JP4182002B2 - Process and apparatus for forming ceramic coatings on metals and alloys, and coatings produced by this process - Google Patents

Description

  The present invention relates to the field of applying protective coatings, and more particularly to plasma discharge coatings, such as plasma electrolytic oxidation coatings, on articles made of metals and alloys. This process can quickly and efficiently form a ceramic coating having wear resistance, corrosion resistance, heat resistance, dielectric properties, and uniform color on the surface of these articles.

  These coatings are characterized by high thickness uniformity, low surface roughness, and the absence of a porous outer layer that usually requires significant costs to remove in conventional coating processes.

  The processes for producing the coatings described herein and the apparatus for performing the processes are in industrial technology, specifically in the manufacture of aircraft and automotive industries, petrochemical and textile industries, electronics, pharmaceuticals, and household products. Can be used.

  A process for producing ceramic coatings using an industrial frequency of 50-60 Hz is known from WO 99/31303. This process can form a hard coating on the surface of an article made of an aluminum alloy having a thickness up to 200 μm and sufficiently bonded to the substrate.

  The main problem with this process is that it forms a very thick porous outer layer with low microhardness and countless microscopic and macroscopic defects (micropores, microcracks, flaky fragments). The thickness of the defect layer depends on the chemical composition of the alloy to be treated and the electrolysis scheme, but reaches 25-55% of the total thickness of the ceramic coating.

  Expensive precision equipment is used to remove the porous layer. If the article has a complex shape of the surface that is difficult to reach the abrasive and diamond tool, the problem of removing the defective layer is difficult to solve. This limits the application range of the process.

Another problem with the known process is that the film formation rate is relatively low and energy consumption is high. By raising the current density above 20 A / dm ² , the productivity of the oxidation process cannot simply be increased. This is because the process is an arc process rather than a spark process, and a strong local burn-off discharge appears, which makes the entire coating extremely porous and flaky, which degrades adhesion to the substrate. is there.

  In order to enhance the oxidation process and improve the properties of the ceramic coating, many researchers have attempted to improve the electrolytic pulse regime and have proposed various shapes and durations of current or voltage pulses.

  A process for forming a ceramic coating having a sinusoidal waveform with a modified current is known from US Pat. No. 5,616,229. This current waveform reduces the thermal stress during the formation of the ceramic layer and makes it possible to apply a coating having a thickness of up to 300 μm. However, this process uses industrial frequency currents, resulting in the formation of a relatively thick porous outer layer with high surface roughness and requires relatively high energy costs.

Other processes are known (Russian Patent No. 2077612) for oxidizing valve metals and alloys by a pulsed anode-cathode system that alternates positive and negative pulses of a particular complex shape. The duration of the pulse and the pause between the positive and negative pulses is 100-130 μsec, and the duration frequency is 50 Hz. During the first 5-7 μs, the current reaches its maximum value (800 A / dm ² ) and then remains constant for 25-50 μs. In this case, the shorter pulse and the power of the very large pulse significantly shorten the discharge ignition time, thus eliminating the main cause of the formation of the defect outer layer. However, as the strong pulse pairs alternate with unduly long pauses, the film formation rate is reduced.

  In addition, a process for generating an oxide film in an alkaline electrolyte using a positive pulse with a voltage of 100 to 1000 V is known (former Soviet Patent No. 1767043). These pulses have a two-stage shape. Initially, during 1-3 microseconds, the voltage rises to a maximum value, then falls to about one-tenth of the maximum value, and continues at a constant level for 10-20 microseconds. However, since only positive pulses are used, it is not possible to produce a good quality coating having high microhardness and wear resistance.

  The closest technique to the proposed invention is the process described in Russian Patent No. 2070942. This process alternates between positive and negative pulses with an amplitude of 100-500V and a voltage of duration 1-10 μs, during which the amplitude 600-1000V and duration 0 at each of the half durations on the anode side. Oxidize by applying a high voltage positive pulse of 1-1 μs. When a pulse is applied, the total current at that moment rises, creating a favorable state for discharge. The problem with this process is that a very short high voltage positive pulse is used, so that a discharge with sufficient power cannot be generated. This reduces process productivity and makes it extremely difficult to technically implement the proposed process for industrial purposes.

[Outline of the present invention]
According to the first aspect of the present invention, in the electrolytic cell to which the first electrode is attached and which is filled with the aqueous alkaline electrolyte, the electrolytic cell in which the article to which the other electrode is connected is immersed, the metal and A process for forming a ceramic coating on an alloy, wherein a pulse current is supplied between the electrodes so that the process is performed by a plasma discharge method. supplying a polarity current pulses, at the same time, a step of generating acoustic vibrations of sonic frequency range predetermined in the electrolyte, such as the frequency range of the acoustic vibrations overlaps with the frequency range of the current pulse step wherein the current pulses are provided processes having pulse duration frequency which is within the range of 500 to 10,000 Hz.

According to a second aspect of the present invention, there is provided an apparatus for forming a ceramic coating on metals and alloys, comprising an electrolytic cell having an electrode, a source for sending a pulsed current to the electrode, and at least one acoustic vibration generator. in equipped device, said source being adapted to adapted to supply a bipolar current pulses of the high frequency of a predetermined frequency range to said electrode, wherein said at least one acoustic vibration generator is included in said tank At the same time as the supply of the bipolar current pulse into the electrolyte , the acoustic vibration has a predetermined acoustic frequency range that overlaps the current pulse frequency range. A device having a pulse duration in which the current pulse is in the range of 500 to 10,000 Hz is provided.

  According to a third aspect of the invention, there is provided a ceramic coating formed by the process or apparatus of the first or second aspect of the invention.

  According to a fourth aspect of the present invention, there is provided a ceramic coating formed on a metal or alloy by a plasma discharge process and having a porous outer layer not greater than 14% of the total coating thickness.

  According to a fifth aspect of the present invention, there is provided a ceramic coating formed on a metal or alloy by a plasma discharge process having a low roughness (Ra) surface of 0.6 to 2.1 μm. The

  Bipolar current pulses may be alternating pulses, or may be provided as a set of pulses, for example, two unipolar followed by one reverse pole.

  Embodiments of the present invention are intended to improve useful properties such as wear, corrosion, heat resistance and dielectric strength of ceramic coatings by improving the physical and mechanical properties of the ceramic coatings. . Embodiments of the present invention also solve the technical problem of producing a hard microcrystalline ceramic coating that has good adhesion to the substrate.

  Also, embodiments of the present invention improve the technical complexity of the process of forming the ceramic coating by significantly reducing the time required to apply the ceramic coating and the time required to finish the coating. Is intended. Not only will the productivity of the oxidation process be increased, but also the specific power cost will be significantly reduced.

  Furthermore, according to the embodiment of the present invention, a film having predetermined characteristics is intentionally formed by introducing a refractory inorganic compound into the electrolytic solution.

  In addition, the embodiment of the present invention may improve the stability of the electrolyte and extend its useful life.

  Embodiments of the apparatus of the present invention are intended to provide improved reliability, versatility, and ease of installation on automated production lines.

Advantageously, the article to be coated is connected to an electrode and placed in an electrolytic cell having another electrode and filled with an alkaline electrolyte. A pulse current may be applied to these electrodes so as to form a film having a required thickness by a plasma discharge method, preferably a plasma electrolytic oxidation method. Current pulses having a pulse duration of 500 Hz or more, preferably 1000 to 10,000 Hz and a preferred pulse duration of 20 to 1,000 μsec may be generated in the cell. Each current pulse preferably has a steep front, and the current reaches a maximum amplitude in a time not greater than 10% of the total pulse duration, then drops sharply and then reaches a maximum value of 50. Gradually decreases to less than%. The current density is preferably 3 to 200 A / dm ² , more preferably 10 to 60 A / dm ² .

  Acoustic vibrations may be generated in the electrolyte by an aerohydrodynamic generator. The generator generates acoustic vibrations in the sonic frequency range that overlap the current pulse frequency range in the vessel.

  An ultra-dispersed powder (nano powder) consisting of metal oxides, borides, carbides, nitrides, silicides, or sulfides having a particle size not larger than 0.5 μm is added to the electrolyte solution to form a stable aqueous sol May be formed by acoustic vibration.

By making the current pulse relatively short, the discharge spark time can be shortened and oxidation can be performed at a high current density of 3 to 200 A / dm ² .

  A short pulse with a high current value can generate a spark with a significantly higher power in the plasma discharge path formed in the film than in the case of the low frequency system. The molten substrate is cooled and solidified more rapidly due to the higher temperature of the plasma discharge path and the smaller microvolume, resulting in the formation of a dense microcrystalline ceramic coating containing a large amount of high-temperature oxide solid phase. Is done. The microhardness of the coating reaches 500 to 2100 HV and the thickness of the porous outer layer preferably does not exceed 14% of the total thickness of the coating.

  By using a current pulse with a duration higher than 500 Hz and a duration shorter than 1,000 μsec, it helps to limit the progress of the arc discharge, making the coating flaky and porous, and at the same time forms the coating Helps reduce specific energy loss. However, as the pulse frequency is further increased, the specific energy loss decreases, but the loss due to surface and capacitive effects begins to increase. These losses become significant at pulse frequencies greater than 10,000 Hz. In addition, using current pulses with a frequency greater than 10,000 Hz and durations shorter than 20 μs requires extremely high power pulses to produce a good quality coating. This makes the technical implementation to achieve industrial objectives extremely complex and costly.

  The characteristics of the plasma discharge itself by the high frequency pulse method are different from those of the discharge for oxidation performed at a conventional industrial frequency (50 or 60 Hz). An improvement in gloss and a reduction in the size of the spark can be observed with the naked eye. Instead of the spark moving across the surface to be oxidized, it can be seen that a myriad of sparks are discharging simultaneously across the surface.

  Due to the preferred shape of the current pulse (FIG. 1), uniform initiation and retention of the plasma discharge can be easily achieved across the surface of the article. The plasma discharge process does not need to maintain a constant high current value. The forefront of the steep pulse, that is, the rapid rise to the maximum value of the pulse, can significantly reduce the discharge start time. Further, the discharge process can be efficiently maintained by reducing the current to 50% or less of the maximum value.

  In addition, the forefront of the positive and negative pulse steep slopes are generated by both the electrode system (bath-electrolyte-article) and the double electrical layer (electrolyte-oxidation-metal) on the surface of the article to be oxidized. Capacitive loads can be charged and discharged rapidly.

  In practice, it is also conceivable to stir the electrolyte during oxidation using a mechanical mixer and a vent. The venting device agitates the electrolyte by bubbling air or oxygen into the electrolyte. These machines average a macroscopic level of electrolyte concentration and temperature by producing a predetermined liquid flow. However, in this type of mixing, it is difficult to eliminate the no-flow and strong-flow zones that occur around the surface of the article. Modern systems with a mixing nozzle that injects electrolyte will mix these zones more efficiently and ensure high turbulence. Vibration and pulsating agitation may be used.

A process for anodizing non-ferrous alloys is known (EP 1042178). In this process, the electrolytic solution is agitated by a vibration motor and a rotor blade. The electrode is vibrated and oscillated, and the supply of compressed air is supplied through a porous ceramic tube having a fine pore diameter of 10 to 400 μm. As a result, the anodization process can be performed at a relatively high current density of 10 to 15 A / dm ² , and the anodization time can be significantly shortened. However, this process is not sufficient for plasma oxidation. This is because the generation rate of relatively large bubbles in the electrolytic solution and the frequency of vibration in the electrolytic solution are low. Also, the stirring of the electrolyte and the supply and removal of the reactants in the electrode region occur at a macroscopic level. Furthermore, it is difficult to realize this process industrially from the viewpoint of design.

  In the case of high energy consumption processes such as plasma electrolytic oxidation, the heat and mass transfer rates and the flow state of the stirring liquid at the microscopic level in the immediate vicinity of the surface to be treated play the most important role. The acoustic effect on the electrolyte helps to create this type of agitation.

  WO 96/38603 describes a spark oxidation process in which ultrasonic vibrations act on the electrolyte. These vibrations facilitate the concentrated circulation of the electrolyte in the discharge zone. However, the ultrasonic vibration in the liquid causes degassing and bubble coupling, and the coupled bubbles float on the surface. Up to 60% of the dissolved gas quickly separates from the liquid. In addition, the high power of ultrasonic vibrations causes surface erosion due to cavitation, destroying the ceramic surface, and increasing the number of microcracks and micropores due to fluid impact such as cavitation bubble rupture.

In contrast, embodiments of the present invention employ a region of acoustic vibration within the acoustic (ie, not ultrasonic) frequency range, preferably a region of acoustic vibration where the magnitude of the vibration does not exceed 1 W / cm ^2. The present invention relates to a technique for forming a ceramic coating in an alkaline electrolyte.

  The acoustic vibration may be generated by at least one aerohydraulic generator. This aero-hydraulic generator is a device that converts the kinetic energy of a liquid and air jet into acoustic vibration energy. Such a generator is characterized by simplicity, reliability, and economy and includes a fluid inlet and a resonance chamber. Acoustic vibration is induced in the generator's resonant chamber as the electrolyte passes through the generator through the fluid inlet of the generator, followed by a discharge of the electrolyte, so that air from the atmosphere is passed through a specific path. Through the generator, mixed with the electrolyte and dispersed.

  A number of fine bubbles of air are trapped in the flow and fill the entire volume of the tank. Air is forcibly dissolved in the electrolyte and saturates the electrolyte with oxygen. The gas saturation of the electrolyte increases to 20-30%.

  Bubbles that vibrate at the frequency of the acoustic vibration flow microscopically in the electrolyte, significantly accelerate the agitation process of the electrolyte, and prevent agitation from being drastically reduced near the surface to be oxidized. The heat generated by the plasma discharge is efficiently removed, local overheating is eliminated, and a good quality ceramic coating having a uniform thickness is reliably formed. The formation of a new part with a higher oxygen content in the electrolyte enhances the plasma chemical reaction in the discharge zone and accelerates the film formation process.

  The aqueous alkaline electrolyte used for plasma oxidation is a colloidal solution, that is, an aqueous sol. Like other colloidal solutions, such electrolytes tend to cause solidification, aggregation, and sedimentation. When the electrolyte reaches a certain level of solidification, agglomeration, and settling, the electrolyte becomes ineffective and the quality of the coating deteriorates rapidly. Therefore, the effectiveness of the electrolyte may be determined by controlling the number and shape of the colloidal particles.

  According to the embodiment of the present invention, the electrolytic solution can be stably and efficiently maintained over a long period of time by continuously breaking large particles that can be generated in the electrolytic solution. Under the influence of the acoustic region generated by the acoustic vibration generator, the rate of movement of the colloidal particles increases, increasing the number of active collisions between particles and between the particles and the walls of the vessel and the surface of the article being oxidized, Causes dispersion of particles.

  To produce a ceramic coating with predetermined functional properties (wear, light, corrosion, and resistance to heat, dielectric properties, uniform color throughout thickness), preferably not greater than 0.5 μm A superdispersed insoluble powder (nanopowder) having a particle size, in some embodiments, a particle size not greater than 0.3 μm and a preferred concentration of 0.1 to 5 g / L is added to the electrolyte. Good.

  Processes using solid dispersion powders for electrolytic spark oxidation are known (UK 2237030, WO 97/03231, US Pat. No. 5,616,229, Russian patent 2038428). And Russian Patent No. 2077612). In all these processes, the powder used has a relatively large particle size of 1 to 10 μm and is used at a relatively high concentration of 2 to 100 g / L. In order for such particles to settle quickly and remain suspended, the circulation rate of the electrolyte in the bath or the supply of air for foaming must be increased. When done in this way, it is substantially difficult to distribute the particles evenly in the volume of the electrolyte and thus in the coating. Furthermore, the large particles that have entered the oxide layer do not have time to melt, resulting in the formation of a brittle flake cake-like film.

The present invention preferably has a particle size of up to 0.5 μm, in some embodiments a particle size of up to 0.3 μm and a developed specific surface area (not less than 10 m ² / g), characterized by high energy conditions. Propose the use of attached nanopowder. The electrolyte into which the powder is introduced by acoustic vibration is in a highly dispersed and stable aqueous sol state.

  Superdispersed particles themselves have greater resistance to coagulation and settling. Moreover, by using acoustic vibration, these particles can be further dispersed in the electrolytic solution and distributed uniformly in the volume of the electrolytic solution.

  The acoustic effect enhances the mixing of the particles and gives them additional energy. The additional charge carried by the microparticles (charge charged by electrolyte ions) activates the plasma / chemical reaction in the discharge zone. Some of the ultra-dispersed particles that enter the plasma discharge zone are sublimated and the other part is completely dissolved in the growing oxide layer. The process of forming the coating is also accelerated, reaching 2 to 10 μm per minute, depending on the substrate material. The resulting coating is characterized by high structural stability and thickness uniformity.

The following refractory materials: oxides (Al ₂ O ₃ , ZrO ₂ , CeO ₂ , CrO ₃ , MgO, SiO ₂ , TiO ₂ , Fe ₂ O ₃ , Y ₂ O ₃ , or mixtures thereof, complex oxidation Or spinel), boride (ZrB ₂ , TiB ₂ , CrB ₂ , LaB ₂ ), nitride (Si ₃ N ₄ , TiN, AlN, BN), carbide (B ₄ C, SiC, Cr ₃ C ₂ , TlC, ZrC, TaC, VC, WC), sulfides (MoS ₂ , WS ₂ , ZnS, CoS), silicides (WSi ₂ , MoSi ₂ ), and other ultra-dispersed powders (nano Used as a powder). By adding particles of such refractory substances with various chemical compositions to the electrolyte, the physical and mechanical properties such as coating structure, microhardness, porosity, strength, and color are fundamentally changed. Can be changed. Accordingly, it is possible to produce a film having optimal characteristics for a specific application.

  By using nanopowder, a high quality film can be obtained at a relatively low concentration of 0.1 to 5 g / L, preferably 0.5-3 g / L. When a higher concentration powder having a particle diameter larger than 0.5 μm is used, a remarkable effect cannot be obtained.

  One feature of the present invention found by the applicant is that a good quality ceramic coating is obtained by using an oxidation process in combination with high frequency electrical pulses and the generation of acoustic vibrations in the sonic frequency range within the electrolyte. Is to remarkably promote the formation of. The acoustic vibration must overlap the current frequency range. This increase in film formation is achieved without significantly increasing electrical wear.

  The above effects, that is, the effect of increasing the frequency of a pulse of a specific shape applied in an electrolyte without an acoustic field and the effect of generating acoustic vibrations in the electrolyte using an industrial frequency pulse, respectively, Improve the productivity of the oxidation process. However, if both effects are used simultaneously, the resulting effect is significantly greater than the simple sum of the two effects.

  In this case, it is believed that energy is additionally concentrated in the boundary area between the electrolyte and the surface to be oxidized, facilitating diffusion processes, thermal processes, and plasma processes during oxidation.

  The apparatus of the present invention for forming ceramic coatings on metals and alloys includes a source and an electrolytic cell (FIG. 2).

  The source generates electrical pulses of alternating polarity and supplies those electrical pulses to the electrodes. The positive and negative pulses of the current may be supplied alternately, i.e. one after the other, or multiple sets of multiple pulses may be supplied alternately. The sequence and frequency of the series of pulses, their duration, and current and voltage amplitudes may be adjusted by a microprocessor that controls the electrolysis process.

  The electrolytic cell functions as one electrode, for example, a stainless steel bath itself, a second electrode to which an oxide-coated article is connected, a cooling system for the electrolyte, and for generating acoustic vibrations. It consists of a system. The bath may be filled with an alkaline electrolyte having a pH of 8.5 to 13.5.

  The electrolyte cooling system may comprise a pump that pumps the electrolyte, a coarse cleaning filter that captures particles larger than 10 μm, and a cooler. The temperature of the electrolyte is preferably maintained within the range of 15 to 55 ° C. during oxidation.

  A system for generating acoustic vibrations in the electrolyte includes one (or several) aero-hydraulic generator attached to the tank, a pressure gauge, and a valve that regulates the supply of electrolyte and air to the generator. It is good to consist of. The parameters of the acoustic region in the electrolyte are adjusted by changing the pressure of the electrolyte flow at the input of the aerohydrodynamic generator. The generator requires substantially no additional energy and is operated by the pressure of the electrolyte jet driven by the pump, which should be between 3 and 7 bar.

  A significant advantage of the process of embodiments of the present invention is that a dense microcrystalline ceramic coating having a thickness of up to 150 μm, preferably 2 to 150 μm and a microhardness of 500 to 2100 HV, can be obtained in a relatively short time (from a few minutes to 1 Is the fact that it can be produced on the metal during

  The coating has a low roughness of Ra 0.6-2.1 μm and has a very thin porous outer layer not greater than 14% of the total thickness of the coating. This eliminates or significantly reduces the need for subsequent cumbersome surface finishes (FIG. 3).

  The coating is characterized by the ability to maintain high thickness uniformity even for complex shaped articles.

  The highly dispersed polycrystalline ceramic coating is composed of molten spheres having a size of several μm or less that are firmly bonded to each other. This structure provides the coating with physical / mechanical properties such as resistance to wear and corrosion and dielectric strength. In addition, solid nanopowder with a specific chemical composition is added to the electrolyte to intentionally change the structure, microhardness, strength and color of the coating to optimize the properties of the coating for a specific application.

  Embodiments of the present invention allow a ceramic coating to be formed at a rate of formation of 2 to 10 μm / min. This formation rate significantly exceeds the formation rate of hard coatings by known conventional processes.

  To gain a better understanding of the present invention and to understand how the present invention is implemented, reference may be made to the accompanying drawings as an example.

[Detailed Description of Preferred Embodiments]
FIG. 1 shows a preferred form of time dependence of the shape of current pulses (positive and negative pulses) passing through the circuit between the source and the electrolyzer. Each current pulse has a steep front, the current reaches a maximum amplitude in a time not greater than 10% of the total pulse duration, then the current drops rapidly and then 50% of the maximum value. Gradually decreases to:

  As can be seen from FIG. 2, this device consists of two parts, specifically an electrolytic cell (1) and a supply source (12) connected to each other by means of electrical bus bars (15, 16).

  The electrolytic cell (1) comprises an alkaline electrolyte (3) and a cell (2) made of stainless steel containing at least one article (4) immersed in the electrolyte. The tank is provided with a transfer pump (5) and a filter (6) for roughly washing the electrolyte.

  An aero-hydraulic generator (7) is mounted in the lower part of the tank (2). A valve (8) is provided for adjusting the pressure of the electrolyte (3) and thus the frequency of the acoustic vibration. The regulating valve (8) and the pressure gauge (9) are attached to the input part of the generator (7). A valve (10) is provided for adjusting the flow rate of the air flowing toward the generator (7). The electrolyte circulation system comprises a heat exchanger or cooler (11) for maintaining the required temperature of the electrolyte (3) during the oxidation process.

  The source (12) consists of a three-phase pulse generator (13) fitted with a microprocessor (14) that controls the electrical parameters of the oxidation process.

FIG. 3 shows a cross section of the ceramic coating formed on the metal substrate (100). The ceramic coating consists of a hard functional layer (200) and a thin porous outer layer (300) (less than 14% of the total coating thickness). The surface of the ceramic coating has a low roughness (Ra: 0.6-2.1 μm).
[Example]

  The present invention is clarified by process examples. In all examples, the shape of the sample to be coated was a disk having a diameter of 40 mm and a thickness of 6 mm. These samples were degreased before oxidation. After oxidation, the sample was washed in deionized water and dried at 100 ° C. for 20 minutes. The electrical parameters of the process were recorded with an oscilloscope. The characteristic parameters (thickness, microhardness, and porosity) of the coating were measured from the fine cross section.

A sample of aluminum alloy 2014 was oxidized for 35 minutes in a pH 11 phosphate-silicate electrolyte maintained at a temperature of 40 ° C. A bipolar alternating electrical pulse with a frequency of 2500 Hz was supplied to the bath. The current density was 35 A / dm ² , and the final voltage (amplitude) was 900 V for the anode and 400 V for the cathode. Acoustic vibrations were generated in the tank by an aerohydrodynamic generator. The electrolyte pressure at the generator input was 4.5 bar. A dark gray dense film having a total thickness of 130 ± 3 μm including a porous outer layer of 14 μm thickness was obtained. The roughness of the surface coated with the oxide was Ra 2.1 μm, the microhardness was 1900 HV, and the porosity of the hard functional layer (not the porous outer layer) was 4%.

A sample of the magnesium alloy AZ91 was oxidized for 2 minutes in a phosphate-aluminate electrolyte containing 2 g / L of superdispersed Al ₂ O ₃ powder having a particle size of 0.2 μm. The temperature of the electrolytic solution was 25 ° C. and the pH was 12.5. A bipolar alternating electrical pulse with a frequency of 10,000 Hz was supplied to the bath. The current density was 10 A / dm ² , and the final voltage (amplitude) was 520 V for the anode and 240 V for the cathode. Acoustic vibrations were generated in the tank by an aerohydrodynamic generator. The electrolyte pressure at the generator inlet was 4.8 bar. The resulting coating was dense, white, and had a total thickness of 20 ± 1 μm, including a porous outer layer having a thickness of 2 μm. The roughness of the oxidized surface was 0.8 μm Ra, the microhardness of the coating was 600 HV, and the porosity of the hard functional layer was 6%.

A sample of the titanium alloy TiA16V4 was oxidized for 7 minutes in a phosphate-borate electrolyte containing 2 g / L of ultradispersed Al ₂ O ₃ with a particle size of 0.2 μm. The temperature of the electrolyte was 20 ° C. and the pH was 9. A bipolar alternating electrical pulse with a frequency of 1,000 Hz was supplied to the bath. The current density was 60 A / dm ² , and the final voltage (amplitude) was 500 V for the anode and 180 V for the cathode. Acoustic vibration was generated in the tank using an aerohydrodynamic generator. The electrolyte pressure at the generator input was 4.0 bar. The resulting coating was dense, grayish blue, had a total thickness of 15 ± 1 μm and included a porous outer layer having a thickness of 2 μm. The roughness of the oxidized surface was 0.7 μm Ra, the microhardness of the coating was 750 HV, and the porosity of the functional layer was 2%.

A sample of AlBemet alloy containing 38% aluminum and 62% beryllium was oxidized in a pH 9 phosphate-silicate electrolyte kept at 30 ° C. for 20 minutes. A bipolar electric pulse with a frequency of 3,000 Hz was supplied to the bath. The current density was 35 A / dm ² , and the final voltage (amplitude) was 850 V for the anode and 350 V for the cathode. Acoustic vibrations were generated in the tank using an aerohydrodynamic generator. The electrolyte pressure at the generator input was 4.5 bar. The resulting coating was dense, light gray and had a total thickness of 65 ± 2 μm, including a porous outer layer having a thickness of 8 μm. The roughness of the oxidized surface was Ra 1.2 μm, the microhardness of the coating was 900 HV, and the porosity of the functional layer was 5%.

A sample of an intermetallic alloy containing 50% titanium and 50% aluminum was oxidized for 10 minutes in a phosphate-silicate electrolyte having a pH of 10 maintained at a temperature of 20 ° C. Bipolar electric pulses (one positive pulse and two negative pulses) with a frequency of 2,000 Hz were supplied to the bath. The current density was 40 A / dm ² , and the final voltage (amplitude) was 650 V for the anode and 300 V for the cathode. Acoustic vibrations were generated in the tank using an aerohydrodynamic generator. The electrolyte pressure at the generator input was 4.0 bar. The resulting coating was dense, dark gray, had a total thickness of 25 ± 1 μm and contained a porous outer layer having a thickness of 2.5 μm. The roughness of the oxidized surface was Ra 1.0 μm, the microhardness of the coating was 850 HV, and the porosity of the functional layer was 5%.

A sample of an intermetallic alloy containing 95% Ni ₃ Al was oxidized for 10 minutes in a phosphate-borate electrolyte at pH 9.5 maintained at 25 ° C. Bipolar electrical pulses with a frequency of 1500 Hz (one positive pulse and two negative pulses) were supplied to the bath. The current density was 50 A / dm ² , and the final voltage (amplitude) was 630 V for the anode and 260 V for the cathode. Acoustic vibrations were generated in the tank using an aerohydrodynamic generator. The electrolyte pressure at the generator input was 6.8 bar. The resulting coating was dense, white and had a total thickness of 30 ± 1 μm, including a porous outer layer having a thickness of 3 μm. The roughness of the oxidized surface was Ra 0.9 μm, the microhardness of the coating was 700 HV, and the porosity of the functional layer was 3%.

  The results of the tests described in the examples are shown in Table 1. For comparison, Table 1 also includes data from known oxidation processes using industrial frequency currents.

  The preferred features of the invention are applicable to all aspects of the invention and may be used in any combination.

  Throughout the description and claims, the terms “comprise” and “contain” and variations of those terms, eg, “comprising” and “comprises” "Means" including but not limited to "and is not intended to exclude (ie, not exclude) other components, whole bodies, parts, additives, or steps.

It is a graph which shows the preferable form of the time dependence of the shape of the electric current pulse (positive pulse and negative pulse) which passes through the circuit between a supply source and an electrolytic cell. It is a conceptual diagram which shows embodiment of the apparatus of this invention. It is sectional drawing which shows the cross section of the ceramic film formed by the process of this invention.

Claims (21)

A process for forming a ceramic film on a metal and an alloy in an electrolytic cell in which a first electrode is attached and is filled with an aqueous alkaline electrolyte, in which an article to which another electrode is connected is immersed. In a process in which a pulse current is supplied between the electrodes so that the process is performed by a plasma discharge method,
Supplying a high-frequency bipolar current pulse having a predetermined frequency range to the electrode, and simultaneously generating acoustic vibration in a predetermined acoustic frequency range in the electrolyte solution, the acoustic vibration The frequency range includes a process that overlaps the frequency range of the current pulse,
The process wherein the current pulse has a pulse duration that is in the range of 500 to 10,000 Hz. The coating is made of a metal such as Mg, Al, Ti, Nb, Ta, Zr, or Hf or an alloy thereof, or Al—Be, Ti—Al, Ni—Ti, Ni—Al, Ti—Nb, Al—Zn, Al—. Al ₂ O _3, the process of claim 1, such as Mg-Al ₂ O ₃ is formed on the compound or complex.   Each current pulse has an initial steeply increasing portion of the current that reaches its maximum value in a time not greater than 10% of the total duration of the pulse, and the subsequent current first decreases rapidly, and then less than 50% of the maximum value The process according to claim 1 or 2, wherein the process has a shape including a portion that gradually decreases until.   The process according to any one of claims 1 to 3, further comprising the step of introducing ultra-dispersed solid particles into the electrolytic solution to generate a stable aqueous sol by the acoustic vibration.   The process of claim 4, wherein the solid particles have a particle size not greater than 0.5 μm.   The process according to claim 4 or 5, wherein the solid particles are composed of a compound in the form of a metal oxide, boride, carbide, nitride, silicide, or sulfide.   The process according to claim 1, wherein the plasma discharge method is a plasma electrolytic oxidation method.   The process according to any one of claims 1 to 7, wherein the ceramic coating is formed at a rate of 2 to 10 m / min. Process according to any one of claims 1 to 8 current applied to the article has a current density from 3 200A / dm ^2. The process of claim 9 current having a current density of 60A / dm ² to 10 to be applied to the article. An apparatus for forming a ceramic coating on metals and alloys comprising an electrolytic cell having electrodes, a source for sending pulsed current to the electrodes, and at least one acoustic vibration generator.
The source is adapted to supply a high frequency bipolar current pulse in a predetermined frequency range to the electrode, and the at least one acoustic vibration generator is in an electrolyte contained in the bath Simultaneously with the supply of the bipolar current pulse to the acoustic wave, adapted to generate acoustic vibrations , the acoustic vibrations having a predetermined acoustic frequency range that overlaps the frequency range of the current pulses;
The device wherein the current pulse has a pulse duration in the range of 500 to 10,000 Hz.   The source has an initial steeply increasing portion of current where each current pulse reaches a maximum value within a time period not greater than 10% of the total duration of the pulse, and the subsequent current initially decreases rapidly and then reaches a maximum value. 12. The apparatus of claim 11, wherein the apparatus is adapted to have a shape including a portion that gradually decreases to less than 50%.   A ceramic coating formed on a metal or alloy by the process of any one of claims 1-10. A ceramic coating formed on a metal or alloy using the apparatus according to claim 11 .   15. A ceramic coating according to claim 13 or 14, wherein the coating has a porous outer layer with a thickness not greater than 14% of the total coating thickness.   The ceramic coating according to claim 15, wherein the porous outer layer has a thickness not greater than 10% of the total coating thickness.   The ceramic coating according to claim 16, wherein the porous outer layer comprises a thickness not greater than 8% of the total coating thickness.   18. The ceramic coating according to claim 13, wherein the coating has a low roughness (Ra) surface of 0.6 to 2.1 [mu] m.   11. A ceramic coating formed by a plasma discharge process on a metal or alloy by a process according to any one of claims 1 to 10, having a low roughness (Ra) surface of 0.6 to 2.1 μm. Ceramic coating.   The ceramic coating according to any one of claims 13 to 19, wherein the coating has a dense fine polycrystalline structure having a microhardness of 500 to 2100HV.   21. A ceramic coating as claimed in any one of claims 13 to 20 having a total thickness of 2 to 150 [mu] m.

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