TEKNOLOGI PENCELUPAN 2

Pencelupan Serat-Serat Sintetik

Ida Nuramdhani, S.Si.T., M.Sc., Ph.D.

Department of Textile Chemistry

Politeknik STTT, Bandung

7SEMESTER
& 14 SEPTEMBER 2018
GANJIL BANDUNG
2019-2020
Fibre – Dyes Interactions 1: Chemical bonds
1. Covalent bond

1. Inonic bond

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY, POLITEKNIK STTT

Fibre – Dyes Interactions 2: Physical
Interactions

Dipole-dipole force

Physical Interaction force

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ADSORPTION ISOTHERMS
 Concentration of a substance adsorbed on a solid surface in
relation to its concentration in the surrounding fluid when the
system at equilibrium at a constant temperature.

 The graph: Adsorbed dye concentration (Cf in g/kg or mol/kg)

vs the solution concentration (Cs in g/l or mol/l).

 Three main types in dyeing: Nernst, Langmuir, and Freundlich

isotherms.
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Nernst Isotherm
 Cf = k Cs (k is constant)
 Distribution of partition of a
solute between two
immiscible solvent.
 Cf vs Cs: linear to the point
corresponding to the dye
saturating the fiber and the
water
 Mostly found in the dyeing
of disperse dyes in many
synthetic fibers

Special Langmuir Isotherm, where KCs is very small compared to unity

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Langmuir Isotherm (1)
 adsorption on specific sites in the solid, of which there are often only a limited number.

 Such a situation exists in the dyeing of nylon with simple acid dyes by an ion exchange
mechanism.

 The counter ion associated with an alkylammonium ion group in the nylon, under
weakly acidic conditions, is exchanged for a dye anion

 The rate of desorption depends only on the fraction of occupied sites (Cf/Cmax).

 The rate of adsorption of dye onto the fibre from solution, however, depends upon the
fraction of unoccupied sites (1 – Cf/Cmax) and the concentration of dye in the solution
(Cs).

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY, POLITEKNIK STTT

 Langmuir Isotherm (2)

the fibre becomes

saturated with dye when
all the available adsorption
sites are filled

K1&K2: rate constant of adsorption-desorption; Cmax isthe maximum number of adsorption sites that dye molecules can
occupy in the
fibre. K is the value of k1/k–1.
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Freundlich Isotherm

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Polyester

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Disperse dyes
 Non-ionic insoluble in water at room T
 Full range of color with a good build up
 Limited solubility in higher T
 Substantivity to hydrophobic fibres such as polyester and polyamide
 In dyebath: fine aqueous suspension with dispersing agent
 Low molecular weight
 Highly sublimed
 More soluble in fibre than in water
 Available: powder, paste, grain, aqueous dispersion

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Typical of disperse dyes

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Classification of disperse dyes

Cla Size Fastn Sublimation T Thermofiksation T

ss ess
A o > 190 200
B o >> 200 210
C >>> 210 220
o
>>>> 220 230
D o

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General step

Disperse dye Hydrophobic

Monomolecular
Dyeing
dispersion/solid
synthetic fiber
solution system

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Dispersion of disperse dyes
 Role of dispersing agent: to coat the surface of each dye particle  monomolecular layer
 The overall negative charge on the surface: prevent coalescence and aggregation
 Addition of dispersing agent in the dyebath  to solve problems with high T
 No addition of electrolyte  aggregation coming from the interaction of salt with anionic part
 Addition of sequestering agent  dispersing agent react with Ca or Mg, dye react with metals
Anionic part (head) of the surfactant
In contact with
Hydrophobic dye particle
Exposed to
the surrounding water
The hydrophobic tail

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Fastness properties of disperse dye

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Dyeing polyester
 Polyester: undyeable below 70-80 oC (GTT1)
 Dyeing rate at any T with given disperse dye: lower than any
other fibers
 Diffusion of disperse dye at below 100 oC: very low (the
smaller dye particle size, the higher the diffusion rate)
 Fiber swelling agent (carrier)  improve the fiber accessibility
 Dyeing at Higher T increses the diffusion of dyes

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY, POLITEKNIK STTT

HOW IS THE EFFECT OF HEAT
TREATMENT (E.G. HEAT SETTING) TO
THE DYE DIFFUSION?

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Main methods of dyeing
 Carrier dyeing (100 oC)
 High temperature high pressure dyeing (130 oC)
 Thermofixation (210-230 oC)

 Let’s talk about JET DYEING

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 Optical / Fluorescence Brightening agent
 The addition of blue-violet light to the total light reflected from the fabric 
producing “whiter than white effect”

Poor light and washing fastness

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The action of OBA/FBA: Remision of
brightened and unbrightened fabric

- Increase the apparent reflectance into blue-violet region

- The treated materials: remit more light in visible region
- A: bleached (clean) unbrightened
- B: bleached (clean) brightened (F/OBA)
- C : unbleached (dirty) fabric unbrightened
- D : unbleached (dirty) brightened (F/OBA)

- Efficient FBA: * absorb strongly in UV region

* e-emit major proportion of the absorbed
energy as visible light
 means: high fluorescence efficency

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Absorption and fluorescence process

S0,S1,S2, …: singlet states  all e have paired spin

T1,T2, …: triplet states  two e have unpaired spin

Ground state (S0) and activated state (S1, S2):

Subdivided into vibrational and rotational energy level

Rotational is ignored here

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Polyamide

Nylon 6 versus Nylon 66?

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IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Acid dyes
 Anionic in water (sulphonate or carboxylate)
 Using any kind of acid to dye (sulphatic acid for pH <2 up to ammonium acetate for pH >6)
 Can dye fibres with cationic part (substituted ammonium such as wol, silk, nylon)
 MW: 300-1000 gmol-1
 Ionic and hydrophobic interactions
 Complete range of colours incl. green and black

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IDA NURAMDHANI OF TEXTILE
- DEPARTMENT CHEMISTRY,
OF TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Classification of acid dyes
 Generally: sulphonated azo, anthraquinone

 Highly substantive: the higher the MW, the less the

suphonate group

 Based on dyeing characteristics:

Levelling, fast acid, milling, super-milling

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IDA NURAMDHANI OF TEXTILE
- DEPARTMENT CHEMISTRY,
OF TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Characteristics of acid dyes

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IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
General structure of acid dyes

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IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Acrylic / polyacrylonitrile

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IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
 Basic and cationic dyes
 Free basic amino groups  capable of reacting with acid (ion exchange)

 Unsoluble in water  pasting in acetic acid (stable pH at 4.5 – 5.5)

 Brilliant colours and high tinctorial strength, some are fluorescent
 Some are very poor light fastness  still used for leather, paper.
 Major applications: acrylic and modacrylic, less: modified nylon and polyester
 Avoid anionic auxiliaries  organic salt precipitate

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IDA NURAMDHANI OF TEXTILE
- DEPARTMENT CHEMISTRY,
OF TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Chemical structure of cationic/basic dyes

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY,

IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
 Dyeing procedures for acrylic
 Free basic amino groups  capable of reacting with acid (ion exchange)

 Brilliant colours and high tinctorial strength, some are fluorescent

 Some are very poor light fastness  still used for leather, paper.
 Major applications: acrylic and modacrylic, less: modified nylon and polyester
 Avoid anionic auxiliaries  organic salt precipitate

IDA NURAMDHANI - DEPARTMENT

IDA NURAMDHANI OF TEXTILE
- DEPARTMENT CHEMISTRY,
OF TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Equilibrium dye adsorption

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY,

IDA NURAMDHANI - DEPARTMENT
IDA NURAMDHANI OF TEXTILE
- DEPARTMENT OFSTTT
POLITEKNIK CHEMISTRY,
TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
Problems in Dyeing Acrylic with
Cationic Dyes

Mostly the risk of unlevel dyeing

Let’s discuss more

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IDA NURAMDHANI OF TEXTILE
- DEPARTMENT CHEMISTRY,
OF TEXTILE POLITEKNIK
CHEMISTRY, STTTSTTT
POLITEKNIK
 SOME ADDITIONAL
MATERIALS

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IDA NURAMDHANI - DEPARTMENT OF TEXTILE
POLITEKNIK STTT CHEMISTRY, POLITEKNIK STTT
 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
1) Exhaustion (penyerapan): kontak antara kain dan
zat warna secara berulang, kain menyerap
(adsorpsi), konsentrasi zw dlm larutan berkurang.

Co: konsentrasi awal zat warna

Cs: konsentrasi zw pada waktu tertentu selama proses

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 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
-Ditentukan pada temperatur konstant
atau pada keadaan setimbang

- Pada umumnya, kenaikan suhu dapat

mempengaruhi kecepatan penyerapan,
biasanya dibantu garam atau asam.

- Bila zat warna yg terserap tidak dapat

melakukan redistribusi pada bagian yang
masih tercelup lebih muda, maka proses
harus lebih terkontrol --- kemampuan
migrasi rendah.

-Slope (gradien kemiringan kurva) = rate

of dyeing (kecepatan pencelupan pada
waktu tertentu)
Grafik penyerapan zat warna v.s. waktu
Equilibrium (kesetimbangan): tidak ada lagi proses penyerapan (taken-up) zw --- keseimbangan adsorpsi-desorpsi (NAMUN
hanya terjadi di permukaan, bukan kesetimbangan yang sesungguhnya, karena terlalu lama untuk dicapai!

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 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
-Equilibrium >>> substantivitas >>>
- Substantivitas: tarik-menarik (attraction) antara
zw dan serat yg mengakibatkan pengurangan
konst. Zw)
- Substantivitas >>>, kecepatan awal penyerapan
>>>, resiko ketidakrataan >>>
- Pengaturan waktu pencelupan agar hasil rata!!!

-Grafik di samping (katun-zw reaktif): penyerapan

lbh kompleks karena melibatkan tiga faktor: suhu,
garam, alkali.
-Tidak memungkinkan migrasi setelah zw
mencapai serat --- sebelum pH tertentu
(penambahan alkali), zat warna masih dapat
bermigrasi dari serat ke serat.
Grafik perbedaan penyerapan zat warna: (1) penambahan zw; (2) penambahan NaCl bertahap (4x, max. 50 g/L)
(3) soda ash (20 g/L); (4) cuci bilas
(a) Penyerapan zw, (b) reaksi dengan serat, (c) penambahan zat kimia

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY, POLITEKNIK STTT

 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
Konsentrasi zat warna dan ketuaan warna (colour yield):
% owf = % zw on the weight of fibre
1% konst. Zw = 1 kg zw mewarnai 100 kg kain
*untuk kain yang menyerap air sangat besar: reproduktivitas warna bisa tidak akurat --- harus diketahui MR
kain, dan perhitungan didasarkan pada berat kering bahan

Konsentrasi >>>, ketuaan warna >>>, tapi lebih suram, dan sedikit pergeseran hue (corak warna)
Ketuaan >>>, ketahanan luntur cuci dan gosok biasanya <<<, ketahan sinar >>>

Colour yield: ketuaan warna --- pengukuran kuantitatif dengan

metoda spektroskopi --- spektrum reflektansi cahaya pada
panjang gelombang cahaya tampak

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 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
3) Vlot (liquor-to-goods ratio/liquor ratio):
perbandingan berat larutan terhadap berat
kering kain yang dicelup – bergantung jenis
serat dan kemampuan mesin celup
LR <<<, penyerapan <<< Cf = konsentrasi zw di dalam serat
Co= konsentrasi awal zw
Cs= konsentrasi zw dalam larutan celup
K= konstanta kesetimbangan
L= liquor ratio
E= penyerapan fraksional
Maka: peningkatan vlot/liquor ratio (L) akan menurunkan kesetimbangan
penyerapan (E)
Peningkatan LR juga meningkatkan konsumsi zat kimia dan air, sehingga LR
harus diprediksi dengan tepat untuk akurasi reproduktifitas warna

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 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
3) Kecepatan pencelupan (rate of dyeing dan kecepatan awal (strike): lebih
signifikan daripada equilibrium, karena mencapai qeuilibrium=tidak
ekonomis.

rate of dyeing depends on liquor circulation in the dyeing machine---- three

steps of dyeing:
1) transfer of dyes from the bulk of solution to the fibre surface (migration)
2) adsorption of dyes onto the fibre surface
3) adsorption of the adsorbed dyes into the fibre interior

Strike: the initial slope of exhaustion versus time (kecepatan awal pencelupan).

HIGH STRIKE === HIGH UNLEVELNESS, controlled by dyeing Temperature,

pH and chemicals added

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 Istilah-istilah pada metoda pencelupan
exhaust langsung (direct exhaust method)
3) Migration (migrasi) vs. Levelling (kerataan)
look at the case from the view of dye-fibre bonds

Typical migration test of GOOD and POOR migration of dyes

(a) Original dyed sample; (b) original undyed sample, (c) bath solution

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Pengaruh Suhu terhadap Penyerapan
Zat Warna dan Kecepatan Pencelupan
Jelaskan, mana lebih baik untuk
kedua jenis pencelupan dengan
karakter zw yang berbeda ini?? Dan
Mengapa?
T>>>, dyeing rate >>>

T>>>, equilibrium <<< Le’Cathelier

principle for exothermic dyeing process
 dye-fibre interaction is stronger than
dye-water interaction  equilibrium
adsorbs heat, shifting the endothermic
direction, desorption stops

Dyebath exhaustion as a function of time for (a) rapidly and (b) slowly dyeing at two
temperatures, where Ti>T2

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 Kompatibilitas zat warna

Does it ring a bell to you???

IDA NURAMDHANI - DEPARTMENT OF TEXTILE CHEMISTRY, POLITEKNIK STTT