Numerical approach to predict wetting and catalyst efficiencies inside trickle bed reactors

Computational fluid dynamics is used to describe both wetting efficiency in simple configurations of stacked solid particles and catalyst efficiency inside such partially wetted catalyst particles. The volume of fluid (VOF) model used to describe hydrodynamics leads to realistic and promising results for surface wetted ratio. Catalyst efficiency simulations have been performed for different shapes of particles and different Thiele modulus values for a first order reaction rate. Results show that for all the shapes studied, catalyst efficiencies of partially wetted particles can be calculated by simply using a modified Thiele modulus defined as ratio of the actual Thiele modulus $\phi$ to the wetting efficiency f.     

Effects of wetting hysteresis on pendular liquid bridges between rigid spheres

The effects of wetting hysteresis on the properties and behaviour of pendular liquid bridges between spherical particles have been investigated both experimentally and theoretically. A thermodynamic analysis shows the existence of metastable states that would account for the observed pinning of the three-phase contact line. The most important findings, with respect to the role of capillary interactions in agglomeration processes, are that (a) some of the kinetic energy of “wet” agglomerates may be dissipated during collisions by such hysteresis, (b) the bridge rupture distance is increased and (c) pinning will result in a maximum in the force–separation characteristics.     

固体表面温度对冻结液滴的相变过程与表面润湿特性的影响

通过液滴可视化实验,发现并归纳了冻结液滴在不同基底温度下于铝板表面融化过程的动态表面润湿特性,结合力学分析,总结了液滴润湿面积、体积、接触角等润湿参数与相变时间之间的变化规律。实验结果表明：液滴的润湿性主要受重力、表面张力、热毛细力的影响,重力对液滴的横向扩散促进作用、表面张力与热毛细力受底板温度影响具有抑制液滴润湿过程的作用;两种不同条件下,冻结液滴高度变化规律相同,随着融化的进行,液滴高度骤降,然后缓慢降低;不同冻结条件下,冻结液滴的润湿过程主要发生在融化初始阶段,重力促进液滴的润湿过程,液滴接触角处于65°～85°之间,而在润湿后阶段,接触角减小,重力的作用减弱,表面张力的作用增强,液滴的扩散进程受阻,体积下降的趋势也变缓;不同升温条件下,冻结液滴的润湿过程几乎没有发生,热毛细力与表面张力在润湿过程中占据主导性,随着基底温度的升高,液滴内部与三相线温差逐渐增大,Ma数呈增加的趋势,数值由1802增至22876,热毛细力始终抑制液滴的运动。     

DC-assisted rapid wetting of 3Y-PSZ by molten 72Ag–28Cu and its application in joining

The effects of current polarity, temperature and current intensity on the wettability of 3 mol% yttria-partially stabilized zirconia (3Y-PSZ) by molten 72Ag–28Cu were investigated using a direct current (DC)-coupled sessile drop method. The wettability was significantly improved with the assistance of a DC, especially when 3Y-PSZ was connected to anode. Noticeably, the contact angle rapidly decreased from 143° to smaller than 20° when the current intensity was larger than +10 mA. The wettability also showed abnormal dependence on temperature, presumably due to the competition between nucleation and growth of the m(AgCu₄Zr) phase at the interface. The mechanisms for the significant improvement in the wettability under the DC application were ascribed to the formation of substoichiometric ZrO_2-δ, the release and adsorption of metallic Zr, and the formation of wettable m(AgCu₄Zr) phase at the interface. The DC-assisted wetting provides a new strategy for the rapid and robust joining of 3Y-PSZ to metals.     

Partial wetting in trickle bed reactors — the reduction of crotonaldehyde over a palladium catalyst

The behavior of a trickle bed in which the catalytic packing was incompletely wetted was investigated using the selective hydrogenation of crotonaldehyde to n-butyraldehyde as a model reaction. The reaction was carried out at near ambient conditions using palladium deposited on porous alumina pellets as the catalyst. It was found that even when the extent of wetting was large, reaction taking place on the dry parts of the catalyst largely dominated the overall reaction rate.     

Reactive wetting behavior and mechanism of AlN ceramic by CuNi-Xwt%Ti active filler metal

In order to propel the application of the developed CuNi-Xwt%Ti active filler metal in AlN brazing and get the universal reactive wetting mechanism between liquid metal and solid ceramic, the reactive wetting behavior and mechanism of AlN ceramic by CuNi-Xwt%Ti active filler metal were investigated. The results indicate that, with the increasing Ti content, surface tension for liquid CuNi-Xwt%Ti filler metal increases at low-temperature interval, but very similar at high-temperature interval, which influence the wetting behavior on AlN ceramic obviously. CuNi/AlN is the typical non-reactive wetting system, the wetting process including rapid wetting stage and stable stage. The wettability is depended on surface tension of the liquid CuNi filler metal completely. However, the wetting process of CuNi-8wt.%Ti/AlN and CuNi-16 wt%Ti/AlN reactive wetting system is composed by three stages, which are rapid wetting stage decided by surface tension, slow wetting stage caused by interfacial reaction and stable stage. For CuNi-8wt.%Ti/AlN and CuNi-16 wt%Ti/AlN reactive wetting system, although the surface tension of liquid filler metal is the only factor to influence the instant wetting angle θ₀ at rapid wetting stage, the reduced free energy caused by interfacial reaction at slow wetting stage plays the decisive role in influencing the final wettability.     

Experimental investigation of the effects of different chemical absorbents on wetting and morphology of poly(vinylidene fluoride) membrane

Membrane wetting is of one the most important factor that affects the CO₂ absorption efficiency in membrane contactors due to the increase of mass transfer resistance. In this study, the effects of different absorbents on the wettability of poly(vinylidene fluoride) membranes were investigated. Four absorbents including monoethanolamine, potassium carbonate–piperazine (PZ), potassium carbonate–monoethanolamine, and methyldiethanolamine–PZ were applied to investigate the effects of different absorbents on membrane wetting. Membrane properties before and after contact with absorbents were investigated using methods of thermogravimetric analysis, Fourier transform infrared spectroscopy, electron scanning microscope, and contact angle measurements. The results revealed that methyldiethanolamine and mixed absorbents containing methyldiethanolamine caused the most morphological changes in membrane. The results showed that reduction percentages of contact angle for water, K2CO3/PZ, K2CO3/MEA, MEA, and MDEA/PZ solutions were 14.52, 16.9, 21.19, 23.7, and 28.33, respectively, after 30 days immersion. The results also showed that potassium carbonate–PZ solution caused the least change in membrane wettability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45543.     

Effect of dopants on wetting properties and electrochemical behaviour of graphite anodes in molten Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-cryolite melts

The effects of anode dopants and alumina bath content on the wetting properties of the anode/bath interface in an aluminium electrolysis cell have been investigated in this study. Increasing the wettability of the carbon anode maximises the anode surface area and prevents a sudden increase in current density that polarises the anode leading to the discharge of fluoride ions and the onset of anode effect. From the contact angle measurements presented in this study, it is clear that the presence of carbonate salts inside and at the surface of the substrate greatly increases the wettability of the graphite substrate/cryolitic melt interface. The higher the carbonate salt content of the substrate, up to a dopant levels of 6 wt%, the better the wetting properties. Furthermore, alumina appears to act as a surface-active component when present in the electrolyte in contact with a pure graphite anode, but these properties diminish when carbonate is present in the anode.     

Patterned polymer surfaces with wetting contrast prepared by polydopamine modification

Patterned polymer surfaces with contrasting wettability are prepared by polydopamine (PD) modification. The fabrication process involves spraying dopamine solution droplets on hydrophobic polymer surfaces and PD deposition derived from the oxidative polymerization of dopamine. Each dopamine solution droplets functions as microreactor leading to the formation of patterned PD thin films on the solid/liquid interfaces. Multiple kinds of polymer substrates, including polypropylene, polystyrene, polycarbonate, polyethylene and polytetrafluoroethylene, are endowed with PD patterns using this method. Two types of wetting behaviors are achieved in relation to the micro morphology of the substrates. If smooth or porous substrates are used, the as‐formed film exhibited hydrophilic‐hydrophobic pattern. When a hierarchical‐structured film is used, the uncoated and coated regions have similar static wettability but different dynamic wetting behavior. This PD modification method is also proved to be suitable for flexible and curved surfaces. The results along with the fact that PD could deposit on virtually any surfaces makes this method find wide practical applications in many fields. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41057.     

Numerical simulation of the wire‐pinning process in PET film casting: Steady‐state results

Poly(ethylene terephthalate) (PET) film casting involves melt flow through a slot die, across a small span, and onto a fast moving quench drum. In the “wire‐pinning” casting process, a thin electrified wire close to the line of contact with the drum creates a strong pinning force that delays air entrainment to higher line speeds. Nonuniform wetting of the die lips by the extruded melt is thought to be responsible for the formation of streaks, a defect in the machine direction. A finite element model of the film casting process with wire pinning was developed to assist in understanding what causes significant wetting of the lips and whether this can be avoided by electrostatic pinning. The solution of the governing equations provide the location of the static and dynamic contact lines, thus finding the wetting and pinning points in the process. The simulations investigate the sensitivity of the static wetting line locations on the die lands to the imposed values of static contact angle and die‐lip gap. It was found that while the contact angle has a small effect on the extent of die‐lip wetting within the parameter ranges examined, there is a considerable chance that the feed slot surfaces can be dewetted. This seems to be the greatest danger for causing streaks rather than excessive wetting of the die lands. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Reactive wetting and interfacial characterization of ZrO2 by SnAgCu-Ti alloy

The reactive wetting behavior of zirconia with SnAgCu-x%Ti (SAC-x%Ti, wt%, x?=?1, 4) alloy was investigated via the sessile drop method in isothermal experiments. As temperatures elevated, the final contact angle decreased and the minimum contact angle of 21° and 7° were obtained at 1000?°C for SAC-1%Ti and SAC-4%Ti droplets, respectively. Kinetic calculations indicated that the spreading of SAC-Ti droplets on zirconia was controlled by interfacial reaction and the wetting activation energy was 108.8?kJ/mol. The reaction products distribution and morphology in droplets were influenced vastly by the addition of Ti. Along with the increase of Ti content from 1% to 4%, a great deal of Ti-Sn intermetallic compounds (IMCs) were generated in droplets, thereby the outline of droplets were transformed from hemispherical into similar trapezoidal due to the limited spreading and fluidity of droplets. Owing to the interfacial reaction between active elements Ti and zirconia and the subsequent formation of the Ti-O layer, the wettability of SAC-Ti/zirconia was greatly promoted. According to transmission electron microscopy (TEM) analysis, the thin Ti-O reaction layer consisted of the Ti₂O, Ti₄O₇, Ti₇O₁₃ and TiO₂ phase.     

Particle-assisted dynamic wetting in a suspension liquid jet impinged onto a moving solid at different flow rates

We provide evidence that the introduction of solid spheres assists the dynamic wetting in suspension jet flows. The onset velocities of air entrainment in the suspension were measured and compared with those in the filler-free fluids to directly access the particle-assisted dynamic wetting. The measured onset velocity increased with increasing the particle contents at Re<20 where the dynamic contact line is located beneath the impinging liquid. The variation in the onset velocity agrees with a simple lubrication theory based on the film-splitting hypothesis. However, the onset velocities of air entrainment become independent of the particle contents at Re>20, higher liquid viscosities or increased jet lengths, showing different air entrainment behaviors from other low-Reynolds number coating flows.     

Solid-liquid contacting effectiveness in trickle bed reactors

Internal and external effective wetting of a porous catalyst in a trickle bed reactor was considered. Experimental tests were carried out based on the analysis of the response curves of the reactor to a step decrease of the tracer inlet concentration.The pore filling of the catalyst pellets was practically total even at very low liquid flow rates, probably due to capillarity.The external effective wetting was interpreted in terms of an apparent internal diffusivity (D_i)_app, determined on the basis of a model which assumes a total external wetting of the catalyst. The values of (D_i)_app increased with the liquid flow rate, tending to the actual internal diffusivity D_i determined in a full reactor. The found values of (D_i)_app/D_i were used to interpret the ratio of the apparent kinetic rate constant determined in a trickle reactor k_app and that for a totally wetted catalyst k_v.The calculated values agree substantially with those proposed by Satterfield[3] from kinetic tests.     

A new method for the characterisation of the wettability of powders

The wetting characteristics of fine powders play an important role in a variety of processes. The most important way of characterising the wettability of a fluid/fluid/solid system is to measure the contact angle. This paper describes a relatively simple method for the determination of the contact angle on powdery materials. The technique involves the measurement of the dynamic contact angle which is formed when a liquid drop is placed on a horizontal porous surface. On the basis of the measured dynamic contact angle as a function of time an “apparent” static contact angle has been defined, which gives a measure of the wettability of porous solid systems by analogy with the wetting of non-porous solids. Determinations with glass beads and NaCl-powders as the test materials indicate that the measured value depends on the particle size of the powder, the porosity and the temperature. It was concluded that the capillary penetration of the liquid droplet into the porous media itself influences the wetting characteristics.     

表面活性剂在多孔介质中的润湿与洗油效率

本文依据物理界面层模型讨论了表面活性剂溶液的润湿现象,提出了润湿系数表征表面活性剂在多孔介质孔隙表面的润湿能力,并研究了润湿系数的计算方法。以十二烷基苯磺酸钠溶液为例,研究了表面活性剂溶液在多孔介质中的润湿性。在非超低界面张力条件下,实验验证了表面活性剂溶液的界面润湿性改善石油采收率的能力,实验结果表明表面活性剂在多孔介质中的润湿性对洗油效率起着重要作用。     

Refinement of solid layers via wetting on homogeneous lyophilic surfaces

Surface control additives (SCAs), or surfactants, can obstruct the wetting of liquid films on lyophilic surfaces even though they lower surface tension. In this work, this unusual behavior was used to decrease the widths of printed organic and nanoparticle lines on different homogeneous surfaces. A decrease in line width accompanied a change in its cross section. The ability of a SCA to decrease the line width was correlated with contact angle but not the surface tension of the solution. Line refinement was consequently attributed to an increase in contact angle. Because there were no reports that surfactants increased contact angles, the mechanisms to increase contact angle were discussed in static and dynamic terms. First, Owens and Wendt’s theory revealed that contact angle changes depended on SCA-induced modification of polar and dispersive interfacial components. However, a definitive increase in contact angle could not be deduced from this theory alone. Second, the effect of solutal Marangoni forces induced by the SCAs on contact angle was discussed by considering the wetting behaviors of binary solvents. SCA concentration dependence of surface tension at higher than the initial SCA concentration correlated well with the ability of the SCA to decrease line width.     

Advancing and receding contact lines on patterned structured surfaces

An experimental investigation of advancing and receding contact lines on patterned surfaces was performed in a controlled environment. Hydrophobic polymers were used to create patterned surfaces to mimic defects and the working fluid was water. Surfaces were prepared with holes or pillars every 200 μm and depth/height from 1 to 11 μm. An optical technique was used to measure contact angle. On smooth (control) surfaces, an advancing or receding contact angle was observed. On the patterned surfaces, pinning and depinning at the defects (holes or pillars, respectively) was observed, with advancing or receding contact lines occurring between these depinning/pinning events. The observed pinning/depinning phenomenon of the contact line was investigated to demonstrate the dynamics of the contact line motion over rough surfaces for a small range of contact line velocity. The competition between the Young unbalanced force and the anchoring forces of the defects is thought to dominate the pinning/depinning process. Stick–slip behaviour of the contact line is observed for larger structures and the results show a strong pinning of the contact line on surfaces with larger defects. The datum contact angle and its deviation were measured and a new concept of scaled energy barrier was calculated for advancing contact lines. This was strongly dependent on defect size. An estimation of the unbalanced Young force per unit length was also made for comparison, which also depended on defect size. This new approach allows new insights into this wetting phenomenon.     

Trickle-bed reactors: Tracer study of liquid holdup and wetting efficiency at high temperature and pressure

Liquid holdup and wetting efficiency were measured by means of stimulus-response (pulse-tracer) experiments in a trickle-bed reactor, packed with a commercial hydrodemetallization catalyst, and operated at 10 MPa and 330–370°C, with a superficial liquid velocity of 1.4 to 8.3 × 10^?4 m/s. The total liquid holdup was obtained from the first moments, and the external wetting efficiency from the second moments, of the response curves. The dynamic holdup obtained from the total holdup lies within the range described by existing correlations, but wetting efficiency is significantly lower than literature data obtained at ambient conditions.     

Wetting of YSZ by molten Sn–8Zr,Sn–4Zr–4Ti,and Sn–8Ti alloys at 800–900 °C

The wetting of 3% yttria-stabilized zirconia (YSZ) by Sn–8Zr, Sn–4Zr–4Ti, and Sn–8Ti alloys was studied at 800–900 °C. Both Zr and Ti improve the wettability via the formation of reaction products and adsorption. In the systems containing Zr additives in the alloys, ZrO_2-x precipitates preferentially, and the wettability is dominated by interface adsorption. An anomalous temperature dependence was found in the final wettability of these systems owing to the decrease in adsorption with an increase in the temperature. The spreading dynamics are controlled by the dissolution of Zr, followed by the formation of a wetting ridge. The wettability of the Sn–8Ti/YSZ system is dominated by the precipitation of reaction products (Ti₂O₃ and Ti_11.31Sn₃O₁₀). The reaction kinetics is the limiting factor for spreading in Sn–8Ti/YSZ, and the adsorption at the interface significantly decreased the energy barrier for wetting.     

Plate wettability and droplet diameter in a pulsed perforated-plate extraction column

The liquid-liquid-plate contact angles of several plate materials were measured using a “preferential wetting method” proposed by the authors. The adhesional work (I_SL), calculated on the basis of contact angles was utilized to evaluate plate wettability. The experimental results indicate that different plate materials affect differently plate wettability. The plate wettability of stainless steel in an aqueous phase was observed to be different from that in an organic phase. The droplet diameter in the mixer-settler region of operation of a pulsed perforated-plate extraction column using several different plate materials, was measured. An empirical correlation of mean droplet diameter: d_p = 0.222(a_f/l_SL^1/3)^?0.13 is proposed except for alumina plates with dispersed aqueous phase operation.