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Applied Surface Science 257 (2011) 7959–7967

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Adsorption behavior of weak hydrophilic substances on low-energy surface in

aqueous medium
Wang Hui ∗ , Guo Chao, Fu Jiangang, He Zhangxing, Liang Wei, Chen Xiaolei, Zhuang Caihong
School of Chemistry and Chemical Engineering, Central South University, Changsha, 410083 Hunan, China

a r t i c l e i n f o a b s t r a c t

Article history: Through the methods such as measurements of contact angle and surface tension, calculations of surface
Received 22 January 2011 energy and interfacial interaction free energy, and four weak hydrophilic substances (WHS) were taken as
Received in revised form 1 March 2011 research objects, some interesting conclusions were obtained as follow. In aqueous medium, the WHS give
Accepted 31 March 2011
priority to adsorb on low-energy surface that is low polar or particularly non-polar. There is a clear corre-
Available online 8 April 2011
sponding relationship between the free energy and Lewis base component  − or the hydrophile index of
low-energy surface, and the specific relationship is obtained. Finally, we find hydrophobic attractive force
Keywords:
of the Lewis acid–base interaction is mainly responsible for the absorption of WHS on low-energy surface.
Weak hydrophilic substances (WHS)
Adsorption
In short, an initial insight into adsorption behavior of WHS on low-energy surface is demonstrated in this
Low-energy surface (LES) paper.
Contact angle Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.
Surface energy

1. Introduction
Low-energy surface (LES) attracted increasing attention in
recent decades [1–5]. Weak hydrophilic substances, WHS for short,
are used very commonly as frother in flotation to assure forma-
tion of a foam having a definite properties [6]. However, it is still
unclear about their adsorption behavior on LES (surface energy
of LES is usually below 100 mJ m−2 , and for polymer is usually
between 20 and 50 mJ m−2 ) in aqueous medium. We conducted this
study to solve the question deserving attention whether the effect
of WHS adsorption can be neglected or not, in order to deal with
system of adsorption of WHS on LES such as plastic [7], coal [8–10],
molybdenite [11], graphite [12–14], talc flotation [15–17] and oil
production [18–20], oil displacement process [20–22]. Garde and
co-workers [23] had found that the adsorption free energies of a
low-energy probe shows a clear correlation with the hydropho-
bicity of the interface. It is clear that inorganic minerals have
high-energy surface subject to strong adsorption by solutes and
establishment of stabilizing electrical forces for flotation. Plastics
have LES, unlikely to adsorb solutes or form any kinds of electrical
stabilizing forces for flotation [24]. About plastics flotation, Fraun-
holcz [25] had discussed the liquid-vapour surface tension control
method. Methyl isobutyl carbinol (MIBC) [26] was used as frother to
separate mixed post-consumer PET–POM–PVC. Pine oil and MIBC
were used together as frother to separate PVC/PET mixtures [27].
∗ Corresponding author. Tel.: +86 31 8836309.
E-mail address: huiwang1968@163.com (W. Hui).
Clint et al. [28] indicated that the order of strengths of adhesion of
“liquid” to solid surface under water is opposite to that for adhe-
sion in air. Lee [29] used  + / − = 1.8 at 20 ◦ C and concluded that
 LW components and  AB components and total surface free energy
were not affected [30,31]. Della Volpe et al. [32] discussed the
results between surface tension component acid–base theory and
equation-of-state theory, and they also explained why square root
of a specific energy is better [33]. Wang Hui et al. [34] determined
the Lifshiitz–van der Walls and the Lewis acid–base components
of the LES energy parameters. Which one is main responsible for
the absorption of WHS on LES in aqueous medium, between the
Lifshitz–van der Waals [35–37] and the Lewis acid–Base interac-
tion [38,39], is another question we will answer. On the whole, our
researches were performed to get an initial insight into adsorp-
tion behavior of weak hydrophilic substances on LES in aqueous
medium.
2. Materials and methods
2.1. Materials
Common flotation frothers are low molecular weight surfac-
tant. Solubility of frothers in water, different from wetting agent,
is usually limited, and overall they are weak hydrophilic [40]. Four
frothers are selected as study object in this paper: Terpineol (TP),
Methyl isobutyl carbinol (MIBC), Tripropylene glycol n-butyl ether
(TPnB) and Diethyl o-phthalate (DOP). Chemical structures and
some information of them are shown in Table 1.

0169-4332/$ – see front matter. Crown Copyright © 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.03.158
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7960 W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967

Table 1
Four frothing agent selected as study object.

Weak Appearance and property Chemical structure Purity Manufacturer

hydrophilic
substance

Terpineol, TP Colorless and transparent oily liquid Analytical pure Chem. Reagent Fty
of Hunan Normal
Agent
University

Methyl isobutyl Colorless and transparent oily liquid Industrial products Zhuzhou flotation
carbinol, MIBC reagent fty

Tripropylene glycol Colorless and transparent oily liquid Industrial products Zhuzhou flotation
n-butyl ether, TPnB reagent fty

Diehyl o-phthalate, Colorless and transparent oily liquid Analytical pure Guangdong Xilong
DOP chem. CO., Ltd.

Contact-angle measurements were used for determining the each time. Ten measurements were taken, and an average value
solid surface-energy. The test liquids include double distilled water, was reported.
glycerol, formamide, diiodomethane and ethylene glycol (all are
analytical purity). 2.2.3. Calculation of surface energy
Young’s Equation [41] describes the relationship among solid
surface energy  S , liquid surface energy (surface tension)  L ,
2.2. Methods
solid–liquid interface interaction free energy  SL , solid surface
membrane pressure ␲0 and the equilibrium contact angle () in
2.2.1. Membrane surface preparation
solid/liquid/gas three-phase system (Eq. (1)).
Before conducting surface inspection, each low-energy plate
(mainly are the latter 35 different kinds of material) was cut into S − 0 − SL = L cos  (1)
20 × 20 mm, and protective membranes were torn off, then they
was put into tap water containing washing powder, tap water, dis- For the LES, surface membrane pressure is negligible [42], ␲0
tilled water in sequence to clean for 10 min in ultrasonic generator and Young’s Equation is transformed into Eq. (2).
(Shanghai Ultrasonic Co. Ltd., China). Take them out and rinse in
S − SL = L cos  (2)
distilled water for 5 min, then put them on filter paper to dry at
room temperature, finally put them together with the filter paper van Oss et al. [43,44] deemed that solid or liquid surface energy
into silica gel dryer (pre-dried 2 h at 150 ◦ C) and dry for 24 h.  is composed of Lifshitz–van der Waals component  LW and Lewis
Membrane surface is prepared in order to detect nonionic acid–base components  AB that is composed of Lewis acid compo-
frothers and surface energy properties of material treated by nent  + and Lewis base component  − . Thus, for solid or liquid,
frothers. The “soaking method” was used for making a surface film surface energy can be expressed as Eq. (3) and Eq. (4), respectively.
of the frother (TP, MIBC, TPnB and DOP). A blank copperplate paper 
was cut to 20 mm × 20 mm and dipped into the frother solution for S = SLW + SAB = SLW + 2 S+ S− (3)
about 1 min and then stored in a silica gel desiccator for about 24 h 
before use, and other membrane treated by frothers is prepared in L = LLW + LAB = LLW + 2 L+ L− (4)
the same way.
Relationship between solid–liquid interface interaction free
energy and surface energy of solid and liquid, respectively, can be
2.2.2. Measurements of contact angle and surface tension expressed as Eq. (5).
A JJC-I contact angle measuring instrument (Changchun Optical   2     
Instrument Factory, China) is applied to measure the contact angle SL = SLW − LLW +2 S+ S− + L+ L− − S+ L− − S− L+ (5)
of liquid on the solid surface. When measuring, at the distance of
3 mm above solid, the liquid is vertical, carefully dropped onto a Expressing the Eq. (2) in the form of Eqs. (3)–(5) gives the rela-
solid surface to form a sessile drop by micro-injector (2.0 mL). Make tionship in solid surface-energy, liquid surface-energy and the
sure the droplet size is 3.5 ␮L, diameter is 1–2 mm, and measuring equilibrium contact angle between the two are obtained (Eq. (6)).
time is less than 1 min. Ten measurements were taken, and an aver-        
age value was reported. All measurements were conducted at room LLW + 2 L+ L− 1 + cos  =2 SLW LLW + S+ L− + S− L+ (6)
temperature, generally 25 ◦ C.
Liquid surface tension is measured by Du Nouy rings method, Thus, through measuring the contact angle between the solid sur-
and the apparatus is type JZHY-180 interface tension meter (Hebei face and three liquids (two of which must be polar) whose LLW , L+ ,
Chengde Test Machine Factory, China). Measurements were con- L− are known, parameters of solid surface energy can be obtained
ducted at room temperature. The glass used to contain the liquid (SLW , S+ , S− ). Detected liquid used in experiment includes sec-
was washed by solution prepared by potassium bichromate and ondary distilled water, glycerol, formamide, diiodomethane and
sulfuric acid, and then repeatedly washed with distilled water for ethylene glycol. There are many reports on parameters of the sur-
5 times. When measuring, measured liquid is consumed 20–25 mL face energy about these liquid (Table 2) from literature [45–47].
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W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967 7961

Table 2
Parameters of the surface energy of detected liquid (mJ m−2 ).

Detected liquid L LLW L+ L−

Secondary distilled Water 72.8 21.8 25.5 25.5

Glycerol 64.0 34.0 3.92 57.4
Formamide 58.0 39.0 2.28 39.6
Diiodomethane 50.8 50.8 0 0
Ethylene glycol 48.0 29.0 1.92 47.0

2.2.4. Calculation of interfacial interaction free energy

Interaction free energy GSW includes the two items, they are
Lifshitz–van der Waals (LW) interaction free energy GSW LW and
AB
Lewis acid–base (AB) interaction free energy GSW (Eq. (9)) [48].
   
LW−AB
GSW LW
= GSW AB
+ GSW = −2 SLW W
LW
+ S+ W
−
+ S− W
+
(9)

Water is taken as the third phase, and the interacting free energy includes LW
interaction free energy and AB interaction free energy (Eq. ).

      Fig. 1. Surface tension of frothers emulsion and pure liquid.

LW −AB LW AB
G1W 2
= G1W 2
+ G1W 2
=2 1LW − LW
W LW
W − 2LW

    
+
+2 W 1− + 2− − −
W in accordance with water–glycerol–diiodomethane (WGD),
water–formamide–diiodomethane (WFD), water–ethylene
       
+ −
W 1+ + 2+ − +
W − 1+ 2− − 1− 2+ (10) glycol–diiodomethane (WED) three combinated program, we
obtained parameters of the surface energy by taking average. The
results are presented in Table 4.
LW−AB
where G1W2 is LW–AB interaction free energy of two compo- It can be found in Table 4 that the four frothers are all sur-
nents 1 and 2 in aqueous phase (mJ m−2 ), subscript W means water; face active, and meanwhile they have some characteristics of Lewis
LW is Lifshitz–van der Waals (LW) interaction free energy of the
G1W2 base. Among them, the lone pair electrons in the alcohol hydroxyl
two components (mJ m−2 ); and G1W2AB is Lewis acid–base interac-
oxygen atom of MIBC and TP molecules have the ability as elec-
tion free energy of the two components in aqueous phase (mJ m−2 ). tron donors, so do the lone pair electrons in two carboxyl of DOP
molecule and the ether group of TPnB molecule and hydroxyl oxy-
3. Surface energy of materials gen atom. The Lewis basic order of the four frothers from strong to
weak is TPnB > DOP > TP > MIBC, which is determined by capacity of
3.1. Surface energy of frother loss electron.
A good consistency was gotten between the results of surface
Table 3 is the contact angle data of double distilled energy tests of frothers membrane surface and the surface ten-
water, glycerol, formamide, diiodomethane and ethylene gly- sion tests of pure liquid frothers. The surface tension of frothers
col on the TP, MIBC, TPnB, DOP membrane surface. Thus emulsion (ultrasound emulsification) and pure liquid is illustrated

Table 3
Detection of contact angle liquid on the membrane surface of frothing agent ( ◦ ).

Membrane surface Water (W) Glycerol (G) Formamide (F) Diiodomethane (D) Ethylene glycol (E)

TP 89.67 80.49 71.00 56.41 66.66

MIBC 99.14 87.46 78.43 63.71 74.68
TPnB 79.92 74.75 65.33 53.89 60.11
DOP 80.78 71.71 61.03 45.35 55.39

Table 4
Surface energy of membrane surface of frothing agent (mJ m−2 ).

Frother S SLW S+ S−

WGD WFD WED WGD WFD WED WGD WFD WED

TP 31.19 30.64 30.64 30.64 0.020 0.019 0.019 3.96 3.98 3.98
Average: 30.64 Average: 0.019 Average: 3.97

MIBC 26.79 26.44 26.44 26.44 0.023 0.023 0.023 1.34 1.34 1.34
Average: 26.44 Average: 0.023 Average: 1.34

TPnB 33.17 32.08 32.08 32.08 0.031 0.032 0.032 9.34 9.33 9.33
Average: 32.08 Average: 0.032 Average: 9.33

DOP 37.89 36.82 36.82 36.82 0.047 0.043 0.043 6.43 6.47 6.47
Average: 36.82 Average: 0.044 Average: 6.46
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7962 W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967

Table 5 4. Results and discussion

Surface energy of polymer resins and other materials (mJ m−2 ).

Name S SLW S+ S− 4.1. Adsorption of weak hydrophilic substances (WHS) on
PP 32.19 32.19 0 0 low-energy surface in aqueous medium
PE 33.71 33.71 0 0
7
PS 37.03 36.58 0.010 5.07
poly-
ABS 44.18 43.12 0.059 4.76 The four frothers mentioned above are all WHS. When WHS
mer
resinsa
PC 45.17 44.02 0.068 4.85 adsorb in different mediums or on different substances with
PET 50.05 46.81 0.60 4.38 different surface energy, adsorption behavior will be significant
PVC 48.33 43.41 1.73 3.50
different. Take the Tripropylene glycol n-butyl ether (TPnB) for
PVC-Ca0 51.39 46.17 0.84 8.11 example, interaction free energy was examined between the
PVC-Ca10 51.80 46.32 0.79 9.49 TPnB and 44 different kinds of materials in aqueous media.
7 PVC-Ca20 52.06 46.38 0.81 9.95 The relationship is shown between hydrophile index1 [51] and
hard PVC-Ca30 52.42 46.51 0.66 13.23
surface energy parameters of the free energy of interface inter-
PVC PVC-Ca40 52.68 46.66 0.58 15.61
PVC-Ca50 52.93 46.83 0.50 18.62 action with the adsorbed material (Fig. 2). It should be noted
PVC-Ca60 53.30 47.11 0.41 23.33 that TPnB is only a general example, and adsorbed materi-
als are not specially selected. For other WHS, such as TP,
PVC-DP0 44.84 40.66 0.67 6.53 MIBC and DOP involved in this article and even neutral oil,
PVC-DP10 43.27 39.46 0.57 6.38
PVC-DP15 42.39 38.74 0.53 6.29
or a number of high-energy surface, similar results can be
7
soft PVC-DP20 41.51 38.02 0.49 6.22 obtained.
PVC PVC-DP25 40.81 37.52 0.44 6.14 It can be seen from Fig. 2:
PVC-DP30 40.13 37.01 0.40 6.07
PVC-DP40 38.45 35.66 0.33 5.89
(1) In aqueous medium, between the WHS and high-energy or
PE-bot 34.34 34.33 0.0029 0.013 low-energy surface with strong polarity, they are excluded
PP-bar 32.19 32.15 0.0028 0.14
each other or weak affinitive. However, a strong affinity
PVC-sho 39.31 36.33 0.37 6.01
PVC-hos 42.00 38.39 0.52 6.26
exists between WHS and LES. In other words, from high
PVC-pac 48.72 43.94 0.72 7.94 to low energy surface, the WHS give priority to adsorb
14 PVC-pip 52.28 46.46 0.74 11.44 on LES that is given. It means that if deal with high-
waste PVC-dec 53.80 47.65 0.38 24.85 energy flotation system, the adsorption of WHS can be
plas- PS-lam 52.52 46.56 0.66 13.47
neglected. While for dealing with LES system such as plastic,
tic PS-fac 45.18 44.03 0.063 5.26
PET-dri 37.26 36.71 0.016 4.81 coal, molybdenite, graphite, talc floatation and oil produc-
ABS-tv 51.87 46.35 0.79 9.66 tion, oil displacement process, the effects should not be
ABS-air 52.82 46.69 0.55 17.08 neglected.
PC-cup 50.22 47.02 0.67 3.81
(2) In aqueous medium, There is no clear corresponding relation-
PC-cd 52.99 46.88 0.64 14.56
ship between interface interaction free energy of adsorption
Calcite CaCO3 51.75 48.12 0.060 54.80 of WHS on the low-energy solid and those components
as follow: total surface energy of the adsorbed substances
PTFE 20.24 0 0 STot , Lifshitz–van der Waals component  LW , Lewis acid-
Paraffin wax 25.50 0 0
Talcum 34.2 0.1 6.9
base component  AB and Lewis acid component  + . However,
Other Mica 40.4 0.9 8.9 there is a clear corresponding relationship between the free
materialsb Kaolin 35.9 0.4 34.3 energy and Lewis base component  − or the hydrophile
Dolomite 37.6 0.2 30.5 index of material surface. The former is the three-order
Quartz 39.2 0.8 41.4
polynomial, while the latter is close to a simple linear relation-
Glass 33.7 1.3 62.2
ship.
a
From Ref. [34]. And other materials except from literature are used the similar
(3) In aqueous medium, interaction free energy of the adsorp-
way in Ref. [34].
b
From Refs. [45,48,49].
tion interface between WHS and the low-energy solid surface
increases to the positive direction, while the Lewis base
component of surface energy of substances adsorbed increas-
(Fig. 1). With increasing of the concentration of liquid frothers, ing. That means the attractive force is reduced. It indicates
the surface tension will reduce. Among them, TP, MIBC and that the WHS is easily to be adsorbed on the low polar in
TPnB show good surface activity in low concentration. Sur- aqueous medium, especially non-polar low-energy solid sur-
face tension of pure liquid of the four frothers is consistent face.
with test results of surface energy of the membrane surface (4) In aqueous medium, interaction free energy of the adsorp-
before. Therefore, this method can be used to determine the tion interface between WHS and the low-energy solid surface
surface tension of frother to replace measuring liquid surface ten- increases to the positive direction, while the surface hydrophile
sion. index of the adsorbed material increasing. The gravitational
force is reduced, and the relationship between the two is
3.2. Surface energy of polymer resin and other materials close to linear. It indicates that the hydrophile index not
only includes necessary condition of solid particles floating
44 different kinds of material and surface energy of those mate- in the flotation system and expresses the polarity of solid
rials are shown in Table 5, including 7 polymer resins [34], 14 PVC surface, but also it can serve as a key indicator that can
plastics with different additives (mainly is CaCO3 and Dn OP), 14
kinds of waste plastics (like from beverage bottle, bucket, hose and
so on) and calcite (CaCO3 ), and the other surface energy data are  
obtained from literature [45,49,50]. It is easily to see that all of those 1
Hydrophile index is S+ + S− , it includes necessary condition of solid par-
materials are LES. ticles floating in the flotation system. See Ref. [51] for further details.
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W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967 7963

Fig. 2. Relationship between the interface interaction free energy of adsorption of TPnB on the solid surface and surface energy parameters or hydrophile index of substances
adsorbed in water medium.

measure the adsorption capacity of WHS on LES in aqueous
medium.
4.2. The main force of adsorption and relationship between
surface energy parameters of adsorbed substances and hydrophile
index in aqueous medium
The Lifshitz–van der Waals and Lewis acid–base interaction
free energy were taken into account, and 35 different kinds of
material and pinitol oil in aqueous medium were taken as the
study object. Relationship was studied between surface energy
parameters of adsorbed substances (or its hydrophile index) and
interface interaction free energy (or its Lewis acid-base component,
respectively) according to adsorption of pinitol oil on low-energy
solid surface. Thus, for total interfacial interaction (Fig. 3) and
Lewis acid–base interaction free energy (Fig. 4), there is almost
an identical trend between them and the surface energy param-
eters of adsorbed substances (or its hydrophile index). There
is no clear corresponding relationship between both of them
and those components as follow: STot ,  LW ,  AB and  + . How-
ever, there is a clear corresponding relationship between the
free energy and Lewis base component  − and the hydrophile
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7964 W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967

Fig. 3. Relationship between interface interaction free energy from adsorption of pinitol oil on low-energy solid surface and surface energy parameters of adsorbed substances
(or its hydrophile index) in aqueous medium.

index of material surface. With the increase of  − and hydrophile
index of surface energy of adsorbed substances, both the inter-
face interaction and the Lewis acid–base interaction free energy
increases to the positive direction in water medium. It can be
judged from Fig. 3 and Fig. 4, hydrophobic attractive force of
the Lewis acid–base interaction is mainly responsible for the
absorption of WHS on LES in aqueous medium between the
Lifshitz–van der Waals interaction and the Lewis acid–base inter-
action.
By using interpolation, it is shown in Fig. 5(a)–(h) that the
relationship between interface interaction free energy of absorp-
tion of four different frothers (TP, MIBC, TpnB and DOP) on
low-energy materials with different surface energy and Lewis
base component of adsorbed substances (or its hydrophile index)
in aqueous media. (See Eqs. (12)–(19), surface energy unit is
mJ m−2 ). Above all, those findings should be useful and at least
can be employed in plastic flotation, and further work need to be
done.
TP:
3 2
GSWF(TP) = 0.0062(S− ) − 0.31(S− ) + 5.84S− − 80.63 (12)
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W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967 7965

Fig. 4. Relationship between Lewis acid-base component from adsorption of pinitol oil on low-energy solid surface and surface energy parameters of adsorbed substances
(or its hydrophile index) in aqueous medium.

     
GSWF(TP) = 8.82 S+ + S− − 82.60 (13) GSWF(DOP) = 8.34 S+ + S− − 71.89 (17)

MIBC:
3 2 DOP:
GSWF(MIBC) = 0.0065(S− ) − 0.33(S− ) + 6.17S− − 87.96 (14)
  
S+ + S−
3 2
GSWF(MIBC) = 9.25 − 89.93 (15) GSWF(DOP) = 0.0059(S− ) − 0.29(S− ) + 5.46S− − 75.65 (18)

TPnB:   
3 2
GSWF(TPnB) = 0.0059(S− ) − 0.29(S− ) + 5.44S− − 69.89 (16) GSWF(DOP) = 8.27 S+ + S− − 77.53 (19)
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7966 W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967

Fig. 5. Relationship between interface interaction free energy of absorption of frothers on low-energy materials with different surface energy and Lewis base component of
adsorbed substances (or its hydrophile index) in aqueous medium.
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W. Hui et al. / Applied Surface Science 257 (2011) 7959–7967
5. Conclusions
Conclusions obtained in our preliminary research are summa-
rized as follow. In aqueous medium, the WHS give priority to
adsorb on low-energy that is low polar or particularly non-polar.
If high-energy flotation system of minerals was dealt with, the
adsorption of WHS can be neglected. While for dealing with LES
system, the effects should not be neglected. There is no clear cor-
responding relationship between interface interaction free energy
of adsorption of WHS on the low-energy solid and those compo-
nent as follow: total surface energy of the adsorbed substances STot ,
Lifshitz–van der Waals component  LW , Lewis acid–base compo-
nent  AB and Lewis acid component  + . However, there is a clear
corresponding relationship between the free energy and Lewis base
component  − or the hydrophile index of material surface, and
specific relationship is obtained. The former is the three-order poly-
nomial, while the later is close to a simple linear relationship. WHS
is easily to be adsorbed on the low polar in aqueous medium, espe-
cially non-polar low-energy solid surface. Hydrophile index can
serve as a key indicator that can measure the adsorption capac-
ity of WHS on LES in water medium. Finally, we found hydrophobic
attractive force of the Lewis acid–base interaction is mainly respon-
sible for the absorption of WHS on LES.
Acknowledgements
The authors acknowledge the Key Laboratory of Resources
Chemistry of Nonferrous Metals (Central South University) for the
laboratories and financial support, and we would like to express our
sincere appreciation to the anonymous reviewer for their insightful
comments, which have greatly aided us in improving the quality of
the paper.
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