DE102007039645A1 - Coating or modifying surface of organic or inorganic wires, fibers or assemblies of them comprises exposing them to flame, plasma or stream of hot gas containing layer-forming organic or inorganic components - Google Patents

Abstract

Coating or modifying the surface of organic or inorganic wires, fibers or assemblies of them, e.g. cords, comprises exposing them to a flame, plasma or stream of hot gas containing layer-forming organic or inorganic components. These produce oxide coatings on their surfaces or modify them. An independent claim is included for a system for carrying out the method which allows a substrate (wire, etc.) (1) to be held at an angle of 0 - 90[deg] to an energy carrier (flame, etc.) (2) and moved relative to it.

Description

The The invention relates to a method and a device for coating and / or modification of inorganic or organic wires, fibers or their associates to give them new material and surface properties, in particular with regard to the resistance to corrosion and adhesion to lend.

Both organic and inorganic layer systems are described as permeation barriers to gases, ions and material additives. The effect is highly dependent on the structure of the layer, based on the molecules to which a barrier effect is to be achieved. Inorganic layers achieve a much higher efficiency than organic systems when optimally designed. For example, with 10 to 20 nm thick SiO ₂ layers on polymer films, OTR values (cm ³ / m ² .atm. D) can be achieved.

The production of such layers is currently carried out by gas phase processes, preferably by vacuum and plasma techniques [see, for example, see. H.-Ch. Langowski: Electroplating, 11/2003, 2800-2807; T. Hachisuka et. al .: Technical Conference Proceedings, Society of Vacuum Coaters (2005), 48th, 634-637 . US 20050249901 ].

In addition, there are a number of attempts of wet-chemical process techniques for the preparation of barrier layers to apply [see R-Ch. Langowski: Electroplating, 11/2003, 2800-2807 ]. The barrier effect is seen both with respect to gases and ions (especially sodium). Frequently, at the same time, a corrosion protection effect can be combined with the barrier effect, and, through the incorporation of functional organic groups, a further functionalization of the layers, such as, for example, hydrophilization or hydrophobicization, can also be achieved.

The production of microporous or nanoporous layer by flame-based CCVD method is known [see, for example. US 4,600,390 ; US 4,620,988 ; DD 253 259 ; DD 256 151 ; DE 100 19 926 . R. Musil, H.-J. Tiller, "The plastic-metal composite", Hüthig-Verlag . Heidelberg 1989; H.-J. Tiller, et. al., "Thin Solid Films" 169 (1989) 159-168 for example. H.-J. Tiller, et. al., "Thin Solid Films" 169 (1989) 159-168 ].

It is also known that the processes mentioned can be used to improve the adhesion of organic layers to a wide variety of substrates [ H.-J. Tiller, et. al., GLAS + FRAME, Verlagsanstalt Handwerk GmbH Dusseldorf, K 42236, 1996 ; H.-J. Tiller, et. al., JOT, 36-38, 07/1997 ; H.-J. Tiller, et. al., GLAS + FRAME, Verlagsanstalt Handwerk GmbH Düsseldorf, 02/1999 ; H.-J. Tiller, et. al., JOT, 08/2002 ]. In accordance with the prior art, SiO ₂ or SiO _x is preferably used as the layer-forming component in these cases. In many cases, this requires the additional use of an adhesion promoter which makes it possible to attach the organic layer to the inorganic layer. In the case of silicone compounds as organic coating can be dispensed with the use of a primer in many cases [see, for example. H.-J. Tiller, et. al., 9th International Symposium Swissbonding, Rapperswil, CH, 1995 ; Ph. Müller, DE 10 2005 035 443 A1 ].

The DE 38 44 522 A1 discloses a method for coating household articles with a release layer. A surface of the household object is provided in the plasma spraying with a hard material layer in several layers one above the other using different hard powder. The hard material layer is then provided with an anti-adhesion layer. In order to improve the adhesion of the layers on the surface of the household article and, above all, to increase the mechanical stability of the layers, the grain size of the hard material powder used increases from the surface towards the top.

Of the Disadvantage of the above-mentioned method is that no wires, fibers with them or their composites can be coated and / or modified.

The Object of the present invention is to provide a method and a Apparatus for coating and / or modifying inorganic and organic wires, To indicate fibers and their compounds, which are the disadvantages of the state avoid the technology and the wires, Fibers and their compounds have new material and surface properties, especially with regard to corrosion and adhesion.

According to the invention This task is characterized by the characterizing features of the first and new main claim and advantageously designed by the features of the subclaims.

The Essence of the invention is that one or more uncoated or coated wires, Fibers or composites between them, such as cords, a flame, a plasma or a stream of hot air.

The flame, the plasma or the hot air stream may be one or more layer forming or surface modifying inorganic or organic components are mixed. For example, inorganic compounds or organometallic compounds in the flames make it possible to produce oxidic coatings on the uncoated or already coated wires, fibers or composites - referred to below as the substrate - of these.

When very cheap have proven compounds, the oxides of silicon, Aluminum, zirconium or titanium. This is also true for magnesium or silver in non-oxidic form.

So Like flames, it is also possible to use oxidizing plasmas or hot air streams for this purpose preferably organometallic compounds are supplied.

By Oxygen-free plasmas or hot gas streams can also be non-oxidic Connections on the surfaces deposit.

The Type of coating or modification can be according to the invention by choosing the surface temperature of the substrate. It has a temperature range between Zero and twice the melting temperature, particularly favorable in the Range between 50 ° C and the melting temperature.

According to the invention you can also flame, plasma or hot air stream also separated by Reaction with the inorganic or organic component on the surface of the substrate to react.

By choosing a surface temperature above the glass transition temperature (T _g ), it is also possible according to the invention to infiltrate the coated component into the surface of the substrate and to change its surface structure to 200 nm in structure and composition and thus to bring about new properties of the substrates.

at the added or added inorganic or organic precursor compounds may be present both a compound and a mixture of several act different compounds.

The Flames can also by a mixture of fuel gas and an oxygen-containing carrier gas, in the simplest case air, be generated.

Of the Percentage of oxygen can be varied between> 0% and 100%. Leave as fuel gas Both organic fuel gases, such as methane, propane, Butane and acetylene as well as hydrogen use.

plasmas and provide hot air streams Furthermore the possibility, by using inert gases, such as noble gases or nitrogen, to produce oxide-free modifications or coatings.

Also can the plasma carrier gas consist of oxygen or an oxygen-containing gas.

The admixed inorganic or organic component causes by Reaction with the carrier gas a modification or coating of the substrates. These can be before the coating or modification are pre-tempered, which is preferred in the Range between 50 ° C and its twice the melting temperature.

When Plasmas are inventively at atmospheric pressure working free-jet plasmas or Barierreentladungen used.

The Hot air flows can be temperatures between 200 ° C and 2000 ° C, but preferably between 400 ° C and 1500 ° C have.

to Coating and / or modification of the substrates can be both a single flame, plasma or hot air flow as well as several or combinations of flames, plasmas or hot air streams.

The principle of the device with which the coating and / or the modification of the substrates is achieved is the enclosed one 1 shown schematically.

at the device according to the invention For example, the substrate (s) is at an angle between 0 ° and 90 ° between 45 ° and 90 °, to Axis of an energy source (the energy carrier) and can be moved relatively.

For each fuels a different angle can be chosen or be advantageous.

Of the Distance between substrate and flame, plasma or hot air flow can over it wide ranges are varied, in the case of flames or plasmas, preferably the immediately luminous flame or plasma region, with the surface of the Substrate is brought into contact.

The Flames, plasmas or hot air streams - called energy sources - can do this individually or in combination, one behind the other in a row, concentric around the substrate or helically be arranged in series on the device side. By using several energy sources can at the same time several substrates are coated and / or modified.

If you use a barium discharge as a plasma, this can, as in 2 shown schematically, either parallel to the substrate or as 3 shows, at an angle> 0 °, preferably 90 °, are arranged to this. It can also be used in combination several Barierreentladungen. In this case, it is possible to coat and / or modify several substrates simultaneously (schematically in FIG 3 shown).

The The temperature of the substrates on the device side can vary widely Be realized manner. Emerge fibers from spinnerets, so can by selecting the distance between spinneret and energy carrier the Temperature of the substrate can be adjusted.

Otherwise, a temperature control over a heat radiation, a hot air flow or a tempering is possible. So shows 4 For example, a device in which a Barierreentladung with a tempering, over which the substrate is guided coupled. Instead of the barium discharge, which has been selected here by way of example, it is also possible to combine the energy sources flame or plasma with the tempering roller and device substrates via these running substrates.

Claims (9)

Process for coating and / or modification of inorganic or organic wires, fibers or their composites in which this a flame or a plasma or a hot gas stream be exposed to the flame or a plasma or a Hot gas stream layer forming contains inorganic or organic components, so these components oxidic coatings or modifications of the surface structure the wires, Form fibers or their composites. Method according to claim 1, characterized in that the oxide coatings as Silicates or oxides of aluminum, zirconium, titanium or mixtures thereof be formed. Method according to claim 2, characterized in that the flame or the plasma or the hot gas stream organometallic compounds are supplied. Method according to claim 1, characterized in that the wires, fibers or their composites in the range of 50 ° C and twice the melting temperature of the flame or the plasma or the hot gas stream get abandoned A method according to claim 1, characterized in that the method is carried out at a surface temperature above the glass transition temperature (T _g ). Method according to claim 1, characterized in that plasma as a Barierreentladung is produced. Method according to one or more of the preceding claims, characterized that the flame or the plasma or the hot gas stream is a precursor compound is added or mixed. Method according to one or more of the preceding claims, characterized that the directly lit flame or plasma area with the surface the wires, Fibers or their composite is brought into contact. Arrangement for carrying out the method according to a or more of the preceding claims in which the wires, fibers or their composites arranged at an angle between 0 ° and 90 ° to the axis of an energy carrier and are movable relative to this.