EP1649100A1 - Procede d'usinage au plasma de materiaux polymeres et inorganiques - Google Patents

Procede d'usinage au plasma de materiaux polymeres et inorganiques

Info

Publication number
EP1649100A1
EP1649100A1 EP03817632A EP03817632A EP1649100A1 EP 1649100 A1 EP1649100 A1 EP 1649100A1 EP 03817632 A EP03817632 A EP 03817632A EP 03817632 A EP03817632 A EP 03817632A EP 1649100 A1 EP1649100 A1 EP 1649100A1
Authority
EP
European Patent Office
Prior art keywords
plasma
mbar
fibres
woven
yarns
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03817632A
Other languages
German (de)
English (en)
Inventor
Claudia Riccardi
Moreno Piselli
Antonino Raffaele Addamo
Maria Rosaria Massafra
Bruno Marcandalli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stazione Sperimentale per la Seta
Universita degli Studi di Milano Bicocca
Original Assignee
Stazione Sperimentale per la Seta
Universita degli Studi di Milano Bicocca
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stazione Sperimentale per la Seta, Universita degli Studi di Milano Bicocca filed Critical Stazione Sperimentale per la Seta
Priority to EP10184545.1A priority Critical patent/EP2287394B1/fr
Publication of EP1649100A1 publication Critical patent/EP1649100A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B19/00—Treatment of textile materials by liquids, gases or vapours, not provided for in groups D06B1/00 - D06B17/00
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/01—Creating covalent bondings between the treating agent and the fibre
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2011—Application of vibrations, pulses or waves for non-thermic purposes

Definitions

  • the present invention relates to a method for working various types of materials such as woven fabrics, non-woven fabrics,. yarns, natural fibres, polymeric and inorganic fibres (in other words, fibres produced from polymeric material such as PET, cotton, wool and similar products, as well as fibres produced from inorganic materials such as carbon, glass and similar products) , alcantara (polymer microfibre) glasses and films of any type, and other similar products.
  • the present invention refers to a method for working said materials including a treatment stage using plasma.
  • woven fabrics, non-woven fabrics and yarns in general are concerned, under present conditions their practical applicability and their commercial value are determined by the appearance, tactile impression, and the physical and mechanical characteristics that make the aforesaid materials suitable for the use for which they are destined.
  • the methods that are generally employed to obtain these characteristics include several stages for woven fabrics, non-woven fabrics and yarns, among which in particular, the stages for dyeing, printing and finishing treatment.
  • the dyeing stage, and the printing stage for woven and non-woven fabrics and yarns are composed of a sequence of processes suitable to provide the material with an established colour.
  • the finishing stage provides the woven and non-woven fabrics with various characteristics such as softness, hand, water and oil- repellent properties, as well as certain colouring and lustrous effects.
  • the finishing stage comprises chemical operations that, among others, include the application of sizing and pigments, painting and mechanical treatments aimed at improving the appearance. More in particular, finishing refers to the application of covering layers, protection, and coatings on the material surface. This treatment can be applied during any one of the working stages.
  • plasma is well known for processing different types of materials in order to obtain special structural and functional characteristics.
  • numerous experiments have been conducted to assess the possibility of using plasma for treating materials as an alternative to some of the treatments described above.
  • plasma treatment would make a large contribution towards avoiding, or at least reducing the use of large quantities of water as well as substances that create pollution and that are toxic for humans.
  • fluorocarbons, silicones, silanes and siloxanes can be used in plasma form, and under these conditions they polymerise to form a film on the surface of the aforesaid materials to create waterproofing characteristics. These polymeric films are adsorbed by the surface of said materials but not necessarily chemically bonded.
  • the basic problem that the present invention aims to resolve is to invent a method that will provide functional surface properties of a different nature that offer characteristics to eliminate the numerous problems created by the methods traditionally employed in treating these materials.
  • the term "materials” refers to any one of the materials described previously, namely woven and non-woven fabrics, yarns, polymeric and inorganic fibres as defined previously, glass and film.
  • the plasma used for processing materials according to the present invention is cold plasma, in other words, the temperature of the total gas mass during the plasma stage is the same level as the environmental temperature.
  • the aforesaid materials used in industrial processing emit various types of gas from their surface, (in other words: degassing) when placed in contact with plasma or when placed in low- pressure chambers.
  • degassing more energetic impact, like the charges produced by plasma provokes a degassing reaction on the surface of water and residue gases from the surfaces or bulk of the material; this degassing is mainly caused as a result of chemical etching (breaking of bonds on the surface, caused by plasma and the degassing of volatile substances, or gases) or as a result of variations in the surface energy, or by the effect of heating on the material surface.
  • the said gas emission or transpiration interferes considerably with plasma processing.
  • the method for working materials comprises at least one stage of cold plasma treatment wherein, during said plasma treatment stage, the emission of gas from the surface of said materials is controlled each time according to the type of material and the particular processing conditions to ensure that it does not influence the plasma processing to an important degree.
  • said method comprises a gas removal stage in sequential order or simultaneously, to remove the gases adsorbed on the surfaces of said materials, and a plasma processing stage on said surface.
  • the removal stage can be performed by subjecting the substrate to vacuum conditions to the level where the pressure obtained is lower than or equal to 10 ⁇ 2 mbar on cmVsec inside the processing chamber, preferably lower than 10 ⁇ 4 mbar cm 3 /sec, and even more preferably lower than 5xl0 -5 mbar cm 3 /sec.
  • this does not depend on the device used for the removal under extreme vacuum, for example, it does not depend on the size of the vacuum chamber or the type of pump use to produce the vacuum to whatever level employed, when the pressure registered inside the treatment chamber reaches said values, then it is considered that the gases adsorbed by the substrate surface have been sufficiently removed to be able to guarantee successive efficient plasma treatment.
  • said gas removal stage can be realised by making the treatment gas flow during plasma application at a tangent to the surface to be processed to "wash" the surface, or remove the gases adsorbed by the surfaces.
  • tangent gas flow since applied with the molecules and charge as explained previously, will remove the gas from the surface of the materials to be processed, blowing them away. In this manner, the length of time the degassed gases remain on the surface is reduced considerably and the surface is able to interact with the plasma much more efficiently.
  • the gas emission from the surfaces of said materials in other words, the degassing phenomenon, can be controlled by using a plasma source that originates substantially neutral particles.
  • the neutral particles have a contrary effect compared to the charged particles described above. In fact, thanks to the considerable absence of charge, these particles do not remove the gases adsorbed by the surfaces of the materials to be processed, but prevent, or at least reduce their detachment so that they cannot affect the plasma process negatively.
  • An example of this further embodiment of the invention is the use of a power-modulated plasma. For example, by modulating the amplitude of the power at the source it is possible to switch the plasma on and off in order to minimize the flow of charged particles on the substrate surface.
  • the plasma treatment stage on materials can be realised with all noble gases, preferably helium, argon, neon, and their blends with air or oxygen or hydrogen, inert gases such as nitrogen and its blends, fluorated gases chosen from the fluorocarbon group, and especially CF 4 and CFC, WF 6 , XeF 2 , on condition that SF 6 is not included, since it is already known and included in the patent application PCT/IT02/00335, hydrocarbons, C0 2 , hydrogen, silicon, silane, s ' iloxane and organosiloxane compounds, chlorine, acrylate, vinylic monomer, styrene, and chloromethylsilane compounds, metals including corresponding blends or polymers.
  • noble gases preferably helium, argon, neon, and their blends with air or oxygen or hydrogen, inert gases such as nitrogen and its blends, fluorated gases chosen from the fluorocarbon group, and especially CF 4 and CFC, WF 6 ,
  • the process can be realised also using aforesaid gases in liquid solution, on condition that the respective vapour pressures are greater than the plasma production pressure.
  • the liquid solution has a vapour pressure lower than the plasma production pressure (for example at atmospheric pressure) , then the solution is vaporised in aerosol form.
  • the plasma used for material processing according to the present invention is cold plasma, in other words, the temperature of the total gas mass is the same as the environmental temperature (room temperature) .
  • Cold plasma can be produced at pressures between 10 "4 mbar and 100 mb ' ar, in other words, under vacuum as defined in the present description, or at pressures over 100 mbar and under or equal to 2 atm, or substantially at atmospheric pressure as defined in the present description.
  • the plasma can be generated with various electromagnetic sources, that is, sources with different frequencies and geometries.
  • the power emitted by the sources can be modulated in amplitude and/or in frequency in order to control, for example to minimise or maximise, the local density of charged species on the surface of the sample, and therefore to select the type of treatment to be applied according to necessity or preference, and at the same time, to control the degassing phenomenon of the material surfaces.
  • the physical-chemical processes that occur on the surfaces of the material depend not only on the degassing, but also on the plasma parameters and the electrical potential values assumed by the sample compared to the plasma potential, or the electrical fields in the proximity of the sample.
  • the electric fields produce positive or negative electric charges that interact with the substrate bombarding it, or simply charging it electrically.
  • These electric fields can be controlled by polarising the sample support, (or the sample itself) or by placing the sample in the ionic sheathe created in proximity to the antenna, which assumes negative electric potential values equal to several hundred volts (from 0 to 800 V) in a spatial area of a few millimetres (from 1 to 10 mm) .
  • This method is preferably adopted to produce physical and chemical etching aimed at cleaning the surface, removing any deposit, modifying superficial roughness, and activating the surface.
  • the source parameters which, for example, have an electrical power ranging 0.1 W/cm 2 and 50 W/cm 2 , the geometry of the source that produces the plasma, (capacitive, inductive source) the frequency of the electromagnetic radiation employed to produce the plasma and the residual vacuum inside the chamber where the processing is conducted.
  • the vacuum level also depends on the residual humidity and the material degassing, or in other words, the flow of the volatile substances that are released by the materials and degassing of the internal structures that make up the reactor.
  • plasma production should preferably occur in pulsed mode, in order to reduce even further the degassed flows caused by the plasma species bombarding on the surface.
  • the gas flows must be at a tangent to the substrate to "wash" the surface of all gases degassed during the process.
  • the substrate at a temperature under 70°C, preferably less than or equal to environmental temperature to create a temperature and pressure difference between the plasma and the substrate, or in other words, a difference between the pressures of the substrate and the plasma in order to facilitate the flow orientation towards the substrate when processing is to be applied, or vice versa, away from the substrate when it. is necessary to facilitate the degassing before plasma processing.
  • the position of the sample can be varied compared to the plasma source: (a) the sample can be placed in the area of diffused plasma mounted on a floating support; (b) the sample is mounted on a metal support that is polarised up to several decades of negative or positive volts (up to 100 V) to facilitate the ionic bombarding on the- surface; (c) the sample is positioned in the ionic sheathe that is created near the plasma source; (d) the sample is moved constantly to render the processing more homogeneous.
  • the time lapse that materials are subjected to cold plasma processing normally never exceeds 20 minutes, preferably less than 15 minutes, and even more preferably, less than 5 minutes.
  • the said process is realised under vacuum or at atmospheric pressure.
  • the cold plasma is produced in a chamber containing gas at a variable pressure between 10 ⁇ 4 mbar and 100 mbar.
  • said type of plasma under vacuum can be employed according to discontinuous, continuous, or semi-continuous methods as well as roll-to-roll methods. Discontinuous method.
  • the discontinuous method envisages a first and second stage wherein during the first stage, the sample is placed in a chamber that is then evacuated to a pressure lower than the working gas.
  • this gas is the air that exists inside the chamber, said air must be evacuated to create a vacuum until a pressure value is attained that is suitable for plasma processing.
  • the working gas is introduced into the chamber. This stage is essential if pure gas is to be obtained inside the process chamber, and in order to produce good degassing levels on the substrate, as will be specified further on, before the application of the following plasma stage.
  • the method also includes a third processing stage wherein, immediately after, or during the plasma process, the sample is made to interact with gases of various types, such as polymeric or polymer gases in gaseous state.
  • degassing can occur by sending a flow of gas at a tangent onto the sample and/or pulsing the plasma.
  • the flow action with pulsed plasma provokes an excellent synergy effect as far as results are concerned.
  • Plasma can be produced with various electromagnetic sources, that is, with sources that have different frequencies.
  • the process working conditions are controlled by measuring the plasma parameters and the physical-chemical properties of the samples.
  • Processing times are shorter than 20 minutes and processing can be repeated several times. Moreover, after each process the materials can be left for a certain time in an atmosphere composed of air or inert or active gas, and then can be subjected to further processing with the same or a ' different gas.
  • the semi-continuous method is preferable for limited material quantities, that is, manufactured pieces or materials, fibres used in sectors of specific applications.
  • an installation composed of several chambers can be used, for example: one chamber for loading and evacuation, the following chamber for plasma processing, and the last for evacuation and material unloading.
  • the chambers can 'be connected through open ducts or isolated using vacuum valves. Once the material has been loaded into the first chamber, in rolls or pieces, said chamber is closed and evacuated to a pressure lower than or equal to processing pressure, in order to be able to obtain also degassing on the material surface, degassing that is of primary importance. This stage also permits a type of surface cleaning process above all when dry gases are applied, meaning inert gases completely free of any humidity.
  • the material is transferred to the processing chamber which has a pressure that is higher than or equal to the adjacent chamber, where plasma is applied. In this manner, the environment where processing occurs is not contaminated by residual gases produced during the evacuation stage and material degassing.
  • partitions can be installed in the form of walls between the adjacent chambers, that act to isolate one chamber from another.
  • the degassing problem can be advantageously resolved by pulsing the plasma and/or making the gas flow onto the surface and/or processing with dry gas in the previous chamber where the plasma process occurs.
  • the material is -processed in the plasma chamber and after processing that lasts less than 20 minutes, it is transferred into the evacuation and unloading chamber that has a lower pressure level than the processing chamber.
  • the material can be maintained in an atmosphere of a gas that is different from air once again. Successively, the evacuation and unloading chamber is opened and the material is unloaded.
  • this last chamber is evacuated again, and the cycle is repeated.
  • the material can be treated either in a single chamber, or in a system composed of several processing chambers. These chambers are located in the intermediate position between the loading and evacuation chamber and the unloading and evacuation chamber. Otherwise, in the case of cyclic treatment, the material can remain in special chambers and then treated again.
  • This method can be applied for fibres used in textile sectors, for material pieces, and manufactured pieces as described above. It must be emphasised that during treatment in the plasma chamber manufactured items or fibres can be moved constantly to ensure homogenous treatment results. Continuous method.
  • the continuous method can be performed using various systems as described, below.
  • the roll-to-roll system is preferably applied to wound materials.
  • This refers to systems composed of an unwinding and rewinding system inside a processing chamber insulated form the environment.
  • the roll-to-roll treatment is carried out at low pressure chamber, wherein the material is unwound and pulled through the plasma for processing, and then rewound inside the vacuum chamber.
  • This system is composed of a vacuum chamber that can be evacuated thanks to a pumping system in which it is possible to maintain a gas flow to the desired pressure.
  • a transmission system such as radio frequency for example, or microwave, or simply using static or low frequency electrical fields.
  • the plasma production systems are similar to those described previously.
  • the continuous process can be performed in a processing chamber wherein the materials are pulled through said chamber in continuous mode through seals that improve the hermetic condition between environmental pressure and the vacuum inside the chamber. In this configuration, the material enters and exits through the seals and the process occurs in continuous mode.
  • a vacuum installation of this type must include several pumping chambers to obtain the vacuum necessary.
  • This technique can be applied to any one of the aforesaid materials and for any kind of employment destination, and can be used with any type of cold plasma reactor, with the aim of improving or modifying surface characteristics without altering the bulk characteristics obtained using previous processing, and without altering the intrinsic natural characteristics of the materials themselves.
  • Cold plasma produced at atmospheric pressure can be preferably of crown type.
  • the plasma is produced at low frequency, that is at a frequency ranging between 1 and 200 kHz, at a pressure more or less at atmospheric pressure as specified previously, between two conductor electrodes or between one conductor and one dielectric type, or between two dielectric types, that is, two dielectric coated conductors .
  • the materials and the relative fibres are placed at a distance from the electrodes that varies preferably between 0,2 cm and 3 centimetres.
  • the sample can be moved in relation to the source using a system such as the aforesaid roll-to-roll system at variable speeds, just as the processing time can be varied according to necessity.
  • the materials and the relative fibres are treated in continuous mode moving under the electrode used to produce the plasma and the processing time is shorter than the second method because the power of the crown system is stronger than that produced at low pressure and this could lead to the materials and the relative fibres becoming damaged.
  • the power employed can range from 300 W for a length of 20 cm of material, while the pressure is close to atmospheric pressure that is in the range specified previously.
  • the material surface is cleaned (and degassed) with inert gas or dry air, or is subjected to a preliminary drying process .
  • the material speed ranges between 1 m/minute and 100 m/minute
  • power ranges between 50 W and 2 kW
  • frequency ranges 1kHz and 200 kHz.
  • the material can be processed once or several times, but each time for a period less than a second in order to avoid the aforesaid damage.
  • the materials can be bombarded with gases of different natures that is different from air.
  • the crown processing is performed in a chamber at controlled atmosphere and the gas is sent in a flow near the electrodes or by the electrode itself.
  • the processing method used on the materials and relative fibres is composed of at least one stage of cold plasma processing wherein, during said plasma processing stage the gas emission from the surface of the said materials and relative fibres occurs each time according to the type of material and the particular treatment conditions, controlled in a manner so that it does not have a strong impact on the plasma process.
  • the aforesaid gas emission control can be obtained by subjecting the sample to be treated to extreme vacuum conditions before the plasma stage.
  • the degassing flow can be controlled by applying pressure that is equal to or lower than 10 ⁇ 2 mbar, preferably equal to or lower than 10 -4 mbar, and even more preferably equal to or lower than 5xl0 ⁇ 5 mbar.
  • plasma treatment is realised before any of the other working stages on the materials following the drying or exsiccation stages, while, for fibres, the treatment is applied before and after the stages that involve the use of water or other solvents.
  • This technique can be applied to any type of material and relative fibre, as well as for any employment destination and can be realised with any type of cold plasma reactor, with the aim of improving or modifying the surface characteristics without altering the bulk characteristics obtained through previous processing, and without altering the intrinsic natural characteristics of the materials and the relative fibres .
  • the plasma treatment stage can preferably include the following stages either singularly, or in any combination whatsoever:
  • the material treatment method comprises a stage of plasma application on material surfaces to improve current properties or to provide new properties .
  • the advantages_ of the method according to the present invention in relation to traditional surface processing can be summarised as follows:
  • this process involves only a few surface layers at molecular level for a depth of a few decades of nanometres as far as a maximum of a few microns;
  • plasma of noble gas inert gas, and preferably oxygen, air, chlorine, ammonia, aforesaid fluorated gas, hydrogen, nitrogen, argon, helium, neon, and their blends, and monomers of various types.
  • plasma produced under vacuum where the gas is represented by air
  • the processing chamber of the material is evacuated in a manner to obtain a pressure between 0,1 and 2 mbar.
  • the processing chamber is evacuated to obtain pressure lower than the pressure used for treatment, and consequently, this provides an adequate degassing control.
  • the chamber is filled with gas and the plasma is generated, for example using a radio frequency electromagnetic source, with a pressure level ranging between 0.01 and 20 mbar, preferably between 0.1 and 2 mbar, and even more preferably between 0.2 mbar and 0.8 mbar and an electronic temperature ranging between 0.1 eV and 20 eV, preferably between 1 eV and 15 eV, and even more preferably between 2 eV and 10 eV.
  • the power employed per surface unit ranges between 0.1 W/cm 2 and 50 W/cm 2 - preferably 1 W/cm 2 and 10 W/cm 2 .
  • the plasma is applied on the material surface for time lapses shorter than 15 minutes, preferably shorter than 10 minutes, and even more preferably between 30 seconds and 5 minutes.
  • the degradation time of a drop of water is calculated, that is the time after a drop of water of 20 ⁇ l looses its shape, expanding and spreading on the material surface without becoming absorbed, followed by the absorption time on the material surface.
  • the plasma employed is an air or oxygen based plasma
  • the degradation time of a drop of water passes from 1 minute, for example, in the case of non plasma-treated materials, to less than a second in the case of treatment according to this invention.
  • the absorption time for a drop of water changes from 5 minutes to less than a second.
  • the duration of the hydrophilic effect in certain cases can be limited in time. Therefore, in the case where said process is used before the dyeing or coating stage, it may be necessary that the following re-wetting or dyeing or coating stages be performed within the successive two weeks.
  • plasma processing is applied to increase hydrophilic and wetting capacity, and can increase or even replace conventional mercerisation methods generally performed using chemical substances " containing chlorine or ammonia, or bleaching products such as hydrogen peroxide.
  • the reduction in absorption and degradation time of the water drop can also be obtained with microwave plasma at higher pressure as high as 200 mbar, or using a low frequency plasma, or yet again, using crown plasma at atmospheric pressure. In this last case, processing times are reduced considerably until they reach a period of less than a few seconds. As a result, it may be necessary to process the material several times to obtain the same effect obtained using plasma under vacuum.
  • a further advantage provided by plasma processing lies in the fact that the angle of contact is reduced considerably.
  • the angle of contact is a parameter used in this sector to calculate the wettability level of a surface: the lesser the value, the greater the wettability level (refer to table I) .
  • Table I contains certain results on the hydrophilic content obtained with atmospheric pressure plasma.
  • Material textile materials for printing that have already been through the printing process but have not yet been subject to impregnation and colour fixing obtained with high pressure and temperature vaporisation .
  • Example 2 Treatments of PET fabric using plasma in a vacuum.
  • Table II is a list of the treatment obtained using radio frequency plasma on PET fabrics before the colouring stage. It should be noted that it is possible to obtain permanent hydrophilic properties by increasing the processing time and/or polarising the sample (polar.) at negative potentials
  • plasma treatment activates the material surface by breaking the chemical bonds and by generating free radicals, modifying the roughness of the surface.
  • a material sample is processed with both plasma produced from a radio frequency source under vacuum, as well as plasma at atmospheric pressure.
  • Plasma is created with gases, for example electronegative gases, oxygen, C0 2 , air, and with chlorine, hydrogen, ammonia, inert gases, noble gases, inert gases and their blends.
  • gases for example electronegative gases, oxygen, C0 2 , air, and with chlorine, hydrogen, ammonia, inert gases, noble gases, inert gases and their blends.
  • the sample is mounted on a mobile support positioned in the chamber where a vacuum is created to produce a pressure- level lower than that used for plasma processing, which is less than 20 mbar.
  • the chamber is filled with gas at a pressure that can vary from 0,01 mbar to 20 mbar, preferably between 0.1 and 10 mbar, even more preferably between 0.2 and 3 mbar and the plasma is generated with a radio frequency source for a period less than 10 minutes, more preferably for a period between 30 seconds and 5 minutes .
  • gas at a pressure that can vary from 0,01 mbar to 20 mbar, preferably between 0.1 and 10 mbar, even more preferably between 0.2 and 3 mbar and the plasma is generated with a radio frequency source for a period less than 10 minutes, more preferably for a period between 30 seconds and 5 minutes .
  • crown plasma can be used with processing at atmospheric pressure with a gas such as air, noble gas, or inert gas for a period less than a second, and repeated up to a maximum number of 20 times.
  • a gas such as air, noble gas, or inert gas for a period less than a second, and repeated up to a maximum number of 20 times.
  • the plasma process is able to influence the first stage of this process, by both increasing surface affinity to colorants (by using reactive gas plasma, such as air) and by increasing the penetration speed of the solution into the fibres (improving the hydrophilic properties) , as well as by increasing the absorbency capacity of the colorant on the surface (increasing the extension through increased micro-roughness, and through etching phenomenon induced by the plasma) .
  • Dyeing was effectuated as described previously, at the Experimental Silk Station.
  • the chosen colours were Palanil Navy Blue (C.I. 4, dispersed in lg/1 concentration in the presence of lOml/l of acetic acid with a bath ratio of 1:300) and Palanil Yellow (C.I.64, dispersed in lg/1 concentration in the presence of 10ml of acetic acid with a bath ratio of 1:300) with opposing properties as far as diffusion speed was concerned.
  • Dyeing was performed using a dye bath containing an excessive amount of colorant. In this manner, samples treated with plasma under different types of condition, as well as non-treated samples were placed in the same dye bath, to prevent competitive effects among the various samples.
  • This method permits direct assessment of dyeing capacity improvement induced by plasma processing.
  • This method can be applied to facilitate material recycling, for example, for facilitating the removal of resin or chemical film from material surfaces or colorants.
  • the method for processing the aforesaid materials and fibres used in the specific sectors in question including the application of plasma according to this invention can also be used to clean material and fibre surfaces.
  • gases such as noble gases, and inert gases can be used, preferably nitrogen, oxygen, air, chlorine, ammonia, hydrogen, fluorated gases and their blends.
  • the plasma employed can be vacuum or atmospheric pressure type.
  • the aforesaid surface cleaning on materials can be realised using plasma under vacuum at a pressure 10 ⁇ 4 mbar and 20 mbar, for a period less than 20 minutes, preferably less than 10 minutes, and even more preferably for a period between 30 seconds and 5 minutes.
  • the power employed corresponds with that specified in the general part of the present description.
  • the processing time is reduced to the extent of only a few seconds and with a surprisingly uniform and hydrophilic surface.
  • the quantity of material removed is performed in a controlled manner and is under 20% of the total weight.
  • This method can be. used in any case for also removing resin from material surfaces.
  • the charged particles must be accelerated towards the sample, for both positive and negative ions.
  • the sample must be polarised at positive or negative potentials in relation to the plasma potential.
  • a further use for the material process with cold plasma application according to the invention lies in the fact that it is possible to obtain a water-repellent effect on material surfaces and the relative fibres.
  • plasma processing can be effectuated using fluorated gas in general, such as fluorocarbons, including for example, CF 4 , CFC, or NF 3 and WF 6 , silicon, silane and siloxane compounds - organosilanes such as hexamethyl-disiloxanes, hydrocarbons, styrenes, and their blends.
  • fluorocarbons including for example, CF 4 , CFC, or NF 3 and WF 6
  • silicon silane and siloxane compounds - organosilanes such as hexamethyl-disiloxanes, hydrocarbons, styrenes, and their blends.
  • the method preferably used to obtain water- repellent properties is with fluorocarbons, that is with a gas that permits the forming of numerous fluoro-carbon bonds, and with organosilanes and their blends.
  • Pressure ranges between 0,1 and 10 mbar, preferably between 0.2 mbar and 5 mbar, more preferably between 0.2 mbar and 3 mbar.
  • the electronic plasma is approximately 10 8 cm -3 while the density of ionic plasma reaches a value of 10 11 cm "3 .
  • Processing time is less than 15 minutes, preferably less than 10 minutes and even more preferably less than 5 minutes, and the power corresponds with that already specified previously.
  • the residual pressure is preferably between 3xl0 ⁇ 6 'mbar and 5xl0 ⁇ 5 mbar.
  • the distance between the sample and the antenna can be between 5 cm and 7.5 cm.
  • organosilanes are used, the residual pressure is between 2xl0 -3 mbar and 8xl0 ⁇ 3 mbar and the distance between the sample and the antenna is between 3 cm and 6 cm.
  • the material sample can also be mounted on a mobile support and positioned in a chamber that is evacuated to a pressure lower than that used for process gas, that is - less than treatment pressure. Following this stage, the chamber containing the sample is filled with gas and the plasma is generated with a radio frequency or low frequency source.
  • the water-repellent effect on materials and fibres does not depend on the source with which the plasma is realised, and can be obtained using radio frequency, microwave, or low frequency sources or crown plasma with pressure at approximately atmospheric pressure that contain numerous fluorine radicals or radicals from organosilanes. However the efficiency and the duration of the effect on the surface improve when the gas used for processing is a fluorated gas that contains CF 4 and its blends, hexamethyldisiloxane and its blends, preferably with oxygen or air.
  • the roll-off angle is reduced up to 10°. There are no traces of ring marks or surface swellings left by the water drop. The reduction of the roll-off angle means that drops of water can slide off the surface far more easily. This process is useful for making materials and fibres water-repellent without varying the organoleptic properties obtained through previous processing, while guaranteeing long duration at the same time.
  • Deposits on the surface are lower than ⁇ m, with organosilanes, preferably lOn and lOOnm. Moreover, permeability tests on gases demonstrate that water vapour and oxygen permeability are reduced, for example on plastic films used for packaging.
  • Oil repellent capacity was also assessed on samples using test-kit standards.
  • oil repellent levels are approximately H .
  • Organosilanes provide grade 1 oil repellent levels.
  • the applications of the aforesaid processing include materials and fibres which for example, can be used for solid and liquid foods, for woven and non-woven fabrics, technical fabrics (such as glass fibre or carbon fibre fabrics, blended fabrics) glass, metals, alcantara and relative fibres.
  • Table VII shows the results obtained on certain materials with organosilane blends (with oxygen) .
  • VI Process of grafting and deposit of polymers, organic and inorganic materials, and metals on material surfaces .
  • the applications of said process also include the generation of a surface barrier film on water repellent, flameproof, anti-static, and biocompatible surfaces.
  • a surface barrier film on water repellent, flameproof, anti-static, and biocompatible surfaces.
  • characteristics designed for use in other sectors such as waterproofing materials after dyeing, resistance to oxidising agents, protective coatings, metalising, printing improvement through material modification before printing, product protection against sunlight and UV radiation, polarising with monomers, barrier films against vapours or gas, synthetic polymer grafting on cellulose, and bio- degradable deposits.
  • the plasma can activate the surface during the deposit process (method a) ) , or the deposit stage can be preceded by the activation stage as described in process II) realising cyclic processes (method c) ) in which the sample is subject to plasma activation, and immediately after or during the activation, the surface is bombarded with gas, whose molecules (monomer or radical, for example) are grafted and/or deposited on the surface itself.
  • gas whose molecules (monomer or radical, for example
  • barrier film for food product protection against the light and UV radiation.
  • Parma Ham tends to oxidise certain amminoacids that contribute to the particular flavour and aroma under sunlight and in the presence of oxygen, vice versa by using a barrier film against radiation and oxygen on the film generally used for food packaging, it is possible to reduce or prevent oxidising.
  • barrier films are realised for organic substances of various types, useful, for example in all food packaging containing liquids, such as cartons for fruit juice, wine, and milk; this packaging must not release any of the. organic substances of which they are composed.
  • organic and inorganic deposits on material surfaces can be obtained using cold plasma containing acrylates, vinylic monomers, fluorocarbons, silanes, siloxanes, organosilanes, saturated hydrocarbons and their blends (method a) ) .
  • the surface can be activated according to process II) and polymers of various types and chemical substances of various kinds can be successively deposited during the gaseous stage under vacuum, several of these being already used in conventional processing (method b) or c) ) .
  • the liquid substances at standard pressure can be used in gaseous stage under vacuum, as long as the vapour pressure is approximately the same as or higher than that in the vacuum chamber.
  • pressures vary from 0,lmbar to 20 mbar, more preferably from 0.2 mbar 5 mbar, and even more preferably between 0.3 mbar and 3 mbar.
  • the layers can vary in thickness: for treatment that lasts only a few minutes, deposits of only a few decades of n are used, for treatment that lasts several decades of minutes, deposits can attain a thickness of over a micron.
  • Deposits can be used to modify the optical properties of materials, for example, to realise absorbent or reflective surfaces. In fact, the deposits are characterised by refraction indexes that can be controlled as necessary, and chosen according to the optical filtering that is required.
  • Certain special effects can be realised through the creation of areas that have a greater or lesser hydrophilic capacity and affinity to dyes for the creation of patterns and designs on materials or metalised areas for special visual effects, for example on fabrics for wearing apparel. These effects can be obtained using cold plasma activating the surface locally, or by depositing material with localised plasma, for example using a plasma brush realised through a limited source (cylindrical or spherical) mounted on a mobile support, that can be moved as required.
  • the processes described above can also be obtained with crown discharge ' , using methods a) b) or c) or d) , at atmospheric pressure that contains blends of the aforesaid gases with noble or inert gases or air.
  • This last method is important for depositing and/or grafting groups of various natures on surfaces, including hydrophobic and hydrophilic groups, and/or that have a close affinity with certain substances, and/or with specific properties such as anti-bacteria, anti-mildew, anti-static, flame-proof, biocompatible, barrier films, and EM radiation protection film.
  • deposits can be made successively, using conventional and non- conventional types, during the gaseous, liquid or solid stage such as that used in method d) ) .
  • the processing method of the aforesaid materials including the application of a plasma on the surface of said materials according to the invention, provides the possibility of satisfying the- requirements listed in the introduction to the present description, and to overcome the problems that exist with current state of the art processing methods at the same time.

Abstract

La présente invention concerne un procédé permettant l'usinage de textiles tissés et non tissés, de filés, de fibres naturelles et polymère, de fibres et films inorganiques, de verre et d'alcantara. L'invention concerne plus particulièrement un procédé permettant d'améliorer les caractéristiques de la surface et également la possibilité d'obtenir de nouvelles caractéristiques de la surface. Ce procédé comporte un traitement de la surface du substrat avec un plasma froid, pendant ou après un dégazage spécifique de la surface.
EP03817632A 2003-07-25 2003-07-25 Procede d'usinage au plasma de materiaux polymeres et inorganiques Withdrawn EP1649100A1 (fr)

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IT1398167B1 (it) * 2010-02-16 2013-02-14 Rovero Processo di tintura a stoccaggio (pad-batch) di articoli tessili comprendente una fase di trattamento con gas ionizzato o plasma.
DE102013212284A1 (de) 2012-06-26 2014-01-02 Zschimmer & Schwarz Mohsdorf GmbH & Co. KG Verfahren zur permanenten Verankerung von Farbstoffen auf der Oberfläche von Wildlederimitaten
US10131134B2 (en) * 2015-10-30 2018-11-20 Canon Kabushiki Kaisha System and method for discharging electrostatic charge in nanoimprint lithography processes
GB201708102D0 (en) * 2017-05-19 2017-07-05 Sensient Imaging Tech Sa Inkjet printing on polyester textiles
CN113737510B (zh) * 2021-09-30 2024-02-23 昆山豆奇电子科技有限公司 一种冷态等离子体高分子聚合物表面处理方法
CN114959941B (zh) * 2022-05-26 2023-01-03 百事基材料（青岛）股份有限公司 一种含茶、橙活性成分的涤纶大生物纤维及其制备方法

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