Multi-layered coating of thin-walled envelope from polymer composite material of space antenna reflector

FIELD: chemistry.

SUBSTANCE: multilayered coating contains three successive layers with an even thickness: a lower mirror metal radio-reflecting skin-layer of pure aluminium, an intermediate protective thermoregulatory dielectric layer of zirconium dioxide and an upper protective wear-resistant highly strong diamond-like carbon layer.

EFFECT: provision of the operation in extreme conditions of open space due to the application of a thin substrate-envelope from a polymer composite material.

3 cl, 1 dwg


The technical field

The invention relates to the field of coatings used in space vehicles, namely multi-layer composite coating of mirror space antennas with reflectors made of polymer composite materials (PCM) - carbon fiber.

The level of technology

Space antenna reflectors require protection from the space environment, exposing them to abrupt temperature changes, wear and tear from exposure to various particulate fluxes, radiative impact of a large flow of charged particles. Protect antennas from the active space environment is a specific problem, because usually the materials used to protect equipment spacecraft interfere with normal passage and the transmission of radio signals.

The urgency of improving the coverage space of the antenna reflector is dictated by the necessity of creation of reflectors for a new generation of communications satellites intended for long-term (>15 years) of service in a geostationary orbit. Upcoming satellites is to be equipped with reflectors with high stability of shape, size and radiotray characteristics (coefficient of radioterapia 0,98) when working in the frequency range from 4 to 40 GHz and having a low linear mass at the level not exceeding 2,5 kg/m2 .

When driving on a geostationary orbit reflector will fall into the Earth's shadow and cool to very low temperatures (down to -150°C) and at the exit from the shadows intensively heated by direct solar radiation (up to +150°C). The resulting temperature can be a major cause of distortion of the shape of the reflector and the violation of the beam, reducing the communication quality. To satisfy the conflicting requirements of low linear mass and high stability of shape and size of the shell of the reflector must be thin and have high rigidity. The best structural material for solving this problem is the carbon fiber. Because the use of active control systems for these ultra-light reflectors are excluded, then the only real way to maintain thermal regime of the reflector can be applied to radiotray layer reflector thermal control coatings and protective wear-resistant coatings on particulate and meteorite impacts.

Thus, it is necessary to create a multifunctional combined coating capable of providing a number of stringent technical requirements of the job reflector in the open space: transparency and radiotrain for a wide range of signals RA is iocality; expansion and wear protection, low weight. All this is practically possible to implement only through the thin multi-layer coating, where each layer has a functional specialization, and together all the layers of the coating in the hard limits affect the execution of the main radiodrama function of the antenna reflector.

In previous prior art has used various materials, meeting some of the above requirements, but not completely and not all at the same time. It was also associated with problem use of specific technologies thin (micro - and nanoscale) of the coating layers is guaranteed to provide reliable high-quality connections (cohesion, adhesion) them to each other.

Selected through a patent search on grounds offer cover for completeness prior art analogues of multilayer coatings divided into 2 groups:

analogs that are closer in composition of the coating layers and the applied technology of their application to the substrate and to each other, but not similar in their areas of application and technical tasks (RF patent 2487190 (IPC C23C 22/34 posted: 10.07.2013) on the basis of a PCT-application WO 2007121898; RF patent 2467878 (IPC B32B 15/04, published: 27.11.2012), RF patent 2360032 (IPC C23C 14/24, C23C 14/06, B32B 15/04, B82B 3/00, published: 27.06.2009));

and Vice versa: the analogues, similar parimenti in space technology, but less similar (in comparison with the first group analogues) on the composition of the layers and their application technologies (RF patent 2269146 (IPC G02B 1/10, B64G 1/58 published: 27.01.2006), RF patent 2087392 (IPC B64G 1/58 published: 20.08.1997) (U.S. patent similar US 5273815 (IPC B32B 7/02; B64G 1/58; H01Q 1/00; H01Q 1/42; H05F 1/00; H05F 1/02; (IPC1-7): B32B 15/08; B32B 27/00; B32B 9/04; H01Q 15/24 published: 28.12.1993)).

From the first group analogues closest object coatings described in the patent of the Russian Federation 2487190. The invention relates to the manufacture protected from corrosion and primarily with gloss metallic or non-metallic substrate, as well as to the most protected from corrosion and primarily with gloss metallic or non-metallic substrate and its application. Specifically in one of the many choices on offer cover can be used on non-metallic substrate (including a plastic layer of pure aluminium with mirror surface and on top of the protective layer, including Zirconia; however, one of the technologies of coatings of possible cathode sputtering (synonym: magnetron deposition of layers) in high vacuum.

However, this coating does not contain a protective wear-resistant almatadema (DLC - diamond like coating) layer, is not intended for use in space technology (the closest thing is the label provided with a coating substrate as the outer parts of the aircraft) and, accordingly, the technical problem is the preservation of the very high corrosion resistance of the substrate even under the influence of mechanical load.

RF patent 2467878 from the first group counterparts, though to protect in the first place vacuum technology magnetron sputtering layers of thermal barrier coatings on articles of copper (similar material with aluminum), but also contains the description and the heat multilayer coating of nanostructured surface layer of the product with nanostructured metal sublayer of zirconium and upper nanostructured ceramic layer of zirconium oxide and yttrium oxide from 2 at.% up to 8 at.% and having a globular grain structure. The obtained heat-shielding coating has high adhesive strength, heat resistance and resistance to cracking when the products in the conditions of thermal Cycling and high temperature. The coating can be used in aerospace and other fields.

However, this coating does not contain a protective wear-resistant almatadema (DLC) layer and is not intended for use in space technology, specifically in the shell space antenna reflectors.

In the patent of the Russian Federation 2360032 the invention is intended for the application of plasma (similar to magnetron) m is Todd superhard diamond-like (DLC) coatings on products from a variety of materials (including ceramics, plastic), before applying a layer of diamond-like film pre-applied layer of metal: aluminum, zirconium, or their oxides, or mixtures thereof. In the structure of the multilayer diamond-like coating on the original product (substrate) applied adhesive layer, then the transition layer metal-carbon, which is diamond-like film. The result is wear-resistant super hard multi-coating, which can be used in mechanical engineering, nanotechnology, etc. Increases the adhesion, wear resistance and thermal stability of diamond-like coatings.

However, this coating is not intended for use in space technology, specifically in the shell space antenna reflectors made of composite material - carbon fiber, and contains no layers of pure aluminium with mirror reflecting surface and Zirconia as the expansion of the protective layer.

From the second group of selected analogs of known protected by patents in many countries layered shell to provide thermal and electrostatic protection elements of space technology, including fairing reflector antenna of the spacecraft (RF patent 2087392, IPC B64G 1/58 published: 20.08.1997). Although the main objective is protection from hostile is Reda, minimizing the total weight of the coating is also significant. As a result, the coating is a durable material capable of thermal and electrical protection, easy and transparent for a wide range of radio frequency signals. Layered membrane that is transparent to radio frequency radiation, contains conductive layer (in the preferred embodiment, conductive layer contains a semiconductor, such as germanium) to dissipate electrostatic discharges and thermal management layer for reflecting heat radiation and reduce the effects of temperature changes on the one hand layered shell on the area on the other side.

The disadvantage of this coating is not taking into account the peculiarities of thin ultra-lightweight Foundation-substrate (parabolic shell antenna) made of polymer composite materials - carbon fiber, designed for operation in space antenna reflector with a high coefficient of radioterapia (value of 0.98) in the extreme conditions of outer space and the requirements of very low deformability complex profile of the shell due to the requirement of high quality reflector, and also wear-resistant enclosure protection from particulate flows. But this coverage provides electrostatic protection, which practically is not required for small space antenna reflector is a torus. Also in this invention does not say anything about the used technologies for the deposition of layers on each other, which does not allow to judge about the reliability of their adhesion to each other.

Finally, the known multi-layer coating for elements of space technology (patent RF 2269146, IPC G02B 1/10, B64G 1/58 published: 27.01.2006) consisting of a substrate with transparent conductive coating on the outer surface and a reflective coating on the back surface, is made in the form of a metal film with high reflectivity in the wavelength interval of 0.3...2.4 μm. Transparent conductive coating includes at least 2 layers, one layer contains a cerium oxide, and the substrate is made of polyimide polymer film. The outer layer of transparent conductive coating may be made in the form of a thin (of the order of 0.05 microns) transparent radiation-resistant and wear-resistant layer, for example of SiO2. One of the layers of transparent conductive coating may be made on the basis of tin oxide SnO2doped cerium oxide CeO2or on the basis of In2O3. The cross-section of the coating consists of a substrate, made in the form of a polymeric film, a conductive coating on the front side of the substrate, and the conductive coating may include a protective wear-resistant layer. Multilayer pokr is ment also includes on the backside of the substrate metal reflecting layer, also provided with a protective coating. A reflective layer made of metal with high reflectivity, such as aluminum. A protective coating deposited on the outer side of the reflecting layer and comprises a solid corrosion-resistant compound, metal or alloy, and the metal or alloy may be partially or fully oxidized. The conductive coating is made of optically transparent radiation resistant inorganic material-based oxide semiconductor, such as indium oxide, and may have wear-resistant inorganic layer (e.g., SiO2) on the outer surface. Multilayer coating is intended for use as a thermal control coating class ”solar reflector” when applying it using a conductive adhesive layer on the outer surface, mostly teploizolyatsii the spacecraft surface. Through the use of not less than 2 layers of conductive coatings, one of which contains cerium oxide (CeO2), increases the resistance to abrasion (due to the high hardness of the cerium oxide) and increases the stability properties of the substrate under the action of electromagnetic radiation from the Sun. Due to the implementation of conductive coatings based oxide semiconductor is provided by the high radiation is donosti coverage, and the outer layer provides a high resistance to atomic oxygen (protects the conductive coating from damage by atomic oxygen in the ascent phase of a spacecraft into orbit and when operating in low-earth orbits).

However, this coating is intended primarily as a multi-layered flexible protective cover shields a large area of space technology and therefore not suitable for use in the shell space antenna reflectors, relatively small in size, but hard and practically very multifariously shaped shell of carbon fiber. And this coverage applies adhesive technology, which is almost impossible to use when applying micro - and nanoscale layers of the multilayer coating on the carbon substrate and to each other.

The analysis of all found and selected analogues none of them can be recognized as an explicit prototype of the proposed coverage due to a mismatch collectively solve their technical problems and their application to that which was specified in the present invention.

Disclosure of inventions

The task of the invention is the development of the multi radiotracer, protective, thermal expansion and wear-resistant coatings for toncontin the x shells reflectors mirror space antennas with regard to thin the substrate-shell made of composite material carbon fiber, designed to work in extreme conditions of outer space.

The task is solved in that the proposed multi-layer coating of thin-walled shell made of composite material, primarily carbon, space antenna reflector, characterized by the presence of three consecutive layers with uniform thickness: bottom mirror metallic radiotray the skin layer of pure aluminum, an intermediate protective thermostatic dielectric layer of zirconium dioxide and the upper protective high-strength wear-resistant diamond-like (DLC), a carbon layer. Diamond-like carbon coating has getbasename and protective properties and high hardness.

For qualitative adhesion layers on the shell and on each other multilayer coating obtained by the method of "cold" magnetron sputtering in a vacuum for a single set of shell reflector in a vacuum magnetron sputtering chamber with cathode emitters all required to cover the material components.

The thickness of the shell parabolic profile of the polymer composite, mainly fibrous carbon is from 1 to 2 mm, thickness radiotracer mirror aluminum (Al) layer is about 2 μm, the thickness of armarego the dominant protective layer of zirconium dioxide (ZrO 2) - about 35 nm and the thickness of the wear-resistant layer of diamond-like (DLC) nanostructured carbon is of the order of 20 nm.

List of figures

Fig.1 - installation diagram of the deposition layers offer coatings by magnetron sputtering in a vacuum.

The implementation of the invention

This invention is located at the intersection of materials science significantly dissimilar materials with different physical-chemical properties and technology almost bezdetonatsionnoy application with the required adhesion layer coatings ultra-small thickness (nano - and micro-size) on the basis of a relatively large area (about 1 m2) in relation to the small thickness (about 1 mm) of complex geometric (first parabolic) profile, which is necessary for the proper functioning of the antenna must be saved with deviations deformation of the profile within a maximum of 0.3 mm as in the coating process and during subsequent operation in various conditions of extreme cosmic impacts, such as large temperature fluctuations (from -150 to +150°C), high exposure to ionizing radiation, corpuscular streams, and so on

In the composition of the multilayer coating included radiotray aluminum skin layer, the optimum thickness of 2 μm, thermal protective layer of zirconium dioxide ZrO2the optimal thickness of 35 nm and protective the layer of diamond-like nanostructured material, the optimum thickness of 20 nm. The result is increased reliability, multi-function protection, weight reduction and long-term resistance to the effect of space factors mirror antenna reflectors spacecraft.

The composition radiotracer coating on the substrate (the shell of the reflector) of the fibrous carbon (with conductive fibers and dielectric filler - polymer (epoxy resin): metal coating (radiotray skin layer of aluminum); thermal control coating (zirconium dioxide) and external protective diamond-like carbon coating type DLC.

When this multilayer coating obtained by the method of "cold" (up to +100°C) magnetron multi-pass spray in vacuum, so that it is almost impossible to thermally deform in the process of applying layers of geometrically ready parabolic profile carbon substrate (shell) of the antenna reflector. For qualitative adhesion layers on the shell and on each other all multilayer coating must be obtained for the desired number of passes in a single set shell reflector in a vacuum magnetron sputtering chamber with cathode emitters (magnetrons) are all required to cover the material components.

In the sputtering process over the cathode surface burning the abnormal glow discharge in the ar environment is it, oxygen and vapors of the cathode material. The ionized atoms of the discharge are accelerated near-cathode voltage and bombard the cathode surface. Under the action of the bombing, the material of the cathode of the magnetron was sprayed, and the resulting flux of sputtered atoms are deposited on the substrate. In the presence of a vacuum chamber of atoms of different gases (oxygen, nitrogen etc) sprayed material forms a film of atoms of the target material atoms of gases (oxides, nitrides, etc.). Structurally, the magnetron sputtering system consists of a vacuum chamber, a cathode target of the anode and the substrate.

In Fig.1 the numbers represent: 1, 2 - magnetrons; 3 - the flux of sputtered atoms; 4 - snap on swivel device; 5 - sample for applying (spraying) layers; 6 - ion source (ion flow is directed to the sample); 7 - vacuum chamber; 8 - base of the vacuum chamber.

The process of deposition of the layers of the proposed coating by magnetron sputtering in a vacuum is the following. After pumping the vacuum chamber to a pressure of 6.7·10-3PA sprayed coating of aluminum. The discharge current of 4 A, the time of spraying 60 minutes. Working pressure of 1.3·10-1PA. In the 58th minute of the second magnetron to clean the surface of the zirconium cathode. At the 60th minute of the magnetron with an aluminum cathode off. After that, the camera putting the desired gas mixture, m is genetron with the cathode of zirconium reaches a stable mode of deposition of Zirconia for 3 minutes. After that, the samples at a turning device to turn the magnetron and sprayed Zirconia. The time of deposition is about 2 minutes. Then put diamond-like carbon coating. The time of deposition is about 3 minutes. In all industrial processes, the residual pressure is 7·10-3up to 8·10-3PA. The working pressure during the deposition of coatings is 1.2·10-1PA. The distance from the cathode magnetrons to the substrate is 300 mm, the Deposition is carried out in inert argon gas OFS brands of 5.5 on THE 2114-006-45905715-2010. Mass fraction of argon 99,9995%. As a reactive gas using oxygen OFS THE 6-21-10-83. Mass fraction of oxygen 99,999%.

1. Multilayer coating of thin-walled shell made of composite material space antenna reflector, characterized by the presence of three consecutive layers with uniform thickness: bottom mirror metallic radiotray the skin layer of pure aluminum, an intermediate protective thermostatic dielectric layer of zirconium dioxide and the upper protective high-strength wear-resistant diamond-like (DLC), a carbon layer.

2. The floor under item 1, characterized in that it is obtained by the method of "cold" magnetron sputtering in a vacuum for a single set of shell reflector in a vacuum magnetron Kama is the cathode emitters all required to cover the material components.

3. The floor under item 1 or 2, characterized in that the shell thickness of the parabolic profile of the polymer composite, mainly fibrous carbon is from 1 to 2 mm, thickness radiotracer mirror aluminum (Al) layer of about 2 μm, the thickness expansion of the protective layer of zirconium dioxide (ZrO2about 35 nm and the thickness of the wear-resistant layer of diamond-like (DLC) nanostructured carbon of the order of 20 nm.


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