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Journal of Membrane Science 204 (2002) 125–137

Analysis of droplet formation and interactions during
cross-flow membrane emulsification
A.J. Abrahamse a,∗ , R. van Lierop a , R.G.M. van der Sman a ,
A. van der Padt b , R.M. Boom a
a Food and Bioprocess Engineering Group, Wageningen University, P.O. Box 8129, 6700 EV Wageningen, The Netherlands
b Friesland Coberco Dairy Foods, Corporate Research, P.O. Box 87, 7400 AB Deventer, The Netherlands

Received 1 October 2001; received in revised form 23 January 2002; accepted 23 January 2002

During cross-flow membrane emulsification, droplet formation at a micro-engineered membrane with uniform pores was
visualized by microscopy. Although the membrane pores were uniform in size, the obtained emulsions were polydisperse.
Observations showed this to be due to steric hindrance of droplets forming simultaneously. At some pores close together, the
droplet formation frequencies were almost identical (0.86 and 0.88 s−1 ). This was confirmed by the cross-correlation value
(around 0.8). Because the droplets hindered each other during growth, the droplet diameter decreased with an increasing
number of active pores. In spite of the uniform pore size and shape, the number of active pores only gradually increased upon
increasing transmembrane pressure. We suggest this to be due to the dynamics of the flow of the to-be-dispersed phase towards
and through the membrane. Under the process conditions used, interactions can only be prevented by using a membrane with
a lower porosity. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Membrane; Emulsion; Droplet formation; Interaction

1. Introduction [1–3] and how to produce monodisperse microspheres
by polymerization after emulsification e.g. to be used
In cross-flow membrane emulsification a liquid as column packing material. The results were recently
phase is pressed through the membrane pores to reviewed by Joscelyne and Trägårdh [4].
form droplets at the permeate side of the membrane; In conventional emulsification processes, severe
the droplets are carried away by a continuous phase process conditions are necessary for break-up of the
flowing across the membrane surface. Under specific emulsion droplets, which puts high shear on the
conditions, monodisperse emulsions can be produced components and is energy intensive. Especially for
using this technique. Substantial research has been producing small droplets (<3 ␮m) the energy require-
carried out how to produce monodisperse emulsions ment is much lower in membrane emulsification
for food, pharmaceutical and cosmetic applications than in conventional processes [5]. Because of the
low shear stresses, new products with shear sensitive
∗ Corresponding author. Tel.: +31-317-482237;
components can be developed [6,7].
fax: +31-317-482240.
Unfortunately, the process is not yet commer-
E-mail address: anneke.abrahamse@algemeen.pk.wag-ur.nl cially feasible because of a low throughput of the
(A.J. Abrahamse). to-be-dispersed phase. The throughput is determined

0376-7388/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 2 ) 0 0 0 2 8 - 5

For exam- fF Fanning friction factor ple. standard deviation (m or s) ameter and the droplet formation time decrease [5. In a system with capillaries in a bundle. it is likely ρc density of the continuous phase that the mechanism for droplet break-up in this sys- ρ c = 1000 (kg m−3 ) tem may not be the same as in the systems described before [15]. with- Xi . droplet formation in a microengi- ηc viscosity of the continuous phase neered silicon microchannel system was visualized by ηc = 1 × 10−3 (Pa s) microscopy [12–14].D.in height of the inflow continuous that the membrane surface porosity should ideally phase vessel (m) not be higher than 1. A high h height difference between the porosity is favorable for the throughput but not for the continuous phase vessels (m) droplet size. Further. In conclusion. coalescence was shown [5]. the tubular microporous ceramic and glass mem- g gravity constant (m s−2 ) branes [8.J.9]. The second h = 2. which are generally used.t value of signal i at time t out emulsifier.i (0) variance of droplet formation signal i droplet formation. we can say cross-section O = 2.1 × 10−2 (m) that there is a careful balance between the disperse pc continuous phase pressure (Pa) phase throughput and the emulsion droplet diameter. have a high h height of the cross-flow channel porosity but quite a thick membrane layer. these characteristics affect f droplet formation frequency (s−1 ) the obtained average droplet diameter too.5%. . tform droplet formation time (s) Increasing the pressure difference also decreases the vc cross-flow velocity of the droplet formation time but results in a larger droplet continuous phase (m s−1 ) diameter. Moreover.out height of the outflow continuous the droplets could touch during droplet formation and phase vessel (m) possibly coalesce.11].24 × 10−8 (m2 ) B help parameter (m) ddr droplet diameter (m) by the transmembrane pressure. among other Dh hydraulic diameter D h = 5. Np. / Journal of Membrane Science 204 (2002) 125–137 Nomenclature ρd density of the disperse phase A area of the channel cross-section ρ d = 773 (kg m−3 ) A = 2. since the geometry of µi mean of the droplet detachment signal i the cross-flow channel is rather different. Abrahamse et al. membrane dp pore diameter (m) porosity and the viscosities of the fluids. pore size.act total number of active pores droplets formed at only 3–40% of the pores [5].1 × 10−4 (m) factors (Fig. In an earlier study [10] we have shown hc. Schröder deduced that J oil throughput (kg m−2 h−1 or kg h−1 ) depending on pore size and transmembrane pressure. However. but the pores themselves could not γ interfacial tension (N m−1 ) be seen.j cross-correlation between two  functions i and j A help parameter (m Pa−1 ) τw wall shear stress (Pa) Am surface area of the membrane Am = 3.6 × 10−6 (m2 ) ρ i . Droplet formation at membrane surfaces was also studied by Greek letters the same author. At a higher surface porosity hc. This n number of droplets formed low percentage of active pores is disadvantageous for O perimeter of the channel the overall productivity.6 × 10−4 (m) feature is not favorable for a high throughput. 1). However. pcrit critical pressure (Pa) Direct examination of the formation of individual pd disperse phase pressure (Pa) emulsion droplets using a microscope video system ptrm transmembrane pressure (Pa) enables one to study the fundamental processes of Ri .126 A. Visualization experiments with sin- Re Reynolds number gle capillaries in a cross-flow channel show that with s translation of a signal (s) an increasing cross-flow velocity both the droplet di- S.

2. we discuss the results of visualization 2. respectively. The channel height. Membrane of droplet formation at the surface of a uniform mi- croengineered membrane during cross-flow emulsifi. To cancel out the effect of differences in pore cation.26. the same as the cross-flow channel height. Before the experiment. In this paper. and length were 0. It was made which affects the droplet diameter. / Journal of Membrane Science 204 (2002) 125–137 127 Fig. implying: (1) uniform pore sizes number of active pores is caused by the dynamics of and shapes. width The disperse phase was n-hexadecane (for synthesis. remain in the channel: all the droplets were removed scribed below. 10 and 39 mm. Further. A. From the known dimensions. we show that over the membrane surface. of silicon nitride of 1 ␮m thickness and contained cir- cular pores arranged in groups of 100 identical pores with pore diameters ranging from 1. Merck). Chemicals of these pores. Merck) colored with Sudan red (7B for microscopy.45 ␮m.2. for synthesis. we used a microengi- formation times. The arrangement 2. this solution was this module differs from the systems studied in liter- passed through a Durapore membrane filter (Millipore) ature. the surface Tween 20 (Polyoxyethylene sorbitan monolaurate. Experimental and calculation methods Only droplet formation at the 100 largest pores with a diameter of 7 ␮m was studied. 1. We suggest that the low uniform membrane. are shown vskip-1pt in Fig.15. . With respect to the height of the cross-flow channel.o.17] which is a with in the oil throughput.5 to 7 ␮m [17]. (2) the pores are uniformly distributed the flow under the membrane. Abrahamse et al.J. with the cross-flow. Parameters in membrane emulsification affecting the droplet formation process and thus the droplet diameter and throughput (a. neered Aquamarijn microsieve® [16. The membrane was a droplets interact due to steric hindrance and collisions. Kuiper and Aquamarijn. they did not Droplet formation was studied with the setup de. used in the results section. the number of active pores and there. 2.: amongst others). Direct examination provides insight in droplet diameters in the membrane. Although the size of some droplets was almost with an average pore diameter of 0. kind gift of S. Merck) (1% (w/w)) dissolved in dem. porosity was calculated to be 0. the distances between the pores and the numbering. Gluing a hollow glass plate on top of the sieve cre- ineralized water was used as the continuous phase.1. ated the cross-flow channel.

3. the pressure was measured.J. Tubing.in + hc. Experimental setup.5 m was used. Meanwhile. 3.1. Wall shear stress at the membrane surface in the cross-flow channel (τ w ) Fig. with demineralized water. Each condition (Table 1) was recorded once. scribed in literature.4. module and pressure vessel were air dried. After that. The cross-flow velocity of the continuous phase (v c ) and the transmembrane pressure (ptrm ) were calculated from the measured height difference between the con- tinuous phase vessels (h) and the measured disperse phase pressure (pd ): v c = 1. Visualization 2. of which the levels were kept sured manually and the times at which droplet forma- tion started and at which the droplet detached were noted. acquired with The experimental setup is shown in Fig. Maximum measurement errors were 4 ␮m for the droplet diam- eter and 0. Abrahamse et al. Experimental setup Images with a magnification of 400×. The quency was 25 images per second.3. Calculation methods 2.2.and outflow vessels.04 s (being the time between two images) for the time. Sili- cone tubing with a total length of 2. cross-flow velocity.1. Symbols concerning the calculation To compare the shear stress on the droplets in our of the cross-flow velocity and the transmembrane pressure are geometry with the shear stresses in experiments de- explained in the list of symbols.out )/2. The pressure vessel was also cleaned with detergent and demineralized water. / Journal of Membrane Science 204 (2002) 125–137 constant by a continuous overflow construction.128 A. 2. 2. At the Sony CCD video camera (type XC-77CI). While replaying. a detergent solution (5– 10% Glorix® with hydrogen peroxide) was flushed through the tubing and the module (including the membrane).3. the module and tubes were flushed for a day Fig.4.75 and 55 s of video was an- alyzed. the module was kept at a temperature of 50 ◦ C. we used the following equations . because the friction in the tubes was negligible compared to the friction in the module. both through the cross-flow channel and through the disperse phase inlet. 3. The fre- outflow of the vessel. The pressure of the contin- uous phase in the module could be calculated in this way. were recorded with a adecane was pressurized in a pressure vessel. which restricted the continuous (aqueous) phase passed through the mem. a Zeiss Axioplan microscope. ptrm = pd − pc = pd − ρc g(hc. Hex. per condition between 2. Arrangement and numbering of the pores in the membrane. Cleaning Before the experiments.3. Experimental methods 2. the diameters of brane module due to a height difference between the the droplets detaching from the membrane were mea- in.11 h.3. 2. depending on the droplet formation time and the width of the droplet size distribution. 2.

71 1.5 0.78 1. The calculation of the wall shear stress is only an ap- proximation of the shear stress on the droplets.D.t+s ) cause in some cases the size of the droplets almost = E{(X1.039 8. (ddr )).5 64 169 43 0.69 0.4.56 5 1.1 (s) = cov(X1.8 0.62 1.20 0. This is explained linearly increases from 0 to 1 until a droplet detached.09 6 1.05 7 1.23 7 0.03 7 0.46 0.028 8. in Fig.49 0. number averaged droplet diameter (ddr and S. the drop- formation. (ddr ) tform (s) S.1 (s) is the covariance of the two droplet detachment vc signals as a function of the translation s.3 47 196 20 0.1 (0)R2.38 3.2.37 0.D.0 133 125 48 0.9 0.6 53 125 20 0. droplet formation time (tform and S. 4c.t .86 4 1.D. (tform )).50 1. be.37 0.19 5 0.5  n aJ = ρ  d 1 (1/6)π ddr /(Am × time of the experiment). the maximum cross-correlation value ap- For each pair of active pores the cross-correlation peared to be at least 0.t+s − µ2 )} (5) equalled the height of the cross-flow channel. The signal range of one period around s = 0.011 7.62 1.8 72 134 35 0.act ) and oil throughput (J) for all experimental conditions v c (m s−1 ) ptrm (kPa) n ddr (␮m) S. cross.32 8 1. Abrahamse et al.34 0.2 (0) are the variances 4A of both droplet detachment signals at translation 0 and Dh = ≈ 2h (2) O R2. a saw wave function is obtained (Fig. A.29 3 2.017 7. The trans- τw = 0.017 6. . (4)) [18]: 16 16ηc ρc vc Dh R2.1.3 62 149 50 0. To determine to which extent the detachment of From each resulting cross-correlation function.017 8.19 2 0. droplet formation frequency (f ).77 0. / Journal of Membrane Science 204 (2002) 125–137 129 Table 1 Number of droplets formed (n).55 0.1 (s) =  (4) Re ρc v c D h ηc R1.19 1. Because detachment pores at which droplets formed.8 0.2 0.7 57 152 74 0. At the moment of droplet detachment the maximum cross-correlation value was taken from the signal is 1 and directly after that it is 0. total number of active pores (Np.77 3 0. maximum cross-correlation and the translation at this correlation functions were calculated for each pair of maximum value were obtained. calculate whether droplets detached at the same rates.017 5. 3 (see list of symbols): function ρ 2.9 45 130 62 0.5fF ρc vc2 = 8ηc (3) lation of signal 1 with regard to droplet detachment 2h signal 2 was discrete.2 (0) (1) In this equation R1.14 2.64 0. respectively [18].D.5 0. This signal does not exactly describe droplet formation functions experimentally found.5 53 133 40 0.71 1. Therefore.6 50 172 76 1. but contains the necessary information to let detachment signals are not completely random. In this way. X2.1 0.1 (s) was calculated (Eq. with steps of 0.00 5 1. Cross-correlation detachment signals 1 and 2.17 4 1.2 0. In this equation µ1 and µ2 are means of the droplet 2.J.31 0.028 6.3 0.36 5.1 (s) fF = = for Re = < 2300 ρ2.0 0.3 0. R2.45 0.t − µ1 )(X2.039 7.028 6.37 7 1.59 1.60 0.9 55 179 71 0.7 51 115 29 0.53 1. the active pore.32 2.09 0.24 3.028 5.028 7. (tform ) f (s−1 ) Np.act Ja (103 kg m−2 h−1 ) (␮m) (s) 0.028 9.01 s.9 58 155 40 0. 4a Due to the imposed saw wave on the droplet and b).028 7.1 (0) and R2.9 0.4 21 221 14 2.1 0. First. the droplets from different pores was coupled. a formalized from one pore is at most half a period behind or be- droplet detachment signal was formulated for each fore detachment of droplets from the other pore.

Results and discussion this ratio is also between 3 and 10 [2. 4. the droplet/pore diameter ratio was between 7 droplet diameter (ddr in m) on the transmembrane and 36. With such a low wall shear stress Finally. 3.19–21].130 A. / Journal of Membrane Science 204 (2002) 125–137 Fig.1. the dimensions times were calculated. (c): cross-correlation function for droplet detachment at these pores at v c = 0.11] and in mem. (3)). Droplet detachment signals of (a) pore (3. However. which will be discussed further membrane is very thin. the droplets were large compared to the pore diameter Concerning the dependency of the number averaged (7 ␮m).62 Pa at most.8 kPa. Thus. the droplet ent from the experiments described in literature: the diameters were measured and the droplet formation cross-flow velocity was low. decrease of the average droplet diameter with increas- brane emulsification with ceramic or glass membranes ing pressure at a cross-flow velocity of the continuous . used. To compare the cross-flow velocity we only a few pores. was 0. 5) show some of the membrane module were different. Next. and the emulsion is less monodis- perse than with a high wall shear stress (>30 Pa) [22].4) and (b) pore (3. Abrahamse et al. With the number of active pores. 5). droplet/pore pressure (ptrm in Pa). velocity did not significantly affect the droplet size.8). we found a significant linear diameter ratios of 3–10 were found [5. The first thing that attracts atten. the cross-flow velocity varies. In experiments with single pores. 10–30 [22]. the we calculated the wall shear stress (Eq. the droplet size of droplets with microscopy. 3.039 m s−1 ). each other sterically (Fig. the Droplet sizes varied between 52 and 255 ␮m. the experimental conditions in our setup were differ- For the conditions listed in Table 1.J.028 m s−1 . Further. Droplet size This is in agreement with our results. was high. it was observed that droplets formed at had to be low. The images (Fig. p trm = 7. it will be discussed that the droplets hindered the droplet/pore diameter ratio was found to be high. besides.011–0. Because the important phenomena. the droplet size and the droplet formation time. In the range of cross-flow velocities used (0. to be able to follow the formation tion is the large droplet size. with conditions in different experimental setups. thus. which total oil flux through the membrane was calculated. >80 [3]. the oil flux through the pores in the next sections.

5 kPa) in visualization experiments with single normally distributed for a few conditions. creases the final droplet volume during the second the emulsions show a high polydispersity and are not stage of droplet formation. the total number uniform droplet size distribution. Droplet formation was hindered sterically by droplets forming 3. should be obtained when using a uniform membrane. / Journal of Membrane Science 204 (2002) 125–137 131 Fig. Although the droplet diameter distribution of each individual pore was quite nar- Direct observation of the droplet formation process row. in droplet formation at the individual pores. A = (2.8 kPa. depending of the variance of the data. Droplet detachment from the membrane due to contact between droplets growing at neighboring pores at v c = 0. eter with increasing transmembrane pressure in our neither at the membrane surface nor in the bulk phase. 5). further studies were . This imental limitations. A. the detachment phase. The visualization showed that Section 3.2.028 m s−1 . experiment can be explained by steric hindrance of the The polydispersity could be attributed to differences droplets. Abrahamse et al. The width of the size 105 Pa) the droplet diameter increased with increas. the data were weighted by the reciprocal diameter was between 115 and 221 ␮m.J.3 ± 1. Measuring between 21 and 132 equation was obtained using the weighted least squares droplets revealed that the number averaged droplet method [23]. In normally distributed. ddr = −A ptrm +B.2) × 10−4 m. which in.35–2. 5. we will discuss that the decreasing diam. The droplet diameter was only (0. Droplet size distribution at other pores (Fig.6.1 × process conditions are shown. To study the non- each individual pore. classes was taken constant (17.3± of formed droplets was not very high. Necessarily. on the transmembrane pressure and the cross-flow nificant changes in droplet diameter at low pressures velocity (Table 1). Schröder did not find sig. 6). 6. phase of 0. the polydispersity was not caused by coalescence. insets in Fig. Peng and the number fractions per size class under several Williams showed that at high pressures (0.028 m s−1 and ptrm = 7. pores and with a bundle of capillaries [5].7) × 10−8 m Pa−1 .5–1. In Fig. B = (3.5 ␮m). Although it ing transmembrane pressure [11]. due to exper- 1. This was explained is generally accepted that monodisperse emulsions by the increased flux at a higher pressure. the average droplet diameter varied from pore gave information on the droplet size distribution for to pore (Table 2.

8 0. 6c and decreased with increasing transmembrane pressure Table 2).9 kPa. 1).5 kPa [5].4 1. (d) v c = 0.D. droplet formation but occasionally single droplets formed within 0. a2: pore (5. under different conditions.1 s.77 0.36 s.D.4 1. 3.2 0. (tform ) (s) f (s−1 ) J (10−6 kg h−1 ) (3.12 0.53 30.4) 9 88 0.12 0.039 m s−1 . Table 2 Number of droplets formed (n). 2). Droplet formation time.7 1.8 kPa pore n ddr (␮m) S.05 and 1.1) 7 185 9. p trm = 5.028 m s−1 .86 0. performed using the results of the process conditions expectation.2 (6. The average droplet formation time was between 0. ptrm = 7. (Table 1). 7). (ddr )).24 1. droplet formation time (tform and S. 4). (a) v c = 0. / Journal of Membrane Science 204 (2002) 125–137 Fig.028 m s−1 and ptrm = 7. (ddr ) (␮m) tform (s) S.11 2.10 0. droplet formation frequency (f ) and oil throughput (J ) for each active pore and for the whole membrane area at v c = 0. a1: pore (1. in the order tion was defined as the moment at which a droplet of 1–2 s with a capillary of diameter 45.J.10) 5 130 14.2 0. the droplet formation time significantly v c = 0.5 (10.7) 22 146 19.6 Membrane 72 134 34.13 0.2 (7.0 1.3 0.8) 9 170 6.92 0.5–1 s with a capillary of the droplet (Fig.028 m s−1 .06 1.9 (3.08 0. 0. number averaged droplet diameter (ddr and S. Droplet diameter distributions obtained at different conditions (number fraction of droplets per size class). c1: pore (3.28 0.6 (4.6 ␮m at low could be seen at a certain pore.3. (b) v c = 0.011 m s−1 .22 10.29 0.37 and 2.86 3. The start of droplet forma.49 1.04 0.8 kPa (Fig.D. (tform )).6 .5 kPa.34 0.60 0.8) 11 90 8.6 (10.6 kPa.5 s The droplet formation time is defined as the time was calculated for droplet formation with Tween 20 between the start of droplet formation and detachment at a ceramic membrane [22].8 kPa.6) 9 134 11. frequency and lag time These droplet formation times have the same order of magnitude as earlier presented values: 1. 6. p trm = 7.88 6. Insets: droplet size distributions of individual pores (same scales as the total droplet diameter distributions).D.75 6. p trm = 7.86 0. (c) v c = 0. c2: pore (3. 8).132 A. Confirming our cross-flow velocities [11]. with a pressure difference of 0. Abrahamse et al.028 m s−1 and ptrm = 7.

7). Number of active pores as a function of transmembrane low-molecular emulsifier like Tween 20 is less than a pressure at different cross-flow velocities of the continuous phase. 7. it might be the case that after de- taking the reciprocal of the average time between the tachment the emulsifier is temporarily depleted. Number of active pores and critical pressure Section 3. the diffusion time of a Fig. lag time and the time between the consecutive detachment of two droplets. / Journal of Membrane Science 204 (2002) 125–137 133 Fig. A. Even at the highest pressure there were still pores For each condition in Table 1 and for some other at which droplet formation was slow. were counted (Fig. Abrahamse et al. 4). This is caused by the fact that sometimes after detachment for a certain time no droplet formed (Fig.4. Droplet formation frequency of each pore as a function of v c = 0. However. . the occurrence of this lag time was most pronounced at pores (4.6. time.6) at the conditions Fig. Droplet formation at pore (4.7). This is a result of steric hindrance of the droplets growing close to each other. explanation is that the pore has to be refilled before a cies of pores (3. Yet. Usually. From the fact transmembrane pressure (Fig.6) and (7. However. 9).6) were very close. Under the conditions v c = 0. There- fore. the number of pores at which one or more maximum droplet formation frequency increased with droplets formed. The second possible pore to pore (Table 2).J. new droplet forms. 7). 8) and (4. that all the pores had the same diameter. the formation frequen. which will be shown in 3. 8). The lag time be- tween droplet detachment and renewed droplet for- mation might be explained by diffusion limitation of emulsifier or by pore refilling after detachment of a droplet. 8. millisecond.028 m s−1 and p trm = 7.028 m s−1 . which is much shorter than the observed The droplet formation frequency was determined by lag times. 9.8 kPa (Table 2). p trm = 7. indicating the droplet formation transmembrane pressure. emulsifier had to diffuse to the interface to reduce the interfacial tension. The successive detachment of two droplets from a pore concentration has to be restored by supply of emulsi- (Fig. it could be Note that the droplet formation frequency is smaller than the reciprocal of the droplet formation time. (3. the conditions.8 kPa. The droplet formation frequency varied from fier with the cross-flowing phase. The applied transmembrane pressure was too low to overcome the critical pressure to form a droplet with a clean interface (no emulsifier).

8 (±0.5 times the critical pressure.4 (±0. to compare this result with literature. this suggest that the pores become active at frequency.J. there pressure) [3]. between −1 and 1. Consid. the a ceramic 0. had the droplet size decreased with increasing transmem- the same results: below a transmembrane pressure of brane pressure. had others started to form droplets. the total flux through the membrane 2. Each time after changing pcrit = 4dp /γ the cross-flow velocity. the number of active pores increased linearly with increasing transmem. while (3. the maximum oil throughput in this Tween 20 is a relatively fast emulsifier. 5). Table 3 . The results in Fig. the assumption that pores with the same di. being located near each other. ferent pores sometimes touched each other while they increases. which affects the transmembrane pres. to be identical. fective pressure = transmembrane pressure − critical sure of pores upstream very slight. Oil throughput as a function of brane pressure and droplets formed only at a few pores. increased. At a higher applied pressure more pores become active. branes with different pore diameters were used. the critical pressure was de- termined by increasing the pressure from 0 until a In fact. Also the ef. the percentage of ac.5 ␮m membrane the largest flux found was pressure in the cross-flow channel only increases a 200 kg m−2 h−1 at an effective pressure of 20 kPa (ef- few Pascals. at a transmembrane pressure of 8. Abrahamse et al. Droplet–droplet interactions to become active. the droplet formation frequency increased.134 A. agrees with the value calculated from the regression is the basis for some standard membrane characteri. droplet started to form. all pores should become active. Due to this steric hindrance. 9 show again that the velocity the droplet formation frequencies can be considered did not affect the emulsification process. The cross-correlation between each pair pressure again. of pores was calculated. because mem- stream of that forming droplet is not a satisfying ex. It was observed that pores (3.4 ± 2. became inactive. because the pressure difference.6). because mental conditions. the cross-correlation ranges random. other pores became active. It only at a few pores droplets formed under the experi- cannot be due to slow diffusion of emulsifier. for planation.25) × 10−3 ptrm − 5. Np. Visualization showed that droplets forming at dif- which is the driving force for flow through the pores.0 theoretically this depends on the pore diameter by the Linear regression with the transmembrane pressure Laplace equation: as the dependent variable gives a critical pressure value of 4. It is difficult which results in a higher pressure above a pore up.7) kPa.8) and (4. which is approx. were growing (Fig.5. is a pressure drop under the membrane as soon as oil flows through a few pores. e. there were still with increasing transmembrane pressure.act = (1. Although eral explanations why only a few pores were active. Although only 16 out of 100 pores active. During the experiments we observed that pores droplets detached.6.9 kPa.g.4). / Journal of Membrane Science 204 (2002) 125–137 expected that at a certain transmembrane pressure. The total oil flux through the membrane increased imately 3 times the critical pressure. therefore. By definition. to quantify the interaction ering the position of the active pores on the mem. the the dependency of the number of active pores on the critical pressure. Sugiura et al. line through all the measured data. 3. Presumably. However. running into a forming droplet. Because the cross-flow velocity is low.46 ± 0. If the absolute value is close to 1. We considered sev. because both the number of active pores and tive pores was below 20% [15]. after raising the (Table 2). which prevents other pores 3.7) kPa) ameter should become active at the same pressure. between pores having the same droplet formation brane. The transmembrane pressure can be described: critical pressure of a pore is defined as the pressure at which just a droplet starts to form at that pore. This value (5. After lowering the approximately the same droplet formation frequency pressure fewer pores were active. transmembrane pressure It should be noted that at the highest transmembrane pressure in the experiment (14 kPa). zation methods [24]. experiment was 30 × 10−12 m3 s−1 (2500 kg m−2 h−1 ) fect of the cross-flow. 0 implies no correlation at all. at which droplets formed.

1) (10.4). plained: at a higher transmembrane pressure more 10) (Fig.14 were found.40 0. this resulted in lower cross-correlations with each pore separately.6) (some of the the other active pores did not influence pore (10.7) 0.29 s (Table 2).39 0. Video images showed that ues between pores (3. This is caused by the irregular droplet formation at pore (7. the binary cross-correlations between pore Fig.8). which is located at the corner of the mem- distance between two pores. 1). 10). Therefore. Abrahamse et al. In the case of pores (3.D. Obviously.16 (10. Finally. Although pore (7.25 Both pores (7.34 0. standard deviation of the droplet formation time was small.7) and (10.34 s).40 0.16 0. it can cause these pores were too far away from pore (10.27 0.4). A.14 0.85 0.8) and (4. there was a bi.8) was found at a translation of binary interactions. / Journal of Membrane Science 204 (2002) 125–137 135 Table 3 Maximum cross-correlation value of each pair of pores Pore (3.7) was influenced by more than one other pore (ternary or higher order interaction). we found droplets detaching from pore (3.48 0. nary interaction between each pair of those pores. No interaction during de- age 0. Video ob- servation showed that the droplet formation at pore (7. droplet detachment The maximum cross-correlation value for the pair of at some pores is strongly coupled.26 0.33 0.1).8) and (4.39 0.48 (6.J.4) 0.80 0. under these conditions.28 0.6).10) 0. (3.85 or pores were active.4) (3.8) (4.1) were the biggest formed formation frequency. This can now be ex- droplets collided with droplets attached to pore (10.47 (3.5.27 0.4) and (3. area II: brane. Therefore. more data could have made the sult. No values higher than 0.54 0.28 0. time intervals (of 1. which means that droplets detached on aver.8) (7. Maximum cross-correlation value as a function of the (10.85 0.25 (10.34 0.33 (7.06 s later from pore (3. the cross-correlation val- ues with these pores were not high.1) be- results are also shown in Fig.26 0. In other words.72 0. As a re- size of the dataset.27 0.7) (10. (t form ) = 0. have occurred at a smaller droplet size.7).7) was close to other active pores. 10.8). 10) was around 0. the ternary or higher order interaction or no interaction. . correlation value (area I).29 0. Area I: binary interaction.20 0. Summarizing with Fig.8) 0.11 s) compared to the droplet formation time of 0.27 0. as we found for the pores (3. which means that droplets formed at regular indeed shows high maximum cross-correlation val. and all other pores were low.06 s.28 0.8) 0.4) than from pore (3.27 0. tachment or ternary or higher interaction result in low Note that the correlation between these three pores cross-correlation values (area II).28 0.14 0. sometimes these a decreasing droplet diameter.80 0. note the high S. and pore (10.72 0.20 0.27 0.54 (4. This is due to the limited were close together will have been bigger.1) were characterized by low cross-correlations.6) 0. so the chance that two active pores lower than 0. Furthermore.29 0.47 0. This was due to With increasing transmembrane pressure. 5d and e). this is shown by a high cross- 0.6) (6. 10. (3. steric hindrance and detachment of droplets will values somewhat more close to the extremes.1) 0.10) (3. be concluded that these pores had the same droplet The droplets formed at (10.

Colloid Interf. [15] S. perse even though the membrane had uniform pores. Kawakatsu. Jpn. [10] A. caused the emulsion to be polydis.A. minimum energy input. Regular-sized cell important effects. resulting from flow of oil through the porösem glas (MPG): vergleich der emulgiereigenschaften active pores. 1987. drop. Gaonkar (Ed. micro-engineered membranes will help clarify all the [12] T. Y. Taylor.W.B. We are grateful for a microchannel emulsification technique. microfiltration phenomena using microscope video system and silicon microchannels. PhD Thesis. Nakashima. R. 76 of pores were sometimes coupled. Am. cross-flow velocity. In this study.G. Clearly. Elsevier. emulsification to produce emulsions with the right [13] T. Trägårdh. [8] T. on the use and cleaning of the modules were obtained. vide a first quantification of the complexity of droplet [11] S. However. Sci. Articles of Porous Notwithstanding. Muschiolik. Nakajima. Surfactant effect on production of monodispersed microspheres by Acknowledgements microchannel emulsification method. Eng. D. Visualization of properties. the cross-flow channel side of the membrane. Schröder. Herstellen Von Öl-in-Wasser-Emulsionen pores increased linearly with the transmembrane pres. The distance between the pores should be J. Nabetani. our experiments show that to obtain mono. H. 46 come active. sure. S. G. Colloid Interf. Whalley. Chem. V. Eng. Joscelyne. M. Mit Mikroporösen Membranen. Y. Processing: Recent Developments. Kawano. J. the droplet detachment rates industrial scale manufacture. . Det. combined with the very low Processing of Food: a Challenge for Quality and Safety.C. collisions [4] S. literature review.C. Food pressure. in: A. References 4. Trans. Williams. Membrane emulsification—a cannot be prevented by this measure. Trans. lets formed only at a few pores. Applications of microporous glass membranes: low number of active pores and a low transmembrane membrane emulsification. the flux of the to-be-dispersed phase Glass and Process for Preparing the Same. Emulsionsbildung mittels mikro- the membrane. Morley. Abrahamse et al.J. was quite high (2. Dräger.M. R. Use of using a crossflow membrane.M. Milchwirtsch.J. Peng.M. Surf.136 A. ceramic membranes. Nakajima. AIChE J. M. 74 (1997) 317. Secondly. N.5 × 103 kg m−2 h−1 ). Tong. O. M. H. J. Kikuchi. even with a [9] K. Controlled produc- interacted through steric hindrance and collisions tion of emulsions using a crossflow membrane. 53. Conclusion [1] V. 6 November 1996. smaller droplets Aquamarijn. J. Effect of dynamic In this study of droplet formation at a uniform interfacial tension on the emulsification process using membrane we found two types of interactions which microporous. Amsterdam. Sci. Wheeler. unterschiedlicher molkenproteine. Inst. Behrend.). Part I: droplet formation from a single pore. Shimizu.J. Chem. Membr. can be prevented by using a membrane with a low [3] S. Joscelyne. 202 affected droplet formation at the membrane surface: at (1998) 334. Kandori. Seki. 169 (2000) 107. J. 227 (2000) 95. Nakajima. Schröder. M. Soc. / Journal of Membrane Science 204 (2002) 125–137 at a higher transmembrane pressure. 1999. Trägårdh. disperse emulsions. Chem. J. M. Sugiura. Inst. 39 (1999) 59. the advices of Cees van Rijn and Wietze Nijdam of Sci. and will also offer the possibility to creation in microchannel emulsification by visual micro- design the best possible system that can provide mild processing method. Houldsworth. de Heij. p. during this research. We think this is due to a pressure drop under [6] G. M. Due to steric hindrance the droplet size (1995) 1041. Food Eng. [14] J. M. The number of active [5] V. larger than the droplet diameter. S. we have attempted to pro. Steric hindrance (1998) 902. Kawakatsu. Eng. J. US 4 657 875. Schröder. Cologne. Y. Boom. 47 (2001) 1285. Kikuchi. Mechanical emulsification with decreased with an increasing number of active pores.A. Food emulsions using memb- rane emulsification: conditions for producing small droplets. G. Nakajima. M. Tong. Kikuchi. Preparation of monodispersed solid lipid microspheres using marijn microsieves and modules. Oil Chem. 3 (2000) 285. van der Padt. Schubert. droplets [2] R. 1995. Part II: downstream. Abrahamse. thus preventing the other pores to be. Williams. We would like to thank Stein Kuiper for the Aqua. Nabetani. 76 (1998) 894. In this way. Technische Hochschule Karlsruhe. Schubert. choosing a uniform membrane is Process fundamentals of membrane emulsification: simulation not sufficient. D.J. A. J.A. 29 (1996) 399. Dtsch. W. Controlled production of emulsions formation during cross-flow emulsification. porosity. with CFD. D. H. [7] H. in: Proceedings of the Minimal The interactions. Peng.

Preparation of food emulsions using a membrane [24] M. M. Dordrecht. Elwenspoek. Emulsification using microporous. Shimizu. M. PWS Publishers. Sci. J. J. emulsification system. Kuiper. using microporous. Membr. Basic Principles of Membrane Technology. W. Mine. 6 [17] S. A. Elwenspoek. Membr. Asano. W. H. Schröder. A: in: M. 113 (1996) 131. Colloid Surf. G. 2491. [22] V. 180 2000 Congress on Chemical Engineering ECCE1. 15. Tomita. Nakashima.C. Priestley.). Sotoyama. Priestley (Ed. Colloid Surf. 1986. Academic Press. p. A. [23] R. microporous glass membrane. in: Proceedings of the First European on a model membrane. in microfiltration: a simple single particle model tested ceramic membranes. Eng. 1991. Y.M. Sci. Schröder. Membr. Kuiper. Myers. H.J. B: Biointerf. Classical and Modern Regression with [19] R. Spectral Analysis and Time Series.C. K. C. (1996) 261. T. . London.B. 1981. / Journal of Membrane Science 204 (2002) 125–137 137 [16] S. Sci. Krijnen.H. Abrahamse et al. Physicochem. Mulder. J.J. Aspects 152 (1999) 103. Preparation and Development and applications of very high flux microfiltration stabilization of simple and multiple emulsions using a membranes. Nijdam. Nijdam. Schubert. ceramic membranes. Multivariate and multidimensional processes.J. C. 150 (1998) 1. M. [20] Y. Applications.J. Production of emulsions [18] M. Boston. Katoh.M.B. Schubert. van Rijn. M. van Rijn.M. Furuya. Determination of the critical pressure [21] V. Kluwer Academic Publishers.