Plasma Treatment for the Production of High Added Value Textiles E. Fatarella 1, S. Bani 1, I. Cioni 1, U. Goransson 2, P. Van Hess 2 1 Next Technology Tecnotessile Società Nazionale di Ricerca r.l., Prato (Italy) 2 University of Lund (Sweden) chemtech@tecnotex.it
Introduction Chemical finishing has always been an import component of textile processing in recent years the trend to high-tech products has increased the interest and use of chemical finishes (source: Chemical Finishing of Textile) With fibers production currently about 60 M tonnes, about 6 M tonnnes of chemicals auxiliaries are consumed. About 40% of textile auxiliaries are used in finishing
Introduction Chemical finishing of textiles Antimicrobial products Non-slip products Antistatic products Repellents Hand builders Easy care products Flame retardants Remainder Coating, laminating, bonding products Softeners 0 5 10 15 20 25 Distribution of finishing product groups by amount (%) 7% (480,000 tonnes per year) of the worldwide production of FRs is committed to textile applications (source Flame Retardant Chemical RC004) whilst 200,000 tonnes per year of auxiliaries ars used for soil repellent finishing
Introduction FR products for Textile finishing Brominated compounds are identified as Priority Substances by the Water Framework Directive 2000/60/EC
Introduction Soil Repellent products for Textile finishing Fluorocarbon finishing facilitate the removal of soil from textile surface by reducing the superficial tension and soil pentration at fibere interface
Objective Production of Flameproof and Soil Repellent textile by means of Plasma Grafting of suitable compounds
Reaction Mechanism for Radical Addition Functional vynil molecule Covalent binding Radiation source Macroradical
Selection of suitable compounds able to react with active species generated by plasma X Phosphorilated compound for FR X X Fluorinated compound for Soil Repellency X (CH 2 ) n X O Acrylates are more reactive then vynil compounds in radical addition
Synthesis of acrylate for FR Di(acryloyloxyethyl)benzenephosphonate O O O O P O O O Selection of acrylate for Soil Repellency Zonyl TM Fluoromonomer (Fluka) O O F 2 C n CF 3 n = 8
FR grafting promoted by Plasma Spraying P-FR PLASMA Process Parameters Process Gases: Argon. Nitrogen Irradiative Process: 0.08 0.4 W/cm 2 Irradiation time: 30 300 s FR amount: 7.5 50%wt in ethanol Washing Procedure Washing in H 2 O Washing in H 2 O with surfactants
Optimal conditions Gas process: Argon Irradiative Power: 0.24 W/cm 2 Irradiation time: 180 s FR Amount: 7.5 50%wt in ethanol FR grafting promoted by Plasma ν P-O-C ν P=O
0,6 0,5 0,4 Optimal FR grafting promoted conditions by Plasma Gas process: Argon Molar ratio 0,3 Irradiative Power: 0.24 W/cm 2 0,2 0,1 Inflammable Irradiation time: 180 s FR Amount: 15 %wt FLAME in ethanol Molar Ratio: area ν P-O-C/area ν C-O-C Flame retardancy: Standard Test AATCC TM 34 (1969) 0 0 5 10 15 20 25 30 35 40 45 DAPB/PET [%wt]
Soil Repellent grafting promoted by Plasma Spraying Zonyl PLASMA Process Parameters Washing Process Gases: Argon. Nitrogen Irradiative Process: 0.08 0.4 W/cm 2 Irradiation time: 30 300 s Procedure Washing in H 2 O Washing in H 2 O with surfactants Soil Repellent amount: 7.5 50%wt in trichloroethylene
Soil Repellent grafting promoted by PLASMA PLASMA Process Parameters Process Gases: Argon. Nitrogen Irradiative Process: 0.08 0.4 W/cm 2 Irradiation time: 30 300 s FR amount: 7.5 50%wt in trichloroethylene Optimal conditions Gas process: Argon Irradiative Power: 0.24 W/cm 2 Irradiation time: 180 s Soil Repellent Amount: 7.5 50%wt in trichloroethylene
Soil Repellent grafting promoted by PLASMA Optimal conditions Gas process: Argon ν C-F Irradiative Power: 0.24 W/cm 2 Irradiation time: 180 s Soil Repellent Amount: 7.5 50%wt in trichloroethylene
0,9 A 0,8 0,7 0,6 0,5 0,4 0,3 Good water and oil repellency Poor water and oil repellency Optimal conditions Gas process: Argon Irradiative Power: 0.24 W/cm 2 0,2 0,1 0 Irradiation time: 180 s Soil Repellent Amount: 15 %wt in trichloroethylene Molar Ratio: area ν C-F/area ν C-O-C Oil repellency test: AATCC Standard test method 118-1984 e INDA Standard Test 80.7-92 0 5 10 15 20 25 30 35 40 45 Zonyl/PET [%wt] Washed with water Washed with water + surfactant
Combination of FR and Soil Repellency 1) Sparying Zonyl + DABP Plasma Not found a compatibiliser for the two active compounds Washing 2) Sparying Zonyl Plasma A Sparying DABP Plasma B Washing
A) Combination of FR and Soil Repellency ν C-F Antimacchia: AATCC Standard test method 118-1984 e INDA Standard Test 80.7-92 Flame retardancy: Standard Test AATCC TM 34 (1969)
B) Combination of FR and Soil Repellency ν C-F ν P=O Antimacchia: AATCC Standard test method 118-1984 e INDA Standard Test 80.7-92 Flame retardancy: Standard Test AATCC TM 34 (1969)
Combination of FR and Soil Repellency Contact angle measurements 107.77 1 111.43 84.42 0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00 Angolo di contatto - acqua - [ ] PET_NT PET_Fluoro PET_Fosfo PET_Fluoro_Fosfo
Combination of FR and Soil Repellency 35 LOI Test 30 29 27 27 27 25 21 LOI [%O2] 20 15 18 10 5 0 Untreated PET Trevira FR_Plasma FR_F_Plasma FR_UV Modacrylic Cotton
TGA Analysis %% 100 100 TGA PETPO PETNT (N2/aria 10 C/min) 15.11.2007 11.2007 12:28:02 13:52:55 %C^-1 0,0 80 80 60 60 40 40? Step -100,0612 % -9,8520 mg Step -8,5407 % -0,9730 mg Step -82,6776 % -8,1404 Step mg -76,3127 % -8,6935 mg Step -13,3920 % -1,5256 mg Esothermic reaction MinMax Min -0,24 C^-1 at 574,69 C -0,5 Max -0,18 C^-1-0,5 at 584,50 C MinMax Min -0,78 C^-1 at 546,15 C Max -0,19 C^-1 at 547,93 C -1,0-1,0 20 20 0 0 Step -98,0971 % -11,1752 mg MinMax MinMax Min Min -1,91-1,57 C^-1 C^-1 at 436,75 C at 436,98 C Max Max -1,21-1,45 C^-1 C^-1 at 447,03 C at 441,90 C -1,5-1,5-2,0 50 50 100 7 International 150 200 Conference 250 on Polymer 300 and Textile 350 Biotechnology 400 & 450 500 550 DCCI: Thermal Analysis METTLER TOLEDO STAR e System C
Cone Calorimeter Test _F The lower irradiative energy transferred to the sample induces: -Less srinking of PET (large surface available) -Lower ignition time -Lower heat released by the system (fire is less dangerous)
Conclusions Irradiative processes are promising for textile finishing! - Less environmetal impact - Dry processes - Good technical performances - Flexibility of the processes Suitable chemical precoursors can not always commercially available Acknowledgements The authors would like to thank the Tuscany Region for funding the project FR-TEX and the European Commission for giving the opportunity to perform Cone Calorimeter Test within a Community Research Infrastructures Action.