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: 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

In conclusion. have a high h height of the cross-flow channel porosity but quite a thick membrane layer.act total number of active pores droplets formed at only 3–40% of the pores [5]. Np.6 × 10−6 (m2 ) ρ i .J. 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. Droplet formation at membrane surfaces was also studied by Greek letters the same author. . 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]. 1). 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].6 × 10−4 (m) feature is not favorable for a high throughput. However. pore size. the tubular microporous ceramic and glass mem- g gravity constant (m s−2 ) branes [8.5%. However. coalescence was shown [5]. membrane dp pore diameter (m) porosity and the viscosities of the fluids. For exam- fF Fanning friction factor ple. with- Xi .1 × 10−4 (m) factors (Fig. A high h height difference between the porosity is favorable for the throughput but not for the continuous phase vessels (m) droplet size.D. The second h = 2.126 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. we can say cross-section O = 2. these characteristics affect f droplet formation frequency (s−1 ) the obtained average droplet diameter too. standard deviation (m or s) ameter and the droplet formation time decrease [5.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. In an earlier study [10] we have shown hc. among other Dh hydraulic diameter D h = 5. / 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. Further.i (0) variance of droplet formation signal i droplet formation. At a higher surface porosity hc.out height of the outflow continuous the droplets could touch during droplet formation and phase vessel (m) possibly coalesce. 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 . but the pores themselves could not γ interfacial tension (N m−1 ) be seen.24 × 10−8 (m2 ) B help parameter (m) ddr droplet diameter (m) by the transmembrane pressure.9]. Schröder deduced that J oil throughput (kg m−2 h−1 or kg h−1 ) depending on pore size and transmembrane pressure. Moreover. since the geometry of µi mean of the droplet detachment signal i the cross-flow channel is rather different.11]. which are generally used. This n number of droplets formed low percentage of active pores is disadvantageous for O perimeter of the channel the overall productivity. In a system with capillaries in a bundle. Abrahamse et height of the inflow continuous that the membrane surface porosity should ideally phase vessel (m) not be higher than 1.1 × 10−2 (m) that there is a careful balance between the disperse pc continuous phase pressure (Pa) phase throughput and the emulsion droplet diameter.t value of signal i at time t out emulsifier.

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

Arrangement and numbering of the pores in the membrane.75 and 55 s of video was an- alyzed. acquired with The experimental setup is shown in Fig. which restricted the continuous (aqueous) phase passed through the mem.11 h. The pressure vessel was also cleaned with detergent and demineralized water.3. 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.3. Experimental setup Images with a magnification of 400×. a Zeiss Axioplan microscope. 2. the pressure was measured. After that. because the friction in the tubes was negligible compared to the friction in the module. The quency was 25 images per second. 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. 3. Each condition (Table 1) was recorded once. Maximum measurement errors were 4 ␮m for the droplet diam- eter and 0. module and pressure vessel were air dried.04 s (being the time between two images) for the time. the module was kept at a temperature of 50 ◦ C. / Journal of Membrane Science 204 (2002) 125–137 constant by a continuous overflow construction. ptrm = pd − pc = pd − ρc g(hc. Meanwhile.5 m was used. 3. the diameters of brane module due to a height difference between the the droplets detaching from the membrane were mea- in. Calculation methods 2.3.2. we used the following equations . Tubing. Experimental methods 2. 2. Hex. The fre- outflow of the vessel.1.1. a detergent solution (5– 10% Glorix® with hydrogen peroxide) was flushed through the tubing and the module (including the membrane).and outflow vessels. Visualization 2. At the Sony CCD video camera (type XC-77CI). cross-flow velocity. 2. 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. While replaying. depending on the droplet formation time and the width of the droplet size distribution.4. with demineralized water. both through the cross-flow channel and through the disperse phase inlet.4.3. scribed in literature. Sili- cone tubing with a total length of 2.3.128 A. per condition between 2. Wall shear stress at the membrane surface in the cross-flow channel (τ w ) Fig. Cleaning Before the experiments.out )/2. were recorded with a adecane was pressurized in a pressure vessel. 2.J. The pressure of the contin- uous phase in the module could be calculated in this + hc. the module and tubes were flushed for a day Fig. Experimental setup. Abrahamse et al.

017 7. in Fig.17 4 1.t − µ1 )(X2.64 0.028 7.028 5.77 0. In this equation µ1 and µ2 are means of the droplet 2.5  n aJ = ρ  d 1 (1/6)π ddr /(Am × time of the experiment).1 (0)R2. droplet formation frequency (f ). but contains the necessary information to let detachment signals are not completely random.act ) and oil throughput (J) for all experimental conditions v c (m s−1 ) ptrm (kPa) n ddr (␮m) S.71 1. (ddr ) tform (s) S. Because detachment pores at which droplets formed.36 5. To determine to which extent the detachment of From each resulting cross-correlation function. The calculation of the wall shear stress is only an ap- proximation of the shear stress on the droplets.9 0. R2.19 2 0.14 2. the active pore.4.D. 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.7 51 115 29 0.37 0.31 0.62 1. 4a Due to the imposed saw wave on the droplet and b).19 5 0.60 0.7 57 152 74 0.1 (s) was calculated (Eq. 4c. be.71 1.028 8. First.028 6.3 47 196 20 0. (ddr )).53 1. Abrahamse et al.03 7 0.3 0.9 55 179 71 0.0 0.38 3.3 62 149 50 0.1 0.D. (4)) [18]: 16 16ηc ρc vc Dh R2.77 3 0.0 133 125 48 0.32 2.56 5 1.01 s.5fF ρc vc2 = 8ηc (3) lation of signal 1 with regard to droplet detachment 2h signal 2 was discrete. (tform )). .05 7 1.5 0.6 50 172 76 1.1 (s) = cov(X1. 3 (see list of symbols): function ρ 2.09 0.1 (s) fF = = for Re = < 2300 ρ2.45 0.8 0. a saw wave function is obtained (Fig.50 1. the drop- formation. maximum cross-correlation and the translation at this correlation functions were calculated for each pair of maximum value were obtained.2.1.8 0.017 6. The trans- τw = 0.act Ja (103 kg m−2 h−1 ) (␮m) (s) 0.32 8 1.D.20 0. This signal does not exactly describe droplet formation functions experimentally found.6 53 125 20 0.9 58 155 40 0.5 0. This is explained linearly increases from 0 to 1 until a droplet detached.028 6.86 4 1.t+s ) cause in some cases the size of the droplets almost = E{(X1.37 0. The signal range of one period around s = 0.5 53 133 40 0.24 3.1 (0) and R2.55 0.23 7 0.J. the maximum cross-correlation value ap- For each pair of active pores the cross-correlation peared to be at least 0.8 72 134 35 0.46 0.028 7. number averaged droplet diameter (ddr and S.9 45 130 62 0. total number of active pores (Np.5 64 169 43 0.2 (0) are the variances 4A of both droplet detachment signals at translation 0 and Dh = ≈ 2h (2) O R2.59 1.028 9.1 0. In this way. calculate whether droplets detached at the same rates.29 3 2.00 5 1. droplet formation time (tform and S.t+s − µ2 )} (5) equalled the height of the cross-flow channel. 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. cross. respectively [18].69 0.78 1. X2.62 1. with steps of 0.t .039 7.D.49 0.19 1. / Journal of Membrane Science 204 (2002) 125–137 129 Table 1 Number of droplets formed (n).2 (0) (1) In this equation R1.1 (s) is the covariance of the two droplet detachment vc signals as a function of the translation s. the droplets from different pores was coupled. (tform ) f (s−1 ) Np. Therefore. A.011 7.2 0.1 (s) =  (4) Re ρc v c D h ηc R1.017 8. Cross-correlation detachment signals 1 and 2.37 7 1.3 0.4 21 221 14 2.039 8.2 0.9 0.017 5.09 6 1.34 0.

Thus. with conditions in different experimental setups. >80 [3]. and the emulsion is less monodis- perse than with a high wall shear stress (>30 Pa) [22]. which will be discussed further membrane is very thin. thus. droplet/pore pressure (ptrm in Pa). 3.039 m s−1 ). The images (Fig.8 kPa. 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 .130 A. the oil flux through the pores in the next sections. the droplet size of droplets with microscopy. 3. (c): cross-correlation function for droplet detachment at these pores at v c = 0. The first thing that attracts atten.011–0. Because the important phenomena.028 m s−1 . In experiments with single pores. Abrahamse et al. the cross-flow velocity varies. the droplet size and the droplet formation time. was 0. the droplet/pore diameter ratio was between 7 droplet diameter (ddr in m) on the transmembrane and 36. the experimental conditions in our setup were differ- For the conditions listed in Table 1. Results and discussion this ratio is also between 3 and 10 [2. 5). Droplet size This is in agreement with our results. p trm = 7. the dimensions times were calculated.4) and (b) pore (3. the Droplet sizes varied between 52 and 255 ␮m. the droplets were large compared to the pore diameter Concerning the dependency of the number averaged (7 ␮m). to be able to follow the formation tion is the large droplet size. it will be discussed that the droplets hindered the droplet/pore diameter ratio was found to be high. With such a low wall shear stress Finally. it was observed that droplets formed at had to be low.19–21]. Further.62 Pa at most. used. the we calculated the wall shear stress (Eq. 4.8).J. we found a significant linear diameter ratios of 3–10 were found [5. To compare the cross-flow velocity we only a few pores. However. which total oil flux through the membrane was calculated.1. was high. In the range of cross-flow velocities used (0. Next. Droplet detachment signals of (a) pore (3. the droplet ent from the experiments described in literature: the diameters were measured and the droplet formation cross-flow velocity was low. 10–30 [22]. velocity did not significantly affect the droplet size. (3)). / Journal of Membrane Science 204 (2002) 125–137 Fig.11] and in mem. each other sterically (Fig. besides. 5) show some of the membrane module were different. With the number of active pores.

A = (2. Droplet size distribution at other pores (Fig. should be obtained when using a uniform membrane.35–2. due to exper- 1. the total number uniform droplet size distribution. This was explained is generally accepted that monodisperse emulsions by the increased flux at a higher pressure. Abrahamse et al. ddr = −A ptrm +B.1 × process conditions are shown.5 ␮m). Droplet formation was hindered sterically by droplets forming 3. 5).3 ± 1. the polydispersity was not caused by coalescence. A. 6). 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. B = (3. in droplet formation at the individual pores.J.2. Measuring between 21 and 132 equation was obtained using the weighted least squares droplets revealed that the number averaged droplet method [23]. Schröder did not find sig. Peng and the number fractions per size class under several Williams showed that at high pressures (0. Although the droplet diameter distribution of each individual pore was quite nar- Direct observation of the droplet formation process row. In Fig. eter with increasing transmembrane pressure in our neither at the membrane surface nor in the bulk phase.028 m s−1 and ptrm = 7. The visualization showed that Section 3. Necessarily. phase of 0. which in. the detachment phase. 5.5–1. The droplet diameter was only (0.8 kPa. 6. insets in Fig. Although it ing transmembrane pressure [11]. The width of the size 105 Pa) the droplet diameter increased with increas. To study the non- each individual pore.5 kPa) in visualization experiments with single normally distributed for a few conditions.7) × 10−8 m Pa−1 . the data were weighted by the reciprocal diameter was between 115 and 221 ␮m. creases the final droplet volume during the second the emulsions show a high polydispersity and are not stage of droplet formation. further studies were . This imental limitations. classes was taken constant (17.3± of formed droplets was not very high. experiment can be explained by steric hindrance of the The polydispersity could be attributed to differences droplets.6. pores and with a bundle of capillaries [5]. on the transmembrane pressure and the cross-flow nificant changes in droplet diameter at low pressures velocity (Table 1).2) × 10−4 m. the average droplet diameter varied from pore gave information on the droplet size distribution for to pore (Table 2. / Journal of Membrane Science 204 (2002) 125–137 131 Fig. we will discuss that the decreasing diam. In normally distributed.028 m s−1 .

05 and 1. Table 2 Number of droplets formed (n).4 1.37 and 2.7) 22 146 19. Confirming our cross-flow velocities [11]. (d) v c = 0. (c) v c = 0.2 (6.6 (4.6 (10.60 0.5 (10.04 0. p trm = 5.D. Abrahamse et al. 6c and decreased with increasing transmembrane pressure Table 2).028 m s−1 and ptrm = 7.2 0.22 10. (tform ) (s) f (s−1 ) J (10−6 kg h−1 ) (3.0 1.6 ␮m at low could be seen at a certain pore. 7).11 2. 1). (ddr ) (␮m) tform (s) S.5–1 s with a capillary of the droplet (Fig. / Journal of Membrane Science 204 (2002) 125–137 Fig.5 kPa.2 0. 6. the droplet formation time significantly v c = 0. 3. (b) v c = 0.28 0.5 kPa [5].039 m s−1 .028 m s−1 .36 s.3 0.7 1.028 m s−1 and ptrm = 7. a2: pore (5. 8).13 0. ptrm = 7.1 s.86 0.08 0.8 0.6 . performed using the results of the process conditions expectation.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]. Droplet diameter distributions obtained at different conditions (number fraction of droplets per size class).86 0. 0.8 kPa pore n ddr (␮m) S. The start of droplet forma.3.34 0. c1: pore (3.6) 9 134 11. droplet formation but occasionally single droplets formed within 0. (Table 1).6 kPa. droplet formation time (tform and S.12 0.9 (3. p trm = 7.75 6. (tform )). under different conditions.028 m s−1 .8) 9 170 6.8) 11 90 8.1) 7 185 9.J.8 kPa. 4).6 Membrane 72 134 34.132 A.011 m s−1 .49 1.12 0.10) 5 130 14. droplet formation frequency (f ) and oil throughput (J ) for each active pore and for the whole membrane area at v c = 0.4) 9 88 0.06 1.10 0.D.92 0. Insets: droplet size distributions of individual pores (same scales as the total droplet diameter distributions).29 0.D.2 (7.9 kPa.D.86 3. frequency and lag time These droplet formation times have the same order of magnitude as earlier presented values: 1.88 6. in the order tion was defined as the moment at which a droplet of 1–2 s with a capillary of diameter 45. p trm = 7.8 kPa (Fig. (a) v c = 0. Droplet formation time. 2).53 30. a1: pore (1. with a pressure difference of 0. number averaged droplet diameter (ddr and S.24 1. c2: pore (3.77 0. (ddr )).4 1. The average droplet formation time was between 0.

8). 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. time. There- fore.4. the occurrence of this lag time was most pronounced at pores (4. / Journal of Membrane Science 204 (2002) 125–137 133 Fig.6) and (7. lag time and the time between the consecutive detachment of two droplets. the formation frequen. 8) and (4. Number of active pores and critical pressure Section 3.8 kPa. (3. 8. A. However. From the fact transmembrane pressure (Fig. Yet. 7. the diffusion time of a Fig.J. This is a result of steric hindrance of the droplets growing close to each other. . 4).028 m s−1 . 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.6) at the conditions Fig. it might be the case that after de- taking the reciprocal of the average time between the tachment the emulsifier is temporarily depleted. explanation is that the pore has to be refilled before a cies of pores (3. emulsifier had to diffuse to the interface to reduce the interfacial tension. which will be shown in 3.6) were very close. 7). Usually.8 kPa (Table 2). that all the pores had the same diameter. it could be Note that the droplet formation frequency is smaller than the reciprocal of the droplet formation time.7). This is caused by the fact that sometimes after detachment for a certain time no droplet formed (Fig. The droplet formation frequency varied from fier with the cross-flowing phase. Under the conditions v c = 0. were counted (Fig. The successive detachment of two droplets from a pore concentration has to be restored by supply of emulsi- (Fig. p trm = 7. However.6.028 m s−1 and p trm = 7. Droplet formation frequency of each pore as a function of v c = 0. The applied transmembrane pressure was too low to overcome the critical pressure to form a droplet with a clean interface (no emulsifier). Droplet formation at pore (4. Abrahamse et al. 7). The second possible pore to pore (Table 2). millisecond. the conditions. which is much shorter than the observed The droplet formation frequency was determined by lag times. 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. the number of pores at which one or more maximum droplet formation frequency increased with droplets formed. 9. 9). new droplet forms. indicating the droplet formation transmembrane pressure.

By definition. At a higher applied pressure more pores become active.8) and (4. there pressure) [3]. between pores having the same droplet formation brane. running into a forming droplet. Each time after changing pcrit = 4dp /γ the cross-flow velocity. Visualization showed that droplets forming at dif- which is the driving force for flow through the pores. to quantify the interaction ering the position of the active pores on the mem. Droplet–droplet interactions to become active.J. After lowering the approximately the same droplet formation frequency pressure fewer pores were active. the a ceramic 0. at a transmembrane pressure of 8. We considered sev. the droplet formation frequency increased. because both the number of active pores and tive pores was below 20% [15]. because mental conditions. the assumption that pores with the same di.5. It only at a few pores droplets formed under the experi- cannot be due to slow diffusion of emulsifier. to compare this result with literature. Although eral explanations why only a few pores were active. after raising the (Table 2). transmembrane pressure It should be noted that at the highest transmembrane pressure in the experiment (14 kPa). Table 3 . Also the ef.6). experiment was 30 × 10−12 m3 s−1 (2500 kg m−2 h−1 ) fect of the cross-flow. of pores was calculated. e.g. the the dependency of the number of active pores on the critical pressure.5 times the critical pressure. Consid. fective pressure = transmembrane pressure − critical sure of pores upstream very slight. increased.134 A. had others started to form droplets. there were still with increasing transmembrane pressure. this suggest that the pores become active at frequency.4 (±0. at which droplets formed.46 ± 0. agrees with the value calculated from the regression is the basis for some standard membrane characteri. The total oil flux through the membrane increased imately 3 times the critical pressure. other pores became active. The cross-correlation between each pair pressure again. which is approx. which prevents other pores 3. became inactive. However. is a pressure drop under the membrane as soon as oil flows through a few pores. Abrahamse et al. 0 implies no correlation at all. This value (5. therefore. branes with different pore diameters were used.4 ± 2. ferent pores sometimes touched each other while they increases. had the droplet size decreased with increasing transmem- the same results: below a transmembrane pressure of brane pressure. Presumably. Although only 16 out of 100 pores active. Oil throughput as a function of brane pressure and droplets formed only at a few pores. The results in Fig. line through all the measured data. 5).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.9 kPa. / Journal of Membrane Science 204 (2002) 125–137 expected that at a certain transmembrane pressure. being located near each other. were growing (Fig. for planation. During the experiments we observed that pores droplets detached. 3. because mem- stream of that forming droplet is not a satisfying ex. the cross-correlation ranges random. the number of active pores increased linearly with increasing transmem. 9 show again that the velocity the droplet formation frequencies can be considered did not affect the emulsification process. It is difficult which results in a higher pressure above a pore up. the maximum oil throughput in this Tween 20 is a relatively fast emulsifier. Np.7) kPa) ameter should become active at the same pressure. Because the cross-flow velocity is low. droplet started to form.act = (1. zation methods [24]. which affects the transmembrane pres.7) kPa.25) × 10−3 ptrm − 5. the total flux through the membrane 2. the percentage of ac.8 (±0.0 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 4.6. to be identical. Due to this steric hindrance. between −1 and 1. Sugiura et al. all pores should become active. It was observed that pores (3. while (3.4). 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. because the pressure difference. the critical pressure was de- termined by increasing the pressure from 0 until a In fact. If the absolute value is close to 1.

8) (7. This is due to the limited were close together will have been bigger. droplet detachment The maximum cross-correlation value for the pair of at some pores is strongly coupled. which is located at the corner of the mem- distance between two pores.D. have occurred at a smaller droplet size.8) 0.39 0. / Journal of Membrane Science 204 (2002) 125–137 135 Table 3 Maximum cross-correlation value of each pair of pores Pore (3. sometimes these a decreasing droplet diameter.29 0.7) 0.14 were found.47 0.1) were the biggest formed formation frequency.29 s (Table 2). Furthermore.26 0. Therefore. 10) was around 0.6).27 0.8) (4.28 0. standard deviation of the droplet formation time was small. more data could have made the sult. we found droplets detaching from pore (3. This is caused by the irregular droplet formation at pore (7.72 0.7) and (10.1) were characterized by low cross-correlations.4) and (3.28 0.80 0.4) (3.72 0.8) and (4.14 0. the cross-correlation val- ues with these pores were not high.4).6) (6. Maximum cross-correlation value as a function of the (10.4) 0. be concluded that these pores had the same droplet The droplets formed at (10.27 0. nary interaction between each pair of those pores.40 0. 10). Finally.26 0. In other words.06 s.8) was found at a translation of binary interactions.6) (some of the the other active pores did not influence pore (10.29 0.20 0. (3.8) and (4.33 (7.28 0.34 s).48 0.06 s later from pore (3.7) was influenced by more than one other pore (ternary or higher order interaction). No values higher than 0.25 Both pores (7.10) 0.33 0. Video ob- servation showed that the droplet formation at pore (7. Therefore. Although pore (7. which means that droplets formed at regular indeed shows high maximum cross-correlation val. tachment or ternary or higher interaction result in low Note that the correlation between these three pores cross-correlation values (area II).25 (10.34 0. Summarizing with Fig. and all other pores were low.27 0.8).85 or pores were active. under these conditions.4) than from pore (3. Abrahamse et al.34 0. This was due to With increasing transmembrane pressure. the ternary or higher order interaction or no interaction.1) 0. which means that droplets detached on aver.47 (3. note the high S.27 0.1) be- results are also shown in Fig.4). Obviously. time intervals (of 1. (t form ) = 0. it can cause these pores were too far away from pore (10.28 0. A.16 0.54 0. so the chance that two active pores lower than 0.11 s) compared to the droplet formation time of 0. plained: at a higher transmembrane pressure more 10) (Fig. as we found for the pores (3.7) (10.85 0.16 (10. this resulted in lower cross-correlations with each pore separately.80 0. As a re- size of the dataset.7) was close to other active pores.J. area II: brane.85 0.48 (6. 5d and e). This can now be ex- droplets collided with droplets attached to pore (10.7). there was a bi. this is shown by a high cross- 0.54 (4.8) 0. Video images showed that ues between pores (3. Area I: binary interaction.1) (10. 1).6) 0.40 0.8).10) (3.27 0.5. the binary cross-correlations between pore Fig. No interaction during de- age 0. 10. and pore (10. steric hindrance and detachment of droplets will values somewhat more close to the extremes. correlation value (area I). (3.27 0.14 0.1).39 0. .20 0. 10. In the case of pores (3.

202 affected droplet formation at the membrane surface: at (1998) 334. M. D. Surfactant effect on production of monodispersed microspheres by Acknowledgements microchannel emulsification method. Controlled production of emulsions formation during cross-flow emulsification.A. sure.G. Conclusion [1] V. van der Padt. O. Part I: droplet formation from a single pore. Eng. Secondly. G. Mit Mikroporösen Membranen. Nakajima. J. Herstellen Von Öl-in-Wasser-Emulsionen pores increased linearly with the transmembrane pres. Tong.J. in: A. can be prevented by using a membrane with a low [3] S. cross-flow velocity. Part II: downstream. Due to steric hindrance the droplet size (1995) 1041. Schröder. Abrahamse. disperse emulsions. G. R.J. Shimizu. PhD Thesis. Abrahamse et al. Dtsch. choosing a uniform membrane is Process fundamentals of membrane emulsification: simulation not sufficient. Chem. Technische Hochschule Karlsruhe. Chem. emulsification to produce emulsions with the right [13] T. 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. the droplet detachment rates industrial scale manufacture. H. Membr.B. Muschiolik. Nabetani. However. In this study. Steric hindrance (1998) 902. lets formed only at a few pores. Food pressure. Sci. Surf. smaller droplets Aquamarijn. 1987. H. Articles of Porous Notwithstanding. 53. 74 (1997) 317. we have attempted to pro. Food Eng.M. We think this is due to a pressure drop under [6] G. vide a first quantification of the complexity of droplet [11] S. 29 (1996) 399. Kawakatsu. The distance between the pores should be J. our experiments show that to obtain mono. Y.J. Morley. Inst. Seki. p. unterschiedlicher molkenproteine. ceramic membranes. Food emulsions using memb- rane emulsification: conditions for producing small droplets. J. Use of using a crossflow membrane. caused the emulsion to be polydis. Applications of microporous glass membranes: low number of active pores and a low transmembrane membrane emulsification. Controlled produc- interacted through steric hindrance and collisions tion of emulsions using a crossflow membrane. Peng. 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. S.). M. Trans. Processing: Recent Developments. 76 (1998) 894. Sci. Eng. Trans. micro-engineered membranes will help clarify all the [12] T. Jpn. 1995.M. Colloid Interf. H. Joscelyne.J. [14] J. Amsterdam. Kikuchi. Clearly. . Schubert. Mechanical emulsification with decreased with an increasing number of active pores. Kikuchi. Det. In this way. [8] T. 227 (2000) 95.136 A. Milchwirtsch. M. V. / Journal of Membrane Science 204 (2002) 125–137 at a higher transmembrane pressure. Am. Soc. 3 (2000) 285. 1999. J. Kawano. larger than the droplet diameter. Chem. in: Proceedings of the Minimal The interactions. porosity. Visualization of properties. Joscelyne. Houldsworth. US 4 657 875. 47 (2001) 1285. Peng. Y. [15] S. perse even though the membrane had uniform pores. Elsevier. J. Inst. Nakashima. We are grateful for a microchannel emulsification technique. even with a [9] K. Regular-sized cell important effects.W. Boom. the advices of Cees van Rijn and Wietze Nijdam of Sci.C. M. D. Emulsionsbildung mittels mikro- the membrane. droplets [2] R. Colloid Interf. Membrane emulsification—a cannot be prevented by this measure. Kandori. Gaonkar (Ed. [7] H. Schröder. Taylor. References 4. during this research. combined with the very low Processing of Food: a Challenge for Quality and Safety.M. S. R.C. AIChE J. Whalley. Trägårdh. the cross-flow channel side of the membrane. collisions [4] S. Nakajima. Williams. Schubert. M. 76 of pores were sometimes coupled. Cologne. drop. Preparation of monodispersed solid lipid microspheres using marijn microsieves and modules.A. literature review. Behrend. de Heij. Trägårdh. J. 6 November 1996. J. 39 (1999) 59. M. microfiltration phenomena using microscope video system and silicon microchannels. Tong. Nabetani. Kawakatsu. Y. Sugiura. Nakajima. 46 come active. on the use and cleaning of the modules were obtained. Schröder. the flux of the to-be-dispersed phase Glass and Process for Preparing the Same.A. with CFD. J. We would like to thank Stein Kuiper for the Aqua. A. D. Eng. W. M. Williams. minimum energy input. thus preventing the other pores to be. M. Nakajima. 169 (2000) 107.5 × 103 kg m−2 h−1 ). Wheeler. resulting from flow of oil through the porösem glas (MPG): vergleich der emulgiereigenschaften active pores. Kikuchi. Dräger. [10] A. N. Oil Chem. The number of active [5] V. was quite high (2.

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