NATIONAL TEXTILE UNIVERSITY

FAISALABAD
B.Sc. Textile Engineering
TP-7

Course Title: Textile Finishing (TE-4031)

ASSIGNMENT#1

Title: Recent development in designing fluorocarbon free oil repellent

SUBMITTED TO: DR. Munir Ashraf

SUBMITTED BY: Mahnoor Malik (18-NTU-0093)

Due date: 13-Dec-2021

Table of Contents
2 Introduction:........................................................................................................................................2
2.1 Why we need oil repellent materials:..........................................................................................2
2.2 Fluorocarbon:..............................................................................................................................2
2.3 Effect of fluorocarbons:...............................................................................................................3
2.3.1 Effect on environment:........................................................................................................3
2.3.2 Effect on human health: ‘....................................................................................................3
3 ADVANCEMENT IN FLUOROCARBON FREE OIL REPELLENT:................................................................4
3.1 Rational design of perfluorocarbon-free oleophobic textiles:.....................................................4
3.2 Silicone coating:...........................................................................................................................4
3.3 Atmospheric plasma treatment :..........................................................................................4
3.4 Stearic Acid-based oil and water Repellent for Cotton Fabric: ‘..................................................5
3.5 Hydrated filter:............................................................................................................................6
4 Conclusion:..........................................................................................................................................7
5 References...........................................................................................................................................7

1 Introduction:
An oil-repellent material is designed to prevent one or more types of oil from adhering to, or absorbing into, the
material’s surface. This also reduces the amount of damage to the material that extended exposure to the oil
would otherwise cause. Oil-repelling materials are referred to as “oleophobic” materials. Oil-repellent textiles
are desirable because they can be easy to clean, reduce upkeep expenses, maintain the natural appearance of the
fabric and improve air permeability and chemical resistance[ CITATION wha211 \l 1033 ].

Figure 1: oil repellent surface

1.1 Why we need oil repellent materials:

Oil repellency is necessary in industries where workers are frequently exposed to oily substances. Oil has very
low surface tension, and as a result, it tends to spread over surfaces very easily, rather than forming into droplets
the way water does. This makes it difficult to clean up and contain oil spills.

 A highly oil-repellent textile is able to avoid absorbing oils that have very low surface tension, such as
heptane oil, whereas materials that are only minimally repellent are only able to repel oil with
moderately low surface tensions, such as mineral oil.
 In addition to their use in protecting surfaces and PPE, oil repellency can also be used to improve the
quality of air filtration units that are exposed to oily particles.
 Oil repellency can improve a filter’s efficiency by preventing oily particles from building up on the
surface of the filter and causing any oil that does stay on the surface to coalesce into a bead[ CITATION
wha211 \l 1033 ].

1.2 Fluorocarbon:
In a polyfluorinated compound most of the hydrogen atoms in the molecular structure are replaced by fluorine
atoms, and if all hydrogen atoms are replaced the compound is called per fluorinated. Fluorinated compounds
are used in a wide range of applications. They are for example used in firefighting foams since they are efficient
for liquid fuel fires.

In the textile industry, fluorinated substances are used to give oil and water repellent finishes. Fluorinated
compounds are also used in paper and packaging, for example to give oil repellency to food-contact papers. The
first per fluorinated compound that gained attention for its toxicity and widespread occurrence in the
environment was PFOS and this substance is now restricted. The second substance to attract concern was
Perfluorooctanoic acid (PFOA). Both PFOS and PFOA are perfluoroalkyl acids (PFAAs) and derivatives of
them, that are used industrially, will degrade or metabolize to the corresponding PFAA as an end-product. PFOS
is a type of perfluoroalkyl sulfonate (PFSA) and PFOA is a perfluoroalkyl carboxylate (PFCA), both PFOS and
PFOA are examples of fluorinated surfactants with a chain length of 8 carbons[ CITATION HER14 \l 1033 ].

A fluorinated surfactant consists of a fluorinated tail and a hydrophilic head. The two groups are connected with
an organic group, called a spacer. The hydrophilic head can be nonionic, anionic, cationic or amphoteric, which
means it can react as both an acid and a base.
 Figure 2:mechanism of fluorocarbon

1.3 Effect of fluorocarbons:

Polyfluorinated compounds have been produced synthetically for 50 years and do not occur naturally. There are
studies that indicate that even the short chain length fluorocarbons have toxic effects on the environment and
human health, although these substances are considered to be less harmful than the ones of longer chain length.

1.3.1 Effect on environment:

PFOA and PFOS have been found in the arctic, far from any source, which means that these substances
are global contaminants. Since 2010 the levels of PFOA and PFOS in the environment have decreased
while the levels of short-chained sulfonates have increased.

1.3.2 Effect on human health: ‘

Exposure to humans of perfluorinated compounds occurs mainly via food, drink and indoor dust.
Fluorocarbons accumulate in internal organs and blood since they bind to proteins in cell membranes
and serum proteins. PFAAs have been found in human blood all over the world. Especially PFOS and
PFOA have been detected frequently. The chemicals have also been detected in human breast milk, but
the levels have been lower than in blood. PFCAs and PFSAs have been shown to have a negative effect
on reproduction, development and immune system.

2 Advancement In Fluorocarbon Free Oil Repellent:

So as it is need of time to use sustainable chemicals in order to safe environment and human health. By knowing
the effects of fluorocarbons different researchers are working on FC free oil repellents. I have studied the work
of different authors who play a significant part in making sustainable oil repellents.

2.1 Rational design of perfluorocarbon-free oleophobic textiles:

Shabanian et al. develop design parameters for fabricating oil-repellent textile finishes using PFC-free surface
chemistries. By adding a secondary, smaller length-scale texture to each fibre of a given weave, robust oil
repellency is achievable when the texture size, spacing and surface chemistry are properly controlled. For
example, a PFC-free, oil-repellent jacket fabric is fabricated that exhibits oleophobicity towards canola, olive
and castor oil in addition to synthetic sweat. The textile remains non-wetted for liquids with surface tension as
low as 23.9 mN m−1. The equations developed in this work allow for the rational design of oil-repellent textile
finishes that do not utilize per fluorinated substances[ CITATION Sad201 \l 1033 ].

2.2 Silicone coating:

Layal Liverpool Use the above equation and by using this equation, he said that a particular weave pattern can be
matched with a carefully designed form of silicone, which is then used to coat the fibres. The silicone coating
makes the fabric repellent to oil and water, and it is more environmentally friendly than per fluorinated
compounds. From the above work which was done Shabanian and her colleagues he concluded that the coating
for a specific woven fabric should be designed with that fabric in mind, it isn’t a one-size-fits-all solution
anymore like perfluorinated compound coatings were. Different fabrics may require different coating
formulations to achieve the same level of oil repellency. Silicone-based finishes have been around for decades
but changing the surface chemistry alone is insufficient to make a fabric oil-repellent. The key was to consider
both surface chemistry and textile structure together[ CITATION Lay20 \l 1033 ].

2.3 Atmospheric plasma treatment :

Another work is studied in which atmospheric plasma treatment was used to reduce the amount of fluorocarbons.
This work is focused on the perfluorinated compounds that are used in outdoor garments to give them oil and
water repellent properties. Atmospheric plasma treatment has been evaluated as a method to reduce the amount
of fluorocarbons that is needed to gain oil and water repellency of polyamide fabrics. The effect of the plasma
treatment on the endurance of the fluorocarbon finish towards washing has been investigated. Atmospheric
plasma was used as a pre-treatment before application of the fluorocarbon finish through a conventional wet
chemical treatment. The effect of the plasma treatment was evaluated with standard test methods for water
repellency and oil repellency. Contact angle measurements were also performed for evaluation. It could be seen
that the plasma treatment increased the ability of the fluorocarbon finish to withstand washing, due to stronger
bonding between fabric and finish. The treatment also made it possible to reduce the chemical content to one
third while retaining the same repellency grades[ CITATION HER14 \l 1033 ].

Figure 3:a, Apparent contact angles of hexadecane, canola oil, olive oil, castor oil, artificial sweat and water on the PDMS-treated
 Figure 4: b–d, Goniometer images of droplets of castor oil (b), olive oil (c) and canola oil (d)

2.4 Stearic Acid-based oil and water Repellent for Cotton Fabric: ‘
Another research showed the synthesis and application of Fluorine-free Environment-friendly Stearic Acid-
based oil and water Repellent for Cotton Fabric. The successful synthesis of fluorine and formaldehyde free bio-
based oil and water repellent finish was accomplished in this research. Stearic acid which previously can only
impart lower and non-durable water repellency exhibited durable water and oil repellency after polymerization
with citric acid. The optimum amount of 16% stearic acid, 7% citric acid in the presence of catalyst sodium
hypophosphite monohydrate, and enhancer triethanolamine at the polymerization temperature of 160⁰C for 3 h
in vacuum conditions exhibited the best results. At these conditions treated cotton fabric exhibited water
repellency rating of ‘4ʹ with isopropyl alcohol and ‘5ʹ with the mixture of isopropyl alcohol and water as solvent.
Oil repellency rating of the treated cotton fabric was rated as ‘1ʹ for isopropyl alcohol and ‘2ʹ for a mixture of
isopropyl alcohol and water. Even after 20 wash cycles, treated cotton fabric showed a rating of ‘4ʹ and ‘1ʹ for
water and oil repellency, respectively, after pressing which is comparable with benchmark Nuva-3585, a toxic
C6-based fluorocarbon finish[ CITATION Rab20 \l 1033 ].

Figure 5: reaction mechanism of stearic acid, citric acid and cellulose

2.5 Hydrated filter:

 Rohrbach et al.  prepared a cellulose-based hydrophilic, oleophobic-hydrated filter that was used for oil–water
separation. As shown in figure, coating the filter with a layer of nano fibrillated cellulose hydrogel, through a
dipping and drying process, took advantage of hydrogel's hydrophilic behavior. This behavior causes the filter to
absorb water until reaching saturation when it creates a hydration layer. The triple interface layers of hydrogel,
water and oil enhanced the oleophobic behavior. The roughness of the hydrogel trapped water in the microscopic
crevices. The big difference in surface energy between oil and water kept oil from penetrating the filter. Without
the coating, both oil and water were capable of penetrating through the filter. Hydrating this coating generated
oleophobic behavior, while retaining hydrophilicity without using traditional Functionalization groups. The
hydrophilic/oleophobic behavior was created by taking advantage of different properties and structures of
cellulose at both the macroscopic and nanoscopic scale without introducing any harmful chemicals[ CITATION
Ami16 \l 1033 ].

Figure 6: Schematic of water oil separation using a hydrated filter

In above figure water passes through, while oil is retained above. The filter is a regular cellulose paper with a
layer of coated cellulose hydrogel. The oil droplets repulsion is due to the surface energy between the hydrogel
and oil, the oil–water–hydrogel interface, and the roughness of the hydrogel surface.

3 Conclusion:
In the past few years, the number of scientific publications related to the development of oil-repellent surfaces
has exponentially increased. Different approaches have been demonstrated above. The materials which are used
in a wide range of different applications like self-cleaning, anti-graffiti, oil–water separation, microfluidics, anti-
icing, anti-fogging, biomedical membranes and devices, etc. are highly depend on oil repellency. Considering
the huge potential impact that oil-repellent surfaces have in all these different applications, it is expected that in
the following years researchers will come up with new techniques and different formulations that will initiate the
next generation of oil-repellent surfaces.

4 References

[1] "what is oil repellency," 11 december 2021. [Online]. Available:

http://www.safeopedia.com/defintion/8226/oil-repellency.

[2] A. HEREGARD, "Durable oil and water repellent outdoor fabric by atmospheric plasma treamtent," pp. 8-
10, 22 june 2014.
[3] Sadaf Shabanian, Behrooz Khatir,Ambreen Nisar and Kevin Golovin, "rational design of perfluorocarbon-
free oleophobic textiles," nature sustainablilty, pp. 11-12, 2020.

[4] L. Liverpool, "fabric repels both oil amd water thanks to clever silicone coating," 2020.

[5] M. M. R. S. W. A. a. H. G. q. Rabia sharif, "synthesis and application of fluorine free envirnomet- friendly
steraic acid- based oil and water repelent for cotton fabric," journal of natural fibers, 2020.

[6] I. B. a. E. A. milionis, "recent advances in oil repellent surfaces," international materials reviews, vol. 61, no.
2, pp. 101-126, 2016.

RUBRIC FOR ASSESSING ASSIGNMENTS

Registration No: 18-NTU-0093 Name: Mahnoor Malik

Subject: Textile finishing Title: Recent development in designing fluorocarbon free oil repellent

Attributes Max. Level 1 Level 2 Level 3 Level 4 Obtained

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Beginning or Developing Accomplished Exemplary
Marks
incomplete

Knowledge Do not have Have basic knowledge Understands major points Shows precise
and basic knowledge. but have no idea how of knowledge with possible understanding of
application to apply it. misunderstanding or knowledge and
2
failure to recall minor concepts. Applies the
points. Major mistakes in concepts correctly.
application of concepts.

Problem The The problem is The problem is interpreted The student has clear
identification interpretation is understood to some largely correctly with understanding of the
2
completely extent. possible minor mistakes problem.
wrong.

Solution Solution is Part of the solution is Right solution is proposed Excellent solution is
completely correct to some but the basis for the proposed
2
incorrectly extent solution are understood
incorrectly

Use of 1 No or rare use of Figures, graphs and Most figures, graphs, All figures, graphs,
figures, figures, graphs tables contain errors tables OK, some still tables are correctly
graphs & and tabs. or are poorly missing some important or drawn, are numbered
tables constructed, have required features and contain
missing titles, titles/captions.
captions or numbers,
units missing or
 incorrect, etc.

Appearance No symmetry, Sections out of order, Sections in order, All sections in order,
and no uniformity, sloppy formatting formatting is rough but well-formatted, very
1
formatting no clear division readable readable
of sections

Spelling, Too many errors, Frequent grammar Occasional All grammar/spelling

grammar, most of the text and/or spelling grammar/spelling errors, correct and very well-
sentence 1 is not errors, writing style is generally readable with written
structure understandable. rough and immature some rough spots in
writing style

References List of references Insufficient Sufficient references are All the relevant
is missing. references or not listed. Some of the references are listed.
1 cited, or too many references are correctly All the references are
mistakes. cited, less than 5 mistakes correctly cited, no
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