust air, which in the generation of the vacuum in the vacuum chamber. 1 arises. At the opening 6, an in-house exhaust air system or an active carbon filter can be connected. On a narrow side of the device is also a compressed air connection 7 and an electrical connection. 8

In FIG. 2 one sees the device in a view seen from the front, with the front cover removed. Under the vacuum chamber 1, two circulation pumps 9 can be seen. At each pump outlet a not fully visible activation device 10 is connected. This activation device 10 is in each case connected by means of a screw connection to the corresponding transversal resonator (not visible here) in the vacuum chamber 1. In the bottom of the vacuum chamber 1 is the drain, which is connected via a T-piece 11 and a screw with the pump inputs. The circulating pumps 9 thus convey the microemulsion via the activation units 10 into the transversal resonators, where they are sprayed as an aerosol / nanoemulsion mixture into the vacuum chamber 1 onto the items to be cleaned. The microemulsion leaves the vacuum chamber 1 via a drain, which is connected via the T-piece 11 and the connecting pipes with the circulation pumps 9. This cleaning cycle just described can alternatively be operated with one or more than two pumps, depending on the cleaning requirement. In addition to the cleaning cycle, the device also contains a cycle for recycling. The two activation devices 10 are connected to each other via a connecting tube 12. In the middle of which there is a valve 13 which, after being switched on via the hose 14, supplies a part of the emulsion to the recycling system 5 for recycling. After the recycling process, the now clean microemulsion is fed back to the vacuum chamber 1 via the line 15 and the valve 16. When the valve 16 is closed, air is blown into the recycling system 5 for backwashing from below. On the backwash will later in the FIG. 4 discussed in more detail. Above the activation devices 10, one recognizes the device-associated electrical circuit 17, which is mounted on the outside of the vacuum chamber 1. This electrical circuit 17 also includes the generators for operating the electrode and the coils and the phase discriminators. With these generators high voltage fields of 1 to 10,000 volts can be generated, with superimposed frequencies of 10 Hz to 1 GHz. To the right of the vacuum chamber 1 is a vacuum valve 18 to recognize. The vacuum valve 18 has the task to put the vacuum chamber 1 under vacuum and the exhaust air through the opening 6 (FIG. FIG. 1 ) dissipate. The 3/2-way valve 19 is used for ventilation of the recycle system 5 and the ventilation of the vacuum chamber. 1

The FIG. 3 shows in an enlarged view the output of a circulation pump 9, an activation device 10 and a transversal resonator 20. With the aid of the activation device 10, the microemulsion is converted into a nanoemulsion. The rotating transversal resonator 20 generates the individual process steps for the 4-phase method. The activation device 10 consists of a shielding housing 21, consisting of a tube which is welded to the bottom outlet of the vacuum chamber 1. An insulator 22 is installed in the shielding housing 21 In the center of the insulator 22, ie in the liquid inlet, there are one or two high-voltage electrodes 23 and two sliding contacts 24. The high-voltage electrode 23 is connected to the waveguides 25 and the permanent magnets 26 via a respective sliding contact 24. Outside the shielding housing 21 is an electromagnetic High-frequency coil 27. In the upper part of the insulator 22, which projects into the vacuum chamber 1, there is a ball bearing 28 and a mounting thread for the transverse resonator 20. At the lower end, below the high-frequency coil 27 is the connection 29 for the high-voltage electrode 23rd On the opposite nden side is the inlet 30, through which the system gaseous, vapor or liquid agents can be supplied. The transverse resonator 20 consists of a cylindrical rotating part 31 made of plastic or ceramic with internal thread for attachment to the activation unit 10 and two laterally mounted threads for the hollow nozzle rods 32 made of plastic. In the upper part of one or more ring permanent magnets 33 are installed. One or more injector nozzles 34 are screwed onto the hollow nozzle rods 32, while a bore 35 is located at the bottom, slightly offset laterally. Due to the exit of the nanoemulsion from the two bores 35, the transversal resonator 20 rotates about its axis. In the hollow nozzle rods 32, a waveguide 25 made of tungsten or stainless steel is fixed in the middle, which on the outer side with a permanent magnet 26 is completed. On the inside, the waveguides 25 are each connected to a sliding contact 24 of the activation device 10. In the lower part of the activation unit 10 is a membrane as a phase resonator 36, which is supplied via the terminal 37 for the production of nanoparticles of defined sizes with a separate high voltage / high frequency generator.

The microemulsion is continuously freed from the absorbed color in the recycling system 5. The recycling system 5, which in FIG. 2 is visible in FIG. 4 shown in a cross section. It is a pot made of chrome steel. In principle, a conventional chromium steel pressure cooker can be used as a recycling system 5. In the bottom of the pot is a drain opening 38. At this drain opening 38, a manifold 39 is fixed with an electromagnetic flow coil 40. The flow coil 40 has the task to reset the microemulsion back to a defined state. Below the coil 40, an air inlet valve 41 with upstream check valve 42 is installed at the distributor 39 for the backwashing. Via the line 15, which is also attached to the distributor 39, the clean microemulsion leaves the recycling system 5. On the side of the pot are four inlets 43,44 and 47,48 with threads pressed. The inlets 43 and 44 are connected to a hose 45. For level control, there is an adjustable capacitive level probe 46 on the hose 45. The upper inlet 47 is connected to the compressed air inlet via a nylon hose with a 3/2-way valve. The lower inlet 48 is connected to the hose 14 with valve 13. A portion of the microemulsion is fed to the recycling system 5 for recycling via this tube 14. In the recycling system 5, a partition plate 49 is put into it. This partition plate 49 is fastened with a T-shaped fastening unit 54 on a sealing ring 55 on the bottom of the pot. It consists of a metal insert 50 with twelve drain holes. Welded into the metal insert 50 is a stainless steel nose plate 51 as a spacer. On top of this lies a piezo foil 52 made of coated stainless steel or plastic fabric. Alternatively, an electrode, consisting of a metal mesh, which is supplied by an external generator with high voltage, are inserted. Above the piezo foil 52 or the high-voltage electrode is a fine-meshed stainless steel mesh 53. The inserted parts are at the edge with a high-resistance potting compound 56 opposite the Metal insert 50 isolated fastened. In the middle of the partition plate 49 is for fastening and removal a stainless steel nozzle with bore 57. The partition plate 49 has next to the structure of a liquid / liquid double layer for color separation the task to prevent the flow of the fine-grained adsorber.

During the first startup or after a color removal, a measuring cup of adsorber or a unit of vacuum-packed adsorber paste is first added to the recycling system 5. The adsorber consists of various organic and inorganic substances which are chosen so that they are able to release the expensive active ingredients of the microemulsion by exchange in the re-use. After the adsorber has been added, the recycling system 5 is sealed, for which purpose the associated lid can be used in the case of a pressure cooker. After the start of the cleaning process, the recycling of the emulsion is active in parallel. In the recycling system 5, the backwashing is started first. It mixes the adsorber with the soiled emulsion. During the cleaning process, the recycling system 5 is cyclically filled via the dirty emulsion valve 13. The fill volume is determined by the capacitive level probe 46. During mixing with the adsorber, the molecular active substances bound to the color agglomerations are released again and replaced by adsorber molecules. The released active substances partially form micelles again and assume a negative charge. Due to the pressure and / or the vacuum acting on the piezomembrane, a liquid / liquid separating layer with a negative field voltage is formed between the adsorber and the separating plate. This field voltage (high voltage) forms an electrostatic filter and separates the positively charged color agglomerations from the negatively charged microemulsion. The liberated from the color microemulsion leaves the recycle system 5 via the bottom of the existing discharge opening 38. The ink residues bound to the adsorbent, however, remain until the color in the pot. Upon passage of the microemulsion through the electromagnetic flow coil 40, the micelles of their charge are restored to their original state. Subsequently, the regenerated microemulsion is fed back to the vacuum chamber 1 via the line 15 and through the valve 16. The deposited amount of color becomes temporal and / or monitored by a probe in relation to the amount. When the maximum allowable amount of ink is reached, a color picker process automatically runs. In the process, the recycling system 5 is emptied and the residual substance is dried with air from the inlet 47. After completion of this process, the lid is opened by hand and manually removed the separation plate 49 with the powdered and dry paint residues bound to the spent adsorber. After removal of the residues, the partition plate 49 is again inserted into the recycling system 5 and firmly screwed to the T-shaped fixing unit 54. A new cleaning process can only be started again when the recycle system 5 has been refilled with adsorber and the lid has been closed. The recycling system allows a practically unlimited use of the microemulsion. Only the carryover losses have to be replaced from time to time.

In the following, the individual phases of the multiphase process will now be described in detail and explained: FIG. 5 shows Phase 1: In the multiphase process, organic layers are degraded from the back and built up from the front side during layer formation. Therefore, in the layer degradation in the phase 1, the organic layer is provided with a void structure, that is, it is made permeable. For this purpose, in a polar, transversal alternating field, gas-loaded nanoparticles with attached left- and right-handed molecules are accelerated from the aerosol mixture generated in the transversal resonator in the direction of the substrate surfaces. For this purpose, a potential difference of Δ _φ0 = 3000 V and a superimposed AC voltage of 4000V between the two electrodes (waveguide) of the transversal resonator is applied. In the alternating field, the energy levels of the nanoparticle phase boundary layers are periodically raised and lowered. This speeds up the injection process. The channel walls of the microchannels generated by the penetration of the gas-loaded nanoparticles are occupied by left- and right-handed molecules. This process is performed by a tandem reaction. This is a reaction sequence in which two different reactions follow one another directly, with the first reaction, the injection, the second, the occupancy of the channel walls, practically enforcing. The capillaries thus produced remain stable for about 30 to 60 seconds.

Phase 2: ( FIG. 6 As a result of the change in the electric double layer on the nanoparticles M ₂ , an injection process takes place in the direction of the substrate or of the organic layer adhering to the substrate. At the phase transition of the (aerosol / liquid) ↔ (layer), a potential drop and thus a change in the resonance frequency at the particle boundary surfaces M ₂ . In order to match the potential of the particle bilayer in the injection channel to the left and right-handed molecules, a polar field adapted to the electrical flow potential is first constructed, which generates a stationary velocity field with an assimetric potential distribution in the microcapillaries. For this purpose, a potential difference of Δφ ₀ = 500 V is applied in the transversal resonator between the two electrodes (waveguide). The dimensionless potential on the substrate is then Φ ₁₁ = 1 and on the walls Φ ₂₁ = 0. By the asymptotic adaptation of the electrical boundary condition and the rotating field, which is established by the rotation of the two electrodes (waveguides), the particles M ₂ flow through the microcapillaries formed in phase 1 in the direction of the substrate surface. Once there, they transfer part of the kinetic energy to the phase interface "substrate ↔ layer", where they form a molecular separation layer due to the local change of the zeta potential.

Phase 3a: ( FIG. 7 In phase 3a non-organic molecules are deposited on the outside of the organic layer. After a molecular occupation of the outer boundary layer, the surface tension is increased in it. The boundary layer thus bulges outward in a concave manner. At the same time, amphoteric molecules diffuse into the open capillaries. After losing their kinetic energy, they remain stuck in the shift system. A distribution in the layer system results from the different amounts of kinetic energy of the individual amphoteric molecules. Phase 3b: ( FIG. 8 In a high-frequency energy field, the low-energy, amphoteric molecules resonate and mutate into anions. At the same time, they form a network of small districts, creating gap-shaped capillaries in the organic layer in which the substances active in phase 4 are transported to the anions.

Phase 4: ( FIGS. 9 and 10 ) Phase 4 involves the method "Phase Transfer Catalysis" for use. This allows reactions between substances that are in different, immiscible phases. When the anionic phase M _x comes into contact with the nanoparticle-laden enzyme phase M _y , nothing happens yet. The reaction does not start until an ion from the phase M _x is extracted through the interface M _{x, y} into the phase M _y . Due to the catalytic action of the enzymes, a violent reaction then occurs in the phase space M _{x, y} , which causes a potential jump in the bilayers, at the interfaces of the nanoparticles. This potential jump leads to an instability of the phase space M _{x, y} , with the result that the phase space cells decay into their constituents within a few microseconds. Due to the binding energy released in this process, large, energetic centers emerge in the organic layer which, in the macro-area, cause large districts (for example color agglomerations) to be ejected in the organic layer.

In principle, no substances are dissolved with the described cleaning process. Depending on the process step, mixtures are formed, some of which regress themselves or under the influence of the process. All these methods have in common that in order to achieve the desired effect interaction forces must exist between the same and dissimilar partners. The range of possible uses of the method is very large. It can be used with a suitable microemulsion not only for defenses but also for coatings. This possibility is given by the targeted generation of desired double layers with a suitable matrix. First and foremost, the process uses the potential changes in physical properties and the self-assembly of nanoparticles as well as the properties of bilayers. It can thus be constructed systems which achieve a large effect at the lowest possible energy consumption. In addition to the physical changes in bilayers, the method can also be used to initiate targeted chemical changes. The process can also be used at the nanoscale for the formation of molecular layers with new solid-state properties.

Claims (10)

1. Process for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same, for which a nanoemulsion is produced, in which an emulsion flows through an actuation device (10), in which electrical and electromagnetic fields produced by a high frequency electrode (23) and electromagnetic high frequency coil (27) by means of generators are superimposed on each other and resonances are produced by means of selectable voltages, frequencies and phase shifts so that, as a result of the modification of the particle double layers, the Zeta potential is so modified that a microemulsion transforms to a nanoemulsion, with which the surfaces of parts are treated afterwards in a vacuum chamber (1) and is recycled afterwards in the recycling system (5) and then used again.
2. Process for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to claim 1 characterised by the fact that high voltage fields of 1 to 10,000 Volt are produced with the generators with superimposed frequencies of 10 Hz to I GHz.
3. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same, consisting of a closed loop with minimum one pump (9) for the supply of an emulsion to a circuit, this closed loop containing a vacuum chamber (1) for the surface treatment of parts therein, in which the closed loop runs through an actuation device (10), as well as a high voltage electrode (23) and a high frequency coil (27) with separate generator each with frequency converter for the production of an electrical field, in which separate fields can be produced from it for the conversion of a microemulsion to a nanoemulsion, and the device further includes a transversal resonator (20) for the production of an aerosol/emulsion mixture as well as injection nozzles (34) for the spraying of the aerosol into the vacuum chamber (1).
4. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to claim 3 characterised by the fact that it has generators for the operation of the electrode and the coil as well as phase discriminators, in which high voltage fields of I to 10,000 Volt can be produced by means of these generators with superimposed frequencies from 10 Hz to 1 GHz.
5. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to claim 3 characterised by the fact that the vacuum chamber (1) is fitted with a vacuum valve (18) for setting the vacuum chamber (1) under vacuum and for leading away the exhaust air via the opening (6) in the housing of the device and further that it has a 3/2 directional control valve (19) for the aeration and deaeration of the recycling system (5) as well for the aeration of the vacuum chamber (1).
6. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to one of the claims 3 to 5 characterised by the fact that it has one or more circulation pumps (9), to whose outlets one actuation device (10) each is connected and which is/are connected via a screwing with an inserted transversal resonator (20) to the vacuum chamber (1) as cleaning tub, on whose floor there is a drain outlet, which is connected to the pump inlets via a T-joint (11) and a threaded connection each.
7. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to one of the claims 3 to 6 characterised by the fact that it contains a circuit for the recycling and the two actuation devices (10) are connected to each other via a connecting tube (12), in which there is a valve (13) in its middle via which a part of the emulsion can be fed to the recycling system (5) for the recycling via the tube (14), as well as a pipe (15) and a valve (16) for the recirculation of the cleaned microemulsion to the vacuum chamber (1).
8. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to one of the claims 3 to 7 characterised by the fact that the actuation device (10) includes a shielding housing (21) and consists of a pipe, which is connected to the floor outlet of the vacuum chamber (1) in which an insulator (22) is assembled in the shielding housing (21) and in the middle of the insulator (22), that is in the liquid inlet, there are minimum one high voltage electrode (23) and two sliding contacts (24) for the connection with the wave guides (25), and that an electromagnetic high frequency coil (27) is fitted outside the shielding housing (21) and there is a ball bearing (28) and a fastening thread for the transversal resonator (20) in the upper part of the insulator (22), which projects into the vacuum chamber, as well as the connection for the high voltage electrode (23) at the lower end, below the high frequency coil (27), and an inlet (30) is present via which gaseous, vaporous or liquid active agents can be supplied to the system.
9. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to one of the claims 3 to 8 characterised by the fact that the transversal resonator (20) consists of a cylindrical rotating part (31) of plastic or ceramic with internal thread for the fixing to the actuation device (10) and has two threads provided sideways for hollow nozzle bars (32) of plastic, in which one or more ring permanent magnets (33) are assembled in the upper part, and one or more injection nozzles (34) are screwed on the hollow nozzle bars (32) each, as well as one wave guide (25) each of tungsten or stainless steel is fixed in the lower third, in the middle of the hollow nozzle bars (32) or in the region in-between, which are closed on the outer side with a permanent magnet and are connected on the inner side with each via a sliding contact (24) to the actuation device (10).
10. Device for the production, application and recycling of nanoemulsions as well as for the surface treatment of parts by means of the same according to one of the claims 3 to 9 characterised by the fact that the recycling system (5) contains a separation plate (49), which is fixed by a T-shaped fixing unit (54) to a sealing ring (55) on the pot floor and consists of a metal tray (50) with discharge holes, to which a stainless steel nose plate (51) is fixed as spacer, and that a Piezo foil (52) or electrode consisting of a wire gauze lies on it, which can be supplied with high voltage by an external generator and a fine-mesh stainless steel grid (53) lies over the electrode, in which these parts put in are fixed at the rim with a high-ohmic sealing compound (56) insulated against the metal tray (50).

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