MXPA00002110A - Jet plasma process and apparatus for deposition of coatings and coatings thus obtained - Google Patents

Abstract

The present invention provides a method for the formation of an organic coating on a substrate. The method includes:providing a substrate in a vacuum;providing at least one vaporized organic material comprising at least one component from at least one source, wherein the vaporized organic material is capable of condensing in a vacuum of less than about 130 Pa;providing a plasma from at least one source other than the source of the vaporized organic material;directing the vaporized organic material and the plasma toward the substrate;and causing the vaporized organic material to condense and polymerize on the substrate in the presence of the plasma to form an organic coating. There is also disclosed a jet plasma apparatus for forming a coating on a substrate (75), comprising a cathode system (40), an anode system (60) and an oil delivery system (120) for providing vaporized organic material such that the organic material and the plasma (160) interact prior to, or upon contact with the substrate.

Description

PROCESS AND PLASMA APPARATUS BY JET FOR DEPOSIT OF COATINGS AND COATINGS OBTAINED IN THIS WAY FIELD OF THE INVENTION The present invention relates to coatings, particularly organic coatings containing carbon and / or silicon coatings, and to a method and apparatus for the plasma deposition of these coatings.

BACKGROUND OF THE INVENTION Plasma processes offer the opportunity to make coatings that can be completely hard, chemically inert, resistant to corrosion, and impervious to water vapor and oxygen. Frequently, these are used as mechanical and chemical protective coatings on a wide variety of substrates. For example, carbon-rich coatings (for example, diamond-like coatings and plasma-spray-carbon coatings) have been applied to rigid disks and flexible, magnetic media. They have also been applied to acoustic diaphragms, polymeric substrates used in lenses. REF .: 32946 -18A., - & ^^^^^^^^ ^ ^^ ^ m ^^^ m ^ mm ^^^ m ^^ m ^ m optical and ophthalmic, as well as photographic, electrostatic drums. Silicon-containing polymer coatings have been applied to polymeric and metallic substrates for abrasion resistance. Also, silicone coatings have been applied to polymeric and non-polymeric substrates to reduce water permeability and to provide mechanical protection. The carbon rich coatings, as used herein, contain at least 50 atomic% carbon, and typically about 70- to 95% atomic carbon, 0.1-20% nitrogen atom, 0.1-15% atomic oxygen, and 0.1-40% atomic hydrogen. These carbon-rich coatings can be classified as "amorphous" carbon coatings, "amorphous, hydrogenated" carbon coatings, "graphitic" coatings, "i-carbon" coatings, "diamond-like" coatings, and so on, depending on their properties. physical and chemical. Although the molecular structures of each of these coating types are not always easily distinguished, they typically contain two types of carbon-carbon bonds, ie S * 4 .- ^ g ^^ - * ^ '- * "^ - links of graphite trigones (sp) and tetrahedral diamond links (sp3), although this is not proposed for limitation. hydrogen and carbon-oxygen bond, etc. Depending on the number of different carbon atoms and the ratio between the sp3 / sp2 radio links, different structural and physical characteristics can be obtained. diamonds have diamond-like properties of extreme hardness, extremely low electrical conductivity, low friction coefficients and optical transparency over a wide range of wavelengths. They can be hydrogenated and not hydrogenated. Diamond-like carbon coatings typically contain non-crystalline material that has both graphite trine bond (sp2) and tetrahedral diamond bonds (sp3); although it is believed that the sp3 union dominates. In In general, diamond-type coatings are harder than graphitic carbon resistances, which are harder than carbon coatings, which have a high hydrogen content, i.e., coatings containing carbon molecules. hydrocarbons or portions thereof.

Silicon-containing coatings are usually polymer coatings containing in random composition silicon, carbon, hydrogen, oxygen, and nitrogen (SiOwNxCyHz). These coatings are usually produced by plasma enhanced chemical vapor deposition (PECVD) and are useful as protective barrier coatings. See, for example, U.S. Patent Nos. 5,298,587 (Hu et al.), 5,320,875 (Hu et al.), 4,830,873 (Benz et al.), And 4,557,946 (Sacher et al). Silicone coatings are polymerized, high molecular weight siloxane coatings, which contain in their structural unit R2SiO in which R is usually CH3, but may be H, C2H5 C6H5 'or more complex substituents. These silicones (often referred to as polyorganosiloxanes) consist of chains of alternating atoms of silicon and oxygen (O-Si -O-Si-0) with the free valences of the silicon atoms usually linked to the R groups, but also to some degree to oxygen atoms that are bonded to silicon atoms (cross-linked) in a second chain , formed in this way a network iij * L extended. These coatings are evaluated for their hardness, lubricity, controlled gas diffusion, and their ability to decrease the desirable surface tension for release coatings and water repellent surfaces. For example, in U.S. Patent No. 5,096,738 (Wyraan) teaches the formation of barrier coatings via the hydrolysis of trialkoxy-methylsilane resulting in highly crosslinked polymeric structures. Methods for preparing coatings by plasma deposition, ie, chemical vapor deposition, improved with plasma are known; however, some of these methods have deficiencies. For example, with certain methods the use of a high gas flow, pressure and power can cause the formation of carbon dust, instead of the hard, smooth, desirable carbon film. U.S. Patent Nos. 5,232,791 (Kohler et al.), 5,286,534 (Kohler et al.), And 5,464,667 (Kohler et al.) Describe a process for plasma deposition of a carbon-rich recovery that exceeds any these deficiencies. These processes use a carbon-rich plasma, which is generated from a gas, such as methane, ethylene, methyl iodide, methyl cyanide or tet ramet ilsilane, in a hollow, elongated cathode, by way of example. The plasma is accelerated to a substrate exposed to a bias voltage of a frequency radius. Although this process represents a significant advantage in the art, another plasma deposition process is needed for depositing a wide variety of coatings containing carbon and / or silicon, using lower energy requirements. Methods for preparing multilayer coatings are described in U.S. Patent Nos. 5,116,665 (Gauthier et al.) And 4,933,300 (Koinuma et al.), And U.S. Patent Application Publication Number GB 2, 225, 344, A (Eniricerche SpA). These methods are based on incandescent discharge processes, which use a reactor and successive changes in the process parameters for the construction of multilayer coatings. However, these methods have practical and technical limitations. A batch type process is required, if gradual and / or abrupt changes in the properties of the layers are desired. These changes are obtained by the deposit in the stationary substrates and successive changes in the conditions of the process. The continuous deposit can be obtained in a reactor that fits a roll-to-roll mesh transport system. A multi-pass operation is required to build the multilayer coatings. Under these circumstances, it is difficult to obtain a gradual change of the properties of the layers and / or the formation of the inner facial layers. In this way, plasma deposition processes are required for the deposition of a wide variety of coatings containing carbon and / or silicon using relatively low energy requirements. Also, plasma deposition processes are needed which can be adjusted to a gradual change of the properties of the layers and / or formation of the inner facial layers.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a method for the formation of organic coating or a substrate, comprising; provide a substrate in a vacuum; provide at least one vaporized organic material comprising at least one component of at least one source, wherein the faith t ~ > ^^. ¿^ ^ ^ ^ ^ ^? Localized organic material is capable of condensing in a vacuum of less than about 130 Pa, providing a plasma from - from at least one source other than the source of the vaporized organic material; direct the vaporized organic material and plasma to the substrate; and causing the vaporized organic material to condense and polymerize in the substrate in the presence of the plasma to form an organic coating. The step of providing a plasma preferably includes generating a plasma in a vacuum chamber by: injecting a plasma gas into a hollow cathode system; provide sufficient voltage to create and maintain a neutral plasma of the hollow cathode system; maintain a vacuum in the vacuum chamber sufficient to maintain the plasma. In a preferred embodiment, the hollow cathode system includes: a cylinder having an outlet end; a magnet that surrounds the outlet end of the cylinder; and another having a guide edge, wherein the tube is placed inside the cylinder and is hollowed out such that the leading edge of the tube is in the plane of the centerline of the magnet. A coating is also provided fr »1ii * p? - lSíhnr? m ~ organic in a preparable substrate: providing a substrate in a vacuum; providing at least one vaporized organic material comprising at least one component of at least one source, wherein the vaporized organic material is capable of condensing in a vacuum of at least 130 Pa; providing a plasma from a different source of at least one source of the vaporized organic material; direct the vaporized organic material and plasma to the substrate, cause the plasma to interact with the vaporized organic material and form a reactive organic species; and contacting the substrate with the reactive organic species to form an organic coating. The coating may include a layer of an individual organic material or multiple organic materials. Alternatively, it may include multiple layers of different organic materials. The present invention also provides a non-diamond organic coating on a substrate, comprising an organic material comprising at least one main component, wherein the coating has a density that is at least 50% greater than the density of the component. . - i. "lyjfrja ^ naiSai-principal of the organic material before coating For a component layer, the non-diamond organic coating preferably has substantially the same composition and structure as that of the starting material.The present invention also provides an apparatus for plasma by jet to form a coating on a substrate, comprising: a cathode system for generating a plasma, an anode system positioned relative to the cathode system such that the plasma is directed from the cathode system beyond the system anode and towards the substrate to be coated, an oil distribution system to provide the vaporized organic material placed in relation to the cathode system such that the vaporized organic material and the plasma interact before, or in contact with, the The present invention further provides a hollow cathode system comprising: a cylinder that At one end of the exit; a magnet that surrounds the outlet end of the cylinder; a tube having a guiding edge, wherein the ceramic tube is placed inside the cylinder and is hollowed out such that the guiding edge of the ceramic tube is in the plane of the centerline of the magnet.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a jet plasma vapor deposition apparatus of the present invention. Figure 2 is a perspective, extended view of a preferred oil distribution system of the present invention. Figure 3 is a perspective, extended view of another preferred oil distribution system of the present invention. Figure 4 is a schematic diagram of a jet plasma vapor deposition apparatus of the present invention. Figure 5 is a cross-sectional side view of a hollow cathode point source, preferred of the present invention. Figure 6 is a graph of the effect of polarization on the transmission of moisture vapor. Figure 7 is a depth profile by Auger spectroscopy coating of the present invention on a silicon wafer.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides methods and systems for forming organic coatings, particularly carbon-containing coatings (e.g., carbon-rich coatings as defined above), silicon-containing coatings (e.g. they are defined previously), combinations thereof, and the coatings themselves. The methods for forming the coatings are presented by means of the interaction by plasma with a vaporized organic material, which is normally a liquid at room temperature and ambient pressure. The systems of the present invention can be used to deposit low cost coatings, you can have a wide range of specific needs. These coatings can be multi-component coatings (e.g., single layer coatings produced from multi-start materials), one-component, uniform coatings and / or multilayer coatings (e.g., alternating layers of carbon-rich material and silicone materials).

In general, the coating processes use a plasma (i.e., reactive, gaseous extended ionized atoms or neutral molecules and molecular fragments) and at least one vaporized organic material containing at least one component, wherein the vaporized organic material is capable of Condense in a vacuum of less than about 1 Torr (130 Pa). These vapors are directed towards the substrate in a vacuum (either in an outer space or a conventional vacuum chamber). This substrate is in close proximity to a radio frequency polarization electrode and is preferably negatively charged as a result of being exposed to the radio frequency bias voltage. Significantly these coatings will be prepared without the need for solvents. For example, using a carbon-rich plasma in a stream from a first source and a high molecular weight vaporized organic liquid such as dimei Isi loxane oil in another stream from a second source, a one-pass depositing process results in a multi-layer coating construction (i.e., one layer of a carbon-rich material, and one layer of dimethyl iloxane that is at least partially polymerized, and an intermediate or interfacial layer of a carbon composite product). / dimet íl s íloxano). Variations in the system result in the controlled formation of multi-component, uniform coatings or laminated coatings with gradual or abrupt changes in the properties of the composition, as desired. Uniform coatings of the material can also be formed from a carrier gas plasma such as argon, and a vaporized, high molecular weight organic liquid, such as dimethoxy loxane oil. Coatings formed using the jet plasma process described herein may have a wide variety of properties. They can be hard, resistant to scratches, chemically resistant and suitable for use as protective coatings. They can be impermeable to liquids and gases, and suitable for use as a barrier coating. They may have a selective controlled pore / pore structure for molecular diffusion, and suitable for use as separation membranes. They may be transparent and antireflective, and suitable for use as an optical coating. They can have surface energies made to measure and conductivity and variable resistivity. Therefore, the coatings can have a variety of uses. Preferred carbon-rich coatings and preferred silicone coatings are impervious to water vapor and oxygen, and are generally resistant to mechanical and chemical degradation. They are also sufficiently plastic that they can be used in flexible, typical substrates used, for example, in magnetic media and packaging films. These preferred coatings are highly polymerized and / or crosslinked materials, i.e., materials having a crosslink density generally higher than that obtained if conventional depositing methods are used, such as conventional PECVD methods. Specifically, for example, the present invention provides a substrate in which a silicone coating, preferably a polymerized diorganos i loxane, having a high concentration of cross-linked siloxane groups (i.e., high Si-O- crosslinking) is coated. Si) and a reduced concentration of organic groups (for example methyl groups) in relation to the starting material. Preferably, the coatings of the present invention are non-diamond type coatings but generally very dense. The density of a coating is preferably at least about 10% (and more preferably at least about 50%) greater than the main component of the organic material before vaporization (preferably, greater than any of the dense materials). Typically, the organic starting materials are in the form of oils, and the organic coating can have a density that is preferably at least about 10% (and more preferably, at least about 50%) greater than that of the used oil in the largest amount. With deposition methods that are not exposed to the substrate at a radio frequency bias voltage, there is only a minor increase (e.g., less than about 10%) of the density of the coatings relative to the starting materials. Here, density is measured by the flotation method, as described later. Silicone coatings, Preferred compositions of the present invention have a density of at least about 1.0. Typically, since the radio frequency polarization to which the substrate of the method described herein is increased, the density and hardness of the coatings are increased. As the density and hardness increase, the barrier properties for water vapor and / or oxygen (and other gases) increase. It is still possible to obtain several orders of magnitude increases in barrier and hardness properties using the methods of the present invention. The present invention also provides a substrate in which polymerized mineral oil (i.e., an aliphatic hydrocarbon) such as Nujol is coated. This provides a decrease in water vapor transmission that is achieved by being associated with an increase in density. In this way, an organic material that can be used with a starting material of the method of the present invention is mineral oil. Other organic materials of the like include other aromatic and aliphatic hydrocarbons as well as hydrocarbons containing silicon and oxygen such as silicone oil and per-fluoropolyethers, which may be used alone or in combination. Suitable organic materials are those that have strong bonds in the structure that do not break easily in a vacuum. They may be aromatic, aliphatic or combinations thereof (for example, compounds containing aralkyl or alkaryl groups). When more than one organic material is used, they can be mixed before vaporization and provide a source or can be provided separately from separate sources. Using the methods described herein, in general, certain physical and chemical properties of the coating materials are maintained. That is, the properties of the starting materials, such as the coefficient of friction, surface energy and transparency in a significant change in the preparation of the coatings using the methods described herein, as opposed to the processes of plasma, conventional. In this way, the methods of the present invention are very different from conventional plasma processes because the molecules are not significantly broken down to a reactive, lower molecular weight species, with the methods of the present invention. For example, it is believed that the Si-O-Si-0- chain of a silicon oil remains substantially intact in the jet plasma process of the present invention. The methods of the present invention include providing a plasma (e.g., an argon plasma or a carbon-rich plasma as described in U.S. Patent No. 5,464,667 (Kohler et al.)) And at least one organic material, vaporized comprising at least one component from separate sources and allowing them to interact during the formation of the coating. The plasma is one that is capable of activating the organic, vaporized material. It can be generated using a well known medium or the dot source described herein, that is, the plasma can cause the vaporized organic material to become reactive, for example, as a result of radical formation, ionization, etc., although these reactive species are still capable of condensing in a vacuum to form a polymerized coating. Alternatively, the plasma can interact with the vaporized organic material as the vaporized organic material condenses to the surface in a manner such that the entire thickness of the coating is polymerized. Therefore, plasma and vaporized organic material can interact either on the surface of the substrate or before contact with the surface of the substrate. Either way, the interaction of vaporized organic material and plasma provides a reactive form of the organic material (eg, loss of the methyl group of silicone) to allow densification of the material in the formation of the coating, as a result of the polymerization and / or crosslinking, by way of example. In this way, the method of the present invention provides a high velocity reservoir medium, which raises what reaches the condensation rate of the organic material as vaporized; it also provides the means to prepare coatings where the physical and chemical composition and structure of the precursor is maintained to a high degree. The methods of the present invention preferably include the use of a radio frequency bias voltage, sufficient Eig = aa ^^ s ^ Asl to provide a coating having a density that is at least about 10% greater (and preferably at least about 50% greater) than the density of the main component of the organic material before vaporization. Preferably, the bias voltage is no more positive than about minus 50 volts, which also creates a plasma in the substrate. Preferably, the bias voltage is no more positive than about minus 100 volts, and more preferably, no more positive than about minus 200 volts. Typically, the polarization voltages can be as negative as approximately minus 2,500 volts. The specific polarization advantage typically depends on the material from which the substrate is made. This high polarization power can be obtained in conjunction with the use of the hollow cathode described herein. As mentioned previously, the greater the power or polarization power, the higher the density of the condensation. Without polarization, the density of a coating made by the method of the present invention is very similar to that with conventional coatings (for example, by silicon polymer coating without crosslinking) made by conventional processes (e.g., conventional PECVD methods). ). In general, high density coatings (eg, diamond-like carbon, carbon with jet plasma) are prepared by the plasma enhanced chemical vapor deposition (PECVD), which utilizes negatively polarized substrate in contact with radio frequency tuned cathodes. Typically, the system provides ion bombardment of the fragmented feed gas species (eg, acetylene) and carrier gas ions (eg, argon) in the substrate to cause the atomic arrangement / re-arrangement of the coating that is formed at a dense structure. Simultaneously, the cathode is used for extensive fragmentation of the feed gas, as described in U.S. Patent No. 4,382,100 (Holland). Because the two parameters of the process, specifically extensive fragmentation and ionic attraction, can not be independently controlled, conventional PECVD methods are limited and not favorable for high-speed deposition. This limitation has been JA-surpassed in U.S. Patent No. 5,464,667 (Kohler et al.), Which teaches that the independent use of the hollow cathode for the fragmentation of the feed gas and a second cathode for the polarization of the film substrate to deposit these fragments . The present invention includes modifications to the systems described in U.S. Patent Nos. 5,286,534 (Kohler et al.) And 5,464,667 (Kohler et al.), Which allows the deposition of dense coatings without extensive fragmentation of the starting material. Significantly, using the process and system of the present invention, high molecular weight organic starting materials can be converted into dense coatings without extensive fragmentation and without a significant loss of physical and chemical properties inherent to the starting material. These differences between the coatings of the present invention and coatings produced by conventional methods are exemplified in examples 1, 3 and 4 and comparative example A to be discussed in more detail below. Plasma is generated from a gas of ^ "&" - plasma using the hollow cathode system, such as a "hollow cathode tube" (as discussed in U.S. Patent No. 5,286,534 (Kohler et al.)) Or a "hollow cathode slot" "(as described in U.S. Patent No. 5,464,667 (Kohler et al.)), preferably a slot comprising two electrode plates arranged in parallel with each other, and more preferably, a tube in line with a slot and tube directed towards and beyond typically of an anode (as described in U.S. Patent No. 5), 464,667 (Kohler et al.)). In a preferred embodiment, the hollow cathode slot system includes the first component having therein a hollow cathode tube, a second compartment connected to the first compartment, and a third compartment connected to the second compartment having the same two plates parallel. Alternatively, a system referred to herein could also be used as a tip source such as the hollow cathode system to generate a plasma. These form a plasma by jet within the hollow cathode, which is driven further or to an anode. This is in contrast to conventional "plasma jet" systems in which plasma is generated between the cathode and anode and directed to a jet stream outside the cathode / anode array. The plasma gas includes a carrier gas, such as argon, and additionally a feed gas. The feed gas can be any suitable source for the desired coating composition. Typically, the feed gas is a source for a carbon rich coating. The feed gas is preferably selected from the group consisting of saturated and unsaturated hydrocarbons, hydrocarbons containing nitrogen, hydrocarbons containing oxygen, hydrocarbons containing halogen, and hydrocarbons containing silicon. Vaporized organic material (preferably a vaporized organic liquid) is typically used to provide other materials that form uniform multi-component or multi-layer coatings, although plasma gas could also be the source of these components. That is, a compound having silicon, of low molecular weight can be used to generate a plasma. Referring to FIG. 1, a particularly preferred jet plasma apparatus for depositing these coatings is shown. This apparatus is similar to that shown in U.S. Patent No. 5,464,667 (Koeler, et al) modified for depositing two materials either in a simultaneous or sequential manner. The apparatus includes a supply gas source 20 and a source 22 of carrier gas connected via the flow controllers 24 and 25 respectively to the inlet tubes 26 and 27, respectively. The carrier gas, for example, argon from the gas source 22 is fed into a vacuum chamber 30 and the hollow cathode system 40 through an inlet orifice 28. The feed gas, for example, acetylene , from the gas source 20 is fed into the vacuum chamber 30 and into the hollow cathode system 40 through an inlet hole 29. The cathode system 40 shown in Figure 1 is divided into three compartments, that is, a first compartment 41, second compartment 42, and a third compartment 43. The carrier gas, if used, is fed into the first compartment 41, while the feed gas is fed into the second compartment 42. It can be formed a plasma from the carrier gas in the first compartment and / or from the feed carrier gases in the third compartment. This hollow cathode system is further discussed in U.S. Patent No. 5,464,667 (Kohler et al.), The discussion of which is incorporated herein by reference. In addition to the hollow cathode system 40, within the vacuum chamber 30 is an anode system 60, which may be either grounded or ungrounded, and preferably contains an adjustable shield 61. Also included is a radio frequency polarization electrode 70, a substrate (eg, polyethylene terephthalate film "PET") 75, and an oil distribution system 120. The oil distribution system 120 provides an organic liquid vaporized by the substrate deposit. Includes an oil reservoir 122, cooling system 123, oil distribution system 124, evaporator chamber 126, outlet port 128, adjustable divider plate 130, and substrate shield 129. Divider plate 130 is used to keep the plasma and vaporizer liquid separated until they are close to the substrate. The substrate shield 129 is used to prevent condensation of the vaporized liquid on the non-vaporized substrate. Both the divider plate 130 and the shield 129 substrate shield are optional. In general, the substrate 75 is unwound from a first roll 76 and wound onto a second roll 78, although it may be a continuous circuit of the material. The plasma gas, the feed gas alone or the feed gas mixture of the carrier gas, are converted into a plasma within the hollow cathode system 40. The plasma 160 is then directed towards the substrate 75, which preferably contacts the radio frequency polarization electrode 70 during the coating deposit from the plasma. The substrate can be made from a wide variety of materials. For example, it can be a polymeric, metallic, or ceramic substrate. In a preferred embodiment, the substrate is a thin polymeric film, that is, less than 0.05 cm, and flexible. Examples of useful films are oriented polyester, nyl, biaxially oriented polypropylene, and the like. * iaaS3t ^ s ^ aeáíé¡? ^ The radio frequency electrode 70 is made of metal, such as copper, steel, stainless steel, etc. and preferably is in the form of a roller, although it is not necessarily a requirement. For example, it may be in the form of a plate. The roller however is advantageous because it reduces the friction between the electrode and the substrate, thereby reducing the distortion of the film. More preferably, the radio frequency biasing electrode 70 is cooled with water at a temperature no greater than about room temperature (i.e., about 25 ° C to about 30 ° C), preferably at a temperature of about 0 / C to about 5 / C, which is advantageous when using heat-sensitive substrates. The radio frequency polarization electrode typically has a frequency of about 25 KHz to about 400 KHz, although it is possible to increase the frequency range up to and including the megahertz range. Typically, it has a bias voltage of about minus 00 volts to about minus 1,500 volts. When the bias voltage is applied, an additional plasma is created in the vicinity of the radio frequency polarization electrode 70, which generates a negative potential of the substrate, and attracts the species of plasma 160 towards the substrate 75 for efficient effect and Quick. To create a plasma, a first DC power supply 80 is electrically connected, directly to the first compartment 41 of the hollow cathode system 40 by a circuit 82 and to the anode system 60 by a circuit 84. The first power supply 80 of CD may be a pulsating CD energy supply or filtered CD power supply, or other plasma generating means with an appropriate arc suppression, such as those used in the sizzle sys- tems. The unfiltered pulsating CD energy supply is generally preferred, however. Also, a second DC power supply 85 is connected electrically directly to the third compartment 43 of the hollow cathode system 40 by a circuit 87 of the anode system 60 also by the circuit 84. In this arrangement, the chamber 41 and the chamber 43 are electrically isolated from each other. The second DC power supply 85 may be a pulsating CD power supply, or filtered CD power supply, or other plasma generation means with an appropriate arc suppression, although a pulsating CD power supply is preferred. . An example of a filtered CD power supply is a 25 ilo filtered CD supply, such as that available from Hippotronics Inc., New York, N.Y. This power supply generates a plasma at high currents up to about 10 amps and relatively low voltage, that is, approximately minus 100 volts. A radio frequency biasing power supply 90 (eg, PLASMALOC power supply 3 from ENI Power Systems, Inc., Rochester, NY) is connected to the radio frequency bias electrode 70 via a circuit 92 and to ground 100 through a circuit 94. The DC power supplies 80 and 85 can also be connected to the ground 100, although this is not a preferred arrangement. This electrical connection is represented in FIG. 1 by dashed line 105. Thus, in this arrangement, where the three power supplies are joined to the ground 100, the anode system 60 is connected to ground. The above arrangement, wherein the anode system 60 is not connected to ground, is advantageous when compared to the later arrangement. For example, when the anode system 60 is not connected to ground, the plasma formed is more stable, because the plasma distinguishes the anode system as distinct from the metal chamber connected to ground. Typically, when the anode system 60 is not connected to ground, the transverse mesh coating thickness, that is, the coating thickness across the length and width of the substrate is more uniform. Additionally, the plasma is more confined and the deposit pattern can be more easily controlled by varying the exposure of the plasma to the anode system 60. As discussed above, the DC power supplies 80 and 85 are pulsating CD energy supplies. . This is because pulsating CD power supplies provide more stable plasma conditions than non-pulsating CD power supplies, which contributes to plasma deposition rates, reporting and therefore to a coating uniformity of the plot down, that is, along the length the ¿S substrate. Additionally, it admits the use of a high current flow, and thus of high deposition speeds, at relatively low voltage. When used as the first DC power supply 80 or the second DC power supply 85 or both, a preferred pulsed DC power supply is one that provides a voltage that typically passes through 0 about 25 times / second to approximately 1000 times / second, preferably approximately 25 times / second to approximately 200 times / second and more preferably approximately 100 times / second to approximately 120 times / second. This allows the plasma to be extinguished and then pre-initiated as the cathode reaches its necessary potential. Examples of these pulsating CD power supplies include the Aireo Temescal CL-2A power supply with a maximum output of 500 mA and a full-wave rectified DC voltage of 120 Hz from 0 volts to minus 5,000 volts, available from Aireo Temescal, Berkeley, CA Another version of this power supply uses two Airemes Temescal transformers in parallel, thus resulting in a maximum output of 1 amp. This pulsating CD energy supply is used in the examples described below. Another power supply is constituted with a maximum output of 20 amps, and is also used in the examples described below. This was achieved with a larger leakage-type transformer (1 kilowatt) obtained from MAG-CON Inc., Roseville, MN, including full rectification to achieve pulsating CD output. As used herein, a "leak-type" transformer is one that provides a stable pressure point for the load of a negative dynamic resistance. The typical output of this 20 amp power supply is direct current from 0 volts (VDC) to direct current of minus 1,500 volts with the current from 0 amps to 20 amps. This power supply is limited by current, which prevents the formation of high arcs of intensity at the cathode surface. If larger currents are required, you can use a larger leak-type transformer, or two smaller transformers can be arranged in parallel. In the particularly preferred embodiments of the present invention, both the power supply 80 and the power supply 85 are pulsating, CD power supplies. In these embodiments, the carrier gas is injected into the first compartment 41 of the hollow cathode system 40 and a pulsating CD energy supply, preferably a pulsating CD energy supply of 500 m is used to create a plasma from the carrier gas Although formation of this initial carrier gas plasma may not always be necessary when a pulsating DC energy supply is used to generate a plasma in the third compartment 43 of the hollow cathode system 40, necessary for the ignition of a plasma in the third compartment when using a CD power supply, filtered, non-pulsating. After the initial ignition of the carrier gas plasma in the particularly preferred embodiments of the present invention, this initial plasma passes into the second compartment 42 of the hollow cathode system 40 where it is mixed with the feed gas. This mixture then passes into the third compartment 43 where a second plasma is created using a CD power supply • * "? SL.-» &SSt-V. pulsating This pulsating CD power supply can be a power supply of 1 amp or 20 amps, as used in the examples, or it can be a power supply of 500 amps or a power supply of 20 amps, 30 amps, 50 amps, 100 amps, etc., depending on the desired concentration of the feed gas fragment and the deposition rate of the coating. In the first compartment 41 of the system 40 hollow cathode, such as a hollow cathode slot system, the created and maintained voltage is preferably close to minus 200 volts at approximately 1,000 volts, more preferably near minus 200 volts to approximately minus 500 volts. The power supplied to this first compartment is typically about 20 watts to about 10,000 watts, more preferably about 20 watts to about 1,000 watts and more preferably about 100 watts to about 500 watts. In the third compartment 43 of the hollow cathode system 40, the created and maintained voltage is approximately preferably less than 50 volts at ? ' It is about 500 volts, and more preferably about 80 volts to about minus 120 volts. The power or energy supplied to this second compartment is typically about 50 watts to about 3,000 watts, and more preferably about 1,000 watts to about 3,000 watts. Given the correct conditions, a plasma 160 is formed by jet, stable in the vacuum chamber extending in a general extended pattern that forms the shape image of the output slot of the hollow cathode system 40. The preferred cathodes have a high concentration of feed gas fragment, i.e., the feed gas fragmentation occurs at a high speed, to provide a rapid deposition rate in the carbon rich coating on the substrate 45. That is, The higher the coating deposition rate and the more uniform the cure, the more desirable will be the plasma formed, which depends on the arrangement of the system and the current and voltage provided. Additionally, if a highly uniform coating can be deposited at a relatively high speed with low energy requirements, the system will be more desirable with respect to practical considerations (eg, cost, similar and overheating). To monitor conditions in the vacuum chamber, while a variety of instruments, such as mass spectrometer, emission spectrometer and a capacitance manometer, can be connected to the vacuum chamber. A vacuum can be created and maintained within the vacuum chamber by any means typically used to create a vacuum (eg, diffusion pump, and / or mechanical pump). The vacuum chamber is typically maintained at a pressure of about 0.13 Pascals (Pa) to about 130 Pa, preferably at about 0.13 Pa to about 1.0 Pa. It will be understood by one skilled in the art that the method and apparatus described herein may be used in a vacuum that is formed naturally, such as occurs in space. In order to distribute liquids in the vapor form in the vacuum chamber 30, the oil distribution system 120 is used to control the oil feed rate for evaporation. As shown in Figure 1, the oil 121 is distributed from a reservoir 122 placed in the vacuum chamber 30, through the oil distribution orifice 124. This distributes the oil in the evaporator 126 for evaporation and out of the orifice output 128 of the evaporator for distribution to the radio frequency polarization electrode 70. The valve system 140 is used to expose the oil 121 to the vacuum to become de-aerated. During this deaeration process, the discharge of oil through the oil distribution orifice 124 is prevented by making the equal pressure above the liquid (e.g., 721) and in the oil distribution orifice 124. The configuration of the valve system 140 is changed to introduce air into the reservoir 122 in the space above the oil 121 to impose a desirable pressure above the oil. Typically, the oil distribution orifice 124 is a tube or needle, such as a syringe needle, although any other dispensing orifice could otherwise be used. The oil feed rate is controlled by the appropriate selection of the temperature of the distribution medium, which controls the viscosity, and the size of the distribution medium, which controls the mass flow rate. Depending on the desired result, the oil feed speed can be varied over a wide range. The temperature of the oil distribution orifice 124 can be regulated by the cooling system 123. This can be a system employed by liquid, gas or electricity. The temperature of the oil distribution orifice 124 and the evaporator 126 can be monitored using a thermocouple, by way of example. Figure 1 also shows the divider plate 130 and the substrate protection shield 129. Typically, these components are made of quartz, although any material, such as metal, plastic or ceramic, can be used as long as it can withstand the temperatures experienced in the system during the deposit. As stated above, these components are optional. In Figure 2, the oil distribution system 120 is shown in greater detail, together with the valve system 140. The oil distribution system 120 includes an oil tank 122 and an instantaneous evaporator 126 consisting of one or more spacers 127 made of a thermally conductive material (e.g., aluminum). The spacers 127 can be connected by any of a variety of means, such as typical resistance heaters to the tuiter, controlled by adjustable ratio autotrans (not shown in Figure 2). A cooling system 123, such as a copper sleeve cooled with water, which fits the oil distribution orifice 124 (eg, a needle) is placed in an inlet 125 of the flash evaporator 126. The inlet 125 it is preferably located in the rear region of the instantaneous evaporator 126 and preferably includes a sleeve insert, such as a silicone rubber sleeve insert, to prevent heat exchange between the flash evaporator 126 and the cooling system 123. However, the tip of the oil distribution orifice 124 (eg, needle) is in immediate contact with the inlet port 125, heated allowing constant and uniform evaporation of the oil. The separate separators 127 provide different separations in different ways ? ~ multiple so that the evaporated oil is sent over the full width of the instantaneous evaporator 126 several times up and down (as shown by the broken line) before the steam is discharged uniformly through an outlet port 128 in the vacuum chamber (not shown in Figure 2). An atomizer may also be used to atomize the organic material (i.e., form liquid drops of the material) before vaporization of the organic material. The atomizer is. Particularly necessary for organic materials that are unsaturated, although it can also be used with saturated organic materials. This is particularly true if prolonged periods of vaporization are used (eg, more than a few minutes) because this can clog the evaporator orifice. In Figure 3 a system including an atomizer is shown, wherein the oil distribution system 220 is shown in greater detail together with the valve system 140. In this embodiment, the oil distribution system 220 includes an oil tank 222, an instantaneous evaporator 226 consisting of one or more spacers 127, a cooling system 223, an oil distribution orifice 224, an inlet 225 in the instantaneous evaporator 226, and an outlet orifice 228 as described with respect to Figure 2. Also included to atomize the organic material is an ultrasonic horn 230 attached to an ultrasonic converter 229, as is known in the art. The useful ultrasonic system is a Branson VC54 unit (40 kHz, available from Sonics and Materials, Inc., Danbury, CT), readjusted to provide maximum atomization. Other means by which the organic material can be atomized are described, for example, in U.S. Patent No. 4,954,371. In Figure 4 there is shown an alternative jet vapor deposition apparatus with jet plasma. This system includes a radio frequency polarization electrode 310 (also referred to herein as a polarized cooling roller or simply a cooling roller) in a portion of the radio frequency polarization electrode 310 preferably covered by a shield 312 of dark space earth , such as an aluminum foil, to form a discrete reservoir area 314. Preferably, at least about 76% of the surface of the radiofrequency polarization electrode 310 is covered by the dark space earth shield 312. The dark space ground shield 312 is connected to ground and placed approximately 0.3 centimeters (cm) up to about 2.5 cm away from the surface of radio frequency polarization electrode 310 to provide a dark space and thus concentrate the wattage of the polarization over the exposed surface area of radio frequency polarization electrode 310. The jet plasma vapor depositor apparatus 300 in Figure 4 also includes a hollow cathode system 315, which includes a point source cathode 316, and a supply gas source 317 and a carrier gas source 318, to generate a plasma, an oil distribution system 320, attached to a valve system 321, and an anode system 322 (for example, an anode wire as described herein). In this arrangement, the oil distribution system 320 and the attached valve system 321 are optional. In the specified embodiment, shown in Figure 4, a horizontal, imaginary plane can be drawn from the center of the radiofrequency polarization electrode 310 to the slot opening of the optional oil distribution system 320, which divides the surface area not covered (ie, deposit area 314 in half) Point source cathode 316 is placed above the imaginary plane and anode system 322 is placed below the imaginary anode Plasma extends as a source point from cathode 316 from point source to vacuum in a cone shape configuration that is concentrated near radio frequency polarization electrode 310 and anode wire 326. Although Figure 4 is not to scale, in one embodiment of that system, the point source cathode 316 is positioned approximately 7.5 cm above the imaginary plane and approximately 7.5 cm away from the electrode 310 surface of the radio frequency polarization. It is inclined from horizontal position by approximately 60 / to ensure a downward expansion of the plasma towards the anode wire 322 and the reservoir area. The anode wire 322 is placed approximately 17.5 cm below the imaginary plane and approximately 5 cm away from the radiofrequency polarization electrode 310. The ground shield 312 of dark space prevents the anode wire 322 from being on the dividing line with the deposit area. These distances, lengths, angles and other dimensions are presented as an example only. It is not proposed that they be limiting. With reference to Figure 5, there is shown a dot source cathode 400, which allows the generation of plasma from a small hole 403 of a recessed cylinder 402 that is surrounded by a magnet 408, preferably of circular magnet, and equipped with a electrode, such as a spherical 410 electrode HV The cathode 400 preferably includes a cylinder 402 cooled with water, which is typically made of copper, although it can be made of graphite or other electrically and thermally conductive metals. A tube 404, preferably having a circular cross section, is inserted into a hole 406 of the cylinder 402 having a guide edge 405 recessed inside the hole 406 of the cylinder 402 such that it is in the plane of the center line of a circular magnet 407 that surrounds the cylinder 402 at its outlet end. The tube 404 is preferably ceramic, although it can be made of other materials that resist high temperatures and are electrical intors. The external surfaces of the cylinder 402 can be protected with quartz 412 (as by the use of a quartz sleeve) to prevent the formation of a plasma arc. This arrangement can best be seen in Figure 5A, which is a cross section of cathode 400 of point source taken along line AA, which also shows a water inlet 417 and water outlet 418. Using this particular configuration , a stable plasma can be held and contained in the region 414 defined by the extensions 416 of the cylinder 402. This configuration of the cylinder 402 together with the placement of the magnet 408 concentrates the plasma such that it extends as a point source towards the vacuum in a cone-shaped configuration. It is important to note that the strongest plasma is generated if the guide edge 405 of ceramic tube 404 is directly in line with the center (with respect to its width) of the circular magnet 408. Also, the flux density of the magnetic field is preferably less about 0.15 Kgauss, and more preferably at least about 1.5 Kgauss. The magnet 408 is preferably made of ceramic material, although metal alloys can be used. Ceramic materials generally have higher temperature stability and a higher Curie point (ie, the point at which magnetism is lost) and are therefore preferred. Particularly preferred embodiments of the present invention include an anode system (60 in Figure 1 or 322 in Figure 4), preferably an adjustable anode system as shown in Figure 4 of U.S. Patent No. 5,464,667 (Kohler et al.) The anode system, particularly the adjustable anode system, contributes to the maintenance of a stable plasma, and to the uniformity of the coatings. In a preferred embodiment of the anode system used herein, however, the closure glass box described in U.S. Patent No. 5,464,667 (Kohler et al.) Is omitted. Typically and preferentially, two tungsten wires function as the anodes. Each wire is of sufficient diameter to provide the desired temperature and a sufficient length to provide the desired coating width. Typically, for a temperature of about 800 / C to about 1100 / C, two tungsten wires from about 0.1 cm to about 0.3 cm in diameter work effectively as anodes with 10 amps at 20 amps of electronic current sustained from the plasma. The portions of the wires can be covered as described in U.S. Patent No. 464,667 (Kohler et al.). Again, the diameter and length of the wire are presented as an example only. It is not proposed that they be limiting. Any anode can be used as long as the plasma is generated at the cathode and directed towards and beyond the anode. It is to be understood that one or more of the additional evaporators / hollow cathode tubes, slots, or dot systems that generate plasma as described herein may also be included within the systems of the present invention. The multiple systems may provide more than one layer on the substrate or may provide an increased rate of deposit. The processes and systems of the present invention can be used to prepare any variety of carbon-containing and / or silicon-containing coatings, such as highly dense, amorphous coatings, stratified coatings, and uniform coatings, of various components, and the like. The composition of the coatings can be controlled by means of the concentration and composition of the feed gas passed through the hollow cathode, and of vaporized organic material in the evaporator. The density of the coating is controlled by means of the pressure chamber, the electrical energy (current and voltage) supplied by the radiofrequency and CD energy supplies. The conditions for the formation of high density coatings are generally chosen to have a balance of polarization energy at the concentration of starting material. That is, the specific density of energy includes the polarization energy density, reaction time, and concentration in starting materials. In general, the specific density of the energy is increased by a higher energy density and longer reaction time and decreases by the increased concentration of the starting material. In general, the higher the density of energy, the denser the coating will be. The density of the polarization energy typically ranges from about 0.1 watt / cm2 to about 10 watts / cm2 (preferably about 0.5 watts / cm2 to about 5 watts / cm2) The polarization voltage typically varies from about minus 50. volts to approximately minus 2000 volts (preferably, approximately minus 100 volts to approximately minus 1000 volts.) The polarization current density typically ranges from about 0.1 mAmper ios / cm2 to about 50 mAm / cm2 (preferably close to 1 mAm / cm2 to approximately 5 mAmperios / cm2 The plasma voltage per jet typically ranges from about minus 50 volts to about minus 150 volts (preferably, about minus 80 volts to about minus 100 volts). The plasma stream per jet is typically at least about 0.1 Amp (preferably at least about 0.5 Amp). The flow of the plasma stream by jet is typically dictated by the limitation of the power supply.

The chamber pressure is typically less than about 1 Torr (130 Pa). Preferably, the pressure in the reaction chamber is less than about 8 milliTorr (1.0 Pa). In general, the lower the pressure (that is, the greater the vacuum), the denser the coating will be. The mesh speed of the substrate (i.e. coating speed) typically ranges from about 1 foot / minute to about 1000 foot / minute (0.3 meter / minute to about 300 meter / minute). Preferably, the mesh speed is from about 0.9 meters / minute to about 6 meters / minute. The reaction time typically ranges from about 0.01 seconds to about 10 seconds, and preferably from about 0.1 seconds to about 1 second. As discussed below is shown in Figure 6, the application of this high polarization energy is a factor in obtaining excellent barrier properties. In order to achieve a high polarization wattage, the hollow cathode is typically placed in the list line of the film / cooling screw substrate. This arrangement makes possible the satisfactory interaction of the plasma by jet with a substrate of polarized film. In the absence of the plasma, the wattage power that can be applied is significantly reduced. When the jet plasma stream is protected from the polarized film substrate, the polarization power or energy is also reduced. This indicates the need for a specific apparatus arrangement to maximize the plasma flow by jet to the polarized film substrate. Preferably, the jet plasma system provides both confinement and di rectionality of the plasma. Conventional systems using plasma sources other than the dot source of the present invention and those described in U.S. Patent Nos. 5,232,791 (Kohler et al.), 5,286,534 (Kohler et al.), And 5,464,667 (Kohler et al.) lack the combination of confinement and directionality. In this way, the preferred systems of the present invention are improved with respect to these parameters. As noted previously, the plasma is created from a carrier or a mixture of a carrier gas and a feed gas. This is ífrs, * # 8Sás: refers in the present as the "plasma gas". The carrier gas flow rate can be from about 50 normal cubic centimeters per minute (sccm) to about 500 sccm, preferably about 50 sccm to about 100 sccm, and the flow rate of the feed gas can be about 100. sccm at about 60,000 sccm, and preferably about 300 sccm at about 2000 sccm. For example, for carbon deposition rates of about 20 X / second to about 800 X / second, the flow rate of the feed gas is from about 50 sccm to about 350 sccm and the flow rate of the carrier gas is about 50 sccm to about 100 sccm, with higher flow rates of the carrier gas in combination with lower carrier gas flow rates (typically, resulting in higher deposition rates). In general, for harder coatings, the carrier gas flow rate increases if the feed gas flow rate decreases. The feed gas, i.e. the carbon source, can be any of a variety of saturated or unsaturated hydrocarbon gases. These gases may also contain, for example, oxygen, nitrogen, halides and silicon. Examples of suitable feed gases include, but are not limited to: saturated and unsaturated hydrocarbons such as methane, ethane, ethylene, acetylene and butadiene; Nitrogen-containing hydrocarbons such as methylamine and methylacyanide; oxygen-containing hydrocarbons such as acetone methyl alcohol; halogen-containing hydrocarbons such as methyl iodide and methyl bromide; and hydrocarbons containing silicon such as tetramethyl, chlorotymethyl silane and t et ramet oxy oxy. The feed gas can be gaseous at the temperature and pressure of use, or it can be a readily volatile liquid. A particularly preferred feed gas is ethylene gas. As discussed previously, a carrier gas with the feed gas can also be used to take advantage. For example, without the auxiliary plasma of the carrier gas, the feed gas plasma is difficult to sustain around minus 100 volts using either a pulsed or filtered CD energy supply. For example, when only the feed gas is used, with a pulsating DC power supply of 1 amp, the voltage-occasionally increases to approximately minus 1000 volts, and with a power supply of 10 amps, filtered, non-pulsating, the plasma is occasionally extinguished jointly. The carrier gas can be any inert gas, that is, gas that is generally non-reactive with the chosen feed gas under the temperature pressure conditions of the process of the present invention. Suitable carrier gases include, but are not limited to, helium, neon, argon, krypton and nitrogen. Typically, high molecular weight gases, for example argon, are preferred. The terms "inert" and "carrier" are not intended to imply these gases do not take part in the deposit process completely. The thickness of the coatings produced by the method of the present invention is in general typically about 5 nanometers (nm), preferably about 10 nm to about 1000 nm, however, thicker coatings are possible, but are typically not they need. The substrate moves through the plasma at a rate designed to provide a coating of a desired thickness. With reference to Figure 1, the speed at which the substrate 75 travels from the roll 76 to the roll 78 can be from about 10 mm / second to about 4000 mm / second, but is typically about 10 mm / second to approximately 1500 mm / second for the gas flow velocity and pressures and the apparatus described above.

Examples 15 The present invention is further described by the following non-limiting examples. These examples are offered to further illustrate the various specific and preferred modalities and techniques. Nevertheless, It should be understood that many variations and modifications may be made as long as they remain within the scope of the present invention.

^ ^ ZS J ^^ 'Test Procedures A brief description of the tests used in some or all of the following examples will be given below. 5 The water vapor permeability in the coatings was measured with a Permatran W6 permeability tester manufactured by Modern Controls, Inc., Minneapolis, Minnesota. The test method of ASTM F 1249-90 included sheet of aluminum and PET sheet for normal calibration, sample conditioning at night, half-filled cell with deionized water and 60-minute test with 15 psi nitrogen gas pressure (1.0 x 105 Pas). 15 The abrasion resistance was measured by a combination and two ASTM test methods. The Taber Abrasion Test, ASTM D4060-95 was used with a "TABER" abrasion wear meter, Model 503 with CS-10F "CALIBRASE" wheels (Teledyne Taber, North Tonawanda, NY). A total weight load of 500 g evenly distributed on the two wheels CS-10F was used. The cycles were varied between 0 and 100 cycles. The second test method was STM D1003 that used a visibility meter Gardener, "HAZEGARD" system, Model XL211 (Pacific , MMfeH ^ ü ^ &&Scientific, Gardner / Neotac Instrument Division, Silver Spring, MD). In this method, the percentage of light scattering before and after the specimen was abraded by Taber abrasion was measured. The lower the value, the greater the resistance to abrasion and hardness. Adhesion was measured by the adhesion method by experiment at a 90 ° angle. The uncoated side of the film samples was fixed via a double-sided adhesive tape to a stainless steel panel. Usually, a silicon-based, pressure-sensitive adhesive tape was attached to the coated side using a seven-pound roller, wound twice in each direction on the tape. The specimens were 1.27 cm wide and approximately 30.5 cm long. The silicone-based tape was removed from the coating at a rate of 12 inches per minute in a 90 ° peel using an Instron Instrument, Model 1122. The hardness was measured by a UMIS 2000 ultramic hardness tester from CSIRO (Australia). The indentation method included a Berkovich indentation with a cone angle of 65 °. The indentor was made of diamond. The hardness values were determined by the analysis of the loading-unloading data. The density was measured by the flotation method. The powder samples were expressed in liquids of variable density and the movement of the suspended particles was observed. The movement towards arria indicates that the particles were less dense of the liquid; the downward movement indicated that the particles were denser than liquid. The movement indicates identical densities. The final readings were made after two hours when the particles had usually risen to the top of the liquid or settled to the bottom. By using liquids with increasing density differences, the density of the particles can be associated. The liquids with variable densities used are listed in Table 1.

Table 1 Liquid Density (g / cm3) 1-bromoheptane 1.14 2-bromopropane 1.31 l-bromo-2-fluorobenzene 1.601 4-bromoveratrol 1.702 The uniformity thickness of the plasma coatings per jet in film substrates was assessed from the interference color produced by the coatings on silicone wafers. Small pieces of silicone wafers were placed in strategic locations in the film substrate before depositing the coatings. One method was suitable for coatings having thicknesses of up to about 1500. For larger thicknesses of coating a gradual profilometer was used, manufactured by Tencor Instruments, Mountain View, California. The instrument measured the pitch formed by the coating and the adjacent uncoated area that was masked by adhesive tape during deposit. 20 Together with the determination of the In addition, the thickness of the coatings was determined from the ipsomet rich values obtained from the coatings in silicon wafers. The measurements were made on a Model 116B ellipsometer, manufactured by Gaertener Scientific Corporation, Chicago, Illinois. The static coefficient of friction was measured by the Inclined Plane method. The sample, typically about 2 cm wide by 5 cm long, was held in a horizontal plane that could be tilted. The free ends of the U-shaped steel wire (1 mm in diameter) were attached to stabilizing arms. The rounded end of the U-shaped wire (type paper clips) was placed upright and in a self-supporting manner on the surface of the sample. The inclined plan was lifted until the sliding of the U-shaped steel wire began. The static coefficient of friction was equal to the tangent of the angle at which the sliding began.

Example 1 ^ Silicone coatings were deposited on untreated polyethylene terephthalate (PET) 30 cm wide by 0.074 mm thick in the system shown in Figure 4. The system is similar to the reservoir chamber described in the United States Patent. No. 5,464,667 (Kohler et al.) With various modifications, including a point source cathode and an oil distribution system. The system included a polarized cooling roller, 48.2 cm in diameter by 33.5 cm in width. Except for the deposit area, approximately 76% of the surface area of the radio frequency polarization electrode was covered by an aluminum foil. The aluminum sheet was ground-connected and placed approximately 0.6 cm from the surface to provide a dark space and thus concentrated the polarization watage over the remaining 24% of the surface area. An imaginary horizontal plane could be drawn from the center of the radiofrequency polarization electrode to the slot opening of the oil distribution system, dividing half of the surface area no r cover. The point source cathode was placed approximately 7.5 cm above the imaginary plane and approximately 7.5 cm from the surface of the radiofrequency polarization electrode. The common point cathode was machined in the shape of a hollowed cylinder and tilted from its horizontal position by approximately 60 / to ensure a downward expansion of the plasma towards the anode wire and the reservoir area. The anode wire was placed approximately 17.5 cm below the imaginary plane and approximately 5 cm away from the cooling roller. The aluminum sheet placed on the ground prevented the anode wire from being in the dividing line with the deposit area. In contrast to the hollow cathode slot of U.S. Patent No. 5,464,667 (Kohler et al.), A hollow cathode point source was used which allowed the generation of a plasma from a small hole. As shown in Figure 5, the cathode consisted of a copper cylinder cooled with water, 5 cm long. A ceramic tube was inserted into the cylinder bore with the recessed tip to be in the plane of the centerline of the magnet. The ceramic tube hole was 0.35 cm. The circular ceramic magnet was placed as shown in Figure 5 at the front end of the cathode, 5.0 cm in outside diameter and 2.0 cm in the inner diameter. The magnetic flux density at the center of the magnet was measured to be approximately 0.45 Kgauss. The external surfaces of the cathode were covered with 0.3 cm thick quartz to avoid the plasma arcing. A stable plasma was sustained with 150 sccm of argon which extends as a point source from the cathode tip into the vacuum and which is concentrated near the radiofrequency polarization electrode and the anode wire. The anode was similar to that shown in Figure 4 of the United States patent number 5, 464,667 (Kohler et al.), Except the enclosing glass box was omitted. Two tungsten wires each 0.1 centimeter in diameter and 40 centimeters long worked as anodes that reached a temperature of 800-1100 / C with 10-20 amps of electric current sustained from the plasma. The middle section of the tungsten wires was covered with quartz tubing.

In order to distribute liquids in the form of vapor in the vacuum chamber, an oil distribution system was developed to control the rate of oil limitation and thus the evaporation of the oil. These are shown in Figures 1 and 4, and in greater detail in Figures 2 and 3. With the valve configuration shown in Figures 2 and 3, the oil was exposed under vacuum to become de-aerated. This was done by first evacuating the chamber 30 (figure 1) and then opening the valves VI and V2 and closing the valve V4, with the valve V3 adjusted to the desired dosing speed. The chamber was allowed to stabilize and the oil was dewatered until all the residual gases boiled. The discharge of oil through the oil distribution needle was prevented by making equal pressure above the liquid and on the needle. By changing the configuration of the valve, such that valve VI was closed and valves V2, V3, V4 were opened, air was introduced into the space above 7. Valve V3, a flow metering valve was adjusted, to control the pressure to impose a desirable pressure above the oil, as measured by the vacuum gauge 141. Once the desired pressure was reached, the valve V2 was closed. In addition, the oil feed rate was controlled by the proper selection of the meter and the temperature of the needle. The temperature of the needle was regulated by a copper sleeve controlled at a temperature by water, attached. As shown in Figure 2, the evaporator consisted of multiple aluminum separators that were heated by two cartridge type resistance heaters controlled by adjustable ratio auto-transformer. The copper sleeve that fits the oil distribution needle was placed in the inlet hole of the heater. The inlet hole was placed in the rear region of the heater and filled with a silicone rubber sleeve insert to prevent heat exchange between the heater and the copper sleeve. However, the tip of the needle was brought into immediate contact with the heated inlet hole allowing constant and uniform evaporation of the oil. The individually formed aluminum spacers provided multiple spacings, so that the evaporated oil was guided over the entire width of the heater several times up and down before the steam was decarbonized uniformly through a slot in the chamber. It was emptied as shown in Figure 1. The cathodic point source was driven by a pulsating DC energy supply, with a maximum output of 20 amps as described in U.S. Patent No. 5,464,667 (Kohler et al). The Aireo Temescal CL-2A power supply consists of a leak-type power transformer that supplies AC power to a full-wave bridge rectifier to produce an output, which is the absolute value of the transformer output voltage, ie the negative absolute value of a sine wave that starts at zero volts and goes to a maximum negative value of approximately 5000 volts of open circuit. Under a single resistive load of 100 ohms, this power supply will increase a voltage of less than 200 volts with the limited current 500 mA. With an arc plasma as a load, the output voltage of the power supply rises to the breakdown voltage in the apparatus and then the voltage immediately drops to the steady-state arc voltage with the current limited to 500 mA. In this way, the leakage transformer employed acts to limit the flow of current through the load or plasma in a manner similar to a resistor ballast in a typical glow discharge system. More specifically, as the cycle of the output voltage of the power supply progresses (starting at T0) through the 120 Hz waveform (starting at zero output volts), the voltage increases with time to a negative voltage value significantly above the steady state arc voltage. At this point, rupture occurs in the plasma jet, an arc is established, and the power supply output drops to the steady state arc voltage of approximately 100 volts and the saturation current of the power transformer, approximately 500 mA for the CL-2A power supply. As time progresses through the cycle, the power supply voltage drops below the arc voltage and the arc dies out. The output voltage of the power supply continues to fall, reaching zero volts at T0 / l-120 seconds and the process starts again. The period of time for this complete cycle is 1/120 of a second, or twice the frequency of the input voltage of the AC line to the power supply. The operations of the one-ampere power supply and the 20-amp power supply are identical except that the limiting currents are 1 amp and 20 amps, respectively. The positive electrode of the power supply was connected to the anode wires. The radio frequency polarization electrode was cooled to 5 C and connected to an RF biasing power supply (e.g., PLASMALOC 3, from ENI Power Systems, Inc., Rochester, NY). The complete vacuum chamber was electrically connected to ground. When the chamber was being pumped, the pressure in the oil tank was the same as the pressure in the chamber. The oil (a dimeti Isi loxane, viscosity of 50 centistokes, molecular weight of 3780, available from Dow Corning under the trade designation "DC200") was de-aerated during the evacuation of the chamber. After a de-aeration time of about 15 minutes, air was introduced into the upper portion of the oil reservoir until a pressure of 325 Pa was obtained. The 22 gauge oil distribution needle was maintained at 20 / C resulting in an oil feed rate of 0.36 ml / minute. The oil evaporator was heated to approximately 370 / C. One hundred fifty sccm of argon was introduced into the point source cathode and a stable plasma was generated which was sustained at minus 100 volts at 15 amps. The chamber pressure was between 0.13-0.26 Pa. A series of experiments was carried out at a frame or mesh speed of approximately 3 meters / minute when the polarization energy or power was varied as shown in Figure 6. As shown in Figure 6, the barrier properties The silicon coatings polymerized by plasma improved with the increase in voltage and polarization voltage. The contact angles of all the coatings were measured around 95 / (water). The contact angle of the uncoated PET film was 72 /. An additional sample of the same oil was prepared in a polarization wattage of 400 watts and a speed of 6 meters / minute. A coating of eleven layers (Sample A) was obtained by reversing the direction of the weft or mesh five times. The coating thickness was approximately 380 X as measured by the gradual filtering of a piece of simultaneously coated silicon placed in the PET film. Based on the eleven layer coating sample, the individual layer coatings were estimated to be approximately 690 X. The coating of Sample A was analyzed by Rutherford's retispersion by elemental analysis. The analysis produced an atomic percentage: C, 30%; Yes, 30% and O, 40%. The theoretical yield for the monomet il ilicón that has a formula of (If (CH30 *) 0) n- in atomic percent is: 28.6%; Yes, 28. 6%; and O, 42.8%. These data, and the spectrum of IR, the peak positions of which are listed in table 6, below, suggest that sample A has a composition similar to that of monomethyl silicon. Table 2 below shows the results of the Taber Abrasion Test of the uncoated PET film and coatings of one and eleven capable in the PET film prepared at a 400 watt polarization wattage. The lower the percent of visibility, the greater the resistance to abrasion. In this way, the abrasion resistance of the silicone coatings with plasma by jet increased with the increase in the thickness of the coating.

Table 2 TABER (% OF BRUMA) The hardness of the coating of eleven layers (3800 Anglestrom) on a silicon wafer was 8.14 GPa. As shown later in Table 3, the hardness of the silicone coating was compared to that of a piece of silicon, uncoated, a glass slide obtained from VR Scientific (catalog number 48300-C25), and a conventional hard coating. of monomet il s iloxane deposited as described in Comparative Example A.

Table 3 These data showed that the silicone coating was significantly harder than the glass slide, but softer than the silicon wafer. Single layer or single layer silicone coatings prepared at a polarization power of 50 and 400 watts and the 11 layer silicone coating prepared at a polarization power of 400 watts were evaluated for adhesion to the substrate film of PET. Measurements of the 90 ° peel strength were carried out with a KRATON-based tape (Box Sealing Tape # 351, commercially available from 3M Company, St Paul, MN). The peel strength values were approximately 2.6 kg / cm. De-lamination occurred through the cohesive failure of the adhesive. Therefore, the silicone / PET coating junction exceeds the measured peel strength values.

Comparative Example A The monome ti 1 s iloxane composition conventionally prepared was found to be similar to that of silicone polymerized by jet plasma. However, when the properties of the conventional coatings of monomet i ls and loxane were compared with those of certain silicon coatings polymerized by jet plasma, significant differences were observed. Monomet i 1 was prepared if loxane (Sample E) by the following procedure: 15 ml of trimethoxymethylsilane ((CH30) 3CH3Si) was added to 85 ml of water, and the pH was adjusted to 4 by glacial acetic acid and the mixture stirred for approximately 5 minutes until the solution became clear. One third of the solution was placed in an oven at 100 ° C for 12 hours. A colorless residue was obtained and used for several analyzes: The density values were between 1.14-1.31 g / cm; the IR spectrum was almost identical to that of silicone polymerized with plasma by jet. The WAXS identified a broad peak at 8.7. The hydrogen was determined by combustion analysis, which yielded 4.2% by weight of H. The silicon was determined by gravimetric analysis and ICP, which produced 40.4% by weight of Si. Because the theoretical values for monome ti 1 s iloxane having the formula - (Si (CH30 *) O) n- were 4.47% by weight of H and 41.9% by weight of Si, the sample appears to be monomet ilsilicon. The rest of the hydrolyzed trimetre oxime tils solution was adjusted to a pH of 8-9 by adding several drops of IN KOH solution and used for the preparation of coatings. Silicon wafer coating: Silicon wafers were immersed in 3N KOH solution for approximately one minute, rinsed with distilled water and immersed in the hydrolyzed trimethoxymethexysilane solution for 10 seconds. The wafers were placed in an oven and heated for 12 hours at 100 ° C. The coating was not uniform in thickness and varied according to the interference values from about 100 to several microns. The hardness of the coating was approximately 1.33 PFA. Coating in PET film: the PET film (0.074 mm) was corona treated in air and immersed in the hydrolyzed trimethoxymethyl-silane solution for 10 seconds. The film samples were dispersed in an oven and heated for 12 hours at 100 ° C. Continuous coating was obtained. The thickness was between 1-2 microns as measured by the film thickness gauge (Sony Magnescale Inc., Digital Indicator, U12A). The coatings do not have gas diffusion barrier properties. The water vapor permeability values of the coated and uncoated PET film were identical and approximately 8 g / (m2 / day) (measured with a Permatran-6 permeability tester manufactured by MODEM Controls, Inc., Mmneapolis, Minnesota). The following table 4 summarizes the comparison in the properties of the monomet i lsi conventional and the silicon polymerized with plasma by jet, typical.

Table 4 Example 2_ Carbon-rich remnants were deposited in a video-grade polyethylene film (PET) film of 30 mcm wide by 1.4 ex 10"3 cm thick which has less than about 1% of the film therein. Slip agent of Si02 (OX-50 from Degussa of Germany), which has been corona treated and rolled up for storage and handling in a packaging film with moisture barrier characteristics (manufactured by 3M company, St. Paul, MN) The experiment was similar to Example 3 of U.S. Patent No. 5,464,667 (Kohler et al), which is incorporated herein by reference, except that the hollow cathode slot is replaced by the cathode point source. hollow (that is, point source cathode) described above in Example 1. The development of the point source cathode simplified the cathode system and eliminated several components of the hollow cathode slot system, including the compartment of the argon plasma together with the argon plasma energy supply and the acetylene compartment. The dot source cathode was placed approximately 17.5 cm from the polarized cooling roller. After the vacuum system was evacuated to approximately 1 mTorr (0.13 Pa), 35 sccm of argon and 1000 sccm of acetylene were introduced together at the point source cathode. A stable plasma was generated and maintained from the cathode orifice and extended cone-shaped to the reservoir area. The pulsating DC power supply was set at 15 amps and minus 75 at minus 95 volts. The radio frequency polarization electrode was polarized at minus 300 volts. The power consumption of 320-400 watts. The mesh speed was approximately 15 meters / minute. The pressure varied between 2.3 Pa and 3.0 Pa. The experiment was run for approximately 3-4 hours time during which no significant changes in the barrier properties of the coating were experienced. The water vapor permeability was established constant at about 1 g / (m2 / day) compared to an uncoated sample, which has a water vapor permeability of about 30 g / (m2 / day) The prolonged period of time of a stable plasma ( that is, approximately 3-4 hours) is a significant advantage of the point source cathode.Without the circular magnet, the same orifice begins to plug with the carbon within several minutes.

Example 3_ Silicone coatings were deposited on a 15 cm wide by 2.54 x 10 ~ 3 cm thick film available under the commercial designation "KAPTON" film from DuPont de Nemours (Wilmington, DE), type 100H. Except for the addition of an oil distribution system (described above) all the other components of the deposit system were identical to those described in Example 1 of U.S. Patent No. 5,464,677 (Kohler et al); however, the arrangement of the deposit system was modified. The hollow cathode slot system was 9 cm away from the cooling roller. The trace of an imaginary horizontal plane from the center of the radio frequency polarization electrode to the cathode, the cathode slot was approximately 1.6 cm below the plane. The anode wire was approximately 4 cm from the cathode slot and approximately 6 cm below the imaginary plane. A Pirex glass plate (20 cm wide, 5 cm long, 0.3 cm thick) was placed parallel to and approximately 0.6 cm below the imaginary plane reaching from the front of the cathode frame to the radio frequency polarization electrode and leaving approximately 4 cm between the glass plate and the front of the cooling roller. The oil evaporator was placed on the glass plate. The evaporator slot was approximately 1.2 cm above the glass plate and approximately 41 cm from the cooling roller. Another glass plate was placed up at an angle of 45 / leaving a slot opening of approximately 1.5 cm between the glass plates. This arrangement allowed the oil vapor to condense and polymerize on the film substrate that was in contact with the cooling roller, polarized. Subsequent condensation of oil vapor above the radio frequency polarization electrode was avoided to a greater degree. The hollow cathode slot was approximately 15 cm wide and the graphite plates had a separation of approximately 0.6 cm. The radiofrequency polarization electrode was 5 cm in diameter, 18 cm long, cooled to 5 ° C. The ground connection box, that is, the anode, was approximately 20 cm wide and included a 0.1 mm diameter tungsten wire. All power or power supplies, including the anode, were connected to a common ground. After the vacuum chamber was evacuated to a pressure of about 0.13 Pa, 100 sccm of argon was introduced into the argon plasma chamber, i.e., the first compartment of the hollow cathode slot system. The plasma was held at approximately minus 450 volts and at a pulsating DC current of 0.5 amps using the Aireo Temescal Model CL-2A power supply (maximum output of 0.5 amps). The hollow cathode slot was powered by the non-pulsating, filtered CD power supply of 25 kilowatts of Hippotronics to improve the argon plasma ignited in the front compartment. The current was 8000 mA at approximately minus 100 volts. The DC 200 silicone oil from Dow Corning having a viscosity of 50 centiestokes (cts) and a molecular weight of 3780 was vaporized according to the procedure described in example 1. the Kapton film of approximately 50 cm, as described with Priority, it was transported in the form of a circuit over the radiofrequency polarization electrode and the two rollers of the mesh drive system. The deposition time was determined from the mesh speed, the number of loop turns in the contact area of the film with the cooling roller. The length of the contact area was 3.3 cm. The film adjusted the travels of silicon and germanium crystal to measure the special properties of silicon deposited by ellipsometry and FTIR spectrometry, respectively. The variation in deposition parameters, in particular the polarization power, resulted in significant differences in the coating properties, as shown in Table 5. Table 5 shows the difference in the properties of a polarized Ano sample and a sample B polarized.

Table 5 SAMPLE SAMPLE SAMPLE B Wattage of 0 250 Polarization polarization 0 -1400 polarization time of 0.96 seconds 1.54 seconds Depth of 0.34 cm velocity / seconds 0.2 cm / seconds Depth Permeability at 55 g / m2 / day 2.5 g / m2dí to moisture ESCA 29.6 / 48.4 / 22.0 29.9 / 48.8 / 21.2 Atomic percent (O / C / Si) index of 1,327 1,464 refraction Thickness 3595 X 1252 X The IR spectra of Sample B and the silicone oil DC200 showed the structural changes as a result of polarized, jet plasma polymerization. The position and intensity of the absorption peaks are listed in £ Ss í-: £ table 6 back TABLE 6 Based on the absorbance intensity ratios, plasma polymerization by polarized jet reduced the coating methyl concentration by approximately 40% and introduced some of it linked to Si-H. The lack of abosorption peaks for the portions of C-H and CH2 suggested a separation of bands between the silicon atoms and the methyl groups and the subsequent polymerization of the formed silicone radicals. As indicated by the results of ESCA, oxygen appeared to be comprised in the polymerization, mainly giving probably Si-O-Si crosslinking. Compared with the atomic percent ratio of a conventional silicone polymer having a SACA ratio of 24.95: 50.66: 24.39, the oxygen concentration of sample B was significantly higher.

Example 4_ The reservoir system, the conditions of the jet plasma and a substrate were the same as described in Example 3, except that the "KAPTON" film was wound around the cooling roller. About 25% of the surface was exposed to the plasma while the rest was covered with a nylon cover creating a separation of approximately 2 mm. The nylon cover was the same as that used in Example 1 for the protection of the bare cooling roller. The DC200 silicone vapor was plasma polymerized by jetting the film for about 15 minutes while the radio frequency polarization electrode was rotating at approximately 10 rpm and polarized at approximately 25 watts and minus 450 volts (sample A, which was prepared from according to a process of the invention). In a second experiment, the radiofrequency polarization was increased to approximately 200 watts and approximately minus 1200 volts (sample B, which was prepared according to a process of the invention). The coatings were scraped off the film and collected as a powder. A third sample was collected from a glass plate placed near the cooling roller. This sample was considered typical of a non-polarized plasma polymerized silicone coating (sample C, which was prepared according to a process of the invention). The data in Table 7 below compare the carbon and hydrogen analyzes of the different coatings. Table 7 also includes the analysis of the silicone oil DC200 (Sample D, starting material), the conventional monomethyl siloxane (Sample E, which was prepared using a conventional process described in the Example Comparative A), and the density values of all the samples.

Table 7 Minor changes in carbon and hydrogen concentrations occurred when the oil Silicon DC200 (Sample D) was plasma by polymerized jet without polarization (Sample C). A significant decrease in carbon or hydrogen concentrations was apparent for the polarized samples (Samples A and B). The atomic ratio C: H was greater than three, which supported the results of FTIR spectroscopy, specifically the loss of methyl groups and the formation of Si-H binding. Samples A, B, C, D, and E were examined by wide-angle X-ray fraction (WAXS) for the purpose of identifying the presence of crystallinity. Data was collected using a Philips vertical diffractometer, Ka radiation of copper, and proportional detector register of the retracted radiation. A type of interference less than 7.2 X was produced by all materials and is the only structural characteristic observed. The position of the maximum interference caused by the oil did not change the position in the polymerization. This indicates that the structural characteristics present in the oil maintained its approximate arrangement after undergoing polymerization. The observed peak was sufficiently broad that the materials were not considered to possess crystallinity, but rather possess a structural characteristic that repeats itself on a scale of a length of 7X. Amorphous carbon and amorphous silica, often used as barrier coatings, produce peaks at a considerably greater angle, usually between 20 and 30 degrees (2Q), corresponding to distances in the order of 4.5-3. These data indicate that the polymerized material is distinctly different from amorphous carbon-on-silica materials. A different structural feature was obtained from sample E, which showed a broad peak at 8.7n Angles t rom.

Example 5_ The Nujol, an aliphatic hydrocarbon oil was deposited on the substrate described in Example 3 using the arrangement of the system described in Example 3. Except for the oil distribution, the procedure was also the same. The pressure of 1300 Pa in the oil tank, the liquid was introduced in the evaporator heated 280 / C. The needle of the oil distribution needle and temperature were 22 / C and 20 / C, respectively. Four turns of the film circuit were made in the space of 123 seconds resulting in a deposit time of 3.5 seconds. The pressure during the plasma polymerization by jet was most of the time below 0.26 Pa. The water vapor permeability of the coating was approximately 40 g / (m2-day). This value was lower than the water permeability of the uncoated film (> 55 g / (m2-day)) and thus indicated barrier properties of a hydrocarbon polymer. The IR spectra of this coating and the original Nujol showed minor structural changes. The corresponding observance intensity ratios varied between 10% and 20%.

Examples 6-8 The deposition procedure was similar to that described in Example 3 except that a mixture of acetylene / argon was used as the plasma gas feed gas and a divider in the form of a glass plate was installed between the two sources of acetylene / argon feed gas and silicone vapor. In the series of examples illustrate the formation of coatings «- 'i ^? ^^ of several layers showing changes in the properties dependent on the position of the divisor.

Emplo 6_ The arrangement of apparatus includes the hollow cathode slot system, the grounding box and the radio frequency polarization electrode were similar to those described in Example 3. The oil distribution system consisted of a defined pump, tubing Teflon (approximately 1 mm in diameter) connected to the syringe and leading to the vacuum chamber, a 25 gauge micro-syringe needle connected to the Teflon tubing and inserted into the evaporator as described in Example 1. The oil of DC200 silicone (50 cts, 'Dow Corning Inc.) was fed at approximately 0.05-0.5 ml / minute in the evaporator heated to approximately 350 ° C. it should be emphasized that due to the imperfections in the stages of the development plan of the oil distribution system, the exact amount of oil available for evaporation and deposit could not be assessed from the flow rates indicated by the settings of the defined pump . PET film (1.27 X 10"3 cm thick and 15 cm wide) was used as a substrate and continuously unwrapped from the first roll and wound on a second roll at a mesh speed of 3 m / minute. The divider was as close as possible to the cooling roller, approximately 0.3 cm.The argon plasma was held at a flow rate of 50 sccm using a punctured DC power supply at 0.5 amp and minus 475 volts. The hollow cathode was powered by a 25 kW filtered DC power supply from Hippot ronics At a flow rate of 200 sccm and acetylene the plasma was maintained at approximately 8 amps and approximately minus 100 volts. radio frequency was cooled to approximately 10 ° C and polarized to approximately minus 1000 volts.A coating of approximately 1350 thickness was obtained.The coating on the PET film had a static coefficient of of 0.15 and water vapor permeability values of approximately 2.5 g / (m2-day). The FTIR spectrum of a coated germanium crystal (placed in the PET film) showed mainly absorption bands characteristic of DC silicone oil 200. After rinsing with toluene, the silicone coating was completely removed, one evidence was that the polymerization of the dimethe 1 -silicon oil did not occur.

Example 1_ This example showed the importance and sensitivity of the position of the divider for the polymerization of dimet i 1-s i licón. Identical conditions were used as those described in Example 6, except to extend the separation between the splitter and the film sulfate to about 0.9 cm. The FTIR spectrum was identical to that of Example 6. However, after complete rinsing with toluene approximately 75% of the coating was removed. This was an indication that an increased interaction of the plasma carbon with the dime vapor i i-i i 1 icon resulted in dimet i 1 -s i 1 partially polymerized icon. The partially polymerized silicone coatings were found to be ascending & | ^^ i < ^^ S | ^ 2 | g ^? I ^ i lubricant coatings. Table 6 summarizes the values of the static coefficient of friction obtained in a film of "KAPTON" coated 1.27 x 10"3 cm before and after extraction in soxhiet (approximately 16 hours in toluene) .The different thicknesses were obtained by varying the frame or mesh speed between approximately 1-18 meters / minute The thickness was estimated from the interference color on the coated silicone wafers Table 8 shows the values of the static coefficient of friction indicating a high degree of lubrication for extremely thin coatings and for a coating construction containing both a portion of highly polymerized silicone (matrix) and a less polymerized or unpolymerized silicone oil.

Table 8 Example 8_ This example confirmed the importance of sufficient separation of the divider for full polarization. The conditions were identical with those in Example 7, except for the greatest distance between the substrate splitter (approximately 1.5 cm). The FTIR spectrum is very similar to the previous one. However, in contrast to Examples 6 and 7, rinsing with toluene does not appreciably decrease the intensity of the FTIR absorption peaks. In this way, the increased distance between the splitter and the substrate caused a sufficient interaction between the plasma carbon from the jet and the vapor from the metal 1 -yes 1 icon to guarantee a completely polymerized dimethylated structure. with excellent adhesion to the substrate. The coating on the PET film had a static friction coefficient of 0.23 and water vapor permeability values of approximately 1.5 g / (m2 / day). A depth profile of the coating on silicone wafers was carried out by the Espect rocky Auger. The spectrum showed two distinct layers: a carbon layer adjacent to the substrate and a silicone layer with a small interfacial region between the carbon and the silicone layer as shown in Figure 7. The adhesion of the multilayer coatings of the Examples 6-8 were evaluated by the non-buried experiment resistance test and are summarized in Table 9. In all cases, delamination occurred at the interface between the coating and the adhesive tape. In particular, the high values of resistance to the experiment obtained with the samples of Example 8 indicated that the adhesion of the layer of dimet i 1 -if 1 icon completely polymerized to the carbon layer and also the adhesion of the carbon layer to the substrate of PET film gave at least 5.5 N / dm or more. The high adhesion and low, intrinsic surface energy values of silicone coatings suggest their use for release coatings or other low surface energy coatings.

Table 9 - $ U & amp; & amp; "Example 9 ^ The polper f luoroeter (Fomblina) of another oil that was polymerized without containing the polymerizable, conventional workable products. Multilayer coatings with excellent lubrication properties were obtained. The process conditions and arrangement of the apparatus were similar to those in Example 7. Thin film of Co / Ni, evaporated, experimental on a PET substrate (3M magnetic recording film) and a "KAPTON" film of 2.5 x 10"3 cm were used as substrates.The radiofrequency vaporization electrode was polarized at minus 300 volts.The FTIR coating spectrum showed typical absorption peaks for the Fomb; however, when the coated germanium crystal was washed in FC77, about 75% of the Fomb was washed. The coatings offered a unique multilayer construction in which the partially polymerized polyperfluoroether top coating functioned as a lubricant and the plasma carbon base by jet as a protective and sizing layer to the substrate. Table 10 shows the values of the static coefficient of friction independence of the thicknesses of coatings before and after the extraction in soxhiet in FC77 (16 hours). In comparison, a ME / Hi 8 ME Co / Ni tape had static friction coefficient values between 0.26-0.32.

Table 10 Example 10 Homogeneous coatings were prepared by a process using two power sources. This method provides the means to obtain new coating properties.

The process conditions and arrangement of the apparatus were similar to those described in Example 3. The hollow cathode slot and the vaporator slot were placed parallel to and in proximity to the radio frequency polymerization electrode (less than 7 cm). A divisor was omitted. A film "KAPTON" of 2.5 x 10"3 is thick and 15 cm wide obtained from DuPont type 100H was used as the film substrate that was transported in a circuit form around two rollers of the weft drive and the radio frequency polarization electrode for multiple deposition passes the "KAPTON" film also adjusted silicon wafers After the main vacuum chamber was evacuated to a pressure of 1 mTorr, 100 sccm of argon was introduced into the plasma chamber of argon, that is, the first compartment of the hollow cathode slot system, the plasma was held at approximately minus 475 volts and a pulsating DC current of approximately 500 mA.At a flow rate of 150 sccm, acetylene was introduced The mixing chamber, that is, the second compartment of the hollow cathode slot system, The hollow cathode slot was operated by a second pulsating CD power supply. The plasma was from 1 amp to approximately minus 100 volts. The radiofrequency polarization electrode was cooled to approximately 5-10 ° C. The polarization voltage of minus 1500 volts. The dimethyl silicon oil was introduced into the oil evaporator by means of a microsyringe pump and a feed of 0.05-0.5 ml / minute. A 25 gauge syringe needle was used. The bullfight was finished after 20 passes. The coating was approximately 2800 thick and showed excellent vapor barrier values to the water of 0. 17 g / (rrAdía) The contact angle and the static coefficient of friction were 90 ° and 0.22, respectively. The depth profile of Auger showed a uniform composition throughout the length of the coating that includes carbon, silicon and oxygen. The present invention has been described with reference to several preferred specific modalities and techniques. It should be understood, however, that you can make many variations and modifications as long as they remain within the spirit and scope of the invention. All Patents, patent applications, publications are incorporated herein by reference as if they will be incorporated on an individual basis. It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention. Having described the invention as above, the content in the following is claimed as property:

Claims (9)

1. CLAIMS 1. A method for the formation of an organic coating in a substrate, characterized in that it comprises: providing a substrate in a vacuum; providing at least one organic, vaporized material comprising at least one component from at least one source, wherein the vaporized organic material is capable of condensing in a vacuum of at least about 130 Pa at or below room temperature; providing a plasma from at least one source other than the source of the vaporized organic material; directing the organic, vaporized material and plasma to the substrate, wherein the substrate is in close proximity to a radiofrequency polarization electrode such that the substrate is exposed to a radiofrequency polarization voltage; and causing the vaporized organic material to condense and polymerize in the substrate in the presence of the plasma to form an organic coating.
2. 2. The method according to claim 1, characterized in that the plasma is formed of an inert gas.
3. 3. The method according to claim 1, characterized in that the coating has a density that is at least about 10% greater than the density of the main component of the organic material before coating.
4. 4. The method according to claim 1, characterized in that the plasma is formed from a carrier gas and a feed gas, wherein the feed gas is selected from a group consisting of saturated hydrocarbons, hydrocarbons containing nitrogen , hydrocarbons that contain oxygen, hydrocarbons that contain halogen, and hydrocarbons that contain silicon.
5. 5. An article comprising a substrate having a coating comprising silicone, coating which is characterized in that it has at least one of the following properties: a) a density of at least about 1.6 grams per cubic meter, b) a moisture permeability to the less than 2.5 grams per square meter per day; c) no infrared absorption peak for CH and C-H2.
6. 6. An article comprising a substrate having a multilayer coating having a first layer comprising a carbon-rich material, a second layer comprising silicon that is at least partially polymerized, and an intermediate layer between the two layers which comprise a carbon and silicone compound.
7. 7. A jet plasma apparatus for forming a coating on a substrate, characterized in that it comprises: a cathode system for generating a plasma; an anode system positioned in relation to the cathode system such that the plasma is directed from the cathode system beyond the anode system and into the substrate to be coated; and an oil distribution system for providing vaporized organic material, placed in relation to the cathode system such that the organic material, vaporized and the interactive plasma before, contacts the substrate, and a divider plate to maintain the plasma and the vaporized liquid, separated until they are close to the substrate.
8. 8. The jet plasma apparatus according to claim 7, characterized in that the cathode system is a hollow cathode slot system comprising two electrode plates arranged in parallel with each other or is a hollow cathode slot system comprising a first compartment having therein a hollow cathode tube, a second compartment connected to the first compartment, and a third compartment connected to the second compartment having two parallel plates therein.
9. 9. A hollow cathode system, characterized in that it comprises: a cylinder having an outlet end; a magnet that surrounds the outlet end of the cylinder; and a tube having a leading edge, wherein the tube is placed inside the cylinder and is hollowed out such that the leading edge of the tube is in the plane of the centerline of the magnet.