INTERFACE PHENOMENA OF CATIONIZED COTTON WITH EPTAC

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1 OF CATIONIZED COTTON WITH EPTAC Ana Marija GRANCARIĆ Anita TARBUK Marijn M.C.G. WARMOESKERKEN INTRODUCTION The most important phase in cotton pretreatment and finishing is adsorption of chemical substances and compounds on textile material surface and wet ability as well. Due to existing repulsion forces, adsorption of dyestuffs, fluorescent whitening agents and other textile auxiliaries is not easy to perform. This can be overcome with large amount of electrolyte addition, what is economically and ecologically unfavorable. 1

2 One of cotton modification is cationization using amines and/or quaternary ammonium compounds. H H H C C O H C H CH 3 N + CH 3 CH 3 + OH - + Cel-OH H Cel H C O H H C C OH H CH 3 N + CH 3 CH 3 EPTAC Cationized cotton In this paper, modification of cotton fabric for achieving electropositive charge was carried out by cationization with 2,3-epoxy-propyl-trimethyl ammonium chloride (EPTAC) before, during and after the mercerization process. Different treatments, and mostly alkaline modifications, change surface charge and adsorption ability of fibers. Interface phenomena, which happen between liquid and solid phase, like water solution and textile material, result in change of textile surface free energy. Electrokinetic phenomena, as zeta potential and specific amount of surface charge, characterize electric charge of textile material, while contact angle characterize its wet-ability. The effect of modification on the change of fabric zeta potential, surface free energy, contact angle, specific amount of surface charge, ionic surfactant and dyestuff adsorption ability were discussed. 2

Fabric B BM BE BEM BME MATERIAL Pretreatment of cotton fabric Standard adjacent bleached fabric of 100% cotton Mercerization (24% NaOH, 8 g/l Subitol MLF)

(Sigma) LR 1:20 35 g/l 50% NaOH ph = 13,0 8 g/l Subitol MLF (Bezema) t = 120 s T = 18 C staying at the room temperature for 24 hours in a glass with plastic cover

Firstly, the cotton fabrics modification by cationization was researched through structural properties of fabrics: FTIR-ATR Fourier Transform Infrared Attenuated

3 Fabric B BM BE BEM BME MATERIAL Pretreatment of cotton fabric Standard adjacent bleached fabric of 100% cotton Mercerization (24% NaOH, 8 g/l Subitol MLF) Bleaching, cationization* (EPTAC) Bleaching, cationization during the mercerization Bleaching, cationization after mercerization *CATIONIZATION 50 g/l EPTAC (Sigma) LR 1:20 35 g/l 50% NaOH ph = 13,0 8 g/l Subitol MLF (Bezema) t = 120 s T = 18 C staying at the room temperature for 24 hours in a glass with plastic cover rinsed and neutralized until ph 7 METHODS The effect of modification on the change of fabric interface phenomena were discussing. Firstly, the cotton fabrics modification by cationization was researched through structural properties of fabrics: FTIR-ATR Fourier Transform Infrared Attenuated Total Reflection Spectrum GX FT-IR (Perkin-Elmer) TGA Thermogravimetric analysis SDT 2960 (TA Instruments) Temp. range: 25 C C Heating rate: 10 C/min Nitrogen atmosphere with a flow rate of 50 ml/min. 3

4 FTIR-ATR 102, , , ,5 3333,3 %T , B BM BE BME BEM 1054,4 1028,6 985,0 1002,8 32,0 4000, ,0 cm-1 TGA B BM BE BME BEM m [%] T [ C] 4

Interface phenomena was investigated throughout the change of: Fabric

adsorption, Ionic surfactant adsorption, Dyestuff adsorption, Zeta potential,

HYDROPHILICITY Characteristic Standard Instrument METHODS SNV 9858:1952 vertical

5 Interface phenomena was investigated throughout the change of: Fabric hydrophilicity, Contact angle Pore volume distribution Surface free energy Water adsorption, Ionic surfactant adsorption, Dyestuff adsorption, Zeta potential, Isoelectric Point, Point of Zero Charge, Specific amount of surface charge HYDROPHILICITY Characteristic Standard Instrument METHODS SNV 9858:1952 vertical test horizontal test Hydrophilicity Chibowski method AATCC Absorbency of Bleached Textiles Drop test 5

6 HYDROPHILICITY Fabric t Drop Test [s] t vertical [s/ 5 cm] t horizontal [s/ 5 cm] B 0 348,8 44,2 BM 0 277,8 37,1 BE 0 300,0 39,4 BME 0 263,2 35,7 BEM 0 254,2 34,8 Contact angle, θ Good wetting Low wetting 1. Hydrophobic surface θ >> Border case θ = Hydrophilic surface θ << 90 6

Structural contact angle and pore volume distribution (TRI auto-porosimeter) cosθ test = γ γ ref test P P test ref θ - structural contact angle within porous network γ ref - surface tension of the

7 Structural contact angle and pore volume distribution (TRI auto-porosimeter) cosθ test = γ γ ref test P P test ref θ - structural contact angle within porous network γ ref - surface tension of the reference liquid (1% Triton X-100) γ test - surface tension of the test liquid (double distilled water) P - Laplace pressure difference across the liquid/air meniscus CONTACT ANGLE measurements is a practical tool for surface characterization. Contact Angle, θ Test liquid of known values γ d, γ p, γ γ sl γ lv θ γ sv cos θ + Models for determination γ ij i.e. γ sl Based on Young s equation and different approaches γ sv = γ sl + γ lv cosθ calculation γ s d,γ s p,γ s LW,γ s +,γ s - γ s = γ s d + γ s p γ s = γ s LW + γ s AB 7

Surface Free Energy, SFE Fabric B BM BE BME BEM Contact angle [ ] θ water θ formamide θ diiodomethane LW SFE (acid-base model) + - AB TOT The surface free energy and pore volume distribution (PVD)

8 Surface Free Energy, SFE Fabric B BM BE BME BEM Contact angle [ ] θ water θ formamide θ diiodomethane LW SFE (acid-base model) + - AB TOT The surface free energy and pore volume distribution (PVD) depends on contact angle measurement. Unfortunately, all the tested fabrics with all test liquids formed a zero contact angle; therefore it was not possible to calculate cos θ, pore radius and distribution or the components of surface free energy (SFE) according to acid-base, Owens-Wendt and Wu. Surface Free Energy, SFE Liquid penetration rate e.g. Bleached fabric, B. Bare fabrics: - - n-heptane, - - water, - - formamide; Thin-layer wicking method according to Chibowski Precontacted fabrics with liquid saturated vapour: - - n-heptane, - - water, - - formamide. t [s] y = 8,25x - 21,25 R 2 = 0,985 y = 4,91x - 22,09 R 2 = 0,940 y = 3,83x - 16,97 R 2 = 0,980 y = 0,77x - 2,10 R 2 = 0, x 2 [cm 2 ] y = 0,64x - 3,18 R 2 = 0,981 y = 0,47x - 1,84 R 2 = 0,985 8

9 Surface Free Energy, SFE Thin-layer wicking method according to Chibowski Washburn 2 x R = γ L t 2η G = W A W C x t 2 R = G 2η van Oss 2 x R = ( γ L cosθa ) t 2η 2 x R = ( γ L cosθr ) t 2η LW - apolar Lifshitz -van der Waals - - polar electron donor + - electron acceptor γ L LW ; γ L- and γ L+ are known. L x - penetrated distance, R - effective radius, t - penetration time of the distance x, η- liquid viscosity and G - free energy change γ L - liquid surface tension W A - work of adhesion W C - work of cohesion θ r - dynamic receding contact angle θ a - dynamic advancing contact angle γ (cosθ cosθ ) = W W WA a LW LW + + = 2 γ S γ L + 2 γ S γ L + 2 γ Sγ L r A C Surface Free Energy, SFE Fabric LW + - AB TOT R [µm] W S B 34,21 1,29 51,68 16,33 50,54 11,35-6,89 BM 43,03 0,13 58,45 5,57 48,60 7,05-3,45 BE 40,71 3,23 41,59 23,20 63,92 7,73-2,71 BME 41,44 4,37 37,43 25,58 67,02 10,23-2,58 BEM 37,43 5,02 39,31 28,09 65,52 14,72-2,52 9

ELECTROKINETIC PHENOMENA Zeta Potential, ζ Charge reversal part of the total potential drop - intermediate

electric double layer moving of two charged surfaces results by zeta potential ELECTROKINETIC PHENOMENA Zeta

SURFACTANT ADDITION Point of Zero Charge (PZC) U p η L ζ = ε ε 0 Q R p U p - streaming potential, ζ - zeta

10 ELECTROKINETIC PHENOMENA Zeta Potential, ζ Charge reversal part of the total potential drop - intermediate surface layer - solid/liquid phases - consequence of ions distribution interface fiber/aqueous solution - electric double layer moving of two charged surfaces results by zeta potential ELECTROKINETIC PHENOMENA Zeta Potential, ζ Streaming current/potential method Electro Kinetic Analyzer, EKA (A. Paar, Austria) ZETA POTENTIAL vs. ph Isoelectric Point (IEP) ULAZ Helmholtz-Smoluchowsky IZLAZ ZETA POTENTIAL vs. SURFACTANT ADDITION Point of Zero Charge (PZC) U p η L ζ = ε ε 0 Q R p U p - streaming potential, ζ - zeta potential, ε o - permittivity of vacuum, ε - dielectric constant, η - dynamic viscosity of solution, R - electrical resistance, Q - cross-section of capillary, L - capillary length and Δp - pressure difference between the inlet and outlet of capillary system. 10

ELECTROKINETIC PHENOMENA PCD, Muetek, Germany Specific Surface Charge, q Back titration method q (V 0 surfac tan t = V ) c F V V q surfactant - amount of fabric charge in a specific surfactant per 1

11 ELECTROKINETIC PHENOMENA PCD, Muetek, Germany Specific Surface Charge, q Back titration method q (V 0 surfac tan t = V ) c F V V q surfactant - amount of fabric charge in a specific surfactant per 1 g of fabric c - concentration of the titrant F - Faraday constant V 0 - used up volume of the titrant for the titration of the starting solution V - used up volume of the titrant for the titration of the solution after the dwell process of fabric V x - total volume of the solution where fabric dwelt V w - taken volume of the solution after dwelling for the determination of charge q fiber w q = NDDS + q m x fiber N-CPC ELECTROKINETIC PHENOMENA B BM BE BME BEM 5 Zeta Potential, ζ ζ [mv] ph Zeta potential (ζ) of the cotton fabrics vs. ph of M KCl 11

12 15 ELECTROKINETIC PHENOMENA 10 B BM BE BME BEM 5 Zeta Potential, ζ ζ [mv] [µg/ml] Zeta potential (ζ) of the cotton fabrics vs. N-CPC addition in M KCl at ph 10 ELECTROKINETIC PHENOMENA Fabric ζ at ph 9 [mv] IEP [ph] PZC [μg/ml] q [C/g] B -20,9 <2,5 67,11-2,26 BM -24,7 <2,5 74,84-1,39 BE -1,5 5,4 1,34 2,16 BME 0,5-1,90 3,19 BEM 0,9-4,06 3,94 12

ADSORPTION Water Retention Value (WRV) According to ASTM D

centrifuged mass test sample G tr dry mass of test sample

dodecyl sulfate (SDS) cationic surfactant -

(Hanau) c = 0,001 M T = 40 C t = 30 min ph 7 Amount of adsorbed

13 ADSORPTION Water Retention Value (WRV) According to ASTM D Water adsorption G f Gtr WRV = G of tr 100[%] G f centrifuged mass test sample G tr dry mass of test sample ADSORPTION Surfactant adsorption anionic surfactant - sodium dodecyl sulfate (SDS) cationic surfactant - dodecyltrimethylammonium bromide (DDTMAB) in Linitest, Original (Hanau) c = 0,001 M T = 40 C t = 30 min ph 7 Amount of adsorbed surfactants was determined indirectly from solution using potentiometric titration method on Titrino 736 (Metrohm). 13

14 Dyestuff adsorption ADSORPTION DYEING 0,1 %; 1 %; 10 % owf Benzopurpurin 4B (Sigma; C.I. 2350; Direct Red 3) LR 1:30 T = 100 C t = 90 min in Linitest (Hanau) neutralization 1 % CH 3 COOH rinsing until ph 7 Dyestuff concentration in the bath was monitored as absorbance on spectrophotometer Cary 50 (Varian) ADSORPTION B BM BE BME BEM w abs [%] WRV 0,001 M SDS 0,001 M DDTMAB 0,1 % owf 1 % owf 10 % owf Benzopurpurin 4B 14

15 CONCLUSION Systematic study of interface phenomena of modified cotton fabrics sets the base that can be used to predict the behavior of cotton in the wet finishing processes, and to some extent to assess the value and utilization characteristics, and environmental acceptability of the product for a particular application. By comparing mercerized and cationized cotton, it was concluded that cationization during the mercerization process with short chain cationic compounds results in new material and a new dimension to cotton pretreatment and finishing. CONCLUSION The modified cotton retains all the beneficial properties of mercerized cotton with a change of surface charge that ensures further quality improvement. It was found that cationization with short chain cationic compounds completely change the system dyestuffcotton fiber and do not obey any known law, which indicates the necessity of further investigations of such modified cotton. Except the above, this modification presents an exceptional potential for environmental disposal of waste as well, since such modified cotton fully adsorbs anionic dyestuff. 15

16 Ana Marija Grancarić Anita Tarbuk Marijn M.C.G. Warmoeskerken 16

ELECTROKINETIC PHENOMENA OF 3-AMINOPROPYLTRIETHOXYSILANE-BASED COTTON FINISHING

ELECTROKINETIC PHENOMENA OF 3-AMINOPROPYLTRIETHOXYSILANE-BASED COTTON FINISHING Ana Marija Grancarić 1, Giuseppe Rosace 2, Anita Tarbuk 1, Claudio Colleoni 2 1 University of Zagreb, Faculty of Textile