Enhancing the Hydrophobic Property of Polyester Fabric Using Nitrogen Atmospheric Pressure

Plasma (APP)

by

Kaye Trixia M. Go

Jyla C. Dolor

Drew R. Doroteo

Chris John I. Treno

Maria Diesa V. Rubis

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Abstract

This study was conducted to determine and compare the effect of hydrophobic property of

polyester fabric samples when treated with Nitrogen Atmospheric Pressure Plasma (APP) against

a commercially available silicone-based water-repellent product. The polyester fabric was

soaked in boiling distilled water and scoured. The fabric was cut in 3 in by 3 in size and a total of

30 samples were made. The 20 fabric sample were industrially-treated with commercially

available Silicone-based water-repellent product, left to dry overnight and then cured in an oven

for 1 min at 160°C. 10 industrially-treated polyester fabric samples were exposed to Nitrogen

Atmospheric Pressure Plasma (APP) for varying intervals of 1s 3s and 5s. All fabric samples

were subjected to contact angle measurement, spray test, and hydrophobic recovery rate

measurement. The untreated fabric sample exhibited the lowest contact angle measurement,

followed by industrially-treated fabric samples, plasma-treated (5s), plasma-treated (3s), and

plasma-treated (1s) respectively. The plasma-treated (1s) exhibited the highest contact angle

measurement showed the most non-wetting of water and poor spreading of water droplet on its

surface thus representing increased hydrophobicity and resistance to adherence of water. Spray

Test results showed that the plasma-treated (1s) fabric sample exhibited the highest rating in the

wettability and visual rating of beading up of water on the surface of the fabric. The hydrophobic

property of the industrially-treated fabric samples reverted to its old surface property and that

Atmospheric Pressure Plasma successfully prolonged the hydrophobic recovery rate of the

polyester fabric samples. Too much exposure to APP proves detrimental to the hydrophobic

properties of the samples and the 1s time interval showed the best result in all test.
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Keywords: Nitrogen Atmospheric Pressure Plasma, Contact Angle Measurement,

Hydrophobicity, Hydrophobic Recovery Rate

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Introduction

Since the early 1980s, significant research work has been done regarding the use of

plasma technology on the finishing processes of textiles; showing immensely promising results

in the enhancement of fabrics’ various functional properties (Shahidi Ghoranneviss and

Moazzenchi 2013). The advantages of using plasma-based technology are widely-known; a few

examples include raised surface energy to improve the bonding characteristics of chemicals,

extended life of chemical treatments over time and reduced surface morphology degradation of

various materials.

One of the newer developments of plasma technology in the textile industry is the

Atmospheric Pressure Plasma (APP) treatment used as an alternative finishing process for

improving the functional properties of a multitude of fabrics, namely, cotton (Sun et. al 2018),

polyester (Wang Ren and Qiu 2007), wool (Wang and Qiu 2007), etc. Atmospheric Pressure

Plasmas (APP) provide a crucial advantage over the more commonly used low pressure plasmas

because they eliminate complications introduced by the need for vacuum operations in terms of

price, size and required maintenance (Park et. al 2000). This significantly reduces the need for

unnecessary heat energy, chemical waste and time consumption thus providing an eco-friendly

alternative to commercialized treatments and older plasma treatments in the finishing process of

textiles. In the Philippine setting, atmospheric pressure plasma has yet to be industrialized as a

finishing process due to our country’s limited resources resulting in a scarcity of advancements

in plasma technology and only a few locations in the Philippines have the means to maintain

such facilities. The Nitrogen Atmospheric Plasma Jet Treatment (APP) used by the researchers in

this study was supplied by Ateneo de Manila’s Physics Department as seen in the figure below.
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Figure 1. A diagram of the structure of the Atmospheric Pressure Plasma Jet Treatment

Polyester is a synthetic fabric inferred from coal, water, air and petroleum. It is

developed from a chemical reaction between acid and alcohol that made two or more particles

join to make a substantial atom whose structure rehashes all through its length (Krapp 1996).

This kind of fabric incorporates naturally occurring chemicals such as synthetics. Because

of its very long molecules that made this fabric stable and strong, it is widely used in textile

industry (n.d. 2016). But then, the highest priority has become the environment-friendly process

of developing fiber modification and finishing treatments for polyester fabric.

Polyester fabric is a synthesized fiber wherein it is formed through chemical reaction of

acid and alcohol. It absorbs oil but not the moisture (Krapp 2016). It is hydrophobic, and it is

manufactured by reacting ethylene glycol with terephthalic acid in the presence of an antimony

catalyst (Smith, n.d).

This study aims to determine and compare the effect and efficiency of hydrophobic

property of polyester fabric samples when treated with Nitrogen Atmospheric Pressure Plasma

(APP) against a commercially available silicone-based water-repellent product and to measure

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the hydrophobic recovery rate of the treated samples. The researchers endeavor to test whether

the verified Atmospheric Pressure Plasma (APP) treatments can be applicable to the Philippine

textile industry as a finishing process.

This study focused on how atmospheric pressure plasma treatment enhances the effects of

the hydrophobic property of polyester fabric samples. Specifically, it aims to:

1. Determine if atmospheric pressure plasma (APP) enhances the hydrophobic

property of polyester fabrics through:

a. Contact Angle Measurement Test

b. Spray Test

2. Measure the Hydrophobic Recovery Rate of APP-treated polyester fabric

samples.

The researchers also aim to answer the following research questions:

1. Is the new plasma technology (APP) effective in enhancing hydrophobic

properties of Polyester fabric?

2. Does the APP treatment yield better hydrophobic results when compared to a

commercially-available silicone-based water-repellent product on Polyester

fabric?

3. Will the surface of Polyester fabric treated with new plasma technology be

modified in terms of the following:

a. Wettability

b. Hydrophobicity

c. Hydrophobic Recovery
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In this study the researchers aim to potentially develop a new finishing process for textiles

in the Philippine setting using Polyester fabric samples that will aid the fabric industry through

industrializing the use of Atmospheric Pressure Plasma (APP). The significant findings provided

by this study such as equal or better results compared to the current industrial treatments will

potentially be beneficial to the traditional Philippine textile industry through the exposure of

atmospheric pressure plasma (APP) and its numerous advantages to the ecology and economy of

the environment.

The researchers hypothesize that the surface modification of Polyester fabric with

Atmospheric Pressure Plasma possesses a significant difference in terms of hydrophobicity

compared to a commercially-available silicone-based water-repellent product. The researchers

also constructed a null hypothesis that the surface modification of Polyester fabric with

Atmospheric Pressure Plasma does not possess a significant difference in terms of

hydrophobicity compared to a commercially-available silicone-based water-repellent product.

This study will only focus on the possible positive/negative effects of Nitrogen

Atmospheric Pressure Plasma (APP) treatment on polyester fabric samples in terms of its

hydrophobic property and how it compares to untreated and industrially treated samples. The

researchers shall only be using specified time intervals (1s, 3s, and 5s) on specified parameters

present in Ateneo de Manila’s APP jet treatment.

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Methodology

Conceptual Framework

Figure 2. Conceptual Framework

The polyester fabric was pretreated using boiling water and scoured to remove dirt. The

fabric samples were grouped as untreated and water repellent treated. Half of the water repellent

treated fabric samples underwent atmospheric pressure plasma treatment. The control and

treatment groups were subjected to contact angle measurement, spray test, and hydrophobic

recovery rate measurement respectively.

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Preparation of Samples

The polyester fabric used was pretreated to remove any dirt present in the fabric. The

pretreatment was done using boiling distilled water where polyester fabric were soaked and

scoured. The fabric was rinsed and dried. The scoured fabric was cut in 3 in by 3 in size and a

total of 30 samples were made.

Experimental Treatment with commercially available Silicone-based Water-repellent Product

The researchers independently performed the industrial treatment on 20 fabric samples

subsequently enhancing their hydrophobic properties through chemical agents present in the

product, specifically the Silicone, that are applicable to any fabric. After treatment, the samples

were left to dry overnight and then cure it in an oven for 1 min at 160°C.

Conducting Atmospheric Pressure Plasma Jet Treatment on Polyester Fabric Samples

Experimental Treatment and Plasma Jet Treatment Parameters

 The power (15000W)

 The distance between the two electrodes (20mm)

 The distance between the sample and the nozzle (9mm)

 Number of cycles through the plasma zone (60 cycles)

 The process gas (Nitrogen)

 The gas flow into the space formed between the two electrodes (1500 psi)

 The current of the plasma generator (2.05amp)

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Plasma treatment was conducted on dry (dried overnight) polyester fabric samples by

mounting them on a framed and exposed to Nitrogen Atmospheric Pressure Plasma (APP) for

varying intervals of 1s 3s and 5s. All Atmospheric Pressure Plasma (APP) equipment used in the

study was provided and conducted in Ateneo de Manila University- Physics Department.

Table 1. Comparison of parameters for Untreated, Industrially Treated and Plasma Treated

Samples

Parameter Untreated Industrial Plasma

Solvent None Water Gas Phase (None)

Energy None Heat Electricity

# of Samples 10 10 10

Contact Angle Measurement Test

Plasma treated, industrially- treated and untreated samples were mounted on an apparatus

and 4-5 µl of water was dropped onto its surface at a vertical angle using a micro syringe. The

droplets were placed at 6 different sections of the fabric’s samples, after 5 seconds, a microscope

was used to capture pictures of the surface and an analysis program was used to measure the left

and right contact angles of the droplets.

Contact angle is defined geometrically as the angle formed by a liquid at the three-phase

boundary where a liquid, gas and solid intersect. (Scientific, Biolin), defined by the equation,

γsv = γsl + γlv cos θY, where γsv is the surface free energy of the solid, γsl is the interfacial

tension between the solid and the liquid and γlv is the surface tension of the liquid. These values

consequently form the “Young contact angle, θY”.

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Low contact angle values represent a spread-out liquid on a surface thus resulting in

increased wettability and decreased hydrophobicity, while high contact values represent poor

spreading of a liquid resulting in decreased wettability and increased hydrophobicity. This test

was used to determine if the surface of an object is prone or resistant to the adherence of liquids.

Spray Test

Plasma treated, industrially- treated and untreated samples were conditioned in a room

with controlled climate of 20 °C and a relative humidity of 64% for 2 hours. Samples measuring

3x3 in will be attached to a makeshift sample holder at a 45° angle, to stimulate rainfall. The

clipboard should be cut to 5x5 in dimensions to accommodate the 3x3 in sample size. 8 clips

have been provided by the researchers to secure sample in place during testing. Distilled water of

a temperature of 20°C and a volume of 100 mL was sprayed 12 cm above the mounted fabric

samples at constant pressure for 15 seconds. that was sprayed on all samples.

The results were graded by the following rubric:

1- Wetting of the entire sprayed surface

2- Wetting of half the sprayed surface

3- Wetting of the surface only on small separate areas

4- No wetting, but small drops adhere to the sprayed surface

5- No wetting and no adherence of any drops on the sprayed surface

The beads of water droplet on the fabric sample was graded by a visual rating of 100

points as the best and 20 as the lowest passing grade, with the images gathered using the USB

microscope for the contact angle measurement test served as the basis for given grades; with the
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droplet having the highest average angle scored as 100 and the droplet having the lowest average

angle scored as 20.

When referring to the traditional Spray Test (AATCC 22) method, samples must be

greater than 6 inches in diameter however due to the APP’s small treatment area, fabric samples

for this study were greatly decreased in size thus the researchers created a makeshift sample

holder to replace the method’s traditional round metal hoop.

Measuring Hydrophobic Recovery Rate of APP-treated Polyester Fabric Samples

The researchers observed the hydrophobic recovery rate of polyester fabric samples each

day for one week by dropping 10 mL of distilled water on the surface of the fabric samples and

tested if the water wetted and passed through the fabric sample. This is to quantify the time

duration before the delay of the expected hydrophobic recovery or the phenomenon where the

treated textile sample revert to its old surface property, thus inhibiting the hydrophobic properties

obtained from the APP treatment. The results were cited in the conclusion.

Results and Discussion

Contact Angle Measurement

Table 2. Contact Angle (Left), Contact Angle (Right), and Average Contact Angle

Measurements of Untreated, Industrially-treated, and Plasma-treated (1s, 3s, 5s) Polyester Fabric

samples

Contact Angle Contact Angle Average Average

(Left) (Right) Contact Angle Contact Angle

of Each Sample of Each Group

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Untreated 1.1 56.547 52.453 54.500 54.516

Untreated 1.2 50.335 58.729 54.532

Industrially- 85.642 77.115 81.379 74.7615

treated 2.1

Industrially- 68.303 67.984 68.144

treated 2.2

Plasma-treated 78.250 64.031 71.141 77.4915

(5s) 3.1

Plasma-treated 87.598 80.086 83.842

(5s) 3.2

Plasma-treated 102.751 111.748 107.2495 101.6146

(3s) 4.1

Plasma-treated 98.039 93.921 95.9800

(3s) 4.2

Plasma-treated 114.621 114.481 114.551 116.387

(1s) 5.1

Plasma-treated 116.832 119.613 118.223

(1s) 5.2

Table 2 shows the left contact angle, right contact angle, and the average contact angle

measurements of untreated, industrially-treated, and plasma-treated (1s, 3s, 5s) polyester fabric

samples. The scores from the left and right contact angles were averaged and ranked from lowest

to highest.
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The untreated samples exhibited the lowest contact angle measurement with 54.516°,

followed by the industrially-treated samples with 74.7615°, the plasma-treated (5s) samples with

77.4915°, the plasma-treated (3s) samples with 101.6146° while the highest-scoring sample was

proven to be the plasma-treated (1s) samples with 116.387°.

This shows that on the untreated sample, exhibiting the lowest contact angle

measurement, the water droplet was highly spread on the surface and having a contact angle less

than 90° indicates that water wets the surface of the fabric. The industrially-treated samples and

plasma-treated (5s) with contact angle measurement close to each other that is less than 90°

indicates that water wets the surface of the fabric and the water droplet was less spread on the

surface compared to untreated samples. The plasma-treated (3s) and plasma-treated (1s) samples

with a measured contact angle of more than 90° indicates that the water does not wet their

surface and shows poor spreading of the water droplet. The plasma-treated (1s) exhibiting the

highest contact angle measurement shows the most non-wetting of water and poor spreading of

water droplet on its surface among the other fabric samples.

Figure 3-4. Microscopic images and contact angle measurement of water droplets on fabric

samples that were untreated

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Figure 5-6. Microscopic images and contact angle measurement of water droplets on fabric

samples exposed to industrial treatments

Figure 7-8. Microscopic images and contact angle measurement of water droplets on fabric

samples exposed to Atmospheric Pressure Plasma (APP) treatment (5s)

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Figure 9-10. Microscopic images and contact angle measurement of water droplets on fabric

samples exposed to Atmospheric Pressure Plasma (APP) treatment (3s)

Figure 11-12. Microscopic images and contact angle measurement of water droplets on fabric

samples exposed to Atmospheric Pressure Plasma (APP) treatment (1s)

Spray Test

Table 3. Wettability of the fabric samples and visual rating of beading up of water of each

polyester fabric samples

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Samples Wettability of the fabric Visual rating of beading

samples up of water

Untreated 1 E

Industrially-treated 3 C

Plasma-treated (5s) 4 C

Plasma-treated (3s) 3 B

Plasma-treated (1s) 5 A

Table 3 shows the wettability and visual rating of beading up of water on the surface of

the polyester fabric samples. The untreated fabric samples exhibited wetting of the entire sprayed

surface and scored 20 points on visual rating which has the lowest average contact angle

measurement. The industrially-treated samples showed wetting of the surface only on the small

separate areas and scored 60 points on visual rating. The plasma-treated (5s) sample showed no

but small drops adhere to the sprayed surface and scored 60 points on the visual rating. The

plasma-treated (3s) sample exhibited wetting of the surface only on small separate areas and

scored 80 points on visual rating. The plasma-treated (1s) sample showed no wetting and no

adherence of any drops on the sprayed surface and scored 100 points on visual rating having the

highest average contact angle measurement of water droplets.

Hydrophobic Recovery Rate

The hydrophobic recovery rate of the polyester fabric samples was observed each day.

The hydrophobic recovery rate of the untreated fabric samples showed that the water completely
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passed through and wetted the surface of the fabric after 7 days consecutive observation. The

industrially-treated fabric showed that the water partially passed through and wetted the surface

of the fabric. The plasma-treated (1s, 3s, and 5s) fabric samples exhibited beading up of water

droplets on the surface of the fabric thus still maintaining its hydrophobic property even after a

week of treatment.

Conclusions

The results of this research enabled the investigators to come up with these conclusions:

a. Based on the Contact Angle Measurements of the fabric samples, the untreated fabric

sample exhibited the lowest measurement, followed by industrially-treated fabric

samples, plasma-treated (5s), plasma-treated (3s), and plasma-treated (1s) respectively.

The plasma-treated (1s) exhibiting the highest contact angle measurement shows the most

non-wetting of water and poor spreading of water droplet on its surface among the other

fabric samples thus representing increased hydrophobicity and resistance to adherence of

water.

b. Spray Test results showed that the plasma-treated (1s) fabric sample exhibited the highest

rating in the wettability and visual rating of beading up of water on the surface of the

fabric, followed by plasma-treated (3s), plasma-treated (5s), industrially-treated samples,

and the untreated fabric sample respectively.

c. The plasma-treated (1s, 3s, and 5s) fabric samples maintained and retained its

hydrophobic property even after a week of treatment showed by the beading up of water

on its surface upon dropping of water compared to the untreated and industrially-treated
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fabric samples wherein the water passed through and wetted the surface of the fabric.

This shows that the hydrophobic property of the industrially-treated fabric samples

reverted to its old surface property and that Atmospheric Pressure Plasma successfully

prolonged the hydrophobic recovery rate of the polyester fabric samples.

d. Too much exposure to APP proves detrimental to the hydrophobic properties of the

samples and the 1s time interval showed the best result in all test.
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