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Page 1

plasma
Article
Physical Properties of Plasma-Activated Water
Mobish Shaji 1 , Alexander Rabinovich 1, *, Mikaela Surace 1 , Christopher Sales 2                             and Alexander Fridman 1

                                         1   C and J Nyheim Plasma Institute, Drexel University, Camden, NJ 08103, USA
                                         2   Department of Civil, Architectural and Environmental Engineering, Drexel University,
                                             Philadelphia, PA 19104, USA
                                         *   Correspondence: ar483@drexel.edu


                                         Abstract: Recent observations of plasma-activated water (PAW)’s surfactant behavior suggest that
                                         the activation of water with non-equilibrium plasma can decrease the surface tension of the water.
                                         This suggested change to the surface tension also indicates that the addition of plasma can lead
                                         to changes in the physical properties of the water, knowledge of which can expand existing PAW
                                         applications and open new ones. While the chemical behavior of PAW has been extensively analyzed,
                                         to the best of our knowledge the physical properties of PAW have not been investigated. This study
                                         focuses on the need for experimental determination of PAW’s physical properties—namely, surface
                                         tension, viscosity, and contact angle. The experimental results of this study show that the addition of
                                         plasma lowers the surface tension of water at room temperature, increases the viscosity of water at
                                         high temperatures, and lowers the contact angle of droplets on glass surfaces at room temperatures.
                                         Potential factors influencing these changes include plasma alteration of the mesoscopic structure
                                         of water at low temperatures and plasma additives acting as foreign particles in water at higher
                                         temperatures. Ultimately, this investigation demonstrates that the physical properties of water change
                                         due to plasma activation, which could lead to potential industrial applications of PAW as a surfactant
                                         or as a washing-out and cleaning agent.

                                         Keywords: plasma-activated water; PAW; physical properties; surface tension; viscosity; contact angle



Citation: Shaji, M.; Rabinovich, A.;
Surace, M.; Sales, C.; Fridman, A.
                                         1. Introduction
Physical Properties of                         Non-thermal plasmas generated in ambient air, as well as in oxygen- or nitrogen-
Plasma-Activated Water. Plasma 2023,     containing working gases and noble gases, produce a variety of reactive oxygen and
6, 45–57. https://doi.org/10.3390/       nitrogen species (RONS), e.g., ozone, hydroxyl radicals, hydrogen peroxide, superoxide,
plasma6010005                            and nitrogen oxides. The interaction of plasma with liquid media leads to the transport
Academic Editor:
                                         of RONS into the liquid and the formation of secondary active species. In water, the
Andrey Starikovskiy                      main reactive species formed by plasma activation are OH radicals, ozone, hydrogen
                                         peroxide, nitrites, nitrates, peroxynitrites, and peroxynitrates; water activated in this way
Received: 22 December 2022               with non-thermal plasma is called plasma-activated water (PAW) [1]. PAW is considered to
Revised: 13 January 2023
                                         be a green and prospective solution for numerous biotechnology applications, due to the
Accepted: 18 January 2023
                                         transient nature of its biochemical activity. The biochemical activity of PAW is derived from
Published: 30 January 2023
                                         the synergistic effects of active species—especially RONS. PAW currently has numerous
                                         applications, including but not limited to surface disinfection, seed germination, use as a
                                         fertilizer, inactivation of plant-based pathogenic organisms, curing fungus-infected plants,
Copyright: © 2023 by the authors.
                                         food preservation, wound healing, deactivation of bacteria and viruses, mouthwash due to
Licensee MDPI, Basel, Switzerland.       its bactericidal and fungicidal efficacy, selective killing of cancer cells, and insecticides [2–8].
This article is an open access article         Plasma-activated water, because of its active biological properties, has been extensively
distributed under the terms and          studied in order to understand plasma’s interactions with water [9], the production and behavior
conditions of the Creative Commons       of active species [1], differences in the production of active species under varying plasma
Attribution (CC BY) license (https://    gases [8], identification and quantification of chemical species [3], transfer of specific active
creativecommons.org/licenses/by/         species—namely, RONS species—to the liquid [10], and differences in the production of active
4.0/).                                   species with varied plasma systems and production parameters [11]. As a result of these detailed



Plasma 2023, 6, 45–57. https://doi.org/10.3390/plasma6010005                                                 https://www.mdpi.com/journal/plasma

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Plasma 2023, 6                                                                                                   46




                 studies into the chemical behavior of PAW, there is an excellent understanding of PAW’s chemical
                 properties and biological behavior. For example, the antiviral behavior of PAW is attributed to
                 the short-lived ONOO- species [5], the plant growth improvement effect of PAW is attributed
                 to the aqueous nitrate, nitrite, and ammonium ions and hydrogen peroxide species [3], and
                 the antibacterial properties of PAW are attributed to the short-lived reactive oxygen species [4].
                 Until this study, the investigated physicochemical properties of PAW included pH, ORP, and
                 electrical conductivity; these properties were investigated in relation to the chemical properties
                 and behavior of PAW, as they are indicators of reactive species in the PAW [12].
                       While scientific interest and the number of publications related to plasma control of
                 the chemical properties of water are growing exponentially, to the best of our knowledge no
                 studies to date have focused on the physical properties and physical behavior of PAW. In a
                 recent study, J He et al. [13] observed that, while deactivating E. coli bacteria on the surface
                 of fresh produce, PAW significantly washed out or physically removed the E. coli from the
                 produce surface. While the RONS in PAW can deactivate bacteria, they cannot physically
                 remove them. This bacterial washing-out behavior of PAW is an indicator of its low
                 surface tension, or surfactancy. Therefore, these results suggest that the addition of plasma
                 brings about changes in the thermodynamic properties (e.g., surface tension) of water. If
                 the surface tension of the water is reduced via, plasma activation as suggested by J He
                 et al. [13], the potential of PAW as a surfactant widens quickly, as there are numerous fields
                 that could benefit from a liquid with anti-pathogenic and surfactant properties. Potential
                 applications for PAW as a surfactant might include use as a washing-out and cleaning agent,
                 an ingredient for eco-friendly detergents and soaps, surfactants for biomedical applications,
                 and more. Furthermore, since we have an indication that the addition of plasma can change
                 the surface tension of water, other physical properties of water could also be affected by the
                 addition of plasma. Investigating these properties is important to finding areas of potential
                 PAW applications.
                       Surface tension is the measure of force acting at the boundary of two phases. It refers
                 to the elastic tendency of fluid surfaces that makes them acquire the least possible surface
                 area. At the liquid–air interface, the greater attraction of liquid molecules to one another
                 than to air molecules results in surface tension. Hence, the cohesive force between the
                 liquid molecules is higher than the adhesive force between liquid and air molecules. This
                 results in an inward force at the liquid surface that causes it to behave as if the surface
                 were covered with an elastic membrane. Because of the high attraction of water molecules
                 to one another, water has a high surface tension (0.0728 N/m at 20 ◦ C) compared to
                 many other liquids. The surface tension of a liquid can provide insights into its capillarity
                 behavior, surfactant properties, etc. As a liquid with growing uses in the cleaning and
                 agriculture industries, insights into the surface tension properties of PAW can be useful for
                 its economical industrial adoption.
                       Viscosity, or more precisely shear viscosity, is the property that defines the quantitative
                 relationship between the applied shear stress and the shear deformation rate in a fluid.
                 Qualitatively, viscosity indicates the resistance to flow of a fluid. Since viscosity is the
                 property that controls and quantifies the shear stress/shear rate behavior in fluids, it is
                 in many regards the most important physical property of a fluid. Viscosity is stated in
                 two different forms: the absolute or dynamic viscosity (µ), and the kinematic viscosity or
                 momentum diffusivity (ν), where ν = µ/ρ and ρ is the fluid’s density [14].
                       The contact angle is another fundamental property of interest when the interface between
                 two fluids is also in contact with a surface, e.g., a water drop resting on a leaf. The contact
                 angle is dependent on the surface energy of the solid and describes how liquids spread on a
                 surface—vital information for dynamic liquid–solid processes such as coating and painting. In
                 addition, precise measurements of the contact angle between a fluid–fluid interface and a solid
                 surface are critical to deduce the wetting and spreading characteristics of liquids on surfaces, as
                 well as to calculate the surface energy of a solid by measuring the contact angle of a series of
                 liquids on one type of surface. These surface properties are important when considering, for
                 example, the application of dyes to surfaces and pesticides to plants [15].

Page 3

coating and painting. In addition, precise measurements of the contact angle between a
                                      fluid–fluid interface and a solid surface are critical to deduce the wetting and spreading
Plasma 2023, 6
                                      characteristics of liquids on surfaces, as well as to calculate the surface energy of a solid 47
                                      by measuring the contact angle of a series of liquids on one type of surface. These surface
                                      properties are important when considering, for example, the application of dyes to sur-
                                      faces and pesticides to plants [15].
                                           Since  studiesinvestigating
                                           Since studies   investigatingthe thephysical
                                                                                 physical    properties
                                                                                          properties       of PAW
                                                                                                       of PAW        (such
                                                                                                                  (such      as surface
                                                                                                                         as surface       tension,
                                                                                                                                     tension,
                                      viscosity, and
                                      viscosity,      contactangle
                                                 and contact    angleare
                                                                       arevery
                                                                            verylimited),
                                                                                  limited),   there
                                                                                            there  is is  a strong
                                                                                                      a strong      need
                                                                                                                 need       to investigate
                                                                                                                        to investigate       these
                                                                                                                                         these
                                      behaviors.   Insights  into  the physical    properties    of PAW     will  provide    users
                                      behaviors. Insights into the physical properties of PAW will provide users with a better      with   a better
                                      understanding
                                      understanding of ofthe
                                                           thephysical
                                                                physicalbehavior
                                                                           behavior  ofof  PAW
                                                                                         PAW   andandof of  plasma’s
                                                                                                         plasma’s                 withwith
                                                                                                                        interaction
                                                                                                                    interaction         waterwater
                                      during
                                      during PAW generation, and they will also help users identify properties that can be ap- be
                                               PAW   generation,     and  they   will   also help   users    identify  properties    that   can
                                      plied to to
                                      applied     present
                                               present and and  future
                                                             future     areas
                                                                     areas     of need.
                                                                           of need.       In order
                                                                                      In order      to address
                                                                                                to address    thisthis
                                                                                                                   research   gap,gap,
                                                                                                                       research    this this
                                                                                                                                        studystudy
                                      focuses     the changes
                                      focuses on the  changesoccurring
                                                                 occurringininthethephysical
                                                                                      physical   properties
                                                                                              properties       of water
                                                                                                            of water  as aasresult
                                                                                                                              a result of plasma
                                                                                                                                   of plasma
                                      activation—namely,
                                      activation—namely, the  thesurface
                                                                  surfacetension,
                                                                           tension,viscosity,
                                                                                       viscosity,and
                                                                                                  andcontact
                                                                                                         contact  angle
                                                                                                                angle  of of PAW.
                                                                                                                          PAW.

                                      2.
                                      2. Materials andMethods
                                         Materials and Methods
                                      2.1.
                                      2.1. PAW
                                           PAW Production
                                               Production
                                             The plasma-activated
                                            The    plasma-activated water   water used
                                                                                     usedininthis
                                                                                                thistudystudywaswasproduced
                                                                                                                       produced    with   gliding
                                                                                                                                        with        arc plasma.
                                                                                                                                              gliding    arc
                                      Gliding
                                      plasma. arc    plasma
                                                 Gliding    arc is    transient
                                                                  plasma            non-equilibrium
                                                                             is a transient                type oftype
                                                                                              non-equilibrium         discharge       with awith
                                                                                                                             of discharge      relatively
                                                                                                                                                     a rela-high
                                      microarc    temperature       (about 1600–1800        ◦
                                      tively high     microarc temperature           (about K).   In the gliding
                                                                                               1600–1800     °K). Inarc theplasmatron
                                                                                                                               gliding arc(Figures     1 and 2),
                                                                                                                                              plasmatron
                                      air is injected
                                      (Figures   1 andtangentially
                                                         2), air is injectedinto the   gap between
                                                                                   tangentially           twogap
                                                                                                   into the     cylindrical
                                                                                                                    between electrodes,          and elec-
                                                                                                                                   two cylindrical     a vortex
                                      of  air isand
                                      trodes,    created     in the
                                                        vortex         gap.
                                                                  of air        As energy
                                                                          is created   in theisgap.
                                                                                                 supplied
                                                                                                      As energybetween        the high-
                                                                                                                    is supplied             and the
                                                                                                                                      between     low-voltage
                                                                                                                                                      high-
                                      electrodes,
                                      and low-voltagethe plasma       discharge
                                                            electrodes,              occurs
                                                                             the plasma        betweenoccurs
                                                                                           discharge       the electrodes.
                                                                                                                  between the      The   air vortex
                                                                                                                                      electrodes.     stretches
                                                                                                                                                    The  air
                                      and
                                      vortexrotates  the gliding
                                               stretches   and rotatesarc, the
                                                                             thereby   producing
                                                                                 gliding  arc, thereby theproducing
                                                                                                            plasma zone         inside the
                                                                                                                          the plasma         plasmatron.
                                                                                                                                          zone  inside the As
                                      plasmatron.
                                      water            As water
                                              is injected            is injected
                                                              into the    plasmatron into axially
                                                                                           the plasmatron
                                                                                                     from theaxially
                                                                                                                  top, the  fromwaterthedroplets
                                                                                                                                          top, the react
                                                                                                                                                     waterwith
                                      droplets   react   with    the  air  that  is coming     out  of  the plasmatron,
                                      the air that is coming out of the plasmatron, producing PAW. After being processed       producing     PAW.     After
                                                                                                                                                          in the
                                      being processed
                                      gliding               in the gliding
                                                arc plasmatron,         differentarc kinds
                                                                                     plasmatron,
                                                                                             of activedifferent
                                                                                                          species kinds
                                                                                                                     (such          OH species
                                                                                                                                active
                                                                                                                            of as        radicals,(such   as
                                                                                                                                                     hydrogen
                                      OH radicals,
                                      peroxide,    NOx,hydrogen
                                                          etc.) areperoxide,
                                                                       produced    NOx,   etc.)
                                                                                      in the    are produced
                                                                                              water.    The pH of  in the
                                                                                                                      PAW   water.    The as
                                                                                                                                is 2–2.9,       of PAW is
                                                                                                                                           pHopposed      to the
                                      2–2.9,of
                                      5.5–6   asdistilled
                                                 opposedwater. to theThe
                                                                       5.5–6   of distilledparameters
                                                                             operational      water. The of  operational      parameters were
                                                                                                                the PAW production            of theasPAW
                                                                                                                                                        follows:
                                      production
                                      60–100    mL/minwere as     follows:
                                                              water    flow60–100       mL/minSLPM
                                                                                rate; 40–100        waterplasma
                                                                                                            flow rate; air 40-100
                                                                                                                            flow rate. SLPMThe plasma    air
                                                                                                                                                   experiment
                                      flowperformed
                                      was    rate. The experiment
                                                           using 400–1900 was performed
                                                                                    W plasma   using
                                                                                                  power.400–1900
                                                                                                              The W      plasma
                                                                                                                    gliding       arcpower.   The gliding
                                                                                                                                       plasmatron      used for
                                      arc plasmatron
                                      PAW     productionused        for study
                                                               in this   PAW production
                                                                                  is shown ininFigure this study
                                                                                                              1, and is ashown
                                                                                                                           schematic in Figure
                                                                                                                                           of the1,gliding
                                                                                                                                                     and a arc
                                      schematic     of the gliding     arc  plasmatron’s
                                      plasmatron’s operational principle is shown in Figure 2.operational    principle     is  shown    in Figure   2.




    Plasma 2023, 6, FOR PEER REVIEW                                                                                                               4

                                      Figure 1. Gliding
                                      Figure    Glidingarc
                                                        arcplasmatron
                                                            plasmatronsetup.
                                                                       setup.




                                      Figure 2.
                                      Figure 2.Working
                                                Workingprinciple
                                                        principleof the gliding
                                                                    of the      arc plasmatron.
                                                                            gliding arc plasmatron.

                                      2.2. Surface Tension Measurement Method
                                           For more than a century, a variety of techniques have been used to measure the in-
                                      terfacial tension between immiscible fluid phases. When we discuss the interfacial ten-
                                      sion between a liquid and a gas, we call it surface tension. The different surface tension

Page 4

Plasma 2023, 6                                                                                                          48




                                    2.2. Surface Tension Measurement Method
                                         For more than a century, a variety of techniques have been used to measure the
                                   interfacial tension between immiscible fluid phases. When we discuss the interfacial
                                   tension between a liquid and a gas, we call it surface tension. The different surface tension
                                   measurements are described in detail by Drelich et al. [16]. The different types of surface
                                   tension measurements can be divided into five groups: The first group of techniques directly
                                   measure the surface tension with a microbalance. Examples from this group include the
                                   Wilhelmy plate and Du Noüy ring methods. The second group of techniques determines
                                   surface tension through direct measurements of capillary pressure. Examples from this
                                   group include the maximum bubble pressure and growing drop methods. The third group
                                   of techniques relies on the balance between surface tension forces and variable volumes
                                   of liquid to determine the liquid’s surface tension. Examples from this group include
                                   the capillary rise and drop volume methods. The fourth group of techniques is based on
                                   fixing the volume of the liquid and measuring the distortion of a drop of the liquid under
                                   the influence of gravity. Examples from this group include the pendant drop and sessile
                                   drop methods. The fifth group of techniques, used to measure ultralow surface tensions,
                                   involves distortion of the shape of the liquid using centrifugal force. The pendant drop
                                   method was chosen for surface tension measurements in this study, as it is the simplest,
                                   most robust, and most versatile method. Surface tension measurement using the pendant
                                   drop method consists of suspension of a liquid droplet from a needle [17].
                                         Pendant drop tensiometry using OpenDrop software was chosen as the surface tension
                                   measurement method for this project because of its accuracy and open-source nature [16,17].
                                   Pendant drop tensiometry is performed by generating droplets of the liquid to be analyzed
                                   using a syringe pump, capturing an image of the generated droplet, and iteratively fitting
Plasma 2023, 6, FOR PEER REVIEW the Laplace equation on this droplet image using image-processing software to determine
   Plasma 2023, 6, FOR PEER REVIEW the surface tension of the liquid. Images of Pendant drop tensiometry performed are shown
                                   in Figures 3 and 4.




                                    Figure3.3.3.
                                    Figure
                                    Figure      Image
                                              Image ofof
                                                 Imageaofaadroplet
                                                         droplet    during
                                                                 during
                                                             droplet    the pendant
                                                                      during        drop drop
                                                                                 pendant
                                                                            the the           method.
                                                                                         method.
                                                                                    pendant  drop method.




                                    Figure4.4.OpenDrop
                                    Figure     OpenDrop  software
                                                       software      fitting
                                                                fitting      a Laplace
                                                                         a Laplace      equation
                                                                                   equation over a over a droplet
                                                                                                   droplet image. image.

                                    Figure 4. OpenDrop software fitting a Laplace equation over a droplet image.
                                        The accuracy of this method was validated by correction factors with respect to
                                    image quality obtained from the image processing software, called Worthington and
                                         The accuracy of this method was validated by correction factors with re
                                    Bond numbers. The recommended numbers for accurate measurements are 0.7–0.8 fo
                                    image   quality
                                    Worthington     obtained
                                                 numbers      from the
                                                          and 0.3–0.35 forimage   processing
                                                                           bond numbers   [17]. software,
                                                                                                The averagecalled Worthing
                                                                                                            Worthington and

Page 5

Plasma 2023, 6                                                                                                        49




                                           The accuracy of this method was validated by correction factors with respect to
                                     image quality obtained from the image processing software, called Worthington and
                                     Bond numbers. The recommended numbers for accurate measurements are 0.7–0.8 for
                                     Worthington numbers and 0.3–0.35 for bond numbers [17]. The average Worthington and
                                     bond numbers for all measurements in this study were 0.77 and 0.31, respectively. The error
                                     in all instances was 0.01 for both Worthington and bond numbers. These measurements
                                     were taken at a room temperature of 18 ◦ C.

                                     2.3. Viscosity Measurement Method
                                      Viscometers make use of the theoretical relationship between shear stress and strain
                                rate to measure viscosity. There are three types of viscometer: flow, drag, and resonant.
                                In flow-type viscometers, the rate of flow of the fluid in a tube or through an orifice is
                                measured, and the shear stress can either be calculated or estimated based on theory.
                                Examples of flow-type viscometers include capillary tube viscometers, with which shear
                                stress is calculated, and cup viscometers, with which shear stress is estimated. Flow-type
                                viscometers measure kinematic viscosity. Drag-type viscometers measure either the force
                                on an object as it moves at a specified rate in the fluid (for example, rotational viscometers)
                                or the time it takes for an object to move a specified distance through the fluid (for example,
                                falling objects and bubble tube viscometers). Drag-type viscometers measure absolute
                                viscosity. The third type of viscometer is the resonant or vibrational viscometer, which is
                                most commonly used for in-line process applications [14].
                                      Among the commercially available viscometers, a capillary viscometer was chosen for
                                viscosity measurements in this study because it was cost-effective and readily available.
                                Capillary viscometers determine viscosity by measuring the liquid flow rate through a
Plasma 2023, 6, FOR PEER REVIEW capillary tube. These viscometers are typically made of glass and consist of a bulb reservoir
                                connected to the capillary tube. The operation of a capillary tube viscometer is based on
                                the Poiseuille model of laminar flow which, describes flow through a round pipe [14].
                                      The capillary viscometer used for this study was a certified, calibrated, size 25 Cannon-
                                was measured
                                Fenske   viscometer. from      10 to 40
                                                        The certified      °C with
                                                                       accuracy        thedevice
                                                                                  of this   helpisof0.16%.
                                                                                                      a water
                                                                                                            The bath.    The
                                                                                                                  viscosity wasetups
                                measured    from  10 to 40 ◦ C with the help of a water bath. The setups of the viscometer and
                                eter and water bath are shown in Figures 5 and 6, respectively.
                                water bath are shown in Figures 5 and 6, respectively.




                                     Figure
                                     Figure 5. Cannon- FenskeFenske
                                               5. Cannon-     viscometer.
                                                                     viscometer.

Page 6

Plasma 2023, 6                                                                                                     50

                 Figure 5. Cannon- Fenske viscometer.




                 Figure   Viscosity
                 Figure6. 6.        measurement
                             Viscosity          setup. setup.
                                       measurement
                       The Cannon-Fenske viscometer has two fluid reservoirs connected by a tilted capillary
                 tube. AThe    Cannon-Fenske
                           measured   volume of theviscometer         has two
                                                      liquid to be analyzed       fluid reservoirs
                                                                               is added                 connected
                                                                                         to the lower reservoir.      by a tilte
                                                                                                                  After
                  lary tube. A
                 equilibration   at ameasured      volume ofthethe
                                      constant temperature,            liquid
                                                                    liquid       to beupanalyzed
                                                                           is drawn        through theiscapillary
                                                                                                          added tube
                                                                                                                  to the low
                 to fill the second   reservoir  until it overfills.  The liquid   is then
                  voir. After equilibration at a constant temperature, the liquid is drawn  allowed  to fall under theup thro
                 influence of gravity, and the time taken for the liquid meniscus to pass between two marks
                  capillary tube to fill the second reservoir until it overfills. The liquid is then all
                 in the viscometer (as seen in Figure 5) is noted as the efflux time. The kinematic viscosity
                  fall
                 of theunder     the influence
                         liquid, which              of gravity,
                                         is the mathematical         and ofthe
                                                               product       thetime
                                                                                  effluxtaken
                                                                                         time andforcertified
                                                                                                      the liquid    meniscus
                                                                                                              viscosity
                  betweenwas
                 constants,   twocalculated
                                     marks in  forthe viscometer
                                                   each  temperature(as    seen in Figure 5) is noted as the efflux ti
                                                                        point.
                 kinematic viscosity of the liquid, which is the mathematical product of the effl
                 2.4. Contact Angle Measurement Method
                 and certified viscosity constants, was calculated for each temperature point.
                      The most common contact angle measurement methods include the telescope–goniometer
                 method, Wilhelmy balance method, captive bubble method, tilting plate method, and the
                  2.4. Contact
                 more             Angle Measurement
                        recently developed                 Method methods. Among these methods, the most
                                              drop shape analysis
                 frequently
                         The used
                               mostis direct
                                      common measurement
                                                     contactofangle
                                                                the contact   angle by telescope–goniometer.
                                                                         measurement       methods include      In the tel
                 this method, a direct measurement of the tangent angle is taken at the three-phase contact
                  goniometer method, Wilhelmy balance method, captive bubble method, tiltin
                 point on a sessile drop profile. Drop shape analysis of sessile drop also measures the tan-
                  method,
                 gent         and
                       angle at the the  more recently
                                    three-phase              developed
                                                  contact point              drop
                                                                 with the help      shape images
                                                                                of droplet  analysisandmethods.
                                                                                                        computer Amon
                  methods,
                 programs      the
                            [18].   most frequently
                                  A simplified             used
                                                experimental       is of
                                                               setup  direct   measurement
                                                                         the drop shape analysis of  the contact
                                                                                                 method   suitable angle
                  scope–goniometer. In this method, a direct measurement of the tangent
                 for researchers  was  used  in this study for the  measuring   contact angle [19]. Droplets com-angle is
                 prising 20 µL of PAW and distilled water on clean glass microscope slides were captured
                 as images, as shown below. The contact angle between the liquid droplets and the glass
                 was measured using OpenDrop image processing software [17]. The contact angle made
                 by 20 µL of distilled water on a glass slide was measured to validate the accuracy of the
                 measurement. The contact angle for distilled water determined by this method was 54.5◦ ,
                 which is consistent with the literature reports of ~55 ◦ [20]. The images of the PAW droplet
                 making a 31◦ contact angle on the glass surface and the distilled water droplet making a
                 54.5◦ contact angle on the glass surface are shown in Figures 7 and 8, respectively. The
                 measurements were conducted at a room temperature of 18 ◦ C.
                      The surface tension and contact angle investigations in this study were limited to room
                 temperature due to the limitations presented by the cost of systems required for accurately
                 measuring these properties at varying temperatures.

Page 7

software [17]. The contact angle made by 20 µL of distilled water on a glass slide was
                               measured to validate the accuracy of the measurement. The contact angle for distilled
                               water determined by this method was 54.5°, which is consistent with the literature re-
                               ports of ~55 ° [20]. The images of the PAW droplet making a 31° contact angle on the glass
                               surface and the distilled water droplet making a 54.5° contact angle on the glass surface
Plasma 2023, 6                                                                                                         51
                               are shown in Figures 7 and 8, respectively. The measurements were conducted at a room
                               temperature of 18 °C.




                               Figure 7. PAW
                                         PAW droplet
                                             droplet making
                                                     makingaa31
                                                             31°◦ contact
                                                                  contact angle
                                                                          angle on
                                                                                on aa glass
                                                                                      glass surface.
                                                                                             surface.




                               Figure 8.
                               Figure 8. Distilled water droplet               ◦ contact angle on a glass surface.
                                                                 making aa 54.5°
                                                         droplet making    54.5°                          surface.

                               3. Results
                                     The surface tension and contact angle investigations in this study were limited to
                               3.1.
                               room Surface Tension of
                                      temperature   duePAW
                                                         to the limitations presented by the cost of systems required for
                                accurately   measuring
                                      The surface       these
                                                   tension      properties
                                                            of two         at varying
                                                                   PAW amples         temperatures.
                                                                                  of pH 2.5 and pH 2.78 was measured using
                                pendant drop tensiometry, at a room temperature of 18 ◦ C. The results obtained are shown
                                3. Results
                                in Figure 9. The literature values of water surface tension [21] is also included as a reference.
                                The  PAW atTension
                                3.1. Surface  pH 2.5 of
                                                      had  a surface tension of 68.7 mN/m, while the PAW at pH 2.78 had a
                                                        PAW:
                                surface tension of 68.6 mN/m—both lower than the surface tension of distilled water at
                                   ◦ CThe  surface tension of two PAW samples of pH 2.5 and pH 2.78 was measured using
Plasma 2023, 6, FOR PEER REVIEW 18     reported in the literature, which was 73.1 mN/m. On average, the PAW displayed a
                                pendant drop tensiometry, at a room temperature of 18 °C. The results obtained are8
                                viscosity 6.1% lower than that of distilled water. The relative accuracy of the measurements
                                shown in Figure 9. The literature values of water surface tension [21] is also included as a
                                was determined to be 3.65%.
                                reference. The PAW at pH 2.5 had a surface tension of 68.7 mN/m, while the PAW at pH
                                2.78 had a surface tension of 68.6 mN/m—both lower than the surface tension of distilled
                                        74
                                water at 18 °C reported in the literature, which was 73.1 mN/m. On average, the PAW
                                   Surface Tension in mN/m




                                displayed
                                        72 a viscosity 6.1% lower than that of distilled water. The relative accuracy of the
                                measurements was determined to be 3.65%.
                                                             70

                                                             68

                                                             66

                                                             64
                                                                  PAW pH 2.5   PAW pH 2.78               DW Literature
                                                                                Samples


                                Figure9.9.Surface
                               Figure      Surfacetension
                                                   tensionof
                                                           ofplasma-activated
                                                               plasma-activatedwater
                                                                                 waterat
                                                                                       at18
                                                                                          18◦°C; thesurface
                                                                                             C; the  surfacetension
                                                                                                             tensionof
                                                                                                                     ofdistilled
                                                                                                                        distilledwater
                                                                                                                                 water
                                (DW)  at this temperature  is shown  for reference.
                               (DW) at this temperature is shown for reference.

                                    Usingthe
                                    Using   themodified
                                                modifiedfreefree energy
                                                              energy      equation,
                                                                      equation,       J He
                                                                                 J He et      et al.
                                                                                         al. [13]     [13] suggested
                                                                                                   suggested            thatwashing
                                                                                                               that PAW’s    PAW’s
                               washing
                               out       out (physical
                                   (physical  removal) removal)
                                                        of E. coli of E. coli is
                                                                   is aided   byaided  by a reduction
                                                                                 a reduction               in the surface
                                                                                                in the surface    tensiontension
                                                                                                                           of waterof
                               water
                               with   with
                                    the    the addition
                                        addition         of plasma.
                                                  of plasma.           The surface
                                                               The surface   tensiontension
                                                                                      of water of is
                                                                                                  water   is lowered
                                                                                                     lowered    by the by the transi-
                                                                                                                       transition of
                               tion of the crystalline mesoscopic structure of water to an amorphous mesoscopic struc-
                               ture with the addition of plasma. This transition in the water’s structure is aided by the
                               plasma lowering the mesoscopic transition temperature. The results of this study are
                               consistent with the suggestion of J He et al. [13], showing that the addition of plasma

Page 8

Plasma 2023, 6                                                                                                52




                 the crystalline mesoscopic structure of water to an amorphous mesoscopic structure with
                 the addition of plasma. This transition in the water’s structure is aided by the plasma
                 lowering the mesoscopic transition temperature. The results of this study are consistent
                 with the suggestion of J He et al. [13], showing that the addition of plasma lowers the
                 surface tension of the water. As the addition of plasma changes the surface tension of water,
                 it also influences its thermodynamic properties.
                       The mesoscopic structure of normal water is crystalline at temperatures below 35 ◦ C,
                 and it transitions to being amorphous at temperatures between 35 and 60 ◦ C [13]. The
                 crystalline structure is characterized by high surface tension and high viscosity, while the
                 amorphous structure is characterized by lower surface tension and viscosity relative to the
                 crystalline structure. One example of differences in the physical properties of water with
                 different mesoscopic structures is that hot water is more effective in cleaning applications
                 than cold water, due to the lower surface tension or surfactancy of hot water’s amorphous
                 structure compared to cold water’s crystalline structure. As J He et al. [13] witnessed
                 surfactant behavior/low surface tension in water at low temperatures, they suggested
                 that the addition of plasma could possibly lower the temperature required for mesoscopic
                 structural changes in water. The theoretical proof presented [13] in support of their claim is
                 discussed later to enrich the understanding of PAW’s physical behavior.
                       Reduction in surface tension increases the surfactant behavior exhibited by a liquid,
                 making it more suitable for cleaning and removal of particles. Since plasma-activated
                 water is biodegradable, it can be suitable for cleaning applications without harming the
                 environment.

                 3.2. Viscosity of PAW
                       The mesoscopic structural changes and foreign plasma additives in PAW influence
                 its viscosity. The structure change at low temperatures should reduce the viscosity of
                 PAW, while the foreign plasma additive should increase its viscosity. The effect of foreign
                 plasma additives in increasing the viscosity of water is similar to how sand added to water
                 can affect its viscosity; foreign additives can lead to increased friction in the liquid flow,
                 resulting in higher viscosities. Since it is proposed that the addition of plasma will result in
                 mesoscopic structural changes in water at low temperatures, PAW should display lower
                 to almost identical viscosity relative to water at low temperatures. This is because the
                 viscosity-reducing effect of mesoscopic structural change at low temperatures can possibly
                 be countered by the viscosity-increasing effect of foreign plasma additives. If the proposed
                 mesoscopic structural change does not occur, PAW should have a higher viscosity at lower
                 temperatures because of the foreign plasma additives. The foreign plasma additives should
                 also cause PAW to have higher viscosity at higher temperatures. At temperatures above
                 35 ◦ C, normal water has an amorphous structure [13], and the only influence differentiating
                 the rheological behaviors of PAW and normal water is that of the plasma foreign additives.
                       The viscosity of PAW at pH 2.78 was measured from 10 to 40 ◦ C using the Cannon-
                 Fenske viscometer and water bath setup described earlier (as shown in Figure 6). The
                 viscosity results obtained for this temperature range are shown in Figure 10. The kinematic
                 viscosity of water from the literature is included for reference [22].
                       The kinematic viscosity of PAW at 10 ◦ C was 1.28 mm2 /s, compared to the 1.30 mm2 /s
                 kinematic viscosity of water at the same temperature. The viscosity of PAW was 1.3% lower
                 than that of distilled water at 10 ◦ C. The slightly lower viscosity of PAW at low temperatures
                 supports the mesoscopic structural changes in water proposed by J He et al. [13]. Under
                 normal conditions, PAW should have exhibited a higher viscosity, since the foreign plasma
                 additives have the natural effect of increasing viscosity. The amorphous structure of PAW
                 at low temperature might have countered the viscosity-increasing effect of the plasma
                 additives, resulting in a lower viscosity than that of distilled water.

Page 9

At temperatures above 35 °C, normal water has an amorphous structure [13], and the
                 only influence differentiating the rheological behaviors of PAW and normal water is that
                 of the plasma foreign additives.
                      The viscosity of PAW at pH 2.78 was measured from 10 to 40 °C using the Can-
                 non-Fenske viscometer and water bath setup described earlier (as shown in Figure 6).
Plasma 2023, 6                                                                                         53
                 The viscosity results obtained for this temperature range are shown in Figure 10. The
                 kinematic viscosity of water from the literature is included for reference [22].



                                                1.4                                         DW Kinematic Viscosity
                                                                                            (Literature)
                                                1.3



                    Kinematic Viscosity mm2/s
                                                1.2                                         PAW pH 2.78 Kinematic Viscosity
                                                1.1
                                                 1
                                                0.9
                                                0.8
                                                0.7
                                                0.6
                                                      10                       20                               40
                                                           Temperature in degree celesius

                  Figure 10.
                 Figure   10. Viscosity of PAW
                              Viscosity of      from 10
                                           PAW from  10 to
                                                         to40
                                                            40°C;
                                                               ◦ C;the
                                                                    theviscosity
                                                                        viscosityofofdistilled water
                                                                                       distilled     (DW)
                                                                                                 water    is shown
                                                                                                       (DW)         for
                                                                                                             is shown
                  reference.
                 for reference.

                        The kinematic
                        With    the increase  viscosity     of PAW at
                                                  in temperature       from    °C ◦was
                                                                           10 10          1.28
                                                                                     C, the   high       /𝑠, compared
                                                                                                  𝑚𝑚viscosity       of normalto the   1.30
                                                                                                                                  water,
                  𝑚𝑚     /𝑠  kinematic      viscosity    of  water  at the   same   temperature.        The   viscosity
                 caused by its crystalline structure, started to decrease due to the transition of its structure          of  PAW     was
                  1.3%
                 to       lower than
                     amorphous.        Asthat   of distilledstructure
                                           the crystalline      water at in 10water
                                                                                °C. The    slightly
                                                                                       began           lower viscosity
                                                                                                to weaken,                   of PAW
                                                                                                                 the relatively    lower at
                  low temperatures
                 viscosity    of PAW, due   supports     the mesoscopic
                                                to its amorphous             structural
                                                                        structure,   becamechanges      in water proposed
                                                                                                 less pronounced                 by J He
                                                                                                                         and began      to
                  et al. [13].
                 match          Under normal
                           the viscosity             conditions,
                                             of normal     water, asPAW    should have
                                                                       demonstrated          about 15 ◦aChigher
                                                                                          at exhibited                 viscosity,
                                                                                                               in Figure    10.      since
                  the foreign      plasma
                        With further          additives
                                          increase          have the natural
                                                      in temperature                ◦ C, he
                                                                         from 15effect     of higher
                                                                                               increasing       viscosity.
                                                                                                         viscosity           The water
                                                                                                                     of normal      amor-
                  phous
                 due   to itstructure
                               crystalline  ofstructure
                                                PAW atbegan   low to temperature
                                                                       decrease as its might      have transitioned
                                                                                           structure        countered further
                                                                                                                           the viscosi-
                                                                                                                                     into
                  ty-increasingresulting
                 amorphous,           effect ofinthePAW plasma
                                                            havingadditives,    resultingthan
                                                                     higher viscosity        in anormal
                                                                                                     lower viscosity
                                                                                                               water. The  than   that of
                                                                                                                              viscosity-
                  distilled water.
                 reducing     effect of the amorphous structure in PAW no longer countered the viscosity-
                 increasing
                        With effect      of its foreign
                                 the increase              plasma additives.
                                                   in temperature       from 10 The °C, kinematic       viscosityof
                                                                                         the high viscosity          of normal     20 ◦ C
                                                                                                                        PAW at water,
                 was   1.04bymm    2                                              1.00 mm   2              ◦
                  caused         its/s,  while that
                                     crystalline       of normal
                                                    structure,      waterto
                                                                 started    was
                                                                              decrease    due /s;toathe20 transition
                                                                                                             C, the viscosity   of PAW
                                                                                                                        of its structure
                 was   2.19% higher
                  to amorphous.         Asthan   that of normal
                                            the crystalline         water.in water began to weaken, the relatively lower
                                                               structure
                        Following
                  viscosity    of PAW,  thisdue
                                             trend    of increased
                                                  to its  amorphous   viscosity
                                                                         structure,in PAW
                                                                                       became at higher      temperatures,
                                                                                                  less pronounced               PAW at
                                                                                                                          and began      to
                 40  ◦ C had a kinematic viscosity of 0.76 mm2 /s, while that of normal water was 0.66 mm2 /s,
                  match the viscosity of normal water, as demonstrated at about 15 °C in Figure 10.
                 meaningWiththat     PAWincrease
                                 further     had a 12.8%       higher viscosity
                                                         in temperature       from than
                                                                                      15 °C,normal
                                                                                               the higher         at 40 ◦ C. of
                                                                                                         water viscosity          40 ◦ C,
                                                                                                                              At normal
                 the
                  waterhigh   viscosity
                            due             caused bystructure
                                  to its crystalline       the crystalline
                                                                     began structure
                                                                              to decrease  wasas minimal
                                                                                                   its structurein normal     water,fur-
                                                                                                                     transitioned       as
                 its mesoscopic
                  ther  into amorphous,structure    might have
                                                 resulting         transitioned
                                                              in PAW                very close
                                                                         having higher             to amorphous;
                                                                                             viscosity     than normal       water. the
                                                                                                                        therefore,    The
                 higher    viscosity demonstrated
                  viscosity-reducing         effect of the  foramorphous
                                                                PAW, whichstructure
                                                                                 also has anin amorphous
                                                                                                PAW no longer     structure,   could the
                                                                                                                        countered      be
                 attributed     to  the  foreign   plasma     additives.
                  viscosity-increasing effect of its foreign plasma additives. The kinematic viscosity of
                  PAW at 20 °C was 1.04 𝑚𝑚 /𝑠, while that of normal water was 1.00 𝑚𝑚 /𝑠; at 20 °C, the
                 3.3. Contact Angle of PAW
                  viscosity of PAW was 2.19% higher than that of normal water.
                      The  difference
                       Following   thisin contact
                                        trend     angles made
                                              of increased        by liquids
                                                             viscosity  in PAWon aatsurface
                                                                                     higher helps  us to understand
                                                                                             temperatures,   PAW at
                 the changes   in surface
                       40 °C had           energy
                                   a kinematic    betweenofthe
                                                viscosity        liquids
                                                              0.76  𝑚𝑚 /𝑠,andwhile
                                                                               the contacting  surface.
                                                                                     that of normal   water   contact
                                                                                                         Thewas  0.66
                 angles made    by PAW    at pH values  of 2.47, 2.68, and  2.85 on  a glass  microscope
                  𝑚𝑚 /𝑠, meaning that PAW had a 12..8% higher viscosity than normal water at 40 °C. At    slide were
                 inspected. The results obtained are summarized in Figure 11. The contact angle made
                 by a distilled water droplet of the same volume in the same setup is shown for accuracy
                 indication. The measurements were conducted at a room temperature of 18 ◦ C.
                      PAW droplets make smaller contact angles on glass surfaces than water droplets,
                 by an average of 20◦ , or 36%. At lower pH or higher plasma production power, PAW
                 makes smaller contact angles. Therefore, the addition of plasma increases the surface
                 energy during interaction between the glass surface and the water. The contact angle is
                 an indication of the adhesive and cohesive forces exhibited by the liquid. If the adhesive
                 force of a liquid is high relative to its cohesive force, the liquid will wet the surface more,
                 resulting in a lower contact angle. If the cohesive force of the liquid is high relative to
                 its adhesive force, the liquid will wet the surface less, resulting in a higher contact angle

Page 10

40 °C, the high viscosity caused by the crystalline structure was minimal in normal water,
                 as its mesoscopic structure might have transitioned very close to amorphous; therefore,
                 the higher viscosity demonstrated for PAW, which also has an amorphous structure,
                 could be attributed to the foreign plasma additives.
Plasma 2023, 6                                                                                                                         54
                 3.3. Contact Angle of PAW
                        The difference in contact angles made by liquids on a surface helps us to understand
                  the  changes
                 formed on the  insurface.
                                   surface energy   between
                                            Since plasma      the liquids
                                                           activation        and the
                                                                         resulted   in contacting   surface.
                                                                                        water forming        The contact
                                                                                                         smaller  contact
                  angles  made   by PAW    at pH  values  of 2.47, 2.68, and   2.85  on a glass  microscope
                 angles, it increased the adhesive force of water during contact with glass. Therefore,       slide were
                                                                                                                  plasma
                 activation might increase the adhesive forces of liquids on surfaces; this could be usefulby
                  inspected.  The  results obtained   are summarized       in Figure   11. The   contact angle  made   in
                  a distilled
                 the  surfacewater   droplet
                               treatment      of the for
                                          industry   same    volume in requiring
                                                         applications     the same setup
                                                                                       betterisadhesion
                                                                                                shown for byaccuracy  in-
                                                                                                             dyes, along
                  dication.
                 with   otherThe  measurements
                              applications         were conducted
                                            that require              at a room
                                                          better wettability    of temperature     of 18 °C.
                                                                                    liquids to surfaces.

                                                 60

                                                 50
                      Contact angle in degrees



                                                 40

                                                 30

                                                 20

                                                 10

                                                 0
                                                      PAW pH 2.47       PAW pH 2.68             PAW pH 2.85         DW
                                                                                      Samples


                  Figure11.
                 Figure  11.Contact
                            Contact angle
                                    angle made
                                          made by
                                               by PAW
                                                  PAWand
                                                      anddistilled
                                                         distilledwater
                                                                   water(DW)
                                                                         (DW)on
                                                                             onglass
                                                                                glassslides.
                                                                                      slides.

                 4. Discussion
                        PAW droplets make smaller contact angles on glass surfaces than water droplets, by
                  an average
                       The lowofsurface
                                      20°, ortension
                                               36%. Atexhibited
                                                          lower pHbyorwater  higher   plasma
                                                                                   after       production
                                                                                          plasma    activationpower,      PAW makes
                                                                                                                 was attributed      by J
                  smaller
                 He           contact
                      et al. [13]        angles.
                                    to the         Therefore,
                                            plasma’s    effect ofthe    addition
                                                                   lowering       theofmesoscopic
                                                                                         plasma increases
                                                                                                     transition the   surface energy
                                                                                                                   temperature.      The
                  during interaction
                 mesoscopic       structure between
                                               of water theatglass
                                                              lowersurface       and theiswater.
                                                                       temperatures                 The contact
                                                                                             crystalline,   whichangle      is an indi-
                                                                                                                     is characterized
                  cation
                 by       of the
                     higher         adhesive
                                surface          andand
                                           tension    cohesive    forces
                                                           viscosity.        exhibitedas
                                                                         However,                                  adhesive past
                                                                                                  liquid. If theincreases
                                                                                             thetemperature
                                                                                         bythe                                         of
                                                                                                                                forcethe
                  a liquid is high
                 mesoscopic             relative
                                  transition       to its cohesive
                                               temperature,            force, the structure
                                                                the crystalline      liquid will ofwet
                                                                                                    waterthechanges
                                                                                                              surfacetomore,     result-
                                                                                                                           amorphous,
                 which    a lower
                  ing in is            contact angle.
                              characterized       by lowerIf the  cohesive
                                                              surface     tensionforceand
                                                                                        of the liquid JisHe
                                                                                           viscosity.       high  relative
                                                                                                               et al.         to its ad-
                                                                                                                       [13] suggested
                  hesive
                 that       force,
                       plasma         the liquid
                                   activation       will the
                                                lowers     wetemperature
                                                                 the surfacerequired
                                                                                   less, resulting
                                                                                             for this in  a highercausing
                                                                                                       transition,      contactPAWangle to
                 display
                  formedlow  on thesurface   tension
                                       surface.   Sinceand   low viscosity
                                                         plasma     activationatresulted
                                                                                    lower temperatures
                                                                                              in water forming compared
                                                                                                                      smallerto contact
                                                                                                                                 normal
                 water.
                  angles,J itHeincreased
                                   et al. [13]the
                                                theoretically
                                                    adhesive forcedemonstrated
                                                                          of water thatduringplasma
                                                                                                 contactactivation    lowers
                                                                                                            with glass.         the free
                                                                                                                            Therefore,
                 energy    of  water.   This   can  be  shown     with    the   following   equation,     where
                  plasma activation might increase the adhesive forces of liquids on surfaces; this could be      the   free  energy    of
                  usefulF in
                 water      is given    by
                                the surface     treatment industry for applications requiring better adhesion by
                  dyes, along with other applications F = U − that T σ+              + (1 −wettability
                                                                               (qVsbetter
                                                                         require              q) Vr )      of liquids to surfaces.
                                                   = qEs + (1?− q) Er + (qVs + (1 − q)?Vr ) P                                          (1)
                  4. Discussion                                            q                 1− q
                                                        +k B T q ln gs + (1 − q)ln gr
                        The low surface tension exhibited by water after plasma activation was attributed by
                  J He etF al.
                 where       is the
                                 [13]free
                                       to energy    of water,
                                           the plasma’s         U isofthe
                                                            effect          internalthe
                                                                        lowering       energy  of water,transition
                                                                                           mesoscopic       σ is the entropy,    q is the
                                                                                                                         temperature.
                 percentage of structured state, Es,r are the specific energies of the structured and random
                  The mesoscopic structure of water at lower temperatures is crystalline, which is charac-
                 states, respectively (Es < Er ), Vs,r are the specific volumes, gs,r are the statistical degeneracy
                  terized by higher surface tension and viscosity. However, as the temperature increases
                 values (gs << gr ), T is the temperature, P is the pressure, and k B is the Boltzmann constant.
                  past the mesoscopic transition temperature, the crystalline structure of water changes to
                       When ions are added to a fluid, it changes the fluid’s free energy. Free energy in the
                  amorphous, which is characterized by lower surface tension and viscosity. J He et al. [13]
                 presence of ions contains an additional term, the Debye–Huckel term (UDH ):
                  suggested that plasma activation lowers the temperature required for this transition,
                                                                             M   Ni z2i e2 κ        1
                                                                    UDH = − ∑                                                        (2)
                                                                            i =1
                                                                                  2    4πe r e 0 1 + καi

                                                                                              M
                                                                                   2e2
                                                                        κ2 =                ∑    z2 n
                                                                               e r e0 k B T i = 1 i i
                                                                                                                                     (3)

Page 11

Plasma 2023, 6                                                                                                 55




                 where i denotes the type of ion species, Ni is the ion’s concentration, αi is the ion’s radius,
                 zi is the charge of an ionic species, e is the charge of the electron, M is the total number of
                 ionic species, er is the dielectric permittivity of the medium, e0 is the dielectric permittivity
                 of a vacuum, and κ is the inverse of the Debye screening length. The ions are unlikely to
                 penetrate the clusters; thus, in the first approximation, their impact is proportional to the
                 percentage of water in the amorphous phase. From this, we can derive the free energy of
                 plasma-activated water (FDH ), modified with the Debye–Huckel term as follows:

                                                    FDH = F + (1 − q)UDH                                      (4)

                       From Equation (4), we can see that the addition of plasma ‘favors’ the amorphous
                 state; thus, the transition temperature decreases.
                       PAW presents interesting behavior as a solution. An ideal solution is a solution whose
                 properties change in proportion to the concentration of solute added to it. As PAW displays
                 changes in properties (i.e., 6.1% for surface tension, 1.3–12.6% for viscosity, 36% for contact
                 angle) that are significantly higher than the concentration of active species added to it
                 (0.01%), we can conclude that PAW behaves non-ideally.
                       The low surface tension characteristic of PAW indicates potential surfactant behavior.
                 Surfactants are required for numerous industrial processes, including but not limited to de-
                 tergents, paints, food emulsions, biotechnological processes, biosciences, pharmaceuticals,
                 and cosmetic products. PAW can be an eco-friendly and cost-effective alternative to current
                 products used for these applications [23]. As PAW is antibacterial, antifungal, and has
                 demonstrated its ability to disinfect bacteria [4] from fresh produce, it can be an excellent
                 washing-out agent—an industrial process that prevents disease breakouts due to microbes
                 on produce. Surfactants with antibacterial and antifungal properties are used in biomedical
                 fields [23]; as PAW has these properties [4,7] and can act as a surfactant, it can potentially
                 be applied as a biomedical industrial surfactant. Surfactants are also important ingredients
                 for the preparation of detergents and cleaning agents. PAW with surfactant properties can
                 potentially be used in these processes as a biodegradable and eco-friendly ingredient [23].
                 One major advantage of using PAW is its biodegradability [1], which means that it can meet
                 the surfactant requirements for industrial processes without harming the environment.
                       The viscosity of PAW is influenced by the mesoscopic structural changes and the
                 presence of foreign plasma additives due to plasma activation. At low temperatures,
                 when the effect of the crystalline structure is dominant in water, PAW with its amorphous
                 structure has a slightly lower viscosity. As temperatures increase beyond low values, the
                 friction-inducing plasma additives result in higher viscosity in PAW when compared to
                 water. Until the crystalline structure of water is transitioned to an amorphous structure,
                 the viscosity of PAW is only nominally higher than the viscosity of water. However, as the
                 temperature increases beyond the mesoscopic transition temperature in water (35◦ C [13]),
                 and the water attains an amorphous structure, the friction-inducing plasma additives cause
                 PAW to have a significantly higher viscosity than water (12.8%). The high viscosity of PAW
                 can lead to higher shear force exerted by the liquid during its flow at high temperatures.
                 The higher shear force exerted by the flow of PAW on a particle in its path can lead to better
                 removal of particles when compared to normal water, making PAW a better cleaning agent
                 at higher temperatures. The higher viscosity of PAW can also cause it to form a thicker
                 boundary layer during flow, thereby reducing transfer losses and making it suitable for
                 augmented oil extraction.
                       In terms of contact angle, the addition of plasma caused water to form smaller contact
                 angles on a glass surface, indicating that the addition of plasma increases the surface energy
                 during interaction between water and a glass surface. The addition of plasma resulted in
                 increased wettability and increased adhesion of water to the glass surface. Increased wetta-
                 bility and adhesion are of great use for applications in the surface treatment industry. These
                 improved surface properties exhibited by PAW suggest that plasma activation of liquids
                 might result in improved adhesion and wettability by liquids thus activated, potentially
                 improving the adhesive behavior of paints, dyes, etc.

Page 12

Plasma 2023, 6                                                                                                                       56




                                  5. Conclusions
                                       The aim of this study was to experimentally investigate the understudied physical
                                  properties of PAW and see the effects of the addition of plasma to application-oriented
                                  physical properties—namely, surface tension, viscosity, and contact angle. This study
                                  inspected the surface tension and contact angle of PAW at room temperature (i.e., 18 ◦ C)
                                  and the viscosity of PAW between 10 and 40 ◦ C. The addition of plasma resulted in changes
                                  to the physical properties of water, as observed and theoretically suggested by J He et al. [13].
                                  The major conclusions drawn from this study are as follows:
                                  1.    The physical properties of water change with plasma activation.
                                  2.    As a solution, PAW behaves non-ideally; since the percentage changes occurring to
                                        the physical properties with the addition of plasma are higher than the percentage of
                                        plasma species added.
                                  3.    The addition of plasma lowers the surface tension of water by 6.1% at room temper-
                                        ature; it also decreases the temperature required for the mesoscopic transition from
                                        crystalline to amorphous structure, resulting in lower surface tension in PAW relative
                                        to normal water.
                                  4.    The addition of plasma increases the viscosity of water by 12.8% at higher tempera-
                                        tures; foreign plasma additives lead to this increased viscosity in PAW. The viscosity-
                                        increasing effect of plasma additives is inhibited at low temperatures due to the PAW’s
                                        amorphous structure.
                                  5.    The contact angle made by water on glass surfaces is reduced by 36% with plasma
                                        activation; thus, the surface energy during the interaction of water with glass is
                                        increased with plasma activation, thereby increasing the wettability and adhesion of
                                        water to the glass surface.
                                  6.    The changes occurring to the physical properties of water with plasma activation can
                                        be attributed to water attaining an amorphous structure at lower temperatures, as
                                        well as the presence of plasma additives at higher temperatures.

                                  Author Contributions: Conceptualization, A.R., C.S. and A.F.; formal analysis, M.S. (Mobish Shaji)
                                  and M.S. (Mikaela Surace); investigation, M.S. (Mobish Shaji) and M.S. (Mikaela Surace); methodology,
                                  C.S.; project administration, A.R. and A.F.; supervision, A.R.; writing—original draft, M.S. (Mobish
                                  Shaji); writing—review and editing, A.R. and A.F. All authors have read and agreed to the published
                                  version of the manuscript.
                                  Funding: This research received no external funding.
                                  Institutional Review Board Statement: Not applicable.
                                  Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
                                  not applicable to this article.
                                  Conflicts of Interest: The authors declare no conflict of interest.

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