FLUOROCARBON FINISHIIG

By
Dr. Pintu Pandit
Asst. Professor, NIFT Patna

Introduction
Finishes that repel water, oil and dry dirt are important in all parts of the textile market – for
clothing, home and technical textiles. Water repellency is achieved using different product
groups, but oil repellency is attained only with fluorocarbon polymers. They are modified to
have a wide range of properties to fit the different demands of the users and the intended
purpose. This is one of the most interesting new developments of chemical finishing [1].

The purpose of this finish is self-evident. Drops of water should not spread on the surface of the
textile and should not wet the fabric. The drops should stay on the surface and easily drip off.
Similarly, oil repellent finishes should prevent oily fluids from wetting treated textiles. In a
similar manner, soil-repellent finishes should protect textiles from both dry and wet soils. In all
cases, the air permeability of the finished fabric should not be significantly reduced. In addition
to the desired repellency effects, other undesirable fabric properties are often found with
repellent finishes. These include problems with static electricity, poor soil removal in aqueous
laundering, stiffer fabric hand, greying (soil redeposition) during aqueous laundering and
increased flammability. Some fabric properties that are often improved by repellent finishes
include better durable press properties, more rapid drying and ironing, and increased resistance
to acids, bases and other chemicals.

The oldest water repellant finishes for fabrics were simply coatings of paraffin or wax – and they
generally washed out eventually. Perfluorochemicals (PFC’s) are the only chemicals capable of
repelling water, oil and other liquids that cause stains. Fabrics finished with PFCs have nonstick
properties; this family of chemicals is used in almost all the stain repellant finishes on the market
today. Other materials can be made to perform some of these functions but suffer when
subjected to oil and are considerably less durable [2].
Mechanisms of repellency
Repellent finishes achieve their properties by reducing the free energy at fibre surfaces. If the
adhesive interactions between a fibre and a drop of liquid placed on the fibre are greater than the

Figure 1 Mechanism of Repellency

internal cohesive interactions within the liquid, the drop will spread. If the adhesive interactions
between the fibre and the liquid are less than the internal cohesive interactions within the liquid,
the drop will not spread. Surfaces that exhibit low interactions with liquids are referred to as low
energy surfaces. Their critical surface energy or surface tension γC must be lower than the

surface tension of the liquid γL (the internal cohesive interaction) that is repelled. γL of water, at
73 mN m–1, is two to three times greater than γL of oils (20–35 mN m–1). Therefore, oil

repellency finishes with fluorocarbons (γC = 10–20 mN m–1) always achieve water repellency,

but fluorine-free products, for example silicones (γC= 24–30 mN m–1) will not repel oil. Low
energy surfaces also provide a measure of dry soil repellency by preventing soil particles from
strongly adhering to fibre surfaces. This low interaction allows the soil particles to be easily
dislodged and removed by mechanical action [3,4].

Fluorochemical Finishes
Fluorochemical finishes (also termed fluorocarbon finishes) were first applied to textiles in the
1960s and their growth, particularly during the 1990s, has been greatly stimulated by the
consumer demands for easy-care properties such as water- and oil-repellency, stain repellency,
and soil- and stain-release properties. Fluorochemicals (fluorocarbons) are a class of
synthetically produced organic chemicals that contain a perfluoroalkyl residue in which all the
hydrogen atoms have been replaced by fluorine. Fluorochemicals exhibit outstanding chemical
and thermal stability, low reactivity through their incompatibility with water and oil, and
considerable reduction in surface tension. It is this latter property which is of particular
importance in the context of water- and oil-repellency, while their chemical and thermal stability
contribute towards the durability of the surface finish to fabric care treatments such as
laundering, dry-cleaning and tumble-drying [4].

Fluorine, first isolated by Moissan in 1886, is the most strongly electronegative element in nature
and is extremely chemically reactive. In the fluorine atom the electrons are held close to the
atomic nucleus. The interaction of fluorine atoms with carbon atoms to form strong carbon–
fluorine bonds leads to the carbon atoms in fluorocarbons being closely surrounded by fluorine
atoms. Thus the basis for the low reactivity of fluorochemical finishes is the high degree of
protection provided by the fluorine atoms to the shielded carbon scaffold. In addition, the
extremely low critical surface tension and high surface activity associated with fluorochemicals
are also a consequence of this unique molecular topography. Fluorochemicals are used in many
fields, for example, as durable lubricants, corrosion protection coatings for metals, flame-
retardant polymers, fluorine elastomers used in the rubber industry and heat transfer fluids in
refrigeration technology. They are widely used as protective agents against water and oil, stains
and soiling in the textile, paper and leather industries. Some fluorochemicals are used for
specialist wetting applications in the textile field, others are used in firefighting, and in the
electroplating and electronics industries [3,4].

Techniques for the formation of fluorochemicals

1. Telomerisation
2. Electrochemical fluorination
3. Oligomerization[
However, the first two techniques have been the most widely used to manufacture
fluorochemicals for repellent finishes, but finishes based on electrochemical fluorination were
discontinued by 3M (Minnesota Mining and Manufacturing Company) in 2001 on
ecotoxicological grounds concerning the type of fluorochemicals produced[5].

In electrofluorination, a hydrocarbon product is dissolved in hydrogen fluoride. Under an

applied electrical current, the hydrogen atoms on the hydrocarbon are replaced by fluorine
atoms. In telomerization, a fluorinated ethylene derivative (taxogen) is reacted with an
initiator for chain growth polymerization (telogen), producing the desired FC. The
oligomerization process is similar to telomerization, but results in high molecular weight
fluoropolymer s, and thus is not generally used for production of FC finishes [4,5].

Figure 2 Electrofluorination and telomerization reactions used to produce fluorinated surfactants

Fabric preparation for fluorochemical application

In accordance with good practice in textile dyeing and finishing, fabrics should be clean and free
from other processing agents. Problems can arise from the following:

• Silicone-containing defoamers must be avoided because they normally impair the oil
repellency performance;
• A typical fabric pH of 5–7 is desirable – any residual alkali may destabilize the
fluorochemical dispersion and/or may impair the curing of applied crosslinking agents;
 • Presence of residual surfactants, which exert a rewetting action, can increase the
interfacial tension and also decrease both the rating of the hydrophobic properties and the
bath stability;
• Presence of spin finishes and/or residues of lubricants may impair uniform fabric wetting
and the formation of a cohesive fluorochemical film [4].

Application methods for fluorochemical finishes

The method of application of the fluorochemical finish to the textile depends upon the form of
the material – for example, flat woven, weft knitted fabric, velvet or pile fabric or carpet – and
whether the fluorochemical finish is required to penetrate the structure and provide a film
covering all the fibres uniformly, or whether a topical (or surface) application is all that is
required. Light- and medium-weight fabrics (linings, apparel, and home furnishing fabrics) may
be saturated by immersion in a pad bath containing the fluorochemical and any appropriate
auxiliaries followed by squeezing in a two-bowl or three-bowl nip. The fibre content and fabric
construction normally dictate the wet pick-up range that is possible, and the wet pick-up is
controlled by the nip bowl pressure. The chemical add-on of fluorochemical deposited on the
fabric is typically around 0.15–0.3% on the weight of the fabric. The chemical add-on is
controlled principally by regulating the fluorochemical finish concentration in the pad bath,
rather than by regulation of the wet pick-up. As an alternative to padding, other methods of
minimum application may be used such as lick-roll or nip padding or vacuum extraction. In the
latter case, excess removal may be recycled back to the pad bath.

The vast majority of the fluorochemical finishes used in the treatment of textiles are cationic in
nature and the recommended pH of the finishing bath should therefore preferably be around pH
5, which can be attained usually by addition of a small amount of acetic or formic acid. This
ensures that any residual alkalinity in the fabric is neutralised and also that the finish bath is
stabilised because the cationic emulsifiers used are much more effective at this pH level.

After impregnation, the fabric is dried at temperatures of about 110–130 °C followed by heat
curing at a temperature normally in the range 150–170 °C. This may be carried out in separate
stages in circulating hot air ovens or more usually in a single-pass treatment on a stenter. The
higher the curing temperature, the shorter is the curing time to avoid yellowing of the textile
material. Thus, heat-curing treatments at 150 °C for 3–4 min, or 160–180°C for 30–45 s, are
typical of the conditions to be encountered in practice. However, carpet products may be heat-
cured at a minimum temperature of 110 °C while other products may be treated for 2 min at 170
°C, or for as little as 30 s at 190 °C. The heat-curing conditions used must provide optimal film
formation and are dependent upon the chemical nature of the fluorochemical, the presence of
extenders used to boost the fluorochemical performance and the durability performance required.
Fibres that are heat-sensitive, such as wool or polypropylene, are cured at lower temperatures.
Where multifunctional finishes are used – for example, fluorochemical combined with an easy-
care finish – the heat-curing conditions selected must ensure that both the fluorochemical and the
easy-care finish are satisfactorily crosslinked to achieve the optimum fabric performance [3, 4, 6]

Pad bath additives

Depending upon the nature of the fibre substrate, the fabric construction and the performance
requirements of the finished fabric, various additives may be mixed into the pad liquor.

Wetting agents

Where thorough wetting of the substrate is necessary to achieve a uniform repellent treatment the
use of a fugitive wetting agent is normally preferred to avoid problems arising from the presence
of residual surfactant. Isopropanol (propan-2-ol) used at 1–3% has been successful in this
respect. However, in cases where extreme hydrophobicity is experienced the use of a thermally
degradable surfactant, or one with a low residual wetting effect is normally satisfactory.

Thermosetting resins

Thermosetting resins and catalysts are used to improve fabric dimensional stability and
resistance to laundering as well as imparting stiffness. Melamine resins are used to improve the
handle of nylon taffeta while glyoxal-based products provide wrinkle resistance on
cotton/polyester fabrics.

Extenders

Hydrocarbon-based water-repellents and resin-wax dispersions may be used as extenders to

boost the repellency performance of the fluorochemical and aid durability. Their addition to the
pad bath frequently improves the pad bath stability. Silicone-based products must be avoided
because these impair the oil-repellency of the fluorochemical through chemical incompatibility
and phase separation problems. Melamine resins, modified by fatty acids, blends of waxes with
zirconium salts, or polyurethane resins, have been quite widely used to improve the final
performance of the fluorochemical finish.

Other products

Chemical additives, such as softeners, antistatic agents, builders, flame-retardants, or fungicidal

or anti-bacterial agents, may also be incorporated into the pad bath to obtain multifunctional
finishes. Their effects upon the pad bath stability, or problems due to chemical incompatibility
that may impair the final finished fabric performance, must be evaluated to optimise both the
process and product performance.

The final polymer, when applied to a fibre, should form a structure that presents a dense -CF3
outer surface for maximum repellency. A typical structure is shown in Fig-3. The length of the
perfluorinated side chains should be about 8–10 carbons. The small spacer group, mostly
ethylene, can be modified to improve emulsification and solubility of the polymer. Comonomers
(X, Y, for example stearyl- or laurylmethacrylate, butylacrylate, methylol- or epoxy-functional
acrylates and block copolymers from α,ω-dihydroxydimethylpolysiloxane) affect fabric hand,
film formation and durability [4].
 Figure 3 Fluorocarbon repellent on fibre surface. m= 8–10. X and Y are comonomers, mainly stearylacrylates. R = H or CH3
(polyacrylic or polymethacrylic acid esters). A is the fibre surface.

The effect of the fluorochemical chain length upon the critical surface tension (𝛾 C) is illustrated
in Figure-4. It can be clearly seen that the critical surface tension decreases fairly rapidly as the

Figure 4 Effect of the fluorochemical chain length on surface tension

chain length (n) increases from 1 to 8, after which little further decrease in critical surface
tension is noted. As the critical surface tension of the fluorochemical film on the fibre surface is
decreased, the water- and oil-repellency rise, reaching their maximum protective value around a
chain length of n= 9. This dramatic improvement in repellency performance is illustrated in
below Table in which the oil-repellency (as measured according to AATCC Test Method 118)
rises from 0 with a –CF3 terminal group to 8 with a – (CF2)8–CF3 side-chain. In addition, the
water-repellency (as determined by the spray test ISO 4920) also rises from 50 up to 80. Thus an
increase in the perfluorinated chain length from CF3 to C9F19 (that is, – (CF2)8–CF3) gradually
enhances the oil-repellency and, to a lesser extent, the water-repellency [4, 7].

Oil- and water-repellency of fabrics treated with acrylic polymers

Traditional commercial FC products

Traditional commercial FC products consist of 15–30 % fluorocarbon polymer, 1–3 %

emulsifier, 8–25 % organic solvents and water. The exhaust air of the drying and curing
processes of fluorocarbon finishes therefore often contains high amounts of volatile organic
compounds (VOC), like glycols and other organic solvents and a lower content of residual
monomers. Cellulosic fibers retain most of the glycols. The exhaust air problem is greater with
FC finishes on synthetic fibers. VOCs can be reduced by more than 90 % by the addition of
corresponding boosters, providing equal effects with lower quantities of finish products.

Toxicology and ecological considerations concerning PFCS

Perfluorochemicals (PFCs) are a group of chemicals used to make fluoropolymer coatings

and products that resist heat, oil, stains, grease and water . During Electrofluorination and
Telomerisation a small amount of PFOS (perfluorooctane sulphonate) and PFOA
(perfluorooctanoic acid) is produced.

PFOA persists in the environment and does not break down. Scientists noticed that PFOS (the C8
fluorocarbon) began showing up everywhere: in polar bears, dolphins, baby eagles, tap water and
human blood. They kill laboratory rats at higher doses, and there are potential links to tissue
problems, developmental delays and some forms of cancer. Below are results which the U.S.
Environmental Protection Agency released from data collected by 3M and DuPont; some
humans have more PFOA in their blood than the estimated levels in animals in this study [2].

PFOA and PFOS, according to the U.S. EPA:

• Are very persistent in the environment.

• Are found at very low levels both in the environment and in the blood of the U.S.
population.
• Remain in people for a very long time.

Cause developmental and other adverse effects in laboratory animals [5].

C6 and C4 Chemistry

C6 – this chemistry produces a by-product called PFHA (perfluorohexanoic acid), which is

supposed to be 40 times less bio accumulative than PFOA. But it’s also less effective, so more
of the chemical has to be used to achieve the same result. Manufacturers are trying to find
smaller and smaller perfluorocarbon segments in their products, and even C 4 has been used. The
smaller the fluorocarbon, the more rapidly it breaks down in the environment. Unfortunatley, the
desired textile performance goes down as the size of the perfluorocarbon goes down. “C 6 is
closest chemically to C8, but it contains no PFOA. It breaks down in the environment – a positive
trait – but it doesn’t stick as well to outerwear and it doesn’t repel water and oil as well as C8,
which means it falls short of meeting a vague industry standard, as well as individual company
standards for durability and repellency [2, 5].”

3M settled on perfluorobutane sulfonate, or PFBS, a four-carbon cousin of the old chemicals.

This new C4-based chemistry is completely safe. According to 3M, the results show that under
federal EPA guidelines, PFBS isn’t toxic and doesn’t accumulate the way the old chemical did.
It does persist in the environment, but 3M concluded that isn’t a problem if it isn’t accumulating
or toxic. PFBS can enter the bloodstream of people and animals but “it’s eliminated very
quickly” and does no harm at typical very low levels [2].

Bionic finishes

A novel FC development is inspired by nature and therefore called bionic finishes. Fluorocarbon
polymers are applied together with dendrimers, causing self organisation where the fluorocarbon
chains are enriched on the surface and cocrystallise with the dendrimers. Dendrimers are highly
branched oligomers with non-polar chains forming a starbrush structure. They force the polar
parts of the FC polymers to form the surface structure mentioned at the beginning of this section.
The resulting polar and non-polar sandwich arrangements are highly ordered, causing equal or
better repellency effects with lower amounts of fluorocarbon compared to dendrimer-free FC
finishes. Other advantages include low condensation temperature (80–130 °C), high abrasion
resistance, good wash permanence and soft hand [3, 8].
Fluorocarbon-free alternatives: Bionic Eco

Fluorine-free, high-performance waterproofing

Properties

• FC-free waterproofing agent

• Excellent water-repellent effects with
• very good Bundesmann ratings
• Low curing temperatures
• Very good washfastness
• Better abrasion resistance than
• FC-finishes
• Environmentally friendly –
• no durable decomposition products
• No APEO, no solvents
• Patented technology [8]

Sustainability vs Performance
The bluesign® system is the solution for a sustainable textile production. It eliminates harmful
substances right from the beginning of the manufacturing process and sets and controls standards
for an environmentally friendly and safe production. This not only ensures that the final textile
product meets very stringent consumer safety requirements worldwide but also provides
confidence to the consumer to acquire a sustainable product [9].

Refrences

1. Paraffin Wax Emulsion as Water Repellent for Cotton/Polyester Blended fabric, M.H.
Abo-Shosha, Z.H. El-Hilw, A.A. Aly, A. Amr and Al Said I. El. Nagdy,journal of
Industrial Textiles
2. http://oecotextiles.wordpress.com/2010/02/10/what-about-soil-resistant-finishes
3. Chemical finishing of textiles, W. D. Schindler and P. J. Hauser, page no-85
4. Textile Finishing, Edited by Derek Heywood, Textile and chemical consultant, Sacola
Associates, Cheadle Hulme, UK
5. sarex, Vol.4, Issue 14,April 2011
6. Finishing reference book of textile technology, by Pietro Bellini ,Ferruccio Bonetti, Ester
Franzetti, giuseppe Rosace, Sergio Vago
7. http://www.anarkimya.com/images/pdf/fluorocarbons.pdf
8. “Waterproofing of textiles at the crossroads“,Dr. Gunther Duschek, Rudolf GmbH /
Geretsried
9. http://www.bluesign.com/