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Particle-stabilized emulsions: Effect of heavy crude oil components pre-adsorbed onto stabilizing solids
Andreas Hannisdal , Marit-Helen Ese, P l V. Hemmingsen, Johan Sj blom a o
Ugelstad Laboratory, Department of Chemical Engineering, Norwegian University of Science and Technology (NTNU), N-7491 Trondheim, Norway Received 5 February 2005; received in revised form 5 October 2005; accepted 8 October 2005 Available online 21 November 2005
Abstract Model emulsions stabilized by means of silica nanoparticles have been investigated. The effect of the modication of the particle surface has been monitored using infrared (IR) spectroscopy, contact angle measurements and zeta potential measurements. It is shown how coating of the nanoparticles with asphaltenes and resins will modify the stabilization prole compared to that obtained with no coating. The stabilization efciency was greatly enhanced by adsorption of crude oil components onto very hydrophilic or very hydrophobic silica. Possible stabilization mechanisms have been discussed. We have demonstrated catastrophic phase inversion of emulsions stabilized by particles with intermediate wetting properties, induced by simply increasing the volume of the disperse phase. In all cases, the stability to gravitational induced separation (coalescence) passes through a minimum approaching inversion in line with a maximum in drop size of the disperse phase. Transitional phase inversion from o/w to w/o emulsion type can be achieved by modifying of the hydrophilicity of the particles, either by silylation or by a controlled coating with heavy components from crude oil. The relevance of this study for real petroleum systems is discussed. 2005 Elsevier B.V. All rights reserved.
Keywords: Adsorption; QCM-D; Asphaltenes; Resins; Silica particles; Wettability; Emulsion stability; Inversion
1. Introduction Every day the complex petroleum industry faces the challenge of resolving emulsions. The process of recovering crude oil from reservoirs to production facilities requires techniques that can introduce pressure drops and large shear energies, resulting in increased interfacial area between the oil and water phases. At these interfaces, inorganic colloids will accompany organic particles and interfacially active molecules from the crude and build up mechanically strong, viscoelastic lms. The build up of such a protective layer will restrain the process of droplet coalescence, and reduce the rate of emulsion destabilization. While previous studies have focused mainly on the stabilizing effect of asphaltenes and asphaltene complexes, it has been shown that emulsions containing inorganic particles can be even more stable than those stabilized by asphaltenes only [14]. With the acknowledgement of the important role of solid particles in stabilizing petroleum emulsions, it has been done a systematic
Corresponding author. Fax: +47 73 59 40 80. E-mail address: Andreas.Hannisdal@chemeng.ntnu.no (A. Hannisdal).
approach in mapping the important parameters for good stabilization efciency in well-dened particle-stabilized systems. In particular, silica particles have been studied extensively because their properties resemble those of natural inorganic colloids like clays. Aveyard et al. [5] have reviewed the studies, which have contributed to the understanding of solid-stabilized emulsions. These studies have allowed for some general conclusions to be drawn on the important parameters for the effectiveness of particles in stabilizing emulsions. Factors that have to be considered are particle-size and shape [6], concentration [712], wettability of the particles, pH and electrolyte concentration in the aqueous phase, and other inter-particle interactions. We will address some of these parameters with results from literature and leave other parameters with only a reference. As concluded by Aveyard et al. [5] and Binks [13], many of the properties of solids in stabilizing emulsion interfaces can be attributed to the very large free energy of adsorption for particles of intermediate wettability (partially wetted by both oil and water phases). This effectively irreversible adsorption leads to extreme stability for certain emulsions and is in contrast to the behavior of surfactant molecules which are usually in rapid dynamic equilibrium between the oil/water interface
0927-7757/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2005.10.011
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and the bulk phases. Since Finkle et al. [14] in 1923 discovered the correlation between the wettability of particles and their ability to stabilize emulsions there has been a large number of studies dealing with wettability alteration and the effect on emulsion stability [7,11,12,1523]. Binks and Lumsdon [20] did an investigation into the inuence of the wettability of spherical, nanometer-sized silica particles on the type and stability of water-toluene emulsions. The silica surface was silylated to various extents by reaction with dimethyldichlorosilane, thus reducing the number of silanol (SiOH) groups at the particle surface end making the hydrophilic silica more hydrophobic. As expected, emulsions stabilized by either very hydrophilic or very hydrophobic particles were unstable to coalescence whereas particles with intermediate hydrophobicity, in which particles were held strongly at interfaces, were stable to coalescence indenitely. In addition, this study demonstrated a type of inversion of emulsions, known as transitional phase inversion, brought about by changing the silanol content of the particles. Just as the water or oil-liking tendency of a surfactant is quantied in terms of the HLB number, so can that of spherical particles be described in terms of its wettability via contact angle measurements [13]. By increasing the hydrophobicity of the particles at xed volume fraction of oil and water, it was possible to invert emulsions from o/w to w/o type. Binks and Lumsdon have also showed that transitional phase inversion is possible in emulsion systems of two types of silica particles, one hydrophilic and one hydrophobic [22]. Tambe and Sharma [12] have demonstrated transitional phase inversion in systems of calcium carbonate, barium sulfate, bentonite and silica modied to different extent by addition of stearic acid. Another unique feature of particle-stabilized emulsions is the possibility of inverting a system stabilized by only one type of particles simply by changing the oil to water ratio [5]. Binks et al. have reported this type of inversion, known as catastrophic phase inversion, for silica systems [7,9,20,24]. Catastrophic phase inversion took place at a particular volume fraction of the dispersed phase depending on the hydrophobicity of the particles and in which phase the particles were initially dispersed [20,24]. Kralchevsky et al. [23] have recently done a theoretical study on the thermodynamics of particle-stabilized emulsions. They have predicted the existence of catastrophic phase inversion in particle-stabilized emulsions from the work of formation (w()) of the normal and reverse emulsion type. These results will be discussed later in comparison to results from this study. Early work led to the formulation of a basic stabilization mechanism, involving steric hindrance to dropletdroplet coalescence provided by interfacially adsorbed colloids (closely packed) extending into the continuous phase of the emulsion. The importance of particles to change the rheology of the interface was also recognized. More recent studies have conrmed the signicance of steric effects and inter-particle interactions and also proven the mechanism of particle stabilization to be very sophisticated. Kralchevsky et al. [23] have explained the stability of particle-stabilized emulsions from the interfacial bending energy ( Wb ()) and dilatation energy ( Wdil ) for both non-closely packed and closely packed particle monolayers. In the case of non-closely packed particle monolayer, the
bending energy leads to an effective attraction between two colliding emulsion drops, which are, however, unable to occulate because of the predominant repulsive effect of the interfacial dilatation. For closely packed particles and < 90 (measured into the continuous phase), both Wb and Wdil are positive and will lead to repulsion between two colliding drops, thus stabilizing the emulsion. In contrast, for > 90 , energy considerations predicted the appearance of spontaneous occulation. The so-called particle bridging effect were discussed. In the contact region between two emulsion drops, it may happen that one particle is adsorbed simultaneously at the two lm interfaces. Depending of the wetting characteristic of the particles the phenomena can lead to stable occulates or coalescence. Bridging of uid interfaces by particles has been observed directly by Vignati et al. [25] and by Stancik et al. [26,27]. In agreement with free energy considerations, bridged particles were able to generate signicant adhesion between the two uid interfaces, which should result in additional emulsion stability in real systems. Friberg [28] has calculated the stabilizing properties of bi-layers of particles. Whereas earlier studies claimed that the formation of a close-packed arrangement of silica particles at the interface was necessary in order to obtain stable emulsions, Midmore [29] showed that very stable emulsions could be formed with only 29% coverage of the interface with silica spheres. Later, Vignati et al. [25] studied oil-in-water emulsions stabilized by monodisperse, silica colloids with a uorescent core. With this clever approach they could keep track of the location of the colloids. Interestingly, they were able to make stable emulsions even with very low droplet surface coverage (5%). No straightforward relation was found between the degree of droplet surface coverage and macroscopic emulsion stability. Vignati et al. also discussed the role of surface dynamics on the stabilization of poorly covered droplets as they observed diffusion constants of the particles at the oil/water interface, comparable to that in the bulk. Tarimala et al. [30] have also observed surprisingly fast Brownian motion of solid particles at the two-dimensional oil/water interface. According to the steric stabilization mechanism, coalescence requires the solid particles to be removed from the dropdrop contact region. Free energy considerations suggest that lateral displacement of the particles is most likely, since forcing droplets into either phases from the interface require extreme energies [12,31,32]. Tambe and Sharma [33,34] early showed how particles could modify the rheological properties of the interfacial region. At sufcient high surface coverage, colloidladen interfaces exhibited viscoelastic properties. They stated that the viscoelastic interface affected emulsion stability both by retarding the rate of lm drainage between coalescing emulsion droplets and by increasing the energy required to displace particles from the contact region between droplets. Recently, these interfacial dynamic features have been observed directly when two colloidladen interfaces are brought into contact with each other under a microscope. Beautiful pictures representing lm drainage, the Marangoni effect, trapped particles and particle morphology have been published [26,27,30,35]. If charged, particles can also impart a degree of electrostatic repulsion, which may affect the approach of particle-laden uid
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interfaces and the occulation-tendency of particles both in the bulk and at the interface [6,12]. The charge on the particles and their extent of occulation can be modied by pH control and addition of electrolytes to the aqueous phase of the emulsion [6,8,10,11,19,31,36]. If silica particles assemble to form a network extending through the coherent phase, bulk viscosity will increase and add stability to the emulsion as the rate of occulation and lm thinning is reduced [7,3739]. At different stages prior to, and during crude oil production, the inorganic material from reservoirs will be exposed to asphaltenes and resins. These components may adsorb onto initially hydrophilic surfaces, primary through their polar functional groups, and inuence the wettability and charge of the particles and their afnity for the oil/water interface [4042]. Yan and Masliyah have studied the partitioning of clay particles with different wettability at the oil/water interface [18,43]. They found a minimum in emulsion droplet size for asphaltene-treated particles with intermediate wettability, indicating that these particles were the most effective stabilizers for the oil-in-water emulsions. It was also demonstrated how the emulsions could be destabilized by the addition of fresh oil [44] or by adjusting the pH of the aqueous phase [19]. Sullivan and Kilpatrick [1] studied the effect of size, concentration, and type of inorganic solid particles on crude oil emulsion stability. They showed that hydrophilic particles, protected from asphaltene adsorption by a preadsorbed water lm, inverted crude oil emulsions from w/o to o/w whereas the same particles added stability to w/o emulsions when dried and added to the asphaltene containing oil phase. Similarly, Gu et al. [11] tuned emulsion type and stability of a toluene-diluted bitumen/water system by adding hydrophilic clay to the water phase (variable pH). Adsorption of asphaltenes and resins onto mineral surfaces has been studied extensively [4554]. In general, Langmuir type adsorption isotherms are reported for asphaltene adsorption from toluene solution at low bulk concentrations with multiple steps or other deviations from the simple model at higher concentrations. This has been explained by surface phase reorientation, multilayer formation or aggregation. Acevedo et al. [45,47,48] have reported formation of asphaltene multi-layers or aggregates at silica surfaces from concentrated asphaltene/toluene solutions. The tendency towards multilayer formation of asphaltenes has been related to the history of deposition problems in their original oils. It has also been shown that desorption of asphaltenes from a silica surface at atmospheric condition is slow enough to be neglected [45]. Whereas the typical adsorption studies in literature are done in combination with spectroscopic techniques, Ekholm et al. [55] used the dissipative quartz crystal microbalance technique (QCM-D) to study adsorption of asphaltenes and resins onto hydrophilic gold surfaces. They found that asphaltenes form a rigid layer on the surface at moderate concentrations. The adsorption at increased concentrations was more extensive than that observed for non-associating polymers, indicating aggregate adsorption. Resins were found to form a compact monolayer when adsorbed from a heptane solution. However, the amount of resins adsorbed was signicantly reduced with increasing toluene content of the solvent. Desorption studies showed that resins did not desorb the already adsorbed
asphaltenes, neither did they adsorb onto the asphaltene-covered surface. In this work, we have studied stabilizing properties of four different types of commercially available silica nanoparticles. Two of these products are hydrophobic; one is extremely hydrophilic, and one is expected to be wet to an intermediate extent by both oil and water. These dry particles have been modied with asphaltenes and resins and the effect on emulsion stability, type and droplet size of the emulsion has been investigated. We will relate the performance of these particles in model systems to their surface properties as monitored by vibrational spectroscopy, contact angle measurements and electrophoretic mobility. To address some important questions related to the adsorption of asphaltenes and resins onto silica, we have performed a preliminary adsorption study using the QCM-D technique with a silica surface. This study is aimed at developing a better understanding of how indigenous inorganic particles interact with heavy crude oil compounds to form stable emulsions. 2. Experimental 2.1. Extraction of asphaltenes and resins from crude oil Asphaltenes were precipitated from a Brazilian heavy crude oil (1213 American Petroleum Institute gravity) in a 1:40 excess of n-hexane and ltrated two times through a 0.45 m Millipore lter. Asphaltenes were washed carefully with nhexane to remove any resins from the asphaltene precipitate. The crude oil has been analyzed with respect to SARA components, density, viscosity, acidity and water content. Table 1 lists characteristics of the crude oil. Details about the SARA fractionation are reported elsewhere [56]. In short, asphaltenes were precipitated in n-hexane (1:40) and the remaining maltenes were separated using amino- and silica chromatography in a fully automated HPLC method with a sample capacity corresponding to 0.6 g of heavy crude oil. The SARA weight fractions were determined gravimetrically after solvent removal and analyzed with IR spectroscopy. In order to extract resins, maltenes from 250 ml oil were shaken with 2.5 kg of silica (4063 m, MERCK) for 2 days on a shaker (IKA HS 501) until the solvent was colorless, indicating that resins and aromatics had adsorbed
Table 1 Characterization of Brazilian crude oil Parameter SARA fractionation Saturates (wt.%) Aromatics (wt.%) Resins (wt.%) Asphaltenes (wt.%) Emulsied watera (wt.%) Density (20 C)b Viscosity (40 C) Acidity (TAN)
a b
26.2 41.5 21.9 10.2 0.1 1213 API 0.98 g/cm3 2497 cP 3.73 mg KOH/mg
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Fig. 1. Fingerprint region of IR. The solid line shows the vibrational features of the extracted resins while the broken line represents the resins from the semipreparative HPLC fractionation.
onto silica. The silica slurry was transferred to a glass column (8 cm diameter) and allowed to settle. Toluene was used as mobile phase to elute aromatics. We collected samples from the chromatographic process and analyzed for aromaticity with UV and for typical vibrational features from resins with IR spectroscopy. Once the aromatics were removed, resins were eluted with a more polar solvent (40:30:30 acetone:toluene:methylene dichloride) as proposed by Spiecker and co-workers [57]. The resin-solvent mixture was ltrated through a 0.45 m Millipore lter to remove any silica nes and rotary evaporated until dry. Resins were diluted in toluene, transferred to a non-transparent ask and dried at 60 C under nitrogen until completely dry. A total of 50 g of resins were extracted from the crude oil. IR spectroscopy was performed in order to compare the extracted resins with the resins from the automated semi-preparative method. Spectra are shown in Fig. 1. 2.2. Coating of silica particles Aerosil particles from Degussa are fumed silica, a synthetic amorphous silicon dioxide manufactured by continuous ame hydrolysis of silicon tetrachloride. Siloxane and silanol groups can be found on the surface of unmodied Aerosil particles, where silanol groups account for the hydrophilic behavior. Reactions of the silanol groups with various organosilanes and siloxanes can chemically modify the surface of the partiTable 2 Chemistry and specication of silica particles Product id Aerosil Aerosil Aerosil Aerosil
a
cles. We used four different products in this study: Aerosil 200, Aerosil 7200, Aerosil 202 and Aerosil 972. Aerosil 200 is an unmodied silica while Aerosil 7200 is a structure modied (3-methacryl-oxypropyl-trimethoxysilane) product based on Aerosil 200. The hydrophobic silica products, Aerosil 202 and Aerosil 972 are fumed silica after-treated with polydimethylsiloxane and dimethyldichlorosilane, respectively. Table 2 summarizes the properties of the four silica products. Note that the fumed silica products do not appear as individual particles in aqueous solution, but occulate to aggregates or agglomerates, which can be several hundred nanometers in size. This common feature of fumed silica is due to siloxane (Si O Si) linkages between primary particles. The difference between fused silica (Aerosil) and silica produced by alkaline hydrolysis of sodium silicate solutions via nucleation and growth is discussed by Binks and Lumsdon [8]. Particles were coated with extracted resin- and asphaltene-fractions from toluene in 24 h batch adsorption experiments. The particles were coated using 1 wt.% asphaltene, 1 wt.% resin and 0.5 wt.% asphaltene + 0.5 wt.% resin mixtures. The mixtures were sonicated for 10 min before particles were added (25 g particles/L). Coated particles were centrifuged and washed thoroughly with toluene to remove any asphaltenes or resins not adsorbed onto the particles. 2.3. Wetting characteristics of nescontact angle measurement When working with particle-stabilized emulsions it is of great importance to be able to estimate the three phase contact angle () the particles makes with the interface as this property determine both the type of emulsion formed, and the degree of steric stabilization of two approaching interfaces. However, for sub-micron sized particles indirect methods have to be used for determining the partitioning of the solids at the oil/water interface. Some of these techniques are reviewed by Binks [13]. We have measured the three phase contact angle of both pure and coated solids with the compressed disk method. We report contact angles, measured into the water phase, of disks in air and immersed in oil. Pictures were taken continuously with a CAM 200 Optical Contact Angle Meter from KSV Instruments (Helsinki, Finland) to record contact angles before any penetration of water into the pellet had started. This is especially important when analyzing hydrophilic surfaces in air. The reported contact angle is the mean value of left and right contact angles with replicates included. We also performed some qualitative powder immersion experiments [20], where the particles
Specic surface area (BET) (m2 /g) 200 25 150 25 100 20 110 20
Volume of product is measured after a standard vibration condition is applied (ISO 787/11).
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were placed on a water/air interface. We then carefully replaced the air phase with oil and monitored the partitioning of the particles (visually, brown particles) after 24 h. Some particles had entered the water phase, some were adsorbed at the interface whereas some could easily be suspended in the oil phase with gentle stirring in the oil phase. The concentration of particles in each phase was not quantied. 2.4. FT-IR spectroscopy of coated particles Infrared (IR) spectra of the pure and coated silica products were recorded in the range between 600 and 4000 cm1 with a Tensor 27 FT-IR spectrometer (Bruker Optics) equipped with a MKII Golden Gate diamond ATR unit (Specac) in single reection conguration. The instrument is tted with a Michelson interferometer and a N2 -cooled MCT detector (Mercury Cadmium Telluride). To improve the signal-to-noise ratio 32 scans were recorded at a resolution of 1 cm1 and averaged. All the spectra were normalized with respect to the absorption band at 10501080 cm1 , assigned to Si O Si bonds, which form the basic network in the silica products [58]. The spectra are dominated by these and will only show weak evidence of crude oil components at the silica surface. We have used the spectral range between 2800 and 3000 cm1 with characteristic absorption bands from C H stretching in methyl and methylene groups (2962 cm1 vas CH3 , 2872 cm1 vs CH3 , 2924 cm1 vas CH2 , 2853 cm1 vs CH2 ) [59] as a measure of hydrocarbons at the silica surface. 2.5. Electrophoretic measurements Zeta potentials () of the solid nes were determined as a function of pH on a Malvern 3000HS Zetasizer connected to a titrator (Malvern Instruments, UK). Particles were suspended in aqueous NaCl (102 M) solution and sonicated for 15 min. Large particle aggregates were allowed to settle and removed prior to the measurement. NaOH (0.5 M) and HCl (0.5 M) solutions were used to adjust pH. The electrophoretic mobility was measured for each pH level in the range from 2 to 10 by laser Doppler velocimetry and the zeta potentials were determined by the Smoluchowski approximation [60]. The zeta potential reported at each pH level is the average value of three measurements. Attempts to measure the electrophoretic mobility of oil-wet particles were not done as a high degree of occulation was expected. 2.6. Adsorption study-quartz crystal microbalance A QCM device consists of a thin quartz disc sandwiched between a pair of electrodes. Due to the piezoelectric properties of quartz, it is possible to excite the crystal to oscillation by applying an AC voltage across its electrodes. The resonant frequency (f) of the crystal depends on the total oscillating mass, including solvent coupled to the oscillation. When a lm is attached to the sensor crystal the frequency decreases. Provided that the lm is thin and rigid, the decrease in frequency is proportional to the mass of the lm and the QCM operates as a
very sensitive balance. The mass ( m) of the adhering layer is calculated using the Sauerbrey relation [55]. m= C f n (2)
where C is 17.7 ng Hz1 cm2 for a 5 MHz quartz crystal and n = 1, 3, 5, 7 is the overtone number. In many situations the adsorbed lm is not rigid and the Sauerbrey relation becomes invalid. A lm that is soft (viscoelastic) will not fully couple to the oscillation of the crystal and the crystals oscillation will be dampened. The dissipation (D) of the crystals oscillation is a measure of the lms viscoelasticity. Dissipation is dened as: D= Elost 2Estored (3)
where Elost is the energy lost (dissipated) during one oscillation cycle and Estored is the total energy stored in the oscillator. The dissipation of the crystal is measured by suddenly disconnecting the oscillator and recording the response of a freely oscillating crystal that has been vibrating at its resonance frequency. By simultaneously measuring the frequency of oscillation and the energy dissipation at several overtone frequencies, we can evaluate the adsorbed amount, adsorption kinetics and rigidity of the adsorbed lm. The dissipative quartz crystal microbalance device from Q-Sense (Gothenburg, Sweden) has been used to study the adsorption behavior of asphaltenes and resins from toluene solutions. We have used a sensor crystal with a silica surface. The instrument has been described in detail by Rodahl et al. [61]. The third, fth and seventh overtones of the fundamental resonance frequency were used to study the adsorption processes. Crystals were treated with a Piranha solution (H2 SO4 :H2 O2 , 3:1), washed in milli-Q water and dried with N2 prior to the measurement. The silica surface was exposed to asphaltene and resin solutions (identical to those used to coat silica particles), followed by several rinses with toluene. 2.7. Emulsion stability measurements and drop size determination Measurements were done on model systems of water (milliQ, 3.5 wt.% NaCl) and oil (heptane:toluene, 70:30 v/v) always adding to a total volume of 12 ml. If not otherwise specied water and oil will refer to these solutions. To disperse possible aggregates, particles were sonicated for 5 min in either water or oil. The other phase was added to the system and dispersed with an Ultra Turrax (IKA, T18 with 10 mm head) rst at 18,000 rpm for 1 min, then at 22,000 rpm for 2 min. The samples were immediately transferred to graded centrifuge tubes. The emulsion stabilities are reported as the amount of dispersed phase resolved after centrifugation at 3000 rpm (1580 g) for up to 30 min. We explored the effect of: (1) Changing the initial location of the particles (dispersed in oil or water) (2) Varying the ratio of the two phases (2080 vol.% oil) (3) The amount of particles added to the system (0.0010.01 g particles/ml oil and water, later referred to as 0.11.0%
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(w/v). Notice that the amount of particles in the system is held constant when changing the oil to water ratio.) The stabilizing efciency of both pure and coated particles was investigated. We identied the type of emulsion formed (water or oil continuous) with a test similar to that explained schematically by Ese and Kilpatrick [62] where a drop of the emulsion was added to oil and water. Water continuous emulsions were easily dispersed in water (as small oil droplets) but remained as a big emulsion drop (o/w/o) when added to oil. The opposite was observed for oil continuous emulsions. For stable emulsion systems, the Sauter mean diameter, d32 , is reported to quantify the average size of dispersed droplets. A sample of the emulsion phase from a freshly prepared system was carefully diluted in its continuous phase at a ratio of 1/40. A Nikon Eclipse ME 600 digital video microscope (DVM) was used to acquire 50 pictures of the droplets in the continuous phase and the images were processed with Image Pro Plus 5.0 to give d32 and the volume distribution of drops. 3. Results and discussion 3.1. Adsorption study In order to address a few important issues related to the adsorption process and the state of adsorbed asphaltenes and resins, we performed a preliminary study using the QCM-D technique. The silica crystal was calibrated with toluene, and exposed to asphaltene and/or resin solutions identical to those used to coat silica particles. Fig. 2 shows the adsorption from toluene-solutions with asphaltenes and resins. The shift in resonance frequency (f) along the left axis is a measure of the adsorbed mass, including bound solvent. The dissipation factor (D) along the right axis shows how fast the energy from the vibrating crystal is dissipated to the surrounding liquid. The higher order overtones (n = 3, 5, 7) are more sensitive to the region close to the surface than the fundamental frequency (n = 1) [63]. Fig. 2a shows an immediate drop in the resonance frequency and an increase in dissipation when the crystal is exposed to the asphaltene solution at 10 min. This behavior suggests a very rapid adsorption of asphaltenes onto the silica surface. The asphaltene solution was exchanged with an identical solution at 15 min without any signicant response in frequency or dissipation, indicating more or less saturation of the silica surface. When rinsed with toluene at 20 min, the resonance frequency increased and the dissipation factor decreased, suggesting that weakly bound asphaltenes desorbed, and were washed off during rinsing. However, a considerable amount of asphaltenes was retained at the surface. By using the Sauerbrey relation with the frequency change of the third overtone after the nal rinse with toluene (30 Hz), we obtain an adsorbed mass of 5.6 0.4 mg/m2 (three replicates). The fth and seventh overtone shear waves are not as sensitive to the outer part of the adsorbed layer and shows, as expected, slightly smaller frequency shifts. The dissipation shifts in Fig. 2a are rather small, taking into account the signicant amount of
Fig. 2. QCM-D measurement of the adsorption behavior of toluene solutions with (a) 1.0 wt.% asphaltenes and (b) 1.0 wt.% resins, onto a silica surface. The solution is introduced at 10 and 15 min followed by rinsing with toluene at 20 and 25 min. The change in frequency (f) and dissipation (D) is monitored for the 3rd, 5th and 7th overtone of the fundamental resonance frequency of the crystal.
irreversible adsorbed asphaltenes. We can see how the three normalized frequency overtones follow each other when the adsorbed layer is rinsed with toluene (time >20 min). A dissipation shift in the third overtone of only 1.5 106 at 30 min conrms that the remaining asphaltene lm is rigid. Similar experiment with a toluene solution of asphaltenes and resins (0.5 wt.% asphaltenes + 0.5 wt.% resins) showed that the frequency and dissipation responses were in the same ranges as those observed for asphaltenes in Fig. 2a. The irreversibly adsorbed mass (6.4 0.5 mg/m2 , 3 replicates) is rigidly attached to the silica surface. As discussed by Ekholm et al. [55], this is considerably more than expected for non-associating polymers (13 mg/m2 ), which may indicate multilayer or aggregate formation at the surface. Acevedo et al. [64] have reported aggregation of asphaltenes in toluene solution at concentrations above 50 mg/L and indications of multilayer formation in even more dilute solutions [45]. Whereas asphaltene and asphaltene + resin systems show more or less the same adsorption behavior as the pure asphaltenes, the resin system stands out as completely different. First of all, the shift in resonance frequency of the crystal,
A. Hannisdal et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 276 (2006) 4558 Table 3 Prescence of hydrocarbons at the silica particles Aerosil 200 7200 972 202 Pure 0.000 0.009 0.003 0.003 R 0.079 0.033 0.044 0.007 A 0.122 0.104 0.057 0.036 R+A 0.125 0.101 0.010 0.028
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when being exposed to resins, is dramatically smaller than when asphaltenes contribute to the adsorption. Moreover, the amount of resins left on the silica surface after rinsing is very small. Earlier studies have shown smaller adsorption rate constants for resins compared to those for asphaltenes [65]. Ekholm et al. [55] concluded with insignicant resin adsorption onto a hydrophilic gold surface from toluene. The results shown in Fig. 2b can conrm a low degree of resin adsorption at the timescale of the experiment. It would be too ambitious to draw conclusions about the lm properties of the adsorbed layer given the weak responses in Fig. 2b. However, it should be emphasized that small amounts of resins adsorbed onto silica surfaces may still have great inuence on the partitioning of solids at oil/water interfaces, and can make a difference in the stabilization of such particle-stabilized emulsions. 3.2. Characterization of particles We have characterized the pure and coated silica particles to be used for emulsion stability with infrared spectroscopy and contact angle measurements. Visual inspection of the resin-coated silica particles clearly showed that the initially hydrophilic silica (Aerosil 200 and 7200) adsorbed considerably more resins than the hydrophobic silica (Aerosil 972 and 202). The resin-coated 200 product seemed to have adsorbed most resins based on its dark brown color. All particles that had been exposed to asphaltene/toluene solutions for 24 h were dark. By analyzing the toluene solutions for remaining asphaltenes with near-infrared (NIR) spectroscopy, we could conclude that the initially hydrophilic particles had adsorbed considerably more asphaltenes than the hydrophobic particles. These ndings were conrmed with IR spectroscopy of the coated solids as summarized in Table 3. The asymmetric stretching vibration from methylene groups at 2924 cm1 was used as a marker for the presence of hydrocarbons at the silica surface. Fig. 3 shows an example of the vibrational features of the unmodied and coated 200 products. It is seen from Table 3 that the initially hydrophilic silicates (200 and 7200) adsorb signicantly more asphaltenes than the hydrophobic silica particles. The hydrophobic silica products, 972 and 202, are surface-modied with dimethyldichlorosilane and polydimethylsiloxane, respectively. These additives occupy a number of the active (silanol) sites on the silica, leaving fewer available sites for asphaltene adsorption. All four products exhibited less adsorption of resins than of asphaltenes. The two hydrophilic silica products adsorbed more or less the same amount of hydrocarbons from asphaltene and asphaltene + resin solutions. Initially hydrophobic products
Fig. 3. Hydrocarbon content of pure and coated Aerosil 200 (hydrophilic) particles was measured by FTIR spectroscopy.
adsorbed more hydrocarbons from asphaltene solutions than from asphaltene/resin solutions. Results from contact angle measurements in air and in oil are presented in Fig. 4. The contact angles at the watersolidoil contact line will generally be lower than those in the real systems. For this reason the watersolidoil contact angle is usually reported, often without any further comments, as a representative parameter for the partitioning of individual particles at the oil/water interface. However, the determination of the true contact angle by the compressed disk method is, by no means, straightforward if possible at all. Binks and Lumsdon [20] and Yan and Masliyah [19] have raised a concern about measurements of the true contact angle. It is clear that the watersolidoil
Fig. 4. Contact angle measurements of particles pressed into disks. The open circles represent the water/solid/air contact angle and whereas the lled squares represent the water/solid/oil contact angle. Both contact angles were measured into the water phase. Contact angles, which exceeded 170 were set to 170 due to high uncertainty in the method for these particular measurements.
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contact angles reported in Fig. 4 is generally higher than the watersolidair contact angles but follows the same trends. When the particle disk is immersed in the oil phase, oil will ll the voids of the porous disk due to capillary forces. When the water drop is placed at the disk it will be partially repelled by the oil in the disk and give too high . This is even more prominent if the disk is rst immersed in water and then contacted by an oil drop due to the protecting water lm. Yan and Masliyah [19] made the same observations when performing contact angle measurements of clays. They showed that, when the clays were rst immersed into oil, the contact angle of the clays was much higher than that when the clays were rst contacted with oil. It will still be possible to rank the products by their hydrophobicity from the results presented in Fig. 4. The inuence of asphaltene and resin adsorption on the wettability of the hydrophilic silica is dramatic. In real systems, the change in particle wettability due to adsorption of resins and asphaltenes from crude oil is the primary reason for the accumulation of particles at the oil/water interface. The 7200 particles show similar alteration of wettability upon resin and asphaltene adsorption as the 200 particles. Considering that hydrophobic particles adsorb less than hydrophilic particles, and that contact angles of resins and asphaltenes have been measured to 101 and 108 in air, it is not surprising to see only minor wettability changes for 972 and 202 particles. So, in summary, very hydrophilic particles like the unmodied 200 or very hydrophobic particles like the 972 and 202 products will most certainly prefer the water and oil phase, respectively. On the other hand, the true partitioning of the remaining particles at the water/oil interface is not obvious from the contact angle results. We performed simple qualitative powder immersion experiments, where the particles were placed on a water/air interface. We then carefully replaced the air phase with oil and visually observed the partitioning of the colored particles (aggregates) between the two phases after 24 h. Some of the 200R particles had left the interface to the water phase and some resided at the interface with a greater portion in the water phase indicating that these particles had a true contact angle less than 90 . The 7200 seemed to be equally partitioned between the two phases whereas the 200A, 200R + A, 7200R, 7200A and 7200R + A preferred the oil phase. These particles could easily be suspended in the oil phase by gently mixing the oil phase with a spatula, which indicated that these particles had a true contact angle larger than 90 . We know that electrostatic forces are generally believed to not play a signicant role in the stabilization of w/o emulsions due to the low dielectric constant of the continuous oil phase. However, for o/w emulsions, electrostatic repulsion from overlapping double layers can signicantly reduce the rate of coalescence if the double layer thickness is large. Increasing ionic strength (salinity of water phase) compresses the electrical double layer, and reduces the electrophoretic mobility of the particles [66]. Consequently, the inuence of electrostatics as a stabilization mechanism will be reduced in systems with high concentration of counter-ions. We have measured the zeta potential of the particles in 0.01 M NaCl solutions, whereas emulsion stability testing was done using aqueous solutions with 0.6 M (3.5 wt.%) NaCl.
Due to experimental limitations (electrode polarization), electrophoretic mobility of the particles could not be measured in 3.5 wt.% NaCl solution. We do not know exactly to what extent electrostatic repulsion will inuence the stability of the particlestabilized emulsions studied here. However, Binks and Lumsdon [8] have investigated the effect of pH and NaCl addition on the stability to occulation of Aerosil 200 particles and on the stability of toluene-in-water emulsions prepared from them. At pH 2, 4 and 5 no occulation occurred with addition of up to 5 M NaCl. At pH 6 and above, occulation was accompanied by a sharp increase in turbidity. The concentration of salt at the onset decreased with an increase in pH, whereas the maximum turbidity increased with pH possibly indicating a large occulation size, which forms when fully charged particles are screened. At pH 6 and pH 7 the critical coagulation concentration of NaCl was reported to be 1.2 and 0.5 M, respectively. As already mentioned, electrostatic repulsion between oil drops covered with particles may not be signicant if the double layer thickness of such colloids is too small to prevent droplet coalescence. However, electrostatic effects may affect the arrangement of particles at the interface. If crude oil components occupy silanol sites and neutralize the surface charge, there is a total contraction of the double layer around the negatively charged particles. Hence, the effective size of the nes is reduced, thus facilitating a closer packing of particles at the oil/water interface [6]. Changing the inter-particle interactions will affect the dynamic properties of the particles as well as the rheological properties of the interface. Fig. 5a shows the zeta potential () of pure and coated 200 particles as function of pH. The pH at which the zeta potential is zero denes the iso-electric point (IEP) of the material. In all cases the silicates show an increasing negative zeta potential when pH is raised above the IEP. At high pH, the silica surface shows a plateau, at which all silanol groups are deprotonated. At neutral pH the particles carry a net negative charge. The 200 particles exhibit an IEP at pH 2 while the coated particles show an IEP at pH 4.55.5. As discussed previously, resins and asphaltenes can occupy silanol sites and neutralize the charge of the silica surface. Surface charges from resins and asphaltenes arise from the dissociation of a large number of different acid functionalities and the protonation of different basic functional groups [67]. Zeta potentials of pure and resin-coated 7200 particles are shown as a function of pH in aqueous solution in Fig. 5b. We know that the 7200 product is a structure-modied product based on unmodied silica (Aerosil 200) where the number of silanol groups is reduced during the treatment to about 30% of the initial value. The pure 7200 particle surface is more positively charged than the pure 200 surface over the entire pH range studied. At high pH, remaining silanol groups are dissociated. The -prole of resin-coated particles is shown in Fig. 8. At low pH, basic functional groups protonate and give rise to positive charge. Resin-coated particles show similar -plateau as the uncoated particles in alkaline solution. However, in the pH range from 4 to 8, the particles are more negatively charged upon adsorption of resins. Due to complex surface chemistry, unknown stoichiometry, and steric effects, we will not account for this behavior.
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Fig. 5. Zeta potential of: (a) pure and coated Aerosil 200 particles and (b) pure and coated Aerosil 7200 particles.
Fig. 6. Separation of emulsions stabilized by: (a) 0.5% (w/v) 200R particles and (b) 0.5 (w/v) 200A particles. The left ordinate axis represents the amount of disperse phase resolved after gravitational induced coalescence (1580 g, 10 min). The Sauter mean diameter d32 is represented along the right ordinate axis for stable emulsion systems in a.
3.3. Performance The efciency of solids to stabilize water and oil emulsion systems was determined from the amount of dispersed phase resolved after centrifugation at 3000 rpm (1580 g) for up to 30 min. To simplify the representation, we will only report the amount of dispersed phase resolved after 10 min of centrifugation. We ensured that the particles (pure or coated) were the only stabilizers in the emulsion system, meaning that asphaltenes or resins did not exist in either oil or water solutions. The coated particles were washed repeatedly with toluene before they were used and the model oil (heptane:toluene, 70:30) showed no traces of asphaltenes or resins. Unmodied silica particles (200) did not act as good stabilizers due to the very hydrophilic character and separated over time even at 1 g. Fig. 6 shows that the stabilization efciency was greatly enhanced by adsorption of crude oil components. When crude oil components adsorb onto hydrophilic silica, the number of silanol sites on the surface is reduced as shown in Fig. 5a. Unlike the 200 particles, the resin-coated particles are interfacially active and will be partitioned at the oil/water inter-
face with a greater portion extending through the water phase. The hydrophilic nature of the 200R particles is reected by the o/w-type emulsions formed even at high volume of the oil phase (80 vol.%), which ts well with the observations from the powder immersion test. Moreover, Fig. 6a shows the importance of the initial location of the 200R particles. The particles stabilized the emulsion to some degree at 1 g when suspended in water but the emulsion separated completely within the rst 10 min of centrifugation. These particles performed much better as stabilizers when rst suspended in the oil phase. The partitioning of particles at the interface is most certainly different depending on the initial location of the particles, which can be seen in conjunction with observations from contact angle measurements. Aveyard et al. [5] have discussed similar observations with contact angle hysteresis and particleuid interactions. Menon and Wasan [41] and Yan and Masliyah [19] have studied water co-adsorption onto clay particles. The phenomenon seems to be very much related to studies of reservoir wettability [68]. Depending on the hydrophilicity of the reservoir, water will adsorb and protect the mineral surface from the oil phase. Rupture of such protective water lms has proven to be very difcult and involve slow kinetics. Both resin coated (Fig. 6a)
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and asphaltene coated 200 particles (Fig. 6b) produce stable emulsions of very large drop sizes (up to 100 m) when rst suspended in oil. This is a typical feature of particle-stabilized emulsions, which is not observed for surfactant-stabilized emulsions [5]. As seen in Fig. 6a the droplet size in the systems were particles were rst immersed in oil increase progressively with increasing volume of the disperse phase and decreasing emulsion stability. The 200 particles coated with asphaltenes (200A) are generally the most efcient in stabilizing emulsions and produced extremely stable o/w systems with gradually increasing drop size (from 20 m at 20 vol.% oil to 57 m at 60 vol.% oil) up to a point between 60 and 70 vol.% oil, where the emulsions invert to w/o-type. The catastrophic phase inversion, brought about by increasing the volume of the disperse phase has previously been shown to be dependent on the wettability [20] and the initial location [24] of the particles. The 200 particles coated with resins + asphaltenes (200R + A) show more or less similar performance as the 200A particles, with slightly less stable emulsions and phase inversion between 60 and 70 vol.% oil. The inuence of coating on the stabilizing efciency can be summarized as: (200A) > (200A+R) 200R > 200. Catastrophic phase inversion is also seen for the 7200 products in Fig. 7. Aerosil 7200 is a structure modied (3-methacryl-oxypropyl-trimethoxysilane) product based on Aerosil 200. We know from contact angle measurements and powder immersion tests that the 7200 particles have intermediate wetting properties. As seen for the 200A particles, the initial location of the particles seems to affect the point of inversion whereas the emulsion stability is more or less the same irrespective of which phase the particles are suspended in. The stability to gravitational induced separation (coalescence) passes through a minimum approaching inversion in line with a maximum in drop size of the disperse phase. Since microscopy indicated unspherical droplets and some degree of aggregation of the particles in the continuous phase, we have not calculated the Sauter mean diameters for these series. It should be mentioned that Binks and Lumsdon [7,20] have reported a maximum in stability to sedimentation/creaming at the point of inversion. However, the stability experiments by Binks and Lumsdon were done by sequential addition of oil or water where the oil phase contained 2 wt.% hydrophobic particles. The particle concentration in the emulsion was not held constant as in our experiments. In another study by Binks and Whitby [9], oil was added continuously to an aqueous phase containing 0.7 wt.% hydrophobic silica particles. The system underwent catastrophic phase inversion with maximum drop size at inversion. Type of coating plays a minor role for the stabilizing efciency of the 7200 solids. All particles show similar stability proles with minimal stability approaching inversion and a shift of the inversion point by 1020 vol.% oil when the particles are rst contacted with the water phase. The stability prole for the asphaltene coated particles (7200A) is shown in Fig. 7b whereas the proles for 7200R and 7200A + R are not presented. From results presented in Figs. 68 it is apparent that transitional phase inversions can be induced by changing the wettability of the particles, either by modifying the surface with silanes or siloxanes or by coating the particles with crude oil components. Thus, one way to
Fig. 7. Separation of emulsions stabilized by: (a) 0.5% (w/v) 7200 particles and (b) 0.5 (w/v) 7200A particles. Catastrophic phase inversion was induced by increasing the volume of the disperse phase.
affect transitional inversion is to simply decrease the silanol content on the particles as done systematically by Binks and Lumsdon [20] for hydrophilic silica particles silylated to different extents by reaction with dimethyldichlorosilane. By coating the 7200 particles with asphaltenes (7200A), hydrophobicity increased and the preferred emulsion type changed from o/w to w/o. The point of phase inversion is shifted to the left in Fig. 7. All 972 particles (pure and coated) are very hydrophobic and we did not succeed to suspend the particles in water. Addition of more particles, from 0.1% (w/v) in Fig. 8a to 0.3% (w/v) in Fig. 8b caused a signicant increase in emulsion stability of the w/o emulsions and resulted in smaller drops as more particles were available to stabilize the interfaces. The stabilizing effectiveness of the particles can be presented in the following order: (972A) (972A + R) > (972R) (972). Sauter mean diameters of the water drops in the emulsions in Fig. 8b are presented in Table 4. Generally, and unlike that for surfactant stabilized systems, these coarse emulsions were very stable to coalescence even when exposed to a high gravitational eld (1580 g for 10 min). The diameter increased progressively with increasing volume of the disperse water phase in line with the decrease
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Fig. 8. Separation of w/o emulsions stabilized by: (a) 0.1% (w/v) and (b) 0.3 (w/v) 972-particles. The Sauter mean diameters for the systems are reported in Table 4.
in emulsion stability, whereas different type of coating did not affect the mean diameter to the same extent. As mentioned in the introduction, Vignati et al. [25] have succeeded in making stable emulsions with particle coverage of only 5%. It was therefore, in our interest to do some kind of evaluation of the total droplet surface and compare it to the amount of particles present to potentially cover the interface. It is generally believed
Table 4 Sauter mean diameter (d3,2 ) of w/o emulsions stabilized by 0.3% (w/v) particles Oil (vol.%) 972 d32 30 40 50 60 70 80 74 63 54 42 32 85 70 58 48 36 2 26 21 13 17 12 972R d32 71 60 47 45 29
that, for a given input of mechanical energy during emulsication, the initial drop size (before any further coalescence) is dependent on the amount of the two phases present, the tension of the interface and the mass density of the continuous phase [23]. After agitation, drop growth will proceed either by coalescence or by Ostwald ripening, thus reducing the total interfacial area, until the particle coverage is sufcient to stabilize drops against further coalescence. The diameter at which all particles are accommodated at the interface is often referred to as the limited coalescence diameter [5,9,10,19,31,69]. The Sauter mean diameter and the volume of the disperse phase in Table 4 provide the necessary information to estimate the total interfacial area of the water/oil interface for the systems stabilized by 972/972R/972A particles. Doing this interestingly show that the total interfacial areas of the 16 different systems are more or less the same (mean = 0.56 m2 , S.D. = 0.07). Microscopy showed no evidence of excess particle aggregates in the continuous phase. It seems like the particle amount, which is equal in all these cases, determines the limiting water/oil interfacial area irrespectively of the ratio between oil and water. For all droplet size results presented in this study, the cumulative volume distributions were tted successfully to a lognormal distribution function (regression residuals <1). We have not observed any multimodal droplet size distributions. Table 4 shows the distribution parameters for the emulsions stabilized by 972 particles. We can see that the size distributions were systematically broadened (increasing 2 ) proportionally with increasing drop size, in contrast to what would be expected for systems where droplet growth had narrowed the drop size distribution. Similar results have been found throughout this study, for both hydrophilic and hydrophobic silica particles. From these observations it seems like fragmentation and coalescence (collision) during emulsication differs for systems with high or low volume concentration of the disperse phase. After emulsication, drops may grow in size until the surface concentration of particles prevents further growth. Results show that these processes lead to different polydispersity of the system with high or low volume concentration of the disperse phase. The measurements were performed within the 10 rst minutes after making the emulsion, which is generally too short time to expect any signicant Ostwald ripening of the drops. We expect any droplet growth to be caused by coalescence, which is rapid initially and ceases to become very slow. The systems seem to be very stable to coalescence only minutes after emulsication. We will not take a decision on whether the
972A 86 67 51 49 32 2 31 22 14 13 8 d32 90 60 56 48 44 30 99 70 60 55 48 33 2 29 21 16 17 12 8
The volume distribution was tted to lognormal distribution function with reported mean () and standard deviation ( 2 ).
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Fig. 9. Separation of w/o emulsions stabilized by 0.3% (w/v) 202A particles. The Sauter mean diameter d32 is represented along the right ordinate axis.
resulting interfacial area is that where all particles are accommodated in a hexagonal closed packed arrangement or not. Since the aggregation state of the silica particles at the interface is unknown it is difcult to say whether the interface is completely covered with particles or not. However, by assuming partitioning of primary particles at the interface, the amount of particles used in our experiment will generally be in large excess to that needed for full coverage of the interface. Since microscopy showed no evidence of particle aggregates in the continuous phase, the silica particles will most likely be present as agglomerates with sizes of several hundred nanometers, which reduces the effective packing of these particles at the interface. Binks and Whitby [9] have done a systematic study of the parameters affecting emulsication of silica-stabilized emulsions. We expect extremely hydrophobic particles to perform poorly as stabilizers since these particles will have low activity for the water/oil interface. Emulsions stabilized by the 202 particles and the resin coated particles (202R) resulted in complete emulsion destabilization under the high centrifugal eld even with particle concentrations up to 1.0% (w/v). These emulsions were stable for at least 30 min at 1 g, but the emulsion stabilized by 202 particles was destabilized within the rst minute of centrifugation at 800 rpm (113 g). Coating the 202 particles with asphaltenes (202A) or asphaltenes + resins (202A + R) dramatically increased emulsion stability and formed very stable emulsions at 0.3% (w/v) particle concentration. Increasing the concentration of particles from 0.1% (w/v) to 0.3% (w/v) signicantly improved stability of these systems. We can see from Fig. 9 that the stability of the 202A emulsions decreased progressively with increasing volume of the disperse water phase, in line with increasing mean drop size of the disperse water phase. The 202A + R particles showed only slightly lower performance as stabilizers. The total interfacial area of the different systems are the same (mean = 0.62 m2 , S.D. = 0.07). The stabilization effectiveness of 202 particles can be summarized as: (202A) > (202A + R) (202R) > (202). All 202-products produced w/o emulsion type even at high
water phase volumes, reecting the hydrophobic nature of the particles. We have in some cases observed stable irregular emulsion droplets like the 500 m droplet presented in Fig. 10 (also smaller drops), which seems to be highly covered with particles. With an oscillating pendant drop measurement similar to that reported by Tambe and Sharma [32], we have proven that such interface will possess very high elasticity which will add stability to the interface (not presented here). If particles are in large excess of that required for accommodation at the water/oil interface, increased viscosity of the continuous phase due to particle network formation (H-bond linkages) can also add a certain stability to the emulsion system [5]. As apparent from the previous section, we have not studied how pH or different salt concentrations will affect the performance of the particles in the emulsions. Both properties will be important in determining the electrostatic forces and particle coagulation in the systems. We did our stability experiments with aqueous phase pH 6.7 and salt concentration of 0.6 M NaCl. For similar studies, we will recommend to measure the degree of particle aggregation in bulk with some kind of light scattering instrument. Microscopic drop size determination may prove aggregation of larger aggregates, but not provide quantitative results. 3.4. Relevance to petroleum industry Wettability alteration of reservoir rock has been extensively studied by geologists, and will not be discussed here even though the surface afnity of heavy crude oil components is a key factor for oil recovery. The presence of inorganic particles at oil/water interfaces, in process equipment like settlers or electrocoalescers, can cause severe operational problems if emulsions are too stable to be destabilized by traditional methods. Even if the initial concentration of inorganic particles is low, particles tend to accumulate in process equipment over time and build up sludge layers of oil/water/particles [70]. Such layers require aggressive treatment methods or removal. Oil trapped in the sludge layer is lost and will constitute an economical loss
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as well as a waste problem. With knowledge about the relevant stabilizing mechanisms as well as information of the production history (pressure cycles, energy input, and chemical additives) of the oil/brine/particle system, particle-stabilized emulsions can be treated or prevented [71]. A correct choice of chemicals may displace particles from the interface, or prevent interfacial partitioning altogether. Gu et al. [11] have discussed the possibility to use particles for viscosity control in transportation of crude oil systems. 4. Conclusions We have coated dry silica nanoparticles with heavy crude oil components and investigated the performance of these solids as stabilizers in model oil/water emulsion systems. Adsorption studies, using the QCM-D technique, have shown multilayer or aggregate formation of asphaltenes at the silica surface. Asphaltenes are irreversibly adsorbed as a rigid lm. The adsorbed amount from resin solution is dramatically smaller than when asphaltenes contribute to the adsorption. The effect of the surface modication has been monitored using infrared spectroscopy, contact angle measurements and zeta potential measurements. Initially hydrophilic particles show signicant adsorption of crude oil components leading to wettability alteration and surface charge effects. Hydrophobic particles adsorb smaller amounts of asphaltenes and resins, and show only minor wettability changes. It is shown how coating of the nanoparticles with asphaltenes and resins will modify the stabilization prole compared to that obtained with no coating. The stabilization efciency was greatly enhanced by adsorption of crude oil components onto very hydrophilic or very hydrophobic silica. Generally, the performance of the particles as stabilizers seems to be strongly dependent on their wettability. We have demonstrated catastrophic phase inversion of emulsions stabilized by particles with intermediate wetting properties, induced by simply increasing the volume of the disperse phase. In all cases, the stability to gravitational induced separation (coalescence) passes through a minimum approaching inversion in line with a maximum in drop size of the disperse phase. The initial location of the particles is important for the stability of the system and the type of emulsion formed. Transitional phase inversion from o/w to w/o emulsion type can be achieved by modifying the hydrophilicity of the particles, either by silylation or by a controlled coating with heavy components from crude oil. Generally, the emulsions consist of a lognormal distribution of droplets centered at a large mean diameter (up to 50 m). The emulsions are still very stable, which is typical for particle-stabilized emulsions. Acknowledgement The technology program Flucha III, Particle-stabilized Emulsions/Heavy Crude Oils, nanced by industry and the Norwegian Research Council (Strategisk omstillings program) are gratefully acknowledged for nancial support. We are also grateful to Degussa for providing us with the samples of the silica particles.
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