MANUFACTURE OF ELECTRO-MAGNETIC SHIELDING TEXTILES WITH CONDUCTIVE ORGANIC POLYMERIC COATING

Description

FIELD OF THE INVENTION

[0001] The present invention relates generally to the field of making wash-water resistant electrically conductive wearable woven textile materials coated with formulations containing intrinsically conductive polymer (ICPs) complex - poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as conductive additive, intended to provide effective protection against non-ionizing electromagnetic radiation (EMR) in frequency ranges that are considered as potential hazards to human health.

BACKGROUND OF THE INVENTION

[0002] Electromagnetic interference is a serious threat that affects both the normal function of sensitive apparatus and human health. The most common type of electromagnetic interference occurs in the radio frequency of electromagnetic radiation (EMR) spectrum from 10⁴ to 10¹² Hz. This energy can be radiated by computer circuits, radio transmitters, fluorescent lamps, electric motors, over-head power lines, lightning, and many other sources [1]. The most utilized microwave range can be defined as 1-40 GHz, as modern point-to-point, wireless, and satellite communications occupy this range. EMR shielding refers to the reflection, absorption and successive internal reflections (usually neglected) of EMR by a material, which may act as a shield against the penetration of the radiation [2]. Electrically conductive woven or knitted fabrics with particular EMR shielding properties due to their structure and flex ability, offer an opportunity to counter these threats. Furthermore textile materials can be subjected to a number of dyeing and finishing processes for providing additional functionality such as electrical conductivity and EMR shielding. There are various techniques to improve the conductivity of textiles: introduction of electrically conductive yarns (carbon fibres, metal fibre); metallization of fabrics or yarns (voltaic, vacuum vaporisation); lamination or coating of conductive layers on the fabric surface with metal particles, transparent organic metal oxides, carbon or intrinsically conducting polymers (ICPs). These conductive polymers are attractive alternative materials for EMR shielding. Comparing with some commonly used metallic shielding materials ICPs are not only reflecting but also absorbing EMR in the microwave frequency range [3, 4]. ICPs combine high conductivity, flexibility, good process ability, relatively low mass, low density and corrosion resistance comparing with metals [5]. The effects on the EMR shielding of the surface of electrostatic properties, the distribution of coating and coating deposit were investigated and compared with textile containing metalized yarns [6].

[0003] The studies of textiles coated with conductive polymers showed that they are not highly effective as EMR shielding materials owing to their medium-level conductivity and therefore large skin depth. Combined with the fact that coatings are naturally thin, they cannot act as effective reflective barriers to EMR. Textile fabrics with inherently conductive polymer coatings mostly demonstrate shielding effectiveness (SE) not exceeding 20 dB in the microwave frequency range [7-9]. However, for EMR shielding applications, typically shielding effectiveness (SE) of at least 20 dB (indicates that 99% of the electromagnetic energy is reflected or absorbed by the material) is needed. An SE of 30 dB indicates that 99.9% of the electromagnetic energy is reflected or absorbed by the material, with only 0.1% exiting the shielding material [10].

[0004] PEDOT:PSS as ICP is often chosen due to its commercial availability, stability, easy processing during film formation on various substrates and high conductivity comparing to other ICPs [11]. The advantages of this polymer system for textile applications were found out in study [8] - the highest attenuation of the electromagnetic energy among tested fabrics with different conductive additives (carbon, metalized yarns, different polymeric coatings) was obtained for fabrics coated with commercially available formulations of CLEVIOS (Heraeus Holding GmbH) based on PEDOT:PSS.

[0005] The application methods of PEDOT:PSS-based conductive polymers in/on to a textile substrate structure and their application thereof was discussed by Granch Berhe Tseghai et al. [31]. Various functional finishing of textile materials can be achieved through conventional dyeing and coating processes by applying chemical compounds that carries ionisable groups, which are a common feature of acid dyes [12]. Most acid dyestuffs acquire their acidity from the present of sulfonic acid functional groups (-SOsH) or nitro (-NO₂) groups in the molecule [13]. Acid dyes being water-soluble anionic dyes are used primarily to nitrogenous fibres such as wool, silk and nylon, all of which contain basic groups [14]. Researches assigned PEDOT:PSS to a "conducting acid dye" which can also tightly bind to protein fibres through electrostatic interaction of PSS chain negatively charged sulfonate (-SO₃^-) ions to protein fibre cationic sites [12]. The fabrication of wash and wear resistant conductive silk threads dyed by conjugated polyelectrolytes was investigated by Müller and Ryan [15-17,32]. A simple method for preparing conductive fabric with different fibre content by soaking in a PEDOT-PSS dispersion was presented in [33]. The fabrication of all-organic conductive wires was demonstrated by utilizing different patterning techniques to apply PEDOT:PSS onto nonwoven polyethylene terephthalate (PET) fabric [34].

[0006] The research of interaction between protein-based fibres and ICPs, PEDOT:PSS and poly(4-(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT:S), at different pH and a given to protein fibres conductivity was carried out in study [18]. The synthetic polyamide being the long chain polymers with recurring cationic amide (-CONH-) groups exhibited similar properties and can ionically bond as protein fibres. An adhesion for polyamides by plasma-treatment applied prior to glycerol doped - PEDOT:PSS polymer coating was improved in study [19]. Some trials to dye cotton yarns with PEDOT:PSS formulations were carried out by [16].

[0007] It is observed that the wash and wear resistance of PEDOT:PSS-coated fibers and textiles remains a challenge [16, 20, 21].

[0008] The regular PET and cotton can't be dyed by acid dyes due to the neutral substantivity of anionic dyes to these fibres. The fabrication of all-organic conductive wires by using patterning techniques such as inkjet printing and sponge stencil to apply PEDOT:PSS onto nonwoven polyethylene terephthalate (PET) fabric was reported by Y. Guo et al. [22].

[0009] It is known that cationization can increase the neutral substantivity of anionic dyes for cotton through introduction of positively charged sites on this fibre [23]. The cationic sites containing acid-dyeable polyester might be prepared by chemical modification with secondary amine derivatives or aminolysis reaction with ethylene diamine as reported by B. Dumecha [24]. Conducting polymer, PEDOT:PSS, ultrathin films with high absolute electromagnetic interference (EMI) SE is highly desirable for their facile processability [25]. However, PEDOT:PSS film is prone to delaminate and disperse due to a presence of a water-soluble PSS chain [26] and this limits their use for EMR shielding [25]. Researchers [27] found that after introducing of divinylsulfone (DVS) crosslinking of the PEDOT:PSS occurs at a room temperature without reduction of its electronic conductivity. DVS having two S-vinyl substituents with two reactive groups at opposite ends of the molecule that are capable of reacting with and thereby forming bridges between macromolecules can react as a crosslinking agent. Study performed by D. Mantione et al. [27,30] identified that the reaction between PEDOT:PSS and DVS possibly is a physical crosslinking.

[0010] U.S. Patent application No. 14/638,793 discloses a method of making an electrically conductive cotton material by incorporating conductive poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) films into a base cotton substrate by drop casting or dip coating. The amount of PEDOT: PSS used in the fabrication process controls the conductivity and sheet resistance of the conductive cotton material, and can be varied by the number of repeated drop casting or dip coating cycles.

[0011] This patent application declares that it can be customized for protection from electrostatic discharge (ESD) as well as EMR, however the electromagnetic shielding effectiveness of this conductive cotton material therein was not evaluated and specified. Also this patent application's disadvantage is that the values of parameters such as the ICP content, resistance and sheet resistance in a conductive cotton material are dependent on how many times the drop casting or dip coating and drying at 90 - 110° C cycles were performed and as a substrate only fabrics made from cotton are suitable. For EMR shielding textiles the sheet resistance should be around 1000 Ω/sq. [28, 29]. However, EMR shielding effectiveness depends not only on resistance, but also on other parameters. Such parameters as shield thickness, structural parameters of fabric, skin depth of shield used, etc. are affecting the performance of shielding materials. As explained in this method of making conductive cotton, not less than 3 times of drop casting or dip coating and drying cycles are required to fulfil this requirement. After this triple treatment with PEDOT:PSS the sheet resistance value in the network cotton fabric was 148.2621Q/sq. It means that in this patent application disclosed method of making an electrically conductive cotton material using organic conductive polymer such as PEDOT:PSS is time consuming and energy-intensive.

[0012] U.S. Patent application No. 12/442,200 discloses making of device for camouflaging objects and/or persons. A knitted or woven material is proposed for camouflaging objects or persons, having a coating that comprises or has at least one conductive polymer (ICP). Suitable substances for the coating are conductive polymers, for example based on polythiophene (PEDOT).

[0013] The efficiency of the camouflage material against radar radiation produced according to this invention was evaluated by shielding of the reflection however results of total shielding (SE) there were not introduced.

[0014] In this patent a radar-shielding textile materials are described, where as a substrate only fabrics made from synthetic fibres are suitable. Moreover the production of proposed fabrics is relatively complicated, as besides coating, containing ICPs polymer, it includes insertion of metal threads into the fabric by in-weaving or by knitting in. Besides the silver coated threads proposed in this invention are quite expensive.

[0015] According to this patent application of proposed fabrics includes clothing (camouflage suit for a troop or soldier), therefore resistance performance (resistance to washing, abrasion and other impacts) is of great importance. However, in this patent only the possibility of resistance performance improvement (additional cross-linking) is mentioned (using polyurethane dispersion and melamine), but there is no data presented regarding the change of shielding properties both after additional cross-linking and after, for example, washing procedures Patent application No. CN108330684A discloses a method of making multifunctional polypyrrole (PPy) adopted cotton fabric with long-lasting electrical conductivity, electromagnetic shielding, water repellence, UV protection and other functions. However, the result of electromagnetic shielding 32 dB in the microwave range 8-12 GHz was achieved after multiple immersion (from 1 to 6 times) in water dispersion of carboxylated multiwall carbon nanotubes (MWCNT-COOH) and then in a pyrrole solution, respectively. It means that process of making polypyrrole adopted cotton fabric is complicated and prolonged. Moreover, usage of strong oxidative agents (especially ferric chloride hexahydrate (FeCl₃• 6H₂O) for pyrrole polymerization can significantly reduce the strength of cotton fabric.

SUMMARY OF THE INVENTION

[0016] In this invention EMR shielding woven fabrics on the basis of wool, polyamide and cotton as well as these fibres' blends coated with conductive polymer PEDOT:PSS formulations were developed and characterized. The aim of this invention also is the creation of water-wash resistant conductive crosslinked PEDOT:PSS film on the above mentioned woven textile materials, to improve the resistance performance of coated fabrics. The present invention in one aspect is based on idea of electrostatic interaction among the water soluble conjugated polyelectrolyte PEDOT:PSS negatively charged sulfonate counter ions with protonated amino groups in the wool and amide bonds in the polyamide as well as positively charged sites of chemically modified cotton. This invention idea in another aspect is based on non - dispersible and non - delaminable conductive polymeric coating on textile material formation through PEDOT:PSS and divinylsulfone (DVS) physical crosslinking which can cause a coagulation of conductive polymer dispersion and decrease in its water solubility but not affect its electrical conductivity [27].

[0017] Coating of the woven fabric with conductive polymer formulation can take place using successive dyeing in exhaust and at least one of roll-to-roll processes such as air knife coating, knife-over-roll coating, gap coating, flat screen and rotary printing methods.

[0018] Before the coating of PEDOT:PSS formulation is applied, textile containing basic groups (amide or peptide groups in the nitrogenous fibres such as wool, silk and polyamide) is preferably pre-activated with low-temperature or atmospheric plasma of inorganic (N₂, O₂, Ar, NH₃, air) gases. This treatment imparts the hydrophilicity, increases adhesion, improves dye ability and ensures that more of PEDOT:PSS negatively charged sulfonate counter ions are electrostatically bound with cationic sites of nitrogenous fibres.

[0019] The pure wool textile fabrics should have an anti-felting finish to impart shrink-resist and prevent felting in order to maintain the original qualities of the fabric surface during washing. The cotton containing textile fabrics should be chemically modified with cationic polymer (for example aziridine, homopolymer, hydrochloride or chloride salt of trimethylammonioethyl acrylate homopolymer) or reactive epoxy groups containing polyamonium compound before the PEDOT:PSS is applied. This cationic treatment increases the neutral substantivity of PEDOT:PSS for cotton as a "conducting acid dye" by introducing positively charged sites on the cotton.

[0020] For improvement of washing resistance, a cross-linker is required which provides the durability and insolubility of conductive PEDOT:PSS film.

[0021] The investigated coated fabrics were characterized by EMR shielding effectiveness (SE) within 4-18 GHz frequency range. Experimental investigations into reflection and transmission of electromagnetic waves normally incident on fabrics have been performed in the far-field area, using a semi anechoic chamber. Results of transmittance are presented in a form of EMR shielding effectiveness SE expressed in decibels. SE was evaluated before and after 5 washing cycles. Washing procedures were performed according to EN ISO 6330 standard, at 40 °C (procedure 4N - normal. The values of SE (dB) obtained before washing, have shown that applied conductive coating may provide sufficiently high EMR shielding - SE ≥20 dB.

BRIEF DESCRIPTION OF THE FIGURES

[0022] 

Fig.1. SE (dB) of PEDOT:PSS coated wool fabric - Sample 1: a) before washing), b) after 5 washing cycles at 40 °C.

Fig.2. SE (dB) of PEDOT:PSS coated cotton/polyamide fabric - Sample 2: a) before washing, b) after 5 washing cycles at 40 °C.

DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention will be explained in greater detail, using an exemplary embodiment that will be described in the following, as an example.

[0024] For manufacturing EMR shielding materials, two types of woven fabrics were used: wool fabric with anti-felting finish (substrate for Sample 1) and cotton/polyamide (80%/20%) blended fabric (substrate for Sample 2), having a mass per unit area, respectively, 123 g/cm² and 257 g/m2.

[0025] Before coating the cotton/polyamide fabric was cationically modified with 4% Denimcol Fix-GF based on aziridine, homopolymer, hydrochloride (CHT/BEZEMA, Germany/Switzerland), pH 9, at 30 °C, 30 min.

[0026] For the initial coating, the aqueous dispersions from company Heraeus Holding GmbH with the name CLEVIOS F ET and CLEVIOS S V3, respectively, i.e. based on conjugated polymer system poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate were used.

[0027] Initial coating of the woven wool fabric with anti-felt finish ( Sample 1) and woven cationized cotton/polyamide (80%/20%) blended fabric (Sample 2) was done in accordance with usually used in textile industry immersion coating method (dyeing in exhaust) at 90 °C for 30 min. in a bath based on PEDOT:PSS formulation - CLEVIOS F ET according to following recipe:

- CLEVIOS F ET:	500 - 998 ml
- Acetic acid 50%:	1 - 2 ml
- Water:	498 - 0 ml

[0028] After initial coating with PEDOT:PSS formulation CLEVIOS F ET, Sample 1 and Sample 2 were squeezed out slightly in padder at 1.5 bar and dried at 110 °C by means of hot air for example, for approximately 240 sec;

[0029] Previously coated with CLEVIOS F ET woven fabrics - Sample 1 and Sample 2 were additionally coated with CLEVIOS S V3 in accordance with generally known knife over roll coating method. In order to achieve homogenous conductive PEDOT:PSS film, the CLEVIOS S V3 before coating was carefully stirred at 1000 rpm for 3 min.

[0030] After this second coating, fabrics were dried at 1 10 °C by means of hot air in oven, for example, for approximately 300 sec. Conductive coating deposit was approximately 9-10 g/m²for Sample 1 (wool fabric) and 16-18 g/m²for Sample 2 (cotton/polyamide blend fabric).

[0031] Crosslinking of conductive film, which is on the surface of PEDOT:PSS coated fabrics, was performed by means of immersion in a bath based on divinyl sulfone dissolved in water in the following recipe:

- Divinylsulfone:	1 - 2 %
- Water:	99-98 %

[0032] The conductive coated fabrics (Sample 1 and Sample 2) were immersed in the aforementioned bath through impregnation in padder, squeezed out slightly at 2 bar and kept up at 50 °C for crosslinking of PEDOT:PSS by means of hot air, for approximately 60 min., slightly rinsed with water and dried at 100 °C, for example, for approximately 240 sec.

[0033] After the fabrics have been dried, they were subjected to reflection and transmission measurements into microwave range. The investigated coated fabrics were characterized by EMR shielding effectiveness (SE) within 4-18 GHz frequency range.

[0034] Measurement results for the developed conductive wool (Sample No.1) and cotton/polyamide blended (Sample No.2) fabrics treated with PEDOT:PSS are presented, respectively, in Fig. 1 and Fig.2.

[0035] The values of SE (dB) obtained before washing, have shown that applied conductive coating may provide sufficiently high EMR shielding, whereas for both tested samples SE was ≥20 dB in all investigated frequency range (see Fig. 1 and 2). After washing procedures EMR shielding properties of these fabrics slightly decreases, but nevertheless remains satisfactory: for Sample No.1 - SE is on average 17.5 dB (see Fig. 1), for Sample No.2 - SE is on average 18.5 dB (see Fig. 2).

[0036] The fabrics with conductive coatings can be considered as a thin layer with particular surface conductivity σ = 1/R where R is surface resistance. Those values for tested samples were calculated with reference to reflection and transmission measurement data. The values of σ and R, calculated as indicated above, strongly correlate with shielding effectiveness in the tested frequency range. Table 1 contains the results of surface resistance of Sample 1 and Sample 2 before washing and after 5 washing cycles at 40 °C.

Table 1. Surface resistance results.

N° of sample	Surface resistance R, Ωm
	Before washing	After 5 washings cycles
SAMPLE 1	21.3	28.8
SAMPLE 2	23.8	25

LITERATURE

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35. US14/638,793

36. US 12/442,200

37. CN108330684A

Claims

1. A method for coating of woven materials with a PEDOT:PSS polymer complex, wherein the coating comprises the steps of:

a) initial coating by dyeing in exhaust of woven fabrics with an aqueous solution of PEDOT:PSS polymer complex at 80-95 ºC for 20-45 min,

b) removing water by drying at 100-120 ºC for 100-300 sec,

c) additional coating by knife over roll at room temperature with an aqueous solution of PEDOT:PSS polymer complex,

d) removing water by drying at 100-120 ºC for 100-300 sec,

e) crosslinking with organic compound.

2. The method according to claim 1, wherein the organic compound of step e) is divinyl sulfone.

3. The method according to claims 1 and 2, wherein the woven material is either a cotton/polyamide blend or wool fabric.

4. The method according to claims 1 to 3, wherein the woven wool fabric has anti-felt finish.

5. The method according to claims 1 to 4, wherein the woven cotton/polyamide fabric at the beginning is cationically modified with at least one compound selected from aziridine, hydrochloride or chloride salt of trimethylammonioethyl acrylate homopolymer or other reactive epoxy groups containing polyamonium compounds.

6. A woven fabric produced by the method according to claims 1 to 5, characterized by EMR shielding properties, as defined in the description, within 4-18 GHz frequency range.

Ansprüche

1. Verfahren zum Beschichten von Webstoffen mit einem PEDOT:PSS-Polymerkomplex, wobei die Beschichtung die folgenden Schritte umfasst:

a) anfängliches Beschichten durch Ausziehfärbung der Webstoffe mit einer wässrigen Lösung eines PEDOT:PSS-Polymerkomplexes 20 bis 45 Minuten lang bei 80 bis 95 °C,

b) Entfernen des Wassers durch Trocknung 100 bis 300 Sekunden lang bei 100 bis 120 °C,

c) zusätzliches Beschichten durch "knife-over-roll" auf Umgebungstemperatur mit einer wässrigen Lösung eines PEDOT:PSS-Polymerkomplexes,

d) Entfernen des Wassers durch Trocknung 100 bis 300 Sekunden lang bei 100 bis 120 °C,

e) Vernetzen mit einer organischen Verbindung.

2. Verfahren nach Anspruch 1, wobei die organische Verbindung aus Schritt e) Divinylsulfon ist.

3. Verfahren nach Anspruch 1 et 2, wobei der Webstoff entweder eine Baumwoll-/Polyamid-Mischung oder ein Wollgewebe ist.

4. Verfahren nach Anspruch 1 bis 3, wobei der Wollwebstoff eine Antifilzbehandlung aufweist.

5. Verfahren nach Anspruch 1 bis 4, wobei das Baumwoll-/Polyamid-Gewebe zu Beginn mit mindestens einer Verbindung, die aus Aziridin, Hydrochlorid oder Chloridsalz eines Trimethylammoniumethyl-Acrylat-Homopolymers oder anderen reaktiven Epoxidgruppen, die Polyammoniumverbindungen enthalten, ausgewählt wird, kationisch modifiziert wird.

6. Webstoff, hergestellt durch das Verfahren nach Anspruch 1 bis 5, gekennzeichnet durch EMR-Abschirmeigenschaften, wie in der Beschreibung definiert, in einem Frequenzbereich von 4 bis 18 GHz.

Revendications

1. Procédé permettant d'enduire des matériaux tissés d'un complexe polymère PEDOT:PSS, l'enduction comprenant les étapes suivantes :

a) enduction initiale par teinture par épuisement de tissus tissés avec une solution aqueuse d'un complexe polymère PEDOT:PSS à 80 à 95 °C pendant 20 à 45 minutes,

b) retrait de l'eau par séchage à 100 à 120 °C pendant 100 à 300 secondes,

c) enduction supplémentaire par « knife-overroll » à température ambiante avec une solution aqueuse d'un complexe polymère PEDOT:PSS,

d) retrait de l'eau par séchage à 100 à 120 °C pendant 100 à 300 secondes,

e) réticulation avec un composé organique.

2. Procédé selon la revendication 1, dans lequel le composé organique de l'étape e) est du divinyl sulfone.

3. Procédé selon les revendications 1 et 2, dans lequel le matériau tissé est soit un mélange de coton/polyamide, soit un tissu de laine.

4. Procédé selon les revendications 1 à 3, dans lequel le tissu de laine tissé présente une finition anti-feutrage.

5. Procédé selon les revendications 1 à 4, dans lequel le tissu de coton/polyamide tissé est au début modifié de manière cationique par au moins un composé sélectionné parmi l'aziridine, l'hydrochlorure ou le sel de chlorure d'un homopolymère d'acrylate de triméthylammonium éthyle ou d'autres groupes d'époxydes réactifs contenant des composés de polyammonium.

6. Tissu tissé produit par le procédé selon les revendications 1 à 5, caractérisé par des propriétés de blindage REM, telles que définies dans la description, dans une plage de fréquence de 4 à 18 GHz.

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