53 rd Man-Made Fibers Congress, Dornbirn Dr. Roland Scholz, Kelheim Fibres GmbH

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1 53 rd Man-Made Fibers Congress, Dornbirn Dr. Roland Scholz, Kelheim Fibres GmbH 1

2 Food filtration Reactive modification Absorbency Intrinsic modification Surface modification 2

3 Permanent Finishing of Ionically Activated Viscose Fibres - Dr. Roland Scholz 3

4 Ionically Activated Viscose Fibres and their Applications Overview 1. Ionic activation of viscose fibres 2. Interaction of ionically activated fibres with polyelectrolytes 3. Properties of ionically activated fibres, before and after finishing with polyelectrolytes dyeing of fibres water imbibition fastness to washing of activation 4. Summary and conclusions 4

5 Special Viscose Fibres Viloft Bellini Danufil Bramante Poseidon Galaxy Bramante 5

6 Special Viscose Fibres Unlimited Applications Viloft Bellini Danufil Bramante Poseidon Galaxy Bramante 6

7 Ionically Activated Viscose Fibres Characteristics Standard Viscose Deep Dye cation exchange surface gel effect cation exchange dyeing effects decolouring anion exchange Poseidon Verdi Danufil Deep Dye 2 µm 2 µm 2 µm 2 µm incorporated resin particles anionic incorporated polyelectrolyte anionic no activation standard fibre incorporated polyelectrolyte cationic 7 sulfonate -SO 3 (1.55 mmol/g) carboxylate -CO 2 (0.50 mmol/g) quart. ammonium - N(CH 3 ) 3 (0.30 mmol/g)

8 Primary Ionic Activation of Viscose Fibres Incorporation of ionic activated particles into cellulose matrix Incorporation of polyelectrolyte molecules into cellulose matrix NR 3 NR 3 Covalent bonding of ionic molecules to cellulose HO H CH 2 OH H H O O H O HO H H HO O CH 2 OH H O Coating of fibre surface HO NMe 3 8

9 Secondary Ionic Activation of Viscose Fibres (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) (+) Coating of ionically activated fibres with polyelectrolyte Principle (dimensions of polyelectrolyte molecules are much smaller than dimensions of fibres) 9

10 Ionic Interaction Effect of Distance Strong Interaction Precipitation Polyelectrolyte Anionic Polyelectrolyte Cationic (+) Interaction? Fibre Properties? Interaction (+) Interaction? Fibre Properties? (+) (+) Cationic Viscose Fibre Anionic Viscose Fibre 10 No Interaction

11 Interaction of Polyelectrolytes Anionic/Cationic anionic (1%) RCO 2 ph = 8 cationic A (1%) NR 4 ph = 11 anionic/cationic A RCO 2 NR 4 ph = 11 anionic/cationic A RCO 2 NR 4 ph = 13 + mix NaOH Polyelectrolytes Mixtures anionic (1%) RCO 2 ph = 8 cationic B (1%) NR 4 ph = 5 anionic/cationic B RCO 2 NR 4 ph = 7 anionic/cationic B RCO 2 NR 4 ph = 13 + mix NaOH 11

12 Coating of Fibres Cationic Polyelectrolyte 7 Adsorption of Cationic Polyamine 4 on Viscose Fibres at 20 C Weight Increase (Coating) [%] Danufil (not activated) Deep Dye (cationic) Poseidon (anionic) Verdi (anionic) Non-activated and cationic fibres low/no adsorption of cationic polyelectrolyte Anionic fibres adsorption of cationic polyelectrolyte Fibre activation for polyelectrolyte adsorption incorporated ionic particles incorporated molecular dispersed polyelectrolytes 0 0 % 0 % 5,6 % 6,8 % 12

13 Coating of Anionic Verdi Fibre Mass of Coating on Fibre Verdi: Adsorption of Cationic Polyelectrolytes (Separate Test for Each Sample) Weight Increase (Coating) [%] Cationic Starch Polydadmac A Polydadmac B Polyamine 3 Polyamine 1 Polyamine 2 Polyamine C 80 C 20 C 80 C 20 C 80 C 20 C 80 C 20 C 80 C 50 % w/w Polyelectrolyte added to fibre Coating at neutral ph (yield depends on ph of solution) Yield depends on type of polyelectrolyte 13 Yield increases slightly with rising temperature

14 Coating of Anionic Verdi Fibre Efficiency 8% Verdi: Adsorption of Polyamine 4 (Separate Test for Each Sample) Weight Increase (Coating) [%] 7% 6% 5% 4% 3% 2% 1% 0% 0% 20% 40% 60% 80% 100% Mass Ratio of Polyelectrolyte/Fibre in Trial Substantive adsorption of polyelectrolyte High efficiency at low loading 14

15 Affinity to Dyes Verdi: Dye Absorption Capacity (Supply of 1 % w/w Dye) Dye Pick-up [%] no coating Coated Verdi Fibres Pick-up of Anionic Dye (1 % w/w Dye per Fibre) (Separate Test for Each Sample) Verdi coated with polyelectrolyte at 20 and 80 C Cationic Starch Polydadmac A 80 C Polydadmac B 80 C Polyamine 1 20 C 80 C Polyamine 2 20 C 80 C Polyamine 3 20 C 80 C 20 C Polyamine 4 80 C Dye absorption capacity depends on polyelectrolyte Good correlation of dye pick-up with yield of polyelectrolyte coating 15 Higher dye pick-up with fibres coated at higher temperature (higher yield of polyelectrolyte coating)

16 Affinity to Dyes Dye Absorption Capacity (Supply of 7 % w/w Dye) Pick-up of Anionic Dye (7 % w/w Dye per Fibre) (Separate Test for Each Sample) Dye Pick-up [%] Fibres coated with Polyamine 4 at 20 and 80 C 80 C 20 C 80 C Poseidon Danufil Verdi Verdi coated with Polyamine 4 highest dye absorption capacity Poseidon coated with Polyamine 4 very low dye absorption (despite high yield of Polyamine 4 on fibre) Higher temperature of polyelectrolyte coating higher yield of polyelectrolyte coating higher dye pick-up + Polyamine 4 16

17 Affinity to Dyes Competitive Dyeing of Different Uncoated Fibres Poseidon Verdi Danufil Deep Dye cationic dye anionic (-) fibre cationic (+) fibre anionic dye 17 High affinity of ionically activated fibres to dyes of opposite electrical charge Affinity of cationic Deep Dye fibre even to cationic dye

18 Affinity to Dyes Competitive Dyeing of Coated Verdi Fibres Anionic Verdi Fibre Coated with Cationic Polyelectrolytes Colour depth after competitive dyeing with anionic dye Direct Blue Verdi + Verdi non coated Danufil Cationic Starch Polydadmac Polyamine A B ,14 % 0,10 % 0,60 % 3,7 % 4,5 % 4,8% 8,5 % 9,6 % 68 % anionic (-) fibre cationic (+) fibre Polarity reversion of Verdi fibre from anionic to cationic with polyelectolytes Positive charge level of fibre surface depends on polyelectrolyte type No polyelectrolyte transfer during dying from coated to non-coated Verdi fibre (lower polyelectrolyte transfer rate than speed of dye pick-up) 18

anionic dye Verdi Verdi - coated no anionic dye in/on anionic fibre anionic dye on cationic surface on anionic matrix

19 Location of Dye in Fibre Matrix and on Fibre Surface cationic dye Verdi cationic dye in anionic matrix anionic matrix anionic surface Verdi anionic dye 1. cationic coating 2. anionic dye Verdi Verdi - coated no anionic dye in/on anionic fibre anionic dye on cationic surface on anionic matrix Dispersion of anionic additive in fibre matrix homogeneous distribution of cationic dye in fibre matrix Cationically coated fibre anionic dye solely located on fibre surface 19

20 Fastness of Coating Washing with Water at Different ph Values 6% Verdi Fibre Coated with Polyamine 4 Mass of Coating after Washing with Water (10 min) Mass of Coating on Fibre 5% 4% 3% 2% 1% 0% before washing ph = 2 (20 C) ph = 7 (20 C) ph = 7 (60 C) after washing ph = 12 (20 C) 20 Cationic coating is partially washed off from anionic fibre matrix in aqueous solutions Under alkaline conditions most of cationic coating is washed off

Fastness of Coating Competitive Dyeing after Washing Anionic Verdi Fibre Coated with Cationic Polyamine 4 Colour depth after competitive dyeing with

21% 20 % 24 % anionic (-) fibre cationic (+) fibre 21 Less dye pick-up after washing of coated Verdi fibre reduced cationic activity (confirmation

21 Fastness of Coating Competitive Dyeing after Washing Anionic Verdi Fibre Coated with Cationic Polyamine 4 Colour depth after competitive dyeing with anionic dye Direct Blue coated Verdi + Washing Verdi non-coated Danufil ph = C ph = 7 60 C ph = 7 20 C ph = 2 20 C nonwashed 2 % 3 % 8 % 22 % 21% 20 % 24 % anionic (-) fibre cationic (+) fibre 21 Less dye pick-up after washing of coated Verdi fibre reduced cationic activity (confirmation that coating is partially washed off) Slight dye pick-up of non-coated Verdi and Danufil polyelectrolyte transfer during dyeing from coated to non-coated fibres

Coating of Cationic Deep Dye Fibre Adsorption of

Cationic Deep Dye Fibre Weight increase 1 % (low

complete wash off of polyelectrolytes with

anionic coating shields cationic matrix of fibre

anionic dye permeates into cationic matrix of

of coated fibre does not keep anionic dye 22

22 Coating of Cationic Deep Dye Fibre Adsorption of Anionic Polyelectrolyte (Carboxylic Groups) on Cationic Deep Dye Fibre Weight increase 1 % (low affinity of polyelectrolyte to fibre) Almost complete wash off of polyelectrolytes with aqueous solutions Competitive dyeing results: anionic coating shields cationic matrix of fibre only partially against pick-up of anionic dye anionic dye permeates into cationic matrix of Deep Dye fibre 0,3 % 27,7 % 72 % anionic surface of coated fibre does not keep anionic dye 22 Danufil + anionic Dye Deep Dye + anionic Coating + anionic Dye Deep Dye + anionic Dye

23 Water Imbibition Uncoated Fibres 140 Water Imbibition of Ionically Activated Fibres (incorporated additives) 120 Water Imbibition [%] Danufil no activation Deep Dye low activation Deep Dye medium activation Deep Dye high activation Verdi Poseidon Water imbibition of ionically activated fibres is higher than that of nonactivated fibres Similar level of water imbibition achievable with anionic and cationic additives ionic particles and polyelectrolytes 23 Water imbibition increases with concentration of ionic additive in fibre

24 Water Imbibition Coated Verdi Fibres 140 Water Imbibition of Verdi Fibre Coated with Cationic Polyelectrolytes 120 Water Imbibition [%] Verdi no coating Cationic Starch Polydadmac 1 Polydadmac 2 Polyamine 1 Polyamine 2 Polyamine 3 Polyamine 4 Water imbibition of ionic activated fibres decreases when fibres are coated with polyelectrolytes The higher the affinity of polyelectrolytes to ionically activated Verdi fibre the lower the water imbibition 24

25 Water Imbibition Different Fibres Coated with same Polyelectrolyte Water Imbibition of Non-Coated and of Coated Fibres (Coating with Polyamine 4) Water Imbibition [%] not coated coated Not coated coated Not coated coated 0 Danufil Verdi Poseidon Water imbibition of ionically activated fibres decreases when fibres are coated with polyelectrolytes 25 Coating of Poseidon delivered less decrease of water imbibition than coating of Verdi

26 Summary and Conclusions (1) Coating of Ionically Activated Fibres Verdi, Poseidon and Deep Dye Steering of fibre properties Polarity revision of ionically activated fibres with polyelectrolytes of opposite charge Charge of fibre surface can be steered with type and amount of polyelectrolyte High efficiency of coating Polyelectrolyte is located solely on fibre surface 26

Summary and Conclusions (2) Coating of Ionically Activated Fibres Verdi, Poseidon and Deep Dye Fastness to washing of polyelectrolytes on fibre surface in the time scale of dye pick-up depends on

27 Summary and Conclusions (2) Coating of Ionically Activated Fibres Verdi, Poseidon and Deep Dye Fastness to washing of polyelectrolytes on fibre surface in the time scale of dye pick-up depends on strength of ionic interaction depends on ph of solution Water imbibition of ionically activated fibres can be steered with coating values similar to non-ionically activated fibres are possible 27

28 Thank you for your attention Please visit our stand in the exhibition area in the foyer at the Dornbirn MFC 2014

Adsorption at the solid/liquid interface

1. Ion exchanger Adsorption at the solid/liquid interface Ion exchange process means an exchange of ions between an electrolyte solution and a solid (ionite). In most cases the term is used to denote the