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Phenomenology and control of buckling dynamics in multicomponent colloidal

droplets
Binita Pathak and Saptarshi Basu

Citation: Journal of Applied Physics 117, 244901 (2015); doi: 10.1063/1.4922980


View online: http://dx.doi.org/10.1063/1.4922980
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JOURNAL OF APPLIED PHYSICS 117, 244901 (2015)

Phenomenology and control of buckling dynamics in multicomponent


colloidal droplets
Binita Pathak and Saptarshi Basua)
Department of Mechanical Engineering, Indian Institute of Science, Bangalore, Karnataka 560012, India
(Received 17 April 2015; accepted 13 June 2015; published online 23 June 2015)
Self-assembly of nano sized particles during natural drying causes agglomeration and shell
formation at the surface of micron sized droplets. The shell undergoes sol-gel transition leading to
buckling at the weakest point on the surface and produces different types of structures.
Manipulation of the buckling rate with inclusion of surfactant (sodium dodecyl sulphate, SDS) and
salt (anilinium hydrochloride, AHC) to the nano-sized particle dispersion (nanosilica) is reported
here in an acoustically levitated single droplet. Buckling in levitated droplets is a cumulative,
complicated function of acoustic streaming, chemistry, agglomeration rate, porosity, radius of
curvature, and elastic energy of shell. We put forward our hypothesis on how buckling occurs and
can be suppressed during natural drying of the droplets. Global precipitation of aggregates due to
slow drying of surfactant-added droplets (no added salts) enhances the rigidity of the shell formed
and hence reduces the buckling probability of the shell. On the contrary, adsorption of SDS
aggregates on salt ions facilitates the buckling phenomenon with an addition of minute concentration
of the aniline salt to the dispersion. Variation in the concentration of the added particles (SDS/AHC)
also leads to starkly different morphologies and transient behaviour of buckling (buckling modes like
paraboloid, ellipsoid, and buckling rates). Tuning of the buckling rate causes a transition in the final
morphology from ring and bowl shapes to cocoon type of structure. V C 2015 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4922980]

I. INTRODUCTION introduce different types of particles in the suspension.


Inclusion of multiple components leads to severe morpholog-
Buckling and collapse of thin spherical shells subjected
ical transitions in the final structure.13 Most of the past works
to external pressure is a universal phenomenon observed
are limited to experiments done in spray dryers.10–13 As such
across a wide plethora of applications ranging from indus-
the dynamics of the morphological and thermo-physical
trial structures (concrete domes, pressurized vessels, soccer
processes at single droplet level is never studied in any
balls, etc.) to microscopic cells and nano scaled viruses.1–4
detail. In our current study, we have attempted to provide
At the onset of buckling, the shell undergoes shape transition
insights to the buckling dynamics of mixed colloidal droplets
beyond a critical pressure, which is characterized by a single
under acoustically levitated condition. Acoustic levitation
or multiple indentations on the surface.1,5 Such indentation
provides an excellent opportunity to study the exact mor-
causes dynamic cavity formation which leads to severe
phology and mechanical properties of the structures without
deformation of the structures. The buckling instability is also
any surface contact effects. Understanding the effect of dif-
observed during drying of colloidal droplets. In drying
ferent colloidal components on buckling transition is a
systems, the loss of solvent induces self-assembly (without
highly complicated problem as it involves the interplay of
external aids) of the colloidal particles into hierarchical order
several interparticle forces. In the present study, we explored
(maximum concentration at the surface).6–8 The interactions
the influence of inhomogeneity induced in a shell (due to
lead to agglomeration of particles which acts as precursor to
mixed colloids and flow) upon the buckling behaviour.
the formation of an elastic membrane (shell) at the surface.4
We incorporated anionic surfactant sodium dodecyl
The shell undergoes viscoelastic transition which leads to the
sulphate (SDS) and anilinium hydrochloride salt (AHC) in
buckling instabilities in the droplet.9,10 The phenomenon of
controlled quantity into aqueous suspension of silica nano-
buckling can be manipulated by varying the concentration,
particles. Introduction of surfactants in nano-suspensions is
size, type, and distribution of the particles in the disper-
found to optimize the mechanical and morphological qual-
sion.7,11,12 Rate of drying plays a key role in the invagination
ities of the final product.14–16 In the current work, it is
process eventually leading to spherical or non-spherical
observed that the rate of buckling is completely altered by
(dough-nut shaped) structures in the droplet.12 Controlled
buckling can be exploited to manufacture custom-tailored increasing the concentration of the surfactant (SDS,
materials which have widespread industrial applications 0.2%–2% by weight) and is completely arrested above a crit-
(pharmaceuticals, cosmetics, detergents, coatings, etc.). ical value (>1% by weight). Addition of salt (AHC) in the
Another methodology to control buckling kinetics is to dispersion causes re-initiation of buckling in the droplets.
We discuss here the dynamics of buckling based upon
the arrangement of particles induced by evaporation of sol-
a)
E-mail: sbasu@mecheng.iisc.ernet.in vent at the surface of the droplets. The complete arrest of

0021-8979/2015/117(24)/244901/9/$30.00 117, 244901-1 C 2015 AIP Publishing LLC


V

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244901-2 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

FIG. 1. Control map illustrating the effect of added surfactant (SDS) and salt (AHC) upon the buckling phenomenon leading to different morphologies of the
final structures (top panel (a) shows the dynamics of TM (2% by weight) droplet). (b) a1–a6 represent the effect of SDS (added to 2% weight aqueous TM dis-
persion) and (c) b1–b5 shows the effect of AHC (added to a6 (a6: 2% TM þ 2%SDS)) at different concentrations. [The first two columns are the high speed
images showing the caving phase and the final structure, respectively, and the last two columns show the SEM images of the final structures (900 and
20k).]

buckling is demonstrated due to changes in the mechanical Pe ¼ tdiffusion/tdrying  18) promotes particle aggregation and
properties (high rigidity against external pressure) of the leads to the formation of a shell of packed particles at the
shell caused by irregular arrangement of protruding SDS droplet surface (of average thickness of h  O (105) m),
crystals among the closely packed silica aggregates. We elu- while the core remains in the viscous liquid phase.18,19 The
cidate that the re-initiation of buckling occurs due to adsorp- effect of acoustic pressure is observed as the droplet gradu-
tion of AHC on SDS, which reduces the effective area of the ally deforms into an oblate spheroid shape ((ii) in Fig. 1(a)).
SDS crystals jammed in between the silica aggregates, thus The deformation of the droplet due to acoustic pressure field
increasing the probability of buckling in the shell. Different has been thoroughly studied previously.18–20 The flattening
modes of buckling (paraboloid, ellipsoid, and conical- continues to a point when there is no significant topological
shaped) are observed by varying the concentration of the change in the droplet. It is proposed that the presence of
different components in the dispersion. The scanning elec- water menisci at the interstices between the particles devel-
tron microscopy (SEM) and energy dispersive X-ray spec- ops capillary pressure (Pcap) in the shell.9,18 The pressure-
troscopy (EDS) provide insight into the overall morphology induced instability in the shell causes buckling of the surface
and the compositional variation across the structures, to relieve the strain (explained in detail later). The buckling
respectively.

II. DYNAMICS OF DRYING DROPLET


The dynamics of the drying colloidal droplet during the
entire process is elaborated in this section. A drying droplet
(initial diameter, d) undergoes shrinkage in volume due to
loss of water ((i) in Fig. 1(a)). The experiments were con-
ducted with dilute dispersions (2% by weight) of colloidal
particles of low elasticity. Hence, deformations of particles
due to surface forces are negligible in the current study.17
Spatial restriction due to reduction in volume causes interac-
tions among the particles, which accumulate at the air-water
interface. The particle interactions are intensified due to
internal circulations in liquid phase caused by the acoustic
streaming (100 kHz) (Fig. 2). However, both the mass and
thermal diffusion timescales (O (102) s) are substantially
larger than the time required for propagation of the sound
wave (O (102) s). The combined effect of orthokinetics FIG. 2. Flow field inside a non-rotating acoustically levitated droplet.30,31
(due to recirculation) and mass diffusion (Peclet number, Adapted from Ref. 31.

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244901-3 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

originates in a small region on the flattened surface (thick- The final structures formed of aqueous TM-SDS disper-
ness is significantly smaller than the rest of the shell) and the sion droplets included as (a1 to a6) in Figs. 1(b) and 1(c) rep-
front propagates inward (caving-in), which eventually leads resent the structures obtained in the aqueous TM-SDS-AHC
to the formation of different types of structures.18 The final dispersion droplets (b1 to b5). The top panel (marked as (a))
structures obtained through natural drying of different types shows the ring and bowl type structures (aspect ratio
of mixed colloidal droplets are explained in Sec. III.20,21 In (z/y)  0.4 (ring), 0.7 (bowl)) obtained in TM dispersion (2%
our previous work,18 we investigated the effect of external by weight in water) droplets. The three different stages
heating rate on the buckling behaviour of single component (marked in arrows) consisting of pure evaporation, flattening,
(nanosilica) droplets. In the current work, we analyze the and the caving-in of the surface leading to the formation of
buckling behaviour in multi-colloid droplets under natural the final structure are observed in the high speed images
drying in acoustically levitated condition. (phases are illustrated schematically in Fig. 3(i) and
explained in Sec. IV B). Closed packing of silica particles
III. EXPERIMENTS
forming the shell of the structures is also evident from the
SEM image (elaborated in Fig. 4(i)).
We used an acoustic levitator to stabilize the droplets in Addition of SDS (0.2% wt.) to aqueous TM (2% wt.)
a contact-free environment (Tec5, ultrasonic levitator, dispersion leads to a bowl-shaped structure due to incom-
100 kHz, 154 dB). The evolution of the droplet during drying plete caving of the top surface. The microscopic image
was monitored using a high speed camera (Photron SA5, depicts particles in aggregate form throughout the surface
coupled with 5 zoom lens) at 250 fps under controlled (marked as a1). An increase in the concentration of SDS
ambient temperature of 25 C and relative humidity of shows a gradual decay in the caving width (w) and depth (H)
approximately 50%. The droplet diameter was maintained to (accompanied by the reduction in cavity tip radius) and a
about 430 (630) lm. The initial colloidal aqueous dispersion complete suppression of the buckling is obtained above the
R
of silica (LUDOXV TM 40, pH  9, average diameter concentration of 1% by weight (a5, a6). The flattening of the
22 nm, 40% in weight, Sigma Aldrich, India) was diluted droplet is greatly reduced with the inclusion of the surfac-
to 2% in weight in distilled water and the dynamics of the tant. The droplets that do not cave-in form cocoon-type of
levitated droplet under natural drying condition was recorded structure (a5, a6) with a high aspect ratio (z/y  0.8). The
as the base case. SDS22–29 (BioReagent, 98.5% (GC), surfactant added droplets show pillar-type features on the
Sigma Aldrich, India) dispersion was prepared in distilled surface of the final structure (columns in the SEM images,
water and added to 2% weight aqueous TM dispersion. The Fig. 3(iii)). The pillars are formed due to SDS crystals
mixed colloidal dispersion was sonicated for 30 min using embedded in the bed of silica aggregates (also explained in
ultrasonicator. The concentration of silica was fixed to 2% later sections).
by weight in the mixed dispersion and the SDS concentration To demonstrate the effect of aniline hydrochloride
was varied from 0.2% to 2% by weight to record the relative (AHC), the salt was added in varying concentration (from
effects. The second set of experiments was conducted with 0.02% to 0.5% by weight) to a fixed concentration of TM
similar sized droplets ((430 6 30) lm) of aqueous TM-SDS and SDS (2% by weight each in the mixed dispersion).
Inclusion of minute amount of AHC (0.02% by weight) has
(2% weight silica þ 2% weight SDS) dispersion, with added
little effect on the buckling dynamics producing a similar
aniline hydrochloride salt (99%, Sigma Aldrich, India).
cocoon type structure (b1 in Fig. 1(c)). It, however, causes a
The salt (AHC) was added in variable amounts (0.02% by
substantial reduction in the droplet aspect ratio from 0.8 to
weight to 0.5% by weight) to the aqueous SDS dispersion
0.5. A gradual increase in the caving depth is observed as the
(2% by weight) by continuous stirring and the mixed disper-
amount of AHC is increased in the droplet. The microstruc-
sion was then added to aqueous TM dispersion (2% by
ture shows a gradual reduction in the number of SDS pillars
weight) and sonicated for 30 min (all the concentration
on the final structures. The depletion of pillars is attributed
are with respect to the final mixed dispersions). The zeta due to the adsorption of AHC ions on SDS. A concentration
potential was measured to be approximately 43 mV to of 0.5% (by weight) of AHC leads to an irregular bowl
52 mV and polydispersity of (19 6 3)% in size using shaped structure (comparatively higher aspect ratio,
Zeta Potential Analyzer (Brookhaven ZetaPALS), which z/y  0.9) and with crystals on the surface (evident in SEM
quantifies the stability of the dispersions. The final micro- image in Fig. 4(iv) (a)).
structures obtained were characterized with scanning elec- Flattening of the droplet which is a precursor for the
tron imaging and energy dispersive X-ray spectroscopy onset of buckling is gradually suppressed with the increase
(SEM with EDS, ULTRA 55). in SDS concentration (flattening is first reduced on the bot-
tom surface as seen in a3, Fig. 1(b) and then on the top sur-
IV. RESULTS AND DISCUSSION face from a5 in Fig. 1(b)) and reinitiated with the addition of
AHC. However, flattening may not always lead to buckling
A. Characterization of the final structures
as observed in the case of 0.02 wt. % addition of AHC to the
The morphologies obtained under different concentra- SDS solution (b1 in Fig. 1(c)).
tions of the added surfactant and the salt are depicted in We define two routes based on the experimental obser-
Fig. 1. The regime is briefly described here and discussed in vations, one path leading towards the arrest of buckling
detail in the succeeding sections. during drying of levitated droplets (path 1) and the other to

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244901-4 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

FIG. 3. Schematic showing the various stages during natural drying of acoustically levitated droplets in (i) 2% by weight of aqueous TM dispersion, (ii) SDS
at a concentration <1% (by weight), (iii) SDS at a concentration >1% (by weight) added to 2% aqueous TM dispersion, and (iv) AHC added to equal concen-
tration of SDS and TM (2% by weight each in aqueous dispersion).

the re-initiation of the same (path 2). We chose (a) aqueous pressure distribution (Pacc) around the droplet (Fig. 2) is
TM (2% by weight) droplet as the base case for reference, maximum at the poles (stagnation pressure) as shown by
(b) TM-SDS droplet (2% by weight TM þ 2% by weight many groups.9,18 The maximum pressure, however, occurs at
SDS) to refer to path 1, and (c) TM-SDS-AHC (2% by the top pole of the droplet due to the location of the droplet
weight TM þ 2% by weight SDS þ 0.5% by weight AHC) away from a pressure node (gravity effect). The acoustic
droplet to demonstrate the path 2. pressure deforms the droplet into an ellipsoidal shape ((c) in
Fig. 3(i)). The pressure distribution also leads to a recirculat-
ing flow field (only for non-rotating droplet; Fig. 231). The
B. Phenomenology of buckling
flow field is asymmetrical and exhibits slight divergence at
The structures demonstrated in Fig. 1 are formed the droplet poles.30,31 As the droplet flattens under acoustic
primarily due to the buckling phenomena. Fig. 3 depicts the loading, this flow divergence near the stagnation point (drop-
schematic of different stages involved in the process (sup- let poles in Fig. 2) is aggravated. Agglomeration of silica
ported by the SEM images in Fig. 4). The average size distri- particles (due to orthokinetics) at the surface causes the
bution of the particles in aqueous TM dispersion (2% by formation of shell of varying thickness ((d) in Fig. 3(i)). The
weight) is measured to be about 22 nm in ZetaPALS. The shell is therefore weakest and thinnest at the two poles due
dispersion shows a low polydispersity of 18% in size, which to the recirculating flow pattern.31 Therefore, it undergoes
indicates relatively good stability and a uniform distribution buckling at the weakest point on the surface ((e) in Fig. 3(i)).
of particles in the dispersion. The inhomogeneous acoustic Buckling prominently occurs at the top surface (droplet pole)

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244901-5 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

FIG. 4. Scanning electron microscopic images showing different features of the final structures obtained in (i) 2% (by weight) aqueous TM dispersion droplets,
(ii) SDS (0.2% by weight) þ TM (2% by weight), (iii) SDS (2% by weight) þ TM (2% by weight), and (iv) SDS (2% by weight) þ TM (2% by weight) þ AHC
(0.5% by weight).

although a relatively small cavity can also appear at the bot- surface (SEM image, Fig. 4(ii)). The presence of SDS crys-
tom surface (depending upon the curvature adopted by the tals acts as a barrier to the buckling of the shell formed at the
surface). Propagation of the buckling fronts causes merging surface (primarily large pore size and columnar structures).
of the cavities and leads to the ring-type morphology in the Thus, the incomplete caving-in of the top surface leads to the
final structure (Fig. 3(i) (f)). However, the droplet with a sin- bowl-shaped structure (Fig. 3(ii)(e)).
gle cavity on the top surface (with no cavity at the bottom) The inclusion of SDS above the optimum value (>1%
leads to a regular bowl-type structure. The microstructural wt.) causes a complete arrest of caving of the surface.
image (Fig. 4(i)) of the final structure shows the aggregation Drying of water and spatial restriction leaves the SDS crys-
of silica particles at different layers, forming the toroid tals deposited within the silica matrix (Figs. 3(iii)(b) and
shaped structure. 3(iii)(c)). The SEM image confirms the SDS reinforced into
The stages involved in drying of surfactant added TM silica matrix as palettes, which is prominent only above a
droplets are dramatically different from the aqueous TM critical concentration (>1% by weight) (Fig. 4(iii)(f)). The
droplets. The adsorption of the anionic SDS (CH3(CH2)11 palettes formed due to aggregation of SDS molecules are of
þ
OSOþ 3 Na ) is not significant on the surface of the negatively different shapes (rods, globules, etc.).26 The EDS spectrum
charged silica substrate.22 The zeta potential of aqueous TM of Na-S-C corroborates the presence of SDS patches into the
is about 43.7 mV and with an addition of SDS, the surface silica matrix (EDS in Fig. 4(iii)). Although the SEM images
potential is approximately 50 mV. The similar potential show the overall morphology of the final structures, it is not
values and the low polydispersity (15%–19%) in size con- possible to interpret the exact morphology of the SDS from
firm that the anionic SDS do not adsorb on the negatively the micrographs. However, we limit and refer to the phase as
charged silica surfaces and a uniform initial dispersion is SDS aggregates/crystals. The heterogeneous distribution of
obtained. The higher affinity of SDS towards water causes SDS slabs in between the locally aggregated silica particles
adsorption of the SO3 headgroups to the liquid interface prevents the buckling of the surface and a globular mass of
from the bulk dispersion and re-orients the water mole- aggregated particles is obtained ((d) in Fig. 3(iii)).
cules.23,24 The initial arrangement of SDS at the interface is The kinetics of buckling is further manipulated with the
shown in Fig. 3(ii)(a). Such an arrangement of headgroups of inclusion of aromatic anilinium hydrochloride (AHC) salt,
the surfactants leads to minimum energy of the system.25 which leads to different morphology of the final structure.
The silica particles continue to interact among each other The influence of added salts in the morphology of the final
and forms aggregates in the spaces available [not occupied structures from precursor droplets was previously studied by
by SDS headgroups] (Figs. 3(ii)(b) and 3(ii)(c)). The cluster varying the concentration of salts in graphene oxide disper-
of silica (22 nm) is evident in the SEM images (Fig. 4(ii)) sion.32 The effect of surfactant (SDS) on the complete arrest
and confirmed with EDS (not shown here). Loss of water of buckling is prominently observed only when incorporated in
from the interstices due to evaporation distorts the arrange- equal proportion to that of silica (2% by weight). Hence, the
ment of SDS crystals attached to the liquid interface.12 salt was added in variable weight fractions (0.02% to 0.5%) to
The distortion causes a random assembly of the amphiphilic a fixed concentration of SDS and TM (2% by weight each) in
molecules (within the matrix of the silica aggregates) leaving water. The ionic strength of the dispersion is enhanced with
their adsorption sites (Fig. 3(ii)(c)) leading to a porous the addition of salt due to its dissociation into the respective

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244901-6 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

ionic dissociation
ions (C6 H5 N þ H3 Cl  ! C6 H5 NH3þ þ Cl ). The
cationic anilinium ion adsorbs onto the negatively charged
SDS and reduces the effective area of the head groups (high-
lighted in Fig. 3(iv)(a)).27 Adsorption of ions greatly reduces
the interactions between the water molecules and the SDS
molecules.28,29 Presence of the salt also decreases the diffu-
sion coefficient of SDS,27 which decreases the tendency of
SDS to form crystals at the droplet surface. The silica par-
ticles, however, continue to collide and agglomerate, which
produces the shell at the surface. The insoluble ion-pair of ani- FIG. 6. Timescales of various stages occurred during drying of the three
different dispersion droplets. (tvap, tppt, tflat, and tcav represent the time
linium on dodecyl-sulphate resists the formation of SDS
required for pure vaporization, precipitation of particles and aggregates,
palettes at the surface and thus facilitates buckling of the shell droplet surface flattening, and the caving-in phase, respectively). F1, F2,
(Fig. 3(iv)(c)). Presence of such ion-pair is evident on the sur- and F3 represent the three different aqueous dispersions (by weight) with
face of the structures (Fig. 4(iv)(a)) and the EDS data confirm (i) 2% TM, (ii) 2% TM þ 2% SDS, and (iii) 2% TM þ 2% SDS þ 0.5%
AHC, respectively.
that the irregular shaped sharp features are composed of chlo-
rine and sodium ions, respectively (Fig. 4(iv)(c)).
droplet is relatively smaller than that of a flattened droplet
C. Analysing the buckling phenomenon (DPflattened/DPspherical  10–11).19 The reduction in DP due to
The evolution of droplets during the drying process is spherical shape is thus far greater than the reduction in the
depicted in d/d0 plots in Fig. 5 (d0 is the initial droplet diam- stress due to surface tension decrease (r/Rc). The resultant
eter and d is the instantaneous diameter). The various stages rate of deformation due to the presence of the inhomogene-
involved in the droplet lifetime are marked in the graph with ous pressure field is thus greatly reduced in such droplets
reference to the various timescales in Fig. 6. The initial va- ((c) in Fig. 5).
porization phase (tvap  80% of total lifetime, ttot  230 s) in At the end of the flattening stage, the shell formed at the
aqueous TM droplet is followed by flattening of the droplet surface acts as an elastic membrane under tension due to the
(already explained) due to the surrounding pressure field capillary pressure (Pcap) developed in the interstices between
(tflat  15% of ttot). The degree of flattening is determined by the particle aggregates. The capillary pressure (Pcap) is cal-
Weber number [We ¼ DP/(r/Rc)] (DP is the difference culated using Darcy’s law as
between the pressures at the pole and at the equator, r is the
Pcap ¼ lJh=k; (1)
surface tension of the droplet, and Rc is the radius of curva-
ture), which is defined as the ratio of the Bernoulli’s stress where l is the viscosity of the dispersion, J is the evaporative
(determined by the sound pressure level) and the stress due flux (dR/dt, R is droplet radius at time t), h is the shell thick-
to surface tension.19 The deformed shape of the droplets ness, and k is the shell permeability. The thickness of the
causes further increase in the pressure difference (DP), shell formed (h) is calculated utilizing the mass conservation
which enhances the flattening of the droplets ((ii) in Fig. equation as9
1(a)). The surfactant added to the nano-particle dispersion 8 9
causes a reduction in the surface tension (r) of the TM-SDS > 2  3 313 >
>
< Ri >
=
droplets due to re-orientation of the surfactant molecules at 6Cf  Ci 7
4 R 5
the interface. However, the uniform and possibly quicker h ¼ Rcav >
:1 
>
cav >
>
;; (2)
agglomeration of SDS pillars in surfactant added droplets ðC f  C i Þ
maintains the spherical shape (Fig. 5). The pressure differ-
ence (DP) between the pole and the equator for a spherical where Rcav is the buckling radius, Ci is the initial particle
concentration (volume fraction), and Cf is the particle vol-
ume fraction in the shell (0.589). The shell permeability is
estimated using Carmen-Kozeny relation as
 2 " #
dp ð1  C f Þ3
k¼ ; (3)
180 C2f

where dp is the particle diameter (22 nm). Evaporation con-


tinues through the pores of the shell at a very slow rate. The
net pressure (Pacc þ Pcap) acting on the shell induces both
bending and stretching of the surface, disrupting the equilib-
rium state.18 It is known that the stress induced in an elastic
FIG. 5. The temporal variation of droplet diameter (d) (non-dimensionalized shell is released through buckling of the shell. The buckling
with the initial diameter, d0). (F1, F2, F3 represent the three different aque-
ous dispersions (by weight) with (i) 2% TM, (ii) 2% TM þ 2% SDS, and originates at the point of minimum Gaussian curvature and
(iii) 2% TM þ 2% SDS þ 0.5% AHC, respectively). shell thickness on the droplet surface (at the top surface),

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244901-7 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

which propagates inward and morphs to a negative Gaussian calculated using Eq. (5) for aqueous TM dispersion (2% by
curvature. Such morphological transition in the shell is weight). This signifies that although the buckling phenom-
favourable towards the stable equilibrium condition. The enon is initiated due to imbalance of capillary pressure and
interfacial capillary force (50 kPa) is primarily responsible restoring elastic energies, the process is controlled by the
for the initiation of buckling in the shell.18 The acoustic pres- changes in the droplet mass due to evaporation of solvent
sure plays a crucial role in causing asphericity in the droplet through the pores in the shell.
(deforms to obloid shape), density variation, and inhomoge- The addition of the surfactant (SDS) at a lower concen-
neity of the shell thickness (polar soft spots), which are pre- tration (<1% by weight) causes non-uniform aggregation of
requisites for the occurrence of the buckling phenomenon. the particles into clusters. The escape of SDS crystals in the
The total elastic energy (bending and stretching) of the shell radially inward direction from the droplet surface due to loss
is localized to a small strip
 of width
 d (energetically favour- of water produces pores in the shell (as explained previ-
5 3
ously). Presence of pores enhances the interstitial spacing
able) and is in order of YhR2cavH2 ,33 where Y is the Young’s
among particle aggregates at the surface leading to larger ra-
modulus of the shell, h is the shell thickness, H is the caving dius of curvature (Rc) and hence results in reduced capillary
depth, and Rcav is the radius of caving. Buckling occurs due pressure (r/Rc). Reduction in the capillary pressure
to imbalance between the external pressure work (PcapDV) (20 kPa) which is the driving potential for the initiation of
and the restoring elastic energy of the shell (Etot). The volu- buckling causes a gradual decay in the caving rate as the
metric change (DV) due to buckling of the surface is esti- concentration of SDS is increased in the droplet (Fig. 7). The
mated by using appropriate topology for the inward caved increase in thickness of the shell from approximately
volume. 17.8 lm at 0% SDS (by weight) to 40 lm at 0.5% SDS (by
The energy balance equation is given as weight) added to 2% aqueous TM  dispersion
 5 3
also indicates
dU dVcav increased strength of the shell YhR2cavH2 for same Young’s
Q_ ¼ W_ þ þ qw hf g ; (4)
dt dt Modulus (Y). Increase in both the porosity and the shell
where U ¼ E þ VdropqdropcvT is the internal energy of the strength restricts buckling in the shell. It can also be noted
shell. Under natural drying condition at constant temperature from Eq. (1) that the capillary pressure required to buckle
T, the external heat is supplied, Q_ ¼ 0. qw , hfg, and cv are the also increases with shell thickness. It is to be noted that while
density, enthalpy, and specific heat of water. The external increase in shell thickness tends to increase capillary pres-
work done (W_ ¼ PDVcav ) and the total elastic energy change sure, rapid increase in pore size effectively nullifies this
(dE/dt) are in the orders of O (108) J/s and O (107) J/s, effect (Eq. (1)). The experimentally obtained shell thickness
respectively, which are significantly lower than the other (17.8 lm) compares well with the theoretical value (13 lm;
terms in Eq. (4), which are of order of O (104) J/s. Since Eq. (2)) for 2% aqueous TM dispersion (by weight).
the change in droplet volume (DVdrop ) is negligible during Presence of multiple components (mixed colloids) agrees
caving phase, a first order scaling approximation implies well as far as the order of the shell thickness is concerned (O
(105) m). However, it is not possible to predict the exact
cv T value for multi-colloid dispersions using the conventional
DVcav ¼ Dq Vdrop ; (5)
qw hf g drop buckling theory (for single component).
Addition of SDS above the optimal value (>1% by
where Vdrop and qdrop are the volume and density of the drop- weight) causes complete suppression of the buckling
let, respectively. The exact change in density of the droplet phenomenon. The arrest of buckling is associated with the
(Dqdrop ) is complicated and hence it is estimated using final volumetric deposition of the aggregates. The micropores are
particle packing fraction of Cf  0.58. It cannot be used for blocked due to the presence of SDS palettes at the surface.
mixed colloidal droplets due to formation of irregular crystal The rapid agglomeration of SDS and formation of palettes
aggregates throughout the surface. The experimentally esti- resist flattening of the droplet due to acoustics. Furthermore,
mated caved volume using paraboloid profile is an order of the trapped water evaporates at a relatively slower rate and
O (1013) m3, which compares well with the volume hence uniform drying is achieved (d/d0 plot in Fig. 5).

FIG. 7. The continuous decay of the


average caving rate (buckling rate)
with an increase in concentration of
SDS to TM dispersion (2% by weight)
and the gradual recovering of the buck-
ling rate with an addition of AHC to a
fixed concentration of TM þ SDS (2%
by weight each).

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244901-8 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

Evaporative flux (dR/dt) of the droplet (O (107) s) is an D. Different buckling modes
order of magnitude smaller than that of the aqueous TM
Inclusion of multiple components in the droplet also
droplets (O (106) s). The slow drying of SDS-TM drop-
changes the morphology of the buckled cavity on the shell
lets (tvap  90% of ttot  400 s, Fig. 6) provides sufficient
alongside the caving rate. The various modes of buckling are
time for the transport of the particles/aggregates within
illustrated in Fig. 9. The cavity adopts a paraboloid curvature
the droplet. The gradual loss of water and slow diffusion of
in aqueous TM dispersion droplets (Fig. 9(a)). The caving tip
particles result in precipitation and agglomeration through-
propagates vertically inward (at an average rate of dH/
out the droplet (tppt  10% ttot) in a more isotropic fashion.
dt  0.05 mms1) forming a toroid or bowl shaped structure
The SEM image (b) in Fig. 4(iii) (broken structure) corrobo-
(with an aspect ratio (x/h)  0.66, Fig. 8). During the cavity
rates the global deposition of palettes and aggregates within
expansion, the liquid trapped within the shell evaporates
the structure. Such volumetric deposition produces a highly
through the pores on the shell. The rate of evaporation of liq-
rigid structure (Y  4 GPa). Uniform drying and rigid homog-
uid is equivalent to the rate of collapse of the shell. Spatial
enous shell (without soft spots) maintain the spherical topol-
restriction in the vertical direction promotes the radial
ogy of droplets against the external pressure field and hence
growth of the cavity (x), although the change in width of the
avoids the geometrical requirement (asphericity) for the
cavity top (w) is not appreciable due to rigidity of the shell
onset of the buckling instability.
formed at the surface (as shown in Fig. 8(i)).
Addition of salt (AHC) produces ions which act as
Addition of SDS to TM dispersion leads to the formation
adsorption sites for the SDS at the surface (as stated earlier).
of thick fibre like features restricted to the surface of the struc-
Adsorption of the ions on SDS leads to the formation of crys-
ture (SDS pillars in Fig. 4(iii)). The presence of the pillars
tal type features which extrudes on the surface (SEM images
resists the deformation of the shell due to surrounding pressure
in Fig. 4(iv)) and provides sufficient space for the silica
field and thus minimizes the width of the weak region for ini-
aggregates to form the shell with nano-meniscii. The droplet
tiation of buckling in the shell (“w” in Fig. 7). Reduction in the
evaporates for about (60–70)% of the total lifetime
size of the buckling region leads to ellipsoidal shaped cavity
(ttot  300 s). Flattening of the droplet continues simultane-
(aspect ratio  0.88, Fig. 9(b)). The cavity develops at a rela-
ously along with the precipitation of the particles/aggregates.
tively slower rate in all the directions (H, x, w) with an increase
The buckling is re-initiated on the upper surface and the in concentration of SDS due to slow drying rate and mass dif-
front propagates inward (tcav  2% of ttot) which produces fusion within the droplet (1% SDS in Fig. 8(ii)). The slower
the bowl-shaped structure. The rate of caving is enhanced rate of radial spread of cavity width (dw/dt  0.009 mm s1) as
with an increase in concentration of AHC due to increased compared to the cavity tip growth rate (dH/dt  0.022 mm
number of sites for SDS adsorption (Fig. 7). Figs. 8(iii) s  1) is due to the tendency of the surfactant to assemble spe-
and 8(iv) also depict an increase in the rate of growth of cav- cifically at the surface (forming palettes). The inertia gained
ity with increased concentration of the added salt. The thick- due to capillary pressure (low due to high porosity) is not suffi-
ness of the shell is reduced from 35.7 lm to 16.8 lm (weak cient for the cavity to propagate completely through the drop-
shell) with an addition of AHC (from 0.05% to 0.5% by let, which leads to the bowl-type structure.
weight to 2% TM þ 2% SDS dispersion) with reduced pore The removal of SDS pillars on the addition of aniline
size (low value of k as shown in Eq. (3)) which assists facilitates the deformation of the droplet due to its adsorption
buckling. on the salt ions and re-initiates the process of buckling in the
shell. The global precipitation of particles, however, restricts
the radial expansion of the cavity, leading to a sharp conical-
shaped cavity (Fig. 9(c)). The cone shape is typically

FIG. 8. Growth of buckled cavity dimensions and the droplet diameter


regression during the buckling phase (tB) (l is the lengthscale representing FIG. 9. The high speed images showing the various buckling modes in drop-
the longitudinal growth (H), radial growth of the base (w) and the width (x) lets of aqueous dispersion (% by weight) of (a) 2% TM, (b) 2% TM þ 1%
at half-length (H/2)) in (i) 2% TM, (ii) 2% TM þ 1% SDS, (iii) 2% SDS, (c) 2% TM þ 2% SDS þ 0.1% AHC, and (d) 2% TM þ 2%
TM þ 2% SDS þ 0.1% AHC, and (iv) 2% TM þ 2% SDS þ 0.5% AHC. SDS þ 0.5% AHC.

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244901-9 B. Pathak and S. Basu J. Appl. Phys. 117, 244901 (2015)

observed in thin shells and hence can be attributed to the ACKNOWLEDGMENTS


maximum flattening of the droplet. The cavity thus expands
We would like to gratefully acknowledge Dr. Debasis
longitudinally with an increase in the tip radius (aspect
Sen (Bhabha Atomic Research Centre (BARC), India) for
ratio  1.25 and conical angle  75 , Fig. 8(iii)). A uniform
the very useful discussions and suggestions during initial
expansion of the cavity is observed in all the three aspects
stage of this work. Dr. Sen initially suggested adding SDS
(H, w, r) specified (0.01 mm s1). The parabolic shape of
and AHC to nanosilica dispersions, which kick started the
the cavity is recovered at a concentration of 0.5% (by
current work. The work was funded by Department of
weight) of aniline salt due to the maximum adsorption of
Science and Technology, Government of India.
SDS crystals on the salt ions (Fig. 9(d)). The rate of growth
of cavity is enhanced with an increase in the concentration 1
G. A. Vliegenthart and G. Gompper, New J. Phys. 13, 045020 (2011).
of the added salt in the dispersion (average rate of 0.03 2
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mms1 in H, w, and r) (Fig. 8(iv)). 3
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The variation in concentration of the added compo- 14159 (2005).
4
L. Pauchard and Y. Couder, Europhys. Lett. 66(5), 667 (2004).
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evaporation through the porous shell, which subsequently 6
D. Sen, O. Spalla, O. Tache, P. Haltebourg, and A. Thill, Langmuir 23,
affects the cavity expansion rate [Eq. (5)]. The vaporization 4296 (2007).
7
rate can be enhanced through external heating as was previ- J. Bahadur, D. Sen, S. Mazumder, S. Bhattacharya, H. Frielinghaus, and
G. Goerigk, Langmuir 27, 8404 (2011).
ously observed by our group.18 Although buckling is an 8
D. Sen, J. Bahadur, S. Mazumder, G. Santoro, S. Yu, and S. V. Roth, Soft
evaporation driven phenomenon, the physiological proper- Matter 10, 1621 (2014).
9
ties of different components also affect the dynamics of N. Tsapis, E. R. Dufresne, S. S. Sinha, C. S. Riera, J. W. Hutchinson, L.
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10
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cursor to caving) depends upon the agglomeration rate, Langmuir 25(12), 6690 (2009).
12
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14
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V. CONCLUSIONS 17
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20
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23
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27
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31
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