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. 2025 Sep 26;10(39):44913–44921. doi: 10.1021/acsomega.5c01410

Development of Breathable Waterproof Polyurethane-Coated Cotton Fabric Using Surfactant

Amna Siddique †,*, Noor Fatima †, Shengkai Liu ‡, Abdul Zahir §, Choon Kit Chan ∥, Zhiwei Xu ‡,*, Munir Ashraf †,*
PMCID: PMC12509000  PMID: 41078794

Abstract

The use of polyurethane (PU) coatings to produce water-resistant textiles has grown in popularity over the past few decades. However, they lack breathability, which is crucial for comfort in textile clothing. This research presents the development of a breathable and waterproof polyurethane-based protective fabric tailored for outdoor apparel. A key innovation involves the incorporation of a surfactant into the PU coating formulation, which enables the creation of micropores within the coating. These micropores allow for efficient heat and moisture exchange while maintaining excellent water resistance. The resulting fabric exhibits superior performance, characterized by a high contact angle of 110°, excellent resistance to water penetration of 6.4 cm H2O, exceptional air permeability of 210 L/m2/s, and water vapor permeability of 480 g/m2/day, making it highly suitable for demanding outdoor activities such as sports. The fabric also demonstrates robust mechanical properties, including high water repellency, strong abrasion resistance, and good tear strength. This innovative technique addresses the challenge of balancing breathability and water resistance in waterproof textiles, leading to more comfortable and functional outdoor apparel. Future investigations may explore its broader applications in other textile sectors, where waterproofness and breathability are critical factors. This study additionally endorses the Sustainable Development Goal (SDG 9, Industry, Innovation, and Infrastructure), through its focus on process innovation.

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Introduction

Textiles can be coated to give them additional properties such as flame retardancy, antimicrobial activity, water repellency, UV shielding, abrasion resistance, and other properties that form a nonhomogeneous structure. These properties can be present solely or combined according to the materials and end-use requirements. The need for waterproof, breathable fabrics is increasing rapidly. The reason is the increasing customer demand for outdoor textiles that provide protection and comfort simultaneously.

Functional, waterproof, and breathable textiles are known to prevent the diffusion of liquid water from textiles while transmitting water vapors, which are widely used in practical applications, including biomedical fields, sportswear, and protective clothing. Protective clothing is used in clothes that protect the human body from external temperature, wind, water, and various other toxic agents while allowing effective moisture vapor transmission from an interior to an exterior atmosphere. Their usage can range from their well-known use in foul-weather recreational clothes to specialist medical and military applications.

Breathability refers to the ability of the fabric to enable water vapors to diffuse through the fabric, allowing for evaporative cooling, thus providing a high level of comfort to the wearer in many situations. Undoubtedly, breathable waterproof fabrics, including active sportswear, would be a premium choice for consumers. Moisture management is a crucial requirement of activewear, such as clothing for jogging and climbing, to maintain body comfort.

There are several ways to make breathable and waterproof fabrics. The ability to offer a high degree of comfort and protection has made poly­(tetrafluoroethylene) (PTFE) microporous membranes one of the most widely used waterproof and breathable textiles. Nevertheless, the limitations of low elasticity (30%) and environmental issues brought about by the widespread use of damaging perfluorooctanoic acid in their production still affect these PTFE-based waterproof and breathable membranes.

Microporous and hydrophilic nonporous films are also used to create breathable, waterproof textiles. Microporous films or coatings allow the passage of water vapors, but water droplets cannot pass through the fabric coatings. Polyurethane (PU) is a versatile polymer used in the textiles’ coatings. PU comes in a wide range of essential features and works well with both natural and synthetic textile fibers. Functional polyurethanes were created for a number of uses, including waterborne inks, shape memory polymer, and flame-retardant PU. Additionally, PU coating has been developed for the creation of protective textiles, smart textiles, and functional textiles.

Polyurethane is widely used in the manufacture of breathable films and coatings. Numerous industrial PU-based breathable microporous films are available. , A common polymer, polyurethane, is produced when isocyanate (−NCO) reacts with polyol (polyether polyol or polyester polyol). It can be divided into four categories: waterborne polyurethanes (WPUs), thermoplastic polyurethane elastomers (TPUs), polyurethane foams (PUFs), and polyurethane fibers (Spandex). The PU is generally hydrophobic and insoluble in water. Thus, it must be changed to disperse in water by introducing ionic groups or nonionic hydrophilic regions into the polymer structure.

Several manufacturers developed breathable coatings using modified polyurethane because the process of PU synthesis and modification was simpler and less expensive. Ionic or nonionic hydrophilic segments are added to PU through chemical modification, making the final polymer soluble in water or solvent. Entrants manufactured by Toray Industries and Porelle, produced by Porvair, are microporous films and coatings derived from PU, designed to offer breathable and waterproof properties. A polyurethane film is created for transfer coating and laminating fabric. It can be used alone as a drop liner, “Permatex,” as introduced by J.B. Broadley. Acordis produced the PU-based microporous film “Tarka”, which was used for transfer coating. Hong et al. developed abrasion-resistant and waterproof polyurethane-coated fabric in another study. Three types of resin concentrations (10%, 15%, and 20%) and two types of base fabric (taffeta and taslan) were utilized in the study. It was reported that the PU coating enhanced the fabric's abrasion resistance and waterproofing properties. Furthermore, the base fabric's flatness is crucial in achieving a more uniform coating and improved performance when waterborne PU is applied to the fabric. Bramhecha and Sheikh et al. synthesized PU from functional polyol and applied it to cotton fabric to impart functional properties. The resultant fabric exhibited high antibacterial water barrier properties and a 1506 g of water vapor transmission rate per day, which indicates nonporous breathable coatings. Another work was done by Jin et al., to develop superhydrophobic and breathable PU materials by incorporating SiO2 nanoparticles (SNPs) using a sol–gel electrospinning method. The addition of SNPs enhanced surface roughness, achieving superhydrophobicity with high water contact angles and low shedding angles. Laminating these PU/SNP webs onto polyester fabrics maintained air permeability and water vapor transmission rate, indicating their potential for practical textile laminate applications.

Gunesoglu et al. presented a facile method, microcracking, applied through a solvent bath that differed in solvent type, concentration, and duration. Furthermore, salt usage has been reported to increase the breathability of PU-based polymer coatings. However, salts do not produce stable emulsions with polymers, resulting in nonuniform porous morphology in the coatings. Developing breathable coatings in such a way is not sustainable and is time-consuming.

The use of polyurethane coatings to produce water-resistant textiles has grown in popularity over the past few decades. However, they lack breathability, which is crucial for comfort in clothing. The existing studies on moisture-permeable waterproof PU-coated fabrics implies the usage of solvents and pore forming materials such as salts. , Thus, this potentially involves higher material and process costs. In this work, breathability was imparted to the fabric using PU polymer coating by surfactant addition and subsequent rinsing, allowing the soluble parts of the coating (surfactant) to dissolve, leaving behind micro spaces that enhance breathability. This work is in alignment with SDG 9 (which advocates sustainable Infrastructure, industrialization through innovation), as this is a simpler and potentially more cost-effective method to introduce breathability in PU-coated cotton fabric, allowing moisture vapor to escape, a fundamental requirement for clothing comfort in outdoor activities.

Materials and Methods

100% cotton woven bleached fabric with a weight of 180 g/m2 and construction of (22 × 22/100 × 80) was purchased from a local market. A commercially available aliphatic polyether-based thermoplastic (water-based) polyurethane was procured from Covestro, Germany. Anionic hydrophilic polyisocyanate cross-linker with 100% Solid Content was purchased from a local supplier in Pakistan. A low viscosity anionic vinyl polymer-based thickening agent, i.e., Lutexal HiT, was procured from Archroma. Fatty alcohol ethoxylates-based surfactant (Felosan RGN) with a specific weight of ∼0.98 was purchased from CHT Group. No modification or functionalization was performed on procured materials and were used as received. The coating formulation was prepared by using PU (50% v/v), cross-linker (5% v/v), and thickener. Felosan RGN surfactant (a liquid nonionic surfactant free from enzyme toxins) was added, and the resultant mixture was mechanically stirred for 2 h at 800–900 rpm. Finally, a paste-like formulation was obtained, which was used to coat the cotton fabric. The thickening agent was used to maintain rheological properties and uniform paste application, while the surfactant was utilized to create microporosity. The paste was placed into a vacuum oven for 24 h for degassing. The surfactant was added in different concentrations, as given in Table .

1. Design of Experiment for the Optimization of Breathable Coatings.

sr. no. polyurethane thickening agent (wt % of PU) sample code surfactant concentration (wt % of PU)
1 100 g 0.4 A0 0
2 A1 1
3 A2 2
4 A3 3
5 A4 4
6 A5 5
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Application of Synthesized Coating on Cotton Fabric

The paste was applied on bleached cotton fabric through knife-over-roller coating. The cotton fabric was coated with one layer of a 0.02 mm-thick paste. Then, the fabric was dried at 100 °C for 5 min and cured at 150 °C for 3 min.

Washing of Coated Cotton Fabric

The coated fabric was loaded between the rollers of a low-pressure jigger machine. Distilled water was added to the machine to wash the coated fabric thoroughly. Washing was carried out on the machine for 1 h at 30 °C; finally, the fabric was rinsed with tap water and air-dried. The systematic process for applying PU-based coating is illustrated in Figure .

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Schematics of PU-based coating preparation and application.

Characterization

The functional groups on controlled (without any coating) and coated fabric samples were analyzed using the Fourier transform infrared Spectroscopy (FTIR) (Perkin-Elmer, Spectrum Two, U.K.). A scanning electron microscope (FEI, Quanta-250, Netherlands) was used to visualize the surface morphology of the controlled and coated fabric samples.

The water repellency of coated fabrics was measured by a spray tester using the standard method AATCC: 22. The samples of 180 × 180 mm2 in size were tied to a 152.4 mm diameter hoop and positioned at an angle of 45°. Later, 250 mL of distilled water was permitted to be sprayed continuously on the front of the test specimen throughout the test. The design formed on fabric samples by water spraying was evaluated using the rating chart provided with the device.

The BS 7209:1990 standard protocol was used to determine the materials’ water vapor permeability (WVP) using a water vapor permeability tester (Refond, RF4319, China). A circular specimen with a diameter of 74 mm was airtight on the open mouth of the cup and kept in standard environmental situations: a temperature of 20 ± 2 °C and a relative humidity of 65 ± 5%. The cup was loaded with 100 mL of distilled water, leaving a difference of 19 mm between the fabric and water level. The air rate above the sample was maintained at 2.8 m/s. After 24 h, the cups were reweighed.

The WVP is given by

WVP=G×24/t×A 1

where WVP is the water vapor permeability (g/m2 /day), G is the weight change (g), t is time during which G occurred (h), and A is the test area (m2).

The fabric’s resistance to water penetration was measured on a hydrostatic head apparatus tester following the AATCC 127 test method. The specimen was clamped at a force of 50 ± 5 N across a test head area of 38.3 cm2. The following conditions were maintained during the test: temperature 21.8 °C, humidity 64.0%, mean pressure (cm H2O) 41.7, water temp. 21 ± 2 °C and a pressure increase rate of 60 cm H2O/min. The air permeability test was performed by following the ISO 9237:1995 protocol.

The tear strength of both coated and controlled fabric samples was evaluated using the Elmendorf tear (Gateslab, GK-2, France), in accordance with the ISO 13937-1:2000 standard test procedure. A sector-shaped pendulum with a moving sample clamp and a stationary clamp on the frame forms the device. A split cut in the specimen between the clamps initiates the rip. The pendulum’s pointer is graded, allowing the ripping force to be read immediately.

The abrasion resistance test was determined using the Martindale Pilling & Abrasion Tester (Roaches, Omron, U.K.), following the ISO 12947-2:2016 standard method. The samples were exposed to abrasion at the specified number of cycles. The endurance of coated textiles to scratches is usually one of the various parameters influencing wear performance in real-world applications.

A contact angle of water droplets and fabric samples was measured by using an optical tensiometer (Theta Lite, Finland). The water contact angle is the measure of the hydrophilicity or hydrophobicity of the fabric samples. ISO:19403 was followed to find the contact angles of the fabric samples.

Results and Discussion

FTIR

The FTIR spectra of the polyurethane-coated and control cotton fabric are portrayed in Figure . As shown in Figure a, the FTIR spectrum of the controlled cotton fabric exhibits characteristic peaks of cellulose and hemicellulose present in cotton. The broad transmittance peak centered at 3295 cm–1 is associated with the stretching vibration of the −OH group linked to cellulose and absorbed water molecules. The peaks at 2930 and 2845 cm–1 are ascribed to the symmetric and asymmetric −CH stretchings associated with cellulose and hemicellulose. The shallow transmittance peaks at 1417 and 1320 cm–1 correspond to the bending vibrations of −CH2 and −OH, respectively. Likewise, the shallow characteristic peaks at 1116 and 1030 cm–1 are ascribed to antisymmetric deformation of the C–O–C bond and −CO stretching, respectively. − The characteristic peaks of cotton reported in this study are consistent with those reported in previous studies. − A significant change in the FTIR spectrum can be observed (Figure b,c) after the uniform polyurethane coating with and without the surfactant. The intense transmittance peak at 1733 cm–1 is associated with the stretching vibration of −CO present in the urethane linkages of the monomer. Moreover, the weak peak at 1548 cm–1 is due to the in-plane bending vibration of −NH–. The presence of these peaks confirms the successful coating of polyurethane on the cotton fabric. Furthermore, it can be seen in Figure d,e that the washing of the fabric does not wipe out the polyurethane coating from the cotton fabric.

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FTIR spectra of (a) cotton fabric, (b) PU-coated cotton without the surfactant before washing, (c) PU-coated cotton with the surfactant before washing (sample A3, surfactant concentration: 3% of PU), (d) PU-coated cotton without the surfactant after washing, and (e) PU-coated cotton with the surfactant after washing (sample A3, surfactant concentration: 3% of PU).

It is important to note that the FTIR technique used in this study did not provide any significant information regarding the presence of the surfactant, as no spectral differences were observed between the PU-coated cotton fabric with and without the surfactant. This could be due to two possible reasons: (i) the surfactant may contain similar functional groups to those in polyurethane and cotton fabric, causing overlapping peaks that merge with the characteristic peaks of these materials, masking any new spectral features associated with the modification, or (ii) the surfactant may have an inorganic composition. Inorganic compounds are sometimes less detectable in IR spectra if they lack polar bonds or their vibrational modes do not generate strong dipole moments, making it difficult for IR light to effectively excite their vibrational states, Moreover, if their vibrational modes occur outside the detection range of FTIR, i.e., wavenumber <400 cm–1, characteristic peaks of those inorganic functional groups may not be observed in FTIR analysis.

Scanning Electron Microscope Analysis

Scanning electron microscopy (SEM) analysis of controlled and PU-coated cotton fabric with and without surfactant provides insights into the microstructural changes and surface morphology of the developed fabric, as shown in Figure . The rinsing of the fabric with distilled water after coating with PU and surfactant, as described in the Materials and Methods, removes the surfactant from the fabric. This leaching of the surfactant during washing results in a less uniform surface with minor delamination; thus, the SEM micrograph of PU-coated cotton with the surfactant exhibits surface roughness and porosity, which enhances the performance of the coated fabric in terms of water repellence, moisture management, and overall durability.

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Morphological analysis of (a) plain cotton, (b) plain PU-coated cotton, and (c) PU-coated cotton fabric with surfactant (sample A3; surfactant concentration: 3% of PU).

Spray Test Rating

The water repellency results of the samples by the spray test may be deduced from the provided images (Figure ), showing the wetting patterns of the PU-coated fabric samples. Water repellency of fabric describes the ability to resist wetting of fabric by water. A standard rating system was used to visually assess the water repellency of uncoated and PU-coated fabric samples. This system gives descriptive and numerical rating scales (0–100) to show the water-repellency results. Cotton fiber has very high wettability, so it is the least resistant to water penetration; as a result, the control cotton fabric sample had the lowest spray rating of 0. In Figure , A0 shows “sticking or wetting of the upper surface”, which is rated 100 on a numerical scale. A1 shows “slight random sticking or wetting of upper surface” (very good water repellency), which is rated 90. Meanwhile, A2 and A3 show “wetting of upper surface at spray points,” which is rated at 80. A4 and A5 are “the partial wetting of the whole of the upper surface,” and they are rated 70. However, the inner surface of the coated fabric was dried entirely. The coating of the PU over the cotton fabric forms a uniform layer that penetrates the porous structure of the cotton fabric. The PU layer blocks the microporous structure of the cotton fabric and thus hinders water droplets’ absorption into the cotton fabric through those pores. However, incorporating surfactant decreases the surface tension of the PU solution, which helps the solution spread homogeneously on the cotton fabric, creating micropores in the PU layer. These micropores compromise the water repellency of the cotton fabric by allowing the diffusion of water droplets into the cotton fabric. This can also be evident from Figure , which shows that the water repellency decreases with the increase in surfactant concentration. Hence, a low surfactant concentration should be used to make the fabric breathable while maintaining its water repellency. These water-repellency values are comparable to the literature on waterproof and breathable textiles.

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Wetting patterns of PU-coated fabric samples.

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Effects of the concentration of surfactant on waterproofness.

Hydrostatic Pressure Test

Polyurethane acts as a sealant, making the PU-coated cotton fabric waterproof. Figure shows that the sample coated with polyurethane without surfactant (A0) exhibited the highest water penetration resistance (8.5 cm H2O) due to the absence of micropores in the coating. The polyurethane coating itself is water-repelling. Without any surfactant, PU forms a continuous, intact film that effectively blocks water penetration. The water penetration resistance of other samples decreased (ranging from 6.4 to 8.5 cm H2O) as surfactant concentration increased, likely due to enhanced micropore formation. As the surfactant concentration increases, the interaction of surfactant molecules with water during the washing process increases, leading to void and pore formation as the surfactant dissolves. The formation of voids and pores disrupts the hydrophobic nature of the PU coating. This disruption weakens the ability of the coating to resist water pressure, hence decreasing the hydrostatic pressure resistance. However, a 2 cm H2O fluctuation in water penetration resistance values of samples is generally considered insignificant. These results align with previous research by Ghezal et al., who applied a polymer coating (acrylic paste and fluorocarbon resin) to create a waterproof, breathable fabric.

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Effect of surfactant concentration on water penetration.

Water Vapor Permeability

Figure presents the water vapor permeability of different fabric samples (A0, A1, A2, A3, A4, and A5). A controlled cotton fabric sample has a water vapor permeability of 530 g/m2/day. We can see that water vapor permeability increases as the concentration of surfactant added to PU coating increases (148–480 g/m2/day). A clear positive correlation between surfactant concentration and WVP. Pure polyurethane forms a relatively dense and hydrophobic film, which acts as a barrier to water vapor transmission. As surfactant concentration increases in PU coating, the chance of generating micropores elevates. This is due to the polarity of the surfactant component in the coating, which is soluble in water. During washing, the soluble part of the coating dissolves and generates micropores. The water vapor permeability results seem promising based on literature comparisons. , According to the literature, textiles with a water vapor permeability of 400 g/m2/day are termed as “breathable”.

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Effects of the concentration of surfactant on water vapor permeability.

Air Permeability

The air permeability of textiles is the measure of the breathability of a fabric, whether controlled or coated, to meet specific requirements. A controlled cotton fabric shows a high air permeability (300 L/m2/s) due to a large number of holes in the fabric structure, which allows air to pass through. However, a PU-coated cotton fabric sample showed a rapid decrease in air permeability (140 L/m2/s), as shown in Figure . The fabric’s cover factor and weave structure significantly affect its air permeability. , Air permeability is inversely proportional to the cover factor. The PU coating gives complete coverage to the fabric after drying and curing, where molecules are fixed. In Figure , the PU-coated cotton sample with zero surfactant showed minimum air permeability, while the air permeability value shows an increasing trend by increasing surfactant concentration. Micropores act as tiny channels through which air passes through the PU-coated fabric. This increase in air permeability is attributed to the generation of micropores; a similar trend was observed in the literature.

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Effect of the concentration of surfactant on air permeability.

Abrasion Resistance

The durability of the PU-coated fabric and the adhesion between the PU coating and cotton were assessed using an abrasion resistance test. It measures the resistance offered by the coated fabric against abrasion. The abrasion resistance of the controlled sample was 35,000 cycles due to the sample’s thread breakage. Figure shows that all of the samples with a coating over them showed an improved resistance toward abrasion. Coated samples show abrasion resistance around 44 000 cycles. These results are supported by a previous study. PU coating makes a protective layer on the cotton fabric’s surface. This layer acts as a barrier between the abrasive surface and the cotton fibers. The smooth surface created by the PU coating reduces friction between the abrasive surface and fabric, which minimizes fabric damage by applying abrasive force.

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Resistance of coated fabric toward abrasion.

Tear Strength

Figure shows that the samples’ tear strength decreased as the surfactant concentration increased. The polyurethane coating acts as a very strong binder and sealant. A PU coating without surfactant strengthens the fabric by acting as a reinforcing layer, increasing the fabric’s strength against physical forces such as abrasion and tear force. Hence, it showed a significant value against the tearing force. Because surfactant creates micropores in the coating, it acts as a weak point on the coated fabric and tends to initiate and propagate tear. That is why the tear strength decreased when surfactant was introduced into the coating. However, the effect of surfactant concentration change on tear strength seems very marginal.

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Effect of the concentration of surfactant on tear strength.

Contact Angle

The hydrophobicity of the coated fabrics was assessed by measuring the static water contact angle. A droplet of distilled water was carefully deposited onto the fabric surface, and the contact angle formed between the water droplet and the fabric was measured at seven different positions on the coated fabric. The mean value of these measurements was used in the current study to report the reliable, accurate, and average contact angle value of each sample. According to the literature, a water contact angle greater than 90° indicates hydrophobic or nonwetting behavior, while an angle less than 90° shows partial wetting. Figures and illustrate the measured contact angles, which ranged from 85 to 110.57°. The plain PU-coated cotton sample exhibited the highest contact angle of 110.57°, confirming the inherent hydrophobic nature of the PU coating. A gradual decrease in the contact angle with increasing surfactant concentration was observed. This decrease suggests enhanced wetting and a decrease in the hydrophobicity. This can be attributed to the increased microporosity in the coating, allowing water to easily penetrate the coating and increasing the contact area between the water droplet and the solid surface, thereby reducing the observed contact angle. This may also be due to the absorption of the surfactant molecules onto the fabric surface, increasing its affinity for water and consequently lowering the contact angle. Figure shows a pictorial representation of the contact angle. Table presents a comparison of the key performance metrics of waterproof breathable fabrics evaluated in this study with those in the existing literature.

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Effect of the concentration of the surfactant on wettability.

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Pictorial representation of contact angle.

2. Comparison of Waterproof, Breathable Fabric Characteristics.
characteristic existing fabric 1 existing fabric 2 existing fabric 3 fabric developed in this study
spray test rating 75–90     65–90
hydrostatic pressure (cm H2O)   8 3.1–6.3 6.5–8.5
water vapor permeability/water vapor permeability index   58–88% 26% 250–480 g/m2/day
air permeability (L/m2/s) 0.5–1.5 50–221 52 150–210
contact angle (deg) 65–85     84–108
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Conclusions

This study successfully developed a breathable, waterproof PU-based protective fabric suitable for outdoor apparel applications. Adding a surfactant into the PU coating formulation proved critical in creating micropores, offering a tradeoff between the coated fabric’s water repellency and abrasion resistance while improving breathability, air permeability, and tear strength.

The proposed method offers a promising solution for addressing the limitations of traditional polyurethane coatings regarding breathability. The treated fabric exhibits highly desirable properties for outdoor clothing, including sports garments, where protection against both water and wind is essential. Adding more to this, operational parameters and the surfactant concentration can influence the coating durability and coating solution’s rheological properties, thereby impacting the coating fabric’s performance and porosity. However, a comprehensive investigation is required to elucidate the influence of these parameters on the fabric’s porosity, water repellency, breathability, air permeability, and tear strength. Such a detailed analysis will help to employ this technique and material for its potential commercialization.

Acknowledgments

The authors would like to acknowledge Dr. Saba Akram for helpful discussion and support concerning this research work.

This research work has been sponsored by the Higher Education Commission of Pakistan under ”Rapid Research Grant” RPG No. 74.

The authors declare no competing financial interest.

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