SPE 37291 Society of Petoloum Engineers Effects of Chemical Heterogeneity and Roughness on Contact Angle Hysteresis : Experimental Study and Modeling M. Robin, SPE, A. Paterson, L. Cuiec, SPE, C. Yang, Institut Francais du Pétrole, ony 57, Sec ot Peni Ege “Wi ppm me sep patina he 187 SPE horse Symposia on as ‘Suey hn Ree, Tc Feo wees Srtted ansible ty he sob). San oe paper a Fret, av ton oes by he Sosa 9 Pena Eg eS Econ osu) Tera pei owe aera ar Pt, Abstract Wettability is an important parameter for oil recovery effi- ciency ; and its heterogeneity character is more and more considered for actual oil reservoir rocks. This paper describes an experimental study through con- tact angles measurement of the influence of the density and spatial distribution of chemical heterogencities, as well as roughness on water/oil wetting. This influence has been demonstrated, and a suitable model has been build. Introduction This paper describes an experimental study of the influence of the density and of the spatial distribution of chemical hetero: ‘gencitis, as well as roughness, on wetting phenomena, Chemical heterogeneities were cteated by using a photo- sensitive resin and applying a micro lithography technique {afer spreading on a glass slide, resin is hardened by heating = oilwet areas - and exposed to UV light through a mask ~ water-wet areas) ‘We have worked with a series of heterogeneous substrates such as horizontal or vertical stripes, checkerboard pattern and small circular oil wetting defects on a water-wet substrate (class) with increasing density. Dynamic contact angles were measured by the Withelmy technique and modeling was per- formed"* This study has been completed by an analysis ofthe effect of roughness and of the influence of spatial distribution of heterogeneities, at a given coverage rate. 715 Experimental Withelmy plate technique. The contact angle was evaluated by measuring the force exerted by a fluid/fuid interface on a solid surface as the latter moves across the interface (immersion and emersion cycles). At any time, the measur force F has three components: weight ofthe slide, buoyancy, and vertical component of te interfacial teasion F = Weight + Pauoyancy +1: ¥-€08@ where 7 denotes the interfacial tension, 1 the length of the triple tine and @ the angle between the interfacial force and the vertical plane The experimental set-up consists of a Mettler AT250 bal- ance (0 - 52g + 10 ug) and a step-by-step motor (I step = 0.1 tum), driven by a frequeney generator. The device allows ver- tical displacement of 10 cm at variable speed with a resolu- tion of 0.1 um. A speed of 0.03 mnvs was used in most cases. The force is measured vs. sample postion. Spatial distribution of heterogeneities. For a given cover- age rate, two spatial distributions of defects were used in order to modify the geometry without changing the "global average wettability" * a uniform distribution, for which the surface is divided into squares. A single defect takes place inside each square. ‘The center of gravity is chosen randomly inside this square. ‘This distribution looks very homogencous (figure la), ‘¢ a more random distribution where the coordinates of the center of gravity of each defect (same size as previously) are randomly chosen on the surface (figure 1b), Roughness. A low surface energy solid (PTFE) was used in the present study. Such a solid is well suited for the investi- gation of several aspects of the wettability problem (Morrow and Mungan’). Specially PTFE pieces were designed to study the effect of roughness on contact angle hysteresis. ‘They were made up of several co-centric cylinders, as shown, in Figure 2.2 M ROBIN, A. PATERSON, L. CUI shi 37291 “.C.YANG Results Influence of chemical heterogencities. Experiments were done with the two types of heterogeneous surfaces previously described. For each type, different coverage rates have been investigated, varying between 10% and 60%. It is possible to plot for each type of distribution the ad- vancing and receding contact angles as a function of the cov- crage rate, Uniform distribution presents larger advancing and receding contact angles than random distribution which ap- proximately follows Cassie theory (figure 3) For increasing coverage rates, surfaces become mote oil wet, which is quite normal, Values start from values close to the ones obtained on glass (resin partially destroyed by UV light) towards the ones obtained for the resin. ‘The two distributions present a different behavior, and uniform distribution behaves globally as more oil-wet, Modeling, The model is made of small patches, which ae distinguished by geometry and chemical heterogeneity Within cach patch, the surface is homogeneous, molecularly smooth, isotropic, and rigid. When the surface of ‘these patches is wetted by a liquid, in presence of another liquid, the condition of Young's equation is satisfied, ie, there is a determined unique contact angle for each patch. The patches intersect at geometric lines ‘Neumann and Good! have pointed out the fact that at a geometric boundary between two petches on a smooth solid, having different surface free energies and intrinsic contact angles for a particular liquid, the contact angle is not a uniquely defined property. The same is true with respect to the ine in which two plane surfaces geometrically intersect. Modeling consists in studying the equilibrium ofthe wet- ting line as it moves across the sample surface. On the surface of each patch, the wetting line moves uniformly with a con- stant contact angle defined by Young's equation. This is also true, in the case of a rough surface, as far as the triple line remains the only contact between the water/oil interface and the sample, Ata boundary, the wetting line either will jump or be pinned according to the movement direction and the relative wetability ofthe two patches Two altematives can take place when the wetting line en- counters a boundary (a chemical one or geometric one) + either the wetting lin shifts to reach a new equilibrium angle corresponding to Young's condition, and hence is equal to the intrinsic contact angle of the next patch (in the direc- tion of motion). + of the wetting line is blocked, in which case energy aust be supplied to deform the meniscus, by the displace- mont of the fluid uid interface ‘The model developed applies the equilibrium test to each step in the movement. The height of the meniscus is calou- Inted using the Laplace equation. “The displacement ofthe fuid/fuid interface is thus simu- lated along the heterogeneous solid surface. At each position ofthe interface, the local contact angle atthe wetting line is calculated, together with the force exerted, the work of ade- sion, and the wetting and de-wetting works 716 Influence of roughness. PTFE surface is oil-wet, so 180° ‘was taken as the intrinsic contact angle of the surface for the simulation. Figure 4 shows the evolution of contact angles versus the immersion position, It is seen that the simulation is in good agreement with the measurement. Differences come essentially ftom oil trap- pping in the comers as the interface is raised. (Figure 5.) during the displacement, the meniscus traps the oil in the comers as coinciding the next upper band. In order to reduce the trapped oil, we have designed piec with the surfaces having a tilting angle of +30° (Figure 2) ‘The results of the simulation are compared to the experiments on Figure 6: The effects of the trapped oil are obviously lightened, but not eliminated. Some values of computed angles corresponding to differ- ent shapes and size of roughness (h) are given on figure 7 In summary, the modeling is found to be well consistent with the experimental measurements, Conclusions © A reproducible technique has been developed to build surfaces presenting wettability heterogencity with a good spatial resolution. Geometry, spatial distribution and cover- ‘age rate of the surface by the defects are very well controled. + Two differen: distributions of heterogeneities of wettabil- ity have been studied. In the case of random distribution, it ‘has been shown that spatial distribution is a very important parameter. For a completely random distribution, the meas- ured contact angles almost fit the ones predicted by Cassie. In the case of a uniform distribution, the measured contact an- gles increase faster with the coverage rate of the surface + The proposed model is satisfactorily consistent with the experiments, This model helps to understand the hysteresis of contact angle due by chemical heterogeneity or/and surface roughness, ‘© This modeling clearly demonstrates that both chemical heterogeneity and roughness have significant effects on con- tact angle hysteresis. This is all the more true as the dimen- sion of the chemical heterogeneity or/and roughness becomes very small - which is the case for reservoir rock porous me- dia. Itcan be expected that, in the case of reservoir rocks, the contact angle within the pore space will exhibit a greater hysteresis than the one observed for a smooth surface. The surface roughness and the chemical heterogeneity due to ad- sorption/deposition of polar material and organic matter, will bbe an important resistance to the waterflooding recovery proc- ences T ROBIN, M, KOCI X,, “Wetsbility Heterogencities On Planar Minerals : Application To Reservoir Rocks". Proceedings of the 3" International Symposium on Evaluation of Reservoir Wettability and Its Effect on Oil Recovery, Laramie, WY, sept, 1994,SPE37291 EFFECTS OF CHEMICAL HETEROGENESTY AND ROUGHNESS ON CONTACT ANG EXPERIMENTAL STUDY AND MODELING. HYSTERESIS 3 2 PATERSON, A. ROBIN, M., FERMIGIER, M.,JENFFER, P. 3. MORROWN.R., MUNGAN, N, *Mouillabilité ot capillarité ang HULIN, J.P. "Effect of Density and Spaial Distribution en mieux poreux", Revue de institut Francais du Pérole, ‘of Wettabilty Heterogencites on Contact Angle". Proceed- (1971) 26, 629. ings of the 4" Intemational Sympostum on Evaluation of Reservoir Wetabilty and Its Effect on Oil Recovery, Mont 4 NEUMANN, A.W.,GOOD,R. J.J Coloid & inter. Se pele, Franes, sep. 1956 (1972) 38, 341 Figure 1 : Uniform (a) and random (b) distributions used to study Figure 2 : Example of co-centric cylinders used to study the effect the effect of chemical heterogeneities. of roughness. comerage rae) Figure 3 : Advancing and receding contact angles as a function of the coverage rate for different distributions. Fore (a iarsondaptven Figure 4 : Comparison of simulation with measurements for a specially designed piece made up of several co-centric cylinders as shown above in figure 2a, n7M. ROBIN, A. PATERSON, L CUIEC, C. YANG SPE 37201 Figure 5 : Oil trapped in the comers as raising the interface. Forcelg Immersion depth/em Figure 6 : Comparison of simulation and measurement for a piece made up of co-centric cones (figure 2b), tilting angles of surface are +30°, h=Smm, (1) calculated forces by simulation, (2) measured forces at 0.18 mm/min, (3) measured forces at 1.8 mm/min, ‘Telangular roughness (45 degrees) Local contact angle = 180 degrees — b-omm —— b+ 08 mm b+ 1.0mm, —— 2+50mm —— Square b= 5.0mm Displacement (em) Figure 7 : Computed angles for different shapes and size of roughness. 718