Colloids and Surfaces A: Physicochem. Eng.

Aspects 509 (2016) 19–31

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Experimental study on stability and rheological properties of aqueous

foam in the presence of reservoir natural solid particles
Roozbeh Rafati ∗ , Amin Sharifi Haddad, Hossein Hamidi
School of Engineering, Kings College, University of Aberdeen, AB24 3UE, United Kingdom

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Foam stability is critical for foam

flooding in enhanced oil recovery
processes.
• Micro- and nano-particles may
improve or downgrade stability of
foam.
• Foaming agent concentration, parti-
cle size/shape/wettability affect foam
stability.
• Calcium carbonate, barium sulfate,
and strontium sulfate particles
improve foam stability.
• Calcium sulfate and iron oxide parti-
cles decrease foam stability.

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

Article history: Gas injection and especially CO2 flooding has been applied in many oil reservoirs globally to increase
Received 13 July 2016 oil recovery factor in addition to its environmental friendly aspects. However, difference between fluid
Received in revised form 29 August 2016 viscosities and densities, can cause interface instability where gas override and fingering may expedite
Accepted 31 August 2016
gas breakthrough. Different types of foam have been proposed to improve interface stability. Yet, a major
Available online 31 August 2016
uncertainty is interaction of foam with natural reservoir particles which may improve or downgrade
the performance and stability of foam. In this study we examined foam stability through solid-fluids
Keywords:
interactions between solid particles of hydrocarbon reservoirs and aqueous foam. We tested five common
Foam stability
Foam apparent viscosity
reservoir particles of calcium carbonate, calcium sulfate, barium sulfate, strontium sulfate and iron oxide
Solid particles with different surfactant and particle concentrations. It is found that stability of foam in the presence
Enhanced oil recovery solid particles is a function of density, shape, size, and wettability of particles where monolayer, bilayer of
Solid-fluids interactions network or particles stabilise foam lamella or rupture foam structure. Results show that solid particles of
Gas mobility control calcium carbonate, barium sulfate and strontium sulfate enhance the thermodynamic stability of foam.
This is due to the distribution of semi-hydrophilic solid particles, which form mono- and multi-layers of
particle chains in foam lamellae and plateau borders. On the other hand, solid particles of iron oxide and
calcium sulfate destabilise foam where particle swelling, adsorbed surfactant solution and settlement
into liquid phase due to their high densities were observed. The results suggest that a comprehensive
study of liquid and solid interaction is critical in design of any foam for enhanced oil recovery processes.
© 2016 Elsevier B.V. All rights reserved.

∗ Corresponding author.
E-mail address: roozbeh.rafati@abdn.ac.uk (R. Rafati).

http://dx.doi.org/10.1016/j.colsurfa.2016.08.087
0927-7757/© 2016 Elsevier B.V. All rights reserved.
20 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31

1. Introduction Concentration of solid particles in liquid phase, their wettability,

size and shape are critical parameters affecting bulk foam stabil-
Gas injection and CO2 flooding as enhanced oil recovery meth- ity [28–39]. Concentration of solid particles defines the quantity of
ods have been used successfully in many places around the world. particle association in foam lamellae and at the plateau borders,
In this kind of processes injected gas phase displaces oil through which is a key factor for apparent viscosity enhancement of bulk
reducing interfacial tension and capillary effects, which improves foam [38–42].
ultimate recovery factor. However, high gas to oil mobility ratio Foam stability of silica and laponite particles at various con-
is an unfortunate that causes gravity override, gas phase chan- centrations with mixture of anionic and non-ionic surfactants
nelling, and viscous fingering. Therefore, high gas to oil mobility were studied by many researchers [30–34,36,38,39,43,44]. A syn-
ratio results in poor sweep efficiencies and early breakthrough of ergistic foam stability trend was reported, where it shows more
displacing phase (gas) [1–3]. prominent effects with increasing in the concentration of particles.
In gas injection processes, stability of displacing front is a main The enhancement of synergistic effect is attributed to an increase
concern, and it is a function of many variables such as injection pres- in the density of adsorbed particle. At low-to-moderate surfac-
sure, oil viscosity, type of the injected gas, miscibility conditions, tant concentrations, foam stability increases about 20% compared
among others. Previous studies were conducted to improve the sta- to the mixtures that have pure hydrophilic particles. The ratio-
bility of displacing front in gas injection processes such as miscible nale for such improved stability is low surfactant concentrations
gas injection, water alternating gas injection and foam flood [4–12]. where bridging flocculation of particles at foam interface produces
Miscible gas injection is designed to mobilize oil as a single phase enlarged and sterically strong interfacial barriers. Furthermore,
flow in porous media and avoid two phase flow system and capil- at moderate surfactant concentrations, surface elasticity increases
lary effects, therefore gas may not breakthrough as a second phase due to the presence of suspended particles in surfactant solution.
[1–3,11–13]. Similarly, in water alternating gas injection, a slug of Horozov suggested the probable mechanisms which foam
injected gas is followed by a slug of water to decrease the likelihood lamella stabilisation may take place. His suggested first mecha-
of early gas breakthrough while decreasing capillary effect through nism is layering of solid particles inside liquid film and categorised
gas phase in porous media. them as a monolayer of bridging particles; a bilayer of close-
While there are many successful projects based on these recov- packed particles and a network of particle aggregates (gel) [32].
ery methods, difficulty in control of processes, cost of high pressure Second, foam stabilising mechanism by particle comes into play
gas injection for miscible gas flood, and oil trapping by water phase if the particles are not completely water-wet. In this case parti-
in water alternating gas process, are challenges in place [11–14]. cles tend to aggregate at foam-liquid interface where they may
Another solution to control gas mobility and increase gas front sta- improve the mechanical stability of lamellae. On the other hand,
bility is the use of surfactant-stabilised foam. This idea was first strongly hydrophobic particles may behave differently, and desta-
introduced by Bond and Holbrook in 1958 [15], and later many bilise foam structure. It was reported that intermediate contact
other investigations have been conducted on characterisation and angles (between about 40◦ and 70◦ ) would be optimum to develop
use of foam in gas injection process [16–22]. a solid-stabilised foam [30,32–34,39,41].
Foam improves the performance of gas flooding processes Analogous bridging mechanisms have been suggested for
through two mechanisms: first, the presence of a foaming agent and antifoaming behaviour of hydrophobic particles or mixtures of par-
aqueous phase creates more favourable mobility ratio of displac- ticles and oil [25]. Hydrophobic particles create a convex shape
ing to displaced fluids, and second, gas diversion from the fractures curvature on the surface of film at gas-liquid interface; thus capil-
and high permeability zones to lower permeability regions can take lary pressure decreases the thickness of liquid film. For hydrophilic
place, where both of these mechanisms increase the stability of dis- particles, liquid film exhibits a concave meniscus at its surface;
placing front and reduce the early breakthrough of gas [17,23–25]. where capillary pressure is exerted in gas phase in opposite direc-
Despite these favourable properties, foam is not thermodynam- tion [45]. Furthermore, it should be noted that based on previous
ically stable and its physical structure can break down easily when investigations, particles with rough edges on their surface, com-
two bubbles approach each other. This collapse in the structure of monly found in commercial antifoams, can cause rapture in liquid
foam happens as liquid film between adjacent bubbles undergoes film at even contact angles less than 90◦ . Consequently, rough
thinning, and as a result liquid film can rupture [25–27]. Various hydrophobic particles are more effective antifoam agents than
methods have been proposed to improve foam stability, such as smooth particles, and therefore rounded solid particles stabilise
increasing surfactant concentration, mixing different types of sur- bulk foam [45].
factants, and addition of co-surfactants and polymers to foaming Alargova demonstrated that rod-shape particles can act as effec-
agents. These solutions create a stable liquid film between bubbles tive foam stabilisers in the presence of sodium dodecyl sulfate
which is called meta-stable super-thin film state, however, they are (SDS) surfactant [46]. They used rod-shape polymer particles with
often expensive and might not be economical for large scale appli- an average length of 23.5 ␮m and diameter less than 1 ␮m, which
cations. Furthermore, these remedies may alter physical properties exhibited a contact angle of ␪ ≈ 80◦ at the air-water surface through
of the reservoir rocks that could result in a poor flow conductivity in the surfactant solution. Their fairly dilute micro-rod suspensions
porous media. Therefore, a thorough analysis of rock-fluids inter- (0.2–2.2 wt%) in pure water, produced foam upon shaking and it
actions is critical for the use of different compositions of foam in showed remarkably a stable structure which last for more than
hydrocarbon reservoirs. three weeks even under drying conditions in an open vessel [46].
Foam stability can also be affected by the presence of dissolved Nowadays, silica and metal nanoparticles are frequently used
species in other phases, such as second liquid phase containing fine as a foam stabiliser agent for enhanced oil recovery processes
solids. These species are naturally in the reservoir that may stabilise [38,39,41,47]. It was found that nanoparticles at concentrations
or destabilise the structure of foam. Foam stability in this condition between 0.05–2 wt% can stabilise foam in the presence of both non-
is a factor of different parameters; firstly whether the solid species ionic and anionic surfactants. These types of nanoparticle foam are
are strongly liquid affinitive and there is a tendency to be accumu- two to eighteen times more stable compared to the same foam
lated at the gas-liquid interface or not, and secondly, what are the without nanoparticles in its structure [34,38,39,41,47].
impacts of accumulated particles on the interfacial properties and Properties and performance of particle-stabilised
lamellae viscosities of gas-liquid interface. foam have been investigated by many researchers
[30–33,36–40,42,43,47–50]. However, the effects of scales and
 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31 21

Fig. 1. Schematic diagram of the apparatus used in foam generation.

precipitates, such as natural particles in porous media, on foam

stability and foam flooding performance have not been investi-
gated. In this study, we explored effects of such naturally occurring
particles on the properties of foam. A series of experiments
were performed to evaluate the effects of solid particles on
foam stability, foam texture and foam apparent viscosity. It can
improve our understanding of foam flooding process, its design
and performance for any specific reservoir. In the other words, the
key findings from this work have potential significance in foam
flooding in reservoirs with inherent large quantities of scale and
precipitates, including offshore foam injection in the presence of
divalent and trivalent cations.

2. Experimental setup and procedure

In this study, three sets of experiments were performed. First set

Fig. 2. Standard foam stability plot [51].
of experiments is related to bulk foam stability where we evaluated
stability of bulk foam in the presence of different solid particles with
different concentrations of surfactant. We measured foam height
and its half life time in these experiments [51,52]. Second set of is fixed with a clamp system in a bath. Bath was used to regulate
experiments deals with foam texture analysis. In these experiments the temperature of the graduated cylinder during each experiment.
we used stereo microscope and image processing tools to identify It provides an isothermal condition with the accuracy of 1 ◦ F at the
the average bubble size in the presence of different solid parti- temperature of 75 ◦ F, and a maximum of 200 ◦ F. A crystalline alu-
cles [53]. And the last set of experiments is designed to find foam mina gas diffuser with diameter of 25.4 mm is located inside the
apparent viscosity in the presence of different particles with the cylinder. The gas diffuser has a maximum pore diameter of 80 ␮m
use of capillary tube [54]. Research strategy and details of each set and was calibrated with the standard of ASTM D892-06. CO2 supply
of experiments are summarized in Table 1. provides gas flow rate of 94 mL per second through gas diffuser and
Sulfotex AOS (Alpha Olefin Sulfonate) was used as a surfac- cumulative volume of CO2 passing through upper exit of cylinder
tant, and was supplied by the Henkel Company with the quality was measured using a volumetric flask. It should be noted that all
of 60% active in the solution, viscosity of 1cp, and pH of 7.5. Alpha experiments were conducted in the absence of oil.
Olefin Sulfonate (AOS) has been widely used in enhanced oil recov- Surfactant solutions with different concentrations were mixed
ery processes as it is effective in attaining low interfacial tension. gently with de-ionized water. Then, surfactant solution was slowly
Furthermore, it is relatively inexpensive and chemically stable poured into the transparent test cylinder. To perform an accu-
surfactant, as it doesn’t adsorb on the surface of the majority of rate bulk foam stability test, surfactant solution should completely
reservoir rocks because of the negative charge on the head group cover porous gas diffusing stone. Flow pressure was set at 3.45 kPa.
of its molecule [3,41]. Solid particles with 99% purity and different Foam was generated with flow of carbon dioxide into the cylinder
range of sizes were used (provided by Sigma Aldrich). List of solid for 25 s, before we start measuring the initial and final heights of
particles and their properties are presented in Table 2. foam. Foam drainage was recorded every 1–3 min following foam
Physical model used in this study, is shown in Fig. 1. It con- generation process. Results are comparable with the presented
sists of a transparent cylinder with the volume of 1000 mL, which trend of bulk stability tests patented by Klaus et al. (Fig. 2) [51].
22 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31

Table 1
Basic property measurements.

Experiment Name Purpose Equipment/Method

Bulk foam stability test Evaluate bulk foam stability with respect to solid particles Foam height measurement/half life
and surfactant concentration
Foam texture analysis Estimate bulk foam average bubble size in the presence of Stereo microscope
solid particles and image processing
Bulk foam apparent viscosity Investigate bulk foam apparent viscosity in the presence of Capillary tube method
investigation solid particles

Table 2
List of reservoir occurring solid particles used in this study.

Name Chemical Formula Density Solubility Average

g/cm3 in 100 mL Water (25 ◦ C) Diameter ␮m

Calcium Carbonate CaCO3 2.71 0.15 g 12.16

Calcium Sulfate CaSO4 2.96 0.21 g 7.61
Barium Sulfate BaSO4 4.50 0.000285 g 1.38
Strontium Sulfate SrSO4 3.96 0.0135 g 64.14
Iron oxide Fe2 O3 5.24 0.0000011 g 131.04

Fig. 2 indicates that foam lifetime might be divided into two Apparent viscosity of bulk foam was determined by capillary
sections, namely “foaming” and “decay” sections, which are shown tube method, using foam with continuous foam quality of 80 ± 5%
with green and orange colour zones, respectively. Foaming sec- with a flow rate of 4 mL per minute at 25 ◦ C. Apparent viscosity of
tion corresponds to foam generation and maximum height which bulk foam was measured using a capillary tube with the length of
is the difference between the top of foam and liquid solution that 25 cm and diameter of 2 mm, where flow rates were between 100
is maintained until the deviation time, tde . Maximum height stays and 500 mL per hour. Then viscosity at different shear rates can be
unchanged until deviation time, tde , at which liquid films inside measured.
foam begin to rupture. A transition time, ttr , corresponds to the Pressure difference across capillary tube with flow of surfactant
half-life of foam with respect to its maximum height. Foam drainage solution was measured every sixty seconds to achieve a stabilised
beyond transition time can also be used to describe foam stability, differential pressure. The flow of initial pre-generated foam was
i.e., ttr < 10 s corresponds to unstable foam, whereas ttr > 10 s corre- directed through the capillary assembly bypass in order to allow the
sponds to meta-stable foam; the longer transition time, the more flow rate and texture of the generated foam to be stabilised. Upon
stable foam system [51]. attaining bubble uniformity, foam was directed through the capil-
To evaluate bulk foam texture (average bubble size), images lary tube assembly and the differential pressure across the tube was
of bulk foam in the presence and absence of solid particles were measured using data-acquisition system. Poiseuille’s equation (Eq.
captured. Fig. 3a shows a 24 bit picture taken from the cross sec- (1)) was used for fluid flow through a horizontal tube with circular
tional area of the cylinder. It was analysed using IMAGEJ digital cross-sectional area, to calculate the apparent viscosity, ␮app ,:
image processing software. Analysis requires conversion of 24-bit
R4 P
 n

image to 8-bit image where an edge detection algorithm can be
app = (1)
applied. Thresholding yields binary images (Fig. 3b), which are then 2QL 3n + 1
calibrated using histogram equalisation to minimise differences
between the image acquisition procedures (Fig. 3c) and the aver- where R (cm) is the radius of capillary tube, P (atm) is pressure
age foam bubble size is extracted. In the next step, similar tests drop across capillary tube, Q (cm3 /s) is the flow rate of foam, L (cm)
were conducted in the presence of different solid particles to iden- is the length of capillary tube and n is the power-law fluid index,
tify their effects on bulk foam stability. Then, to characterise solid which in this study, it was assumed to be 0.7 for foam quality in the
particle size and shape, high resolution SEM images of particle sam- range of 80–90% [54].
ples after drying them for 24 hours in an oven at the temperature of Since it is assumed that foam is a non-Newtonian fluid, viscosity
100 ◦ C, were analysed using an image processing tool, IMAGETOOL was determined with respect to the shear rate through Eq. (2):
[53].
Q
 3n + 1 
˙ w = (2)
r 3 n

Fig. 3. Bubble size determination using IMAGEJ software: (a) 24-bit coloured foam image, (b) 8-bit image and (c) histogram equalisation and average bubble size determination.
 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31 23

Fig. 4. a) bulk foam stability for different concentrations of AOS, b) a sample image of foam stability test in a transparent cylinder (scale size of 5 mm is shown) [1 ppm of
AOS solution = 3.17 × 10−6 mol/L].

Fig. 5. Bulk foam stability in the presence of calcium carbonate solid particles at different concentrations of AOS, (a) 200 ppm (b) 500 ppm, (c) 1000 ppm, (d) 5000 ppm
[1 ppm of AOS solution = 3.17 × 10−6 mol/L].

where ˙ w is the shear rate (1/s). Foam flow through smooth capil- 1
lary tubes at flow rates of 100, 300, 500 and 1000 mL per hour and
foam quality of 80% was conducted. Based on the monitored data,
Apparent Viscosity μ, cp

No Particle
one can develop graph of apparent viscosity versus shear rate. This
test has been conducted for foam flow in the presence of different 1 wt% CaCO3
solid particles. In the following section results of different tests and 1 wt% CaSO4
detailed analyses were presented. 1 wt% BaSO4
1 wt% SrSO4
3. Results and discussion 1 wt% Fe2O3

In the first series of experiments bulk foam was generated with

0.1
Alpha Olefin Sulfonate (AOS) at different concentrations (50, 100, 10.00 100.00 1000.00
200, 500, 1000 and 5000 ppm). Generated foam was used to under- Shear Rate γw, 1/sec
stand the behaviour of bulk foam without the presence of other
phases. Fig. 6. Comparison of bulk foam apparent viscosities versus shear rate in the absence
Fig. 4 shows the effect of surfactant concentration on foam and presence of 1 wt% of: calcium carbonate, calcium sulfate, barium sulfate, stron-
tium sulfate and iron oxide.
height and its stability. It can be seen that higher surfactant con-
24 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31

Fig. 7. Bubble size distribution (a) in the presence of calcium carbonate particles, (b) in pure foam (in the absence of calcium carbonate particles).

Fig. 8. Foam stability in the presence of calcium sulfate at different concentrations of AOS (a) 200 ppm, (b) 500 ppm, (c) 1000 ppm, (d) 5000 ppm [1 ppm of AOS
solution = 3.17 × 10−6 mol/L].

centration enhances bulk foam stability and also the maximum such as capillary, gravity, viscous and elasticity forces. These inter-
foam height. Inset plot of Fig. 4 magnifies first two minutes of actions are dominant in the lamellae and at the plateau borders
foam stability test. It shows that AOS bulk foam with concentrations which are critical for foam stability at lower concentrations. On the
less than 500 ppm exhibit different profiles in the first thirty sec- other hands at higher concentrations of surfactant, foam stability
onds compared to foam with higher concentrations of surfactant is predominantly developed by micelles formation. Due to these
(foam agent). This might be attributed to intermolecular forces; molecular interactions, foam that corresponds to higher concen-
 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31 25

Fig. 9. Bulk foam stability in the presence of barium sulfate at different concentrations of AOS (a) 200 ppm, (b) 500 ppm, (c) 1000 ppm, (d) 5000 ppm [1 ppm of AOS
solution = 3.17 × 10−6 mol/L].

Fig. 10. Foam stability and drainage of a) barium sulfate multilayer particles (particle gel), b) iron oxide and c) strontium sulfate.
26 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31

Fig. 11. Foam stability in the presence of strontium sulfate at different concentrations of AOS (a) 200 ppm, (b) 500 ppm, (c) 1000 ppm, (d) 5000 ppm [1 ppm of AOS
solution = 3.17 × 10−6 mol/L].

Fig. 12. Foam stability in the presence of iron oxide at different concentrations of AOS (a) 200 ppm, (b) 500 ppm, (c) 1000 ppm, (d) 5000 ppm [1 ppm of AOS solu-
tion = 3.17 × 10−6 mol/L].

trations of surfactant has more stable behaviour as shown in Fig. 4, ruptured, which leads to a rapid draining process; (e.g. 50 ppm AOS
where concentrations more than 500 ppm show a plateau trend solution).
for a period of time, before the collapse in foam structure. These In the rest of this study we explored the effect of naturally occur-
results are consistent with the reported behaviour of foam stability ring solid particles on foam generated with different concentrations
by Osei-Bonsu et al. [55]. They showed that foam that is generated of surfactant. In the first series of solid particle tests, we used cal-
using lower concentrations of AOS has a significant tendency to be cium carbonate. The effects of calcium carbonate, 0.05–1 wt%, on
 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31 27

Fig. 13. Average particle size of different solid particles.

bulk foam stability generated from 200, 500, 1000, and 5000 ppm flow for foam, which in turns increases apparent viscosity of foam.
AOS solutions were evaluated. This behaviour has been observed in the experiments where appar-
Fig. 5 shows improved bulk foam stability in the presence of ent viscosity of foam increased by about 0.2 cp in the presence of
calcium carbonate. There is no chemical reaction to be considered, calcium carbonate at different shear rates as shown in Fig. 6.
however, it seems solid-fluids interactions of suspended particles Foam texture is also affected by the same solid-fluids interac-
and foam result in an effect associated with apparent viscosity tions in the presence of such particles. As particles have a tendency
enhancement and average bubble size reduction. to stay on the surface of foam bubbles, and consequently avoid bub-
Suspended particles attract bubbles, and liquid film of bubble ble from merging into adjacent bubbles, the average bubble size
sticks on the surface of particles where the chance of bubble coa- (diameter) reduces from about 6 mm (in the case of pure foam) to
lescence decreases and as a result bubbles stay small and do not 2.75 mm (in the presence of suspended calcium carbonate), there-
merge into each other, therefore foam structure breaks down at fore, majority of bubble sizes were found to be in the range 1–4 mm
a longer time period. Also these interactions as a balance between (Fig. 7). It is shown that bubble size distribution changes from right
capillary, gravity, viscous and elasticity forces, create a resistance to skewed shape (b) to left skewed shape (a), due to addition of solid
28 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31

Fig. 14. Effect of particle shape on foam stability.

calcium carbonate particles. These particles avoid the enlargement interfacial tension in foam lamellas increases as the surfactant solu-
of bubbles and their film rupture. On the other side, bubbles in tion gets adsorbed on the surface of the calcium sulfate.
pure foam can easily merge into each other and create larger bub- Another type of solid particles that naturally exist in the reser-
bles which are thermodynamically unstable and film rupture would voir is Barium Sulfate. We examined their effects on foam and
happen fast. results are presented in Fig. 9. It indicates the addition of barium
And as a result, decrease in the average bubble size diame- sulfate (0.05–1 wt%) to surfactant solution of AOS with concentra-
ter translates into a more stable bubble structure, which can be tions between 200 and 5000 ppm, increases the stability of bulk
achieved through a thicker lamellae and plateau borders. foam compared to foam in the absence of solid particles. It can be
Similar trend was observed at higher surfactant concentrations, seen from Fig. 9 that foam stability in the presence of barium sulfate
as it is shown in Fig. 5(d), prominent enhanced foam stability was particles was slightly improved for all solid concentrations.
developed. These results show that surfactant solution of 5000 ppm The reason for foam stability enhancement is due to the physical
AOS in the presence of 1 wt% calcium carbonate is able to maintain properties of barium sulfate particles. These particles are very small
foam structure for approximately 300 min; more than twice the life (average diameter of 1 ␮m) and exhibit an intermediate degree of
span of foam in the absence of calcium carbonate particles. hydrophilicity, which results in a smaller and more homogeneous
Next series of experiments were conducted for calcium sulfate bubble size distribution. These small solid particles form multi-
particles (0.05–1 wt%). Unlike calcium carbonate, calcium sulfate layered connected chains (particle gel) within foam structure.
appears to destabilise foam generated by surfactant solution of AOS, Developed chains increase the thickness of lamellae and plateau
with concentrations between 200 and 5000 ppm as shown in Fig. 8 . borders which result in a more viscous bulk foam as it was observed
This might be due to high tendency of sulfate particles to adsorb during apparent viscosity measurements (Fig. 6). However, bar-
water which makes the lamellae and plateau borders thinner and ium sulfate particles have relatively high density (4.4 g/mL), which
eventually leads to bubble rupture. This destabilising effect is sup- means there is a larger gravity force, therefore, this decreases the
ported by the results observed in apparent viscosity tests (Fig. 6). overall stability of foam compared to lighter solid particles. As a
Apparent viscosity was decreased in the presence of calcium sul- result barium sulfate multilayer slugs were separated from foam
fate; by about 0.1 cp. Fig. 8 shows the degree of foam destabilisation lamellae and plateau borders after some time, and they sink down
for various AOS solutions at different particle concentrations. For into the surfactant solution, as shown in Fig. 10.
example for the solution of 1000 ppm of AOS, the duration of bulk Forth type of solid particles used in this study was strontium
foam collapse is approximately 51 min in the presence of 1 wt% sulfate particles. The results of the addition of strontium sulfate
calcium sulfate, which is less than half of the period that observed (0.05–1 wt%) to the surfactant solution of AOS with concentrations
for foam in the absence of calcium sulfate (120 min). Based on the between 200 and 5000 ppm are presented in Fig. 11. These results
results shown in Fig. 8, it should be noted that destabilisation effects indicate that the presence of strontium sulfate increases bulk foam
can be seen for all solutions, however it is more dominant at lower stability. Strontium sulfate particles with the density of 3.69 g/mL
surfactant concentrations. Therefore, foam generated by lower sur- give this enhanced stability through increased viscosity in a similar
factant concertation is more prone to instability source of calcium manner to barium sulfate particles; however the size and shape of
sulfate particles. Foam destabilisation occurs when calcium sulfate the larger strontium particles impinges on the degree of enhance-
particles adsorb surfactant solution in foam lamella and plateau ment and can lead to drainage. Fig. 11 shows different surfactant
border which rapidly changes the aqueous foam from wet to dry. solutions of AOS have more stability in foam structure in the pres-
Dry foam can break easily as the lamellas become very thin, and ence of various strontium sulfate concentrations. As it can be seen,
 R. Rafati et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 509 (2016) 19–31 29

Fig. 15. Surface tension of AOS solution in the absence and presence of solid particles (a) no solid particle, (b) calcium carbonate, (c) calcium sulfate, (d) barium sulfate, (e)
strontium sulfate, (f) iron oxide (1 ppm of AOS solution = 3.17 × 10−6 mol/L).

increased foam stability, manifested at higher surfactant concen- edges can easily break the lamellas by film bridging and dewet-
trations. ting mechanisms. Fig. 14 presents the schematic effect of particle
Last type of solids used in this study is iron oxide particles. Iron shape on bulk foam stability. As it is shown in this figure, foam
oxide particles are magnetic particles which have good capacity of breakage with round shaped particles occurs in four steps with dif-
heat transfer through foam structure. The results of foam stability ferent mechanisms. Initially, particles move into thick liquid film
test show that the addition of iron oxide (0.05–1 wt%) to surfactant between gas bubbles and push the surfactant solution out of liq-
solution of AOS with concentrations between 200 and 5000 ppm, uid film. This phenomenon increases the interfacial tension in the
significantly destabilises foam (Fig. 12). Iron oxide is denser than area of liquid film as a result of decrease in surfactant concentration
other particles, and significantly larger in size with hydrophilic and liquid film thickness, which increases the disjoining pressure
properties which fall down through lamellas and lead to an increase in foam lamella. In the next step rounded shape particle bridges
of disjoining pressure and interfacial tension in the thin liquid films foam lamella with a contact angle of more than 90◦ because of their
between gas bubbles. These characteristics of iron oxide cause rapid geometry. The foam breakage usually happen faster and with par-
foam degradation even at high surfactant (AOS) concentrations. ticles with sharp edges solid particles as they skip lamella thinning
Fig. 10b shows that larger black spots were deposited in surfactant (deweting) step and bridge the thick lamella foams directly.
solution which left foam structure due to gravity force and bubbles Furthermore, in order to investigate the effect of solid parti-
can merge into each other fast. Exhibited instability was confirmed cles on surface tension of AOS solution, a series of complementary
with apparent viscosity measurements which indicated that iron experiments on surface tension were carried out using Du Noüy
oxide particles decrease bulk foam apparent viscosity (Fig. 6). ring method. In these tests, surfactant concentration showed the
Fig. 13 shows SEM images of different particles used in this dominant effect on surface tension reductions, and different solid
study. As can be seen in Fig. 13a and b, the average particle size for particles used in this study, regardless of their concentration
strontium sulfate is 50 times larger than barium sulfate which can (0.05–0.5 wt%), have very negligible effect on surface tension of
probably make only monolayer particle stabilised foam lamellas. AOS solution. However, as calcium sulfate has higher adsorption
It is also found that rounded solid particles stabilise bulk foam rate of aqueous solution than the other solid particles discussed in
more than particles with sharp edges, since particles with sharp this study, it contributes to a larger number of sulfate ions in bulk
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