Analysis of droplet expulsion in stagnant single water-in-oil-in-water double emulsion globules

Double emulsions created by phase inversion can be used for fast liquid–liquid separation; therefore, the coalescence behaviors of these types of multiple emulsions need to be predictable for different physical properties and drop size ratios. The aim of this study is to determine the influence of the effective overall drop diameter and the internal droplet size on the coalescence time and the coalescence behavior. Experimental investigations on the physical stability of single stagnant water-in-oil-in-water (W₁/O/W₂) double emulsion globules are performed. For this investigation, a formation device to inject one water droplet into an oil drop inside a water bulk phase is developed. The coalescence process of the sole internal water droplet floating on the O/W₂ interface with the water bulk phase, often termed droplet expulsion or external coalescence, is recorded with a high speed camera. Based on image analysis, the diameters of the effective overall drop D, containing the oil and entrapped water volume, and the internal water droplet d are determined. Additionally, the coalescence time τ, including the time from the first contact of the internal droplet and the drop-bulk interface to the film rupture is measured. A large increase in coalescence time with increasing water droplet diameters is found. For the investigated paraffin oil–water system and initial drop sizes, partial coalescence occurs. In this case, the diameter ratio of daughter-to-mother droplet ψ is determined.     

Effect of roughness as determined by atomic force microscopy on the wetting properties of PTFE thin films

The influence of film roughness on the wetting properties of vacuum-deposited polytetrafluorethylene (PTFE) thin films has been investigated using atomic force microscopy (AFM) and contact angle goniometry. Surface roughness has been characterized by atomic force microscopy in terms of RMS roughness (R_q) and fractal dimensions. A contact angle correlation with surface roughness, as determined by AFM, is evident from these results, which are discussed on the basis of wetting theory. The results also confirm that the high water contact angles (as high as 150°) recently observed at the surface of a new water repulsive coating material (mixture of PTFE and binder) are because of surface roughness. Such measurements clarify the effect of nanometer-size surface asperities on the wetting properties of hydrophobic coating.     

Facile preparation and strong adhesive strength of honeycomb polyurethane films with small pore diameter

With the continuous development of bionics, such as, geckos and virginia creeper with both superhydrophobic and super-adhesive, the surface wetting and super-adhesive properties of various porous materials have attracted extensive attention of the scientific and medical communities. Here, the honeycomb polyurethane (PU) porous films with strong adhesion were successfully prepared by microphase separation method and the effects of growth parameters on their microstructure and adhesive strength to ice were investigated. It was found that a high relative humidity (e.g., 100%) and a low solution concentration (e.g., 2%) facilitated the formation of ordered honeycomb PU porous films, and as-prepared PU pores with average pore diameter as small as 5 μm are better ordered and more uniform than these in related documents. Although the contact angle of water droplets on the surface of PU porous films increased from the premodification value of 85–130° to more than 160° after surface modification with polydopamine (PDA), the corresponding rolling angle remained approximately constant (180°), indicating that the surface of PU porous films has strong adhesion similar to geckos and virginia creeper. Furthermore, at lower temperature, the PU porous films exhibited the high adhesive strength of 142.13 kPa on ice, which was strongly dependent on the porous microstructures and surface compositions. The improved adhesive behavior to ice of honeycomb PU porous films modified with PDA provides new strategies for surface modification of materials and potential applications in medical domain.     

Wetting properties of glycerol on silicon,native SiO2, and bulk SiO2 by scanning polarization force microscopy

Scanning polarization force microscopy, a relatively new non-contact scanning probe microscopy technique, was applied in order to investigate the properties of liquid surfaces (droplets), such as: topography, microscopic contact angle θ, surface potential energy P(e), spreading coefficient S, and disjoining pressure П. Investigations were carried out on glycerol droplets deposited on surfaces of bare silicon, silicon covered with native oxide, and bulk silicon oxide. Contact angle values were determined from directly measured topography profiles of micro- and nanodroplets. Values of surface potential energy, spreading coefficient, and disjoining pressure were calculated based on a model of the dependence of contact angle on droplet height. The results of these experiments offer valuable insights into the mechanisms of wetting phenomena at the microscopic scale.     

Hydrophilic and hydrophobic poly(l‐lactic acid) films by building porous topological surfaces

Surface wettability of thin films is significant for their functional properties. Poly(l ‐lactic acid) (PLLA) is proposed as film matrix for building porous topological surfaces. By controlling the dope composition and ambient conditions, the films with ordered pores at micrometer scale are obtained. The results demonstrate that the hydrophilic or hydrophobic surface can be realized by building the porous topological surfaces. Increasing polymer concentration can lead to decreased pore size. The transition behavior of surface pores from discrete bowl‐like to interconnected honeycomb‐like structure with the increasing humidity is observed. The contact angle of top surface of film is higher than that of bottom surface, which verified the different roughness performance. The morphology and scale of topological structure are markedly related with the template effect of water droplets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44572.     

EFFECTS OF GLYCEROL ON THE DRYING OF GELATIN AND SUGAR SOLUTIONS

ABSTRACT

The water diffusion coefficients D of gelatin, sucrose arid maltodextrin solutions were determined from the isothermal drying (desorption) rates as a function of water content u ( 0.1 < u < 1.0 ) and temperature (303, 323K) for various glycerol contents ( W_G = 0 – 0.43 kg-glycerol/kg-total solid). When W_G was above 0.2, D increased especially at low water contents (u < 0.25). The desorption isotherms were measured for the same systems. The equilibrium water content at a given water activity A_w decreased with an increase in W_G when A_w < 0.5. This indicates that adding glycerol weakens the water-solute interaction especially at low water contents. Glycerol also softened gelatin films and resulted in loss possibilities of surface cracks during drying.     

Fabrication of honeycomb‐structured porous films from poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) via the breath figures method

Formation of porous films from poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) using the breath figures (BF) method was investigated by evaporating solutions in chloroform in humid air and examining film structure using optical and scanning electron microscopy (SEM). BF films were successfully fabricated from PHB (M_w = 486,000 g/mol) and displayed hexagonal arrays of pores, which varied in diameter (D = 7–2 μm) with solution concentrations (0.5–2.00%). SEM of fractured films also showed subsurface closed nano‐pores (D = 500–700 nm). BF films cast from PHBV (5% HV) formed arrays with smaller pores and apparent surface defects. Differential scanning calorimetry showed that porous PHB and PHBV films produced using the BF method were more crystalline than nonporous solvent cast films of PHB and PHBV. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Droplet impingement and wetting behavior on a chemically heterogeneous surface in the Beyond–Cassie–Baxter regime

Droplet impingement and anisotropic wetting on chemically heterogeneous stripe-patterned surfaces is simulated by means of many-body dissipative particle dynamics. The ratio of the stripe width and initial droplet diameter, defined as β, ranges from 0.5 to 1.0 so that the wetting process is in the Beyond–Cassie–Baxter regime and is highly anisotropic. At zero Weber number (that is, without considering droplet inertia) and with superhydrophobic stripes, β is the only factor affecting the droplet perpendicular contact angle and aspect ratio. For inertial droplets, β and the Weber number are found to have an effect on the eventual droplet morphology on multi-striped surfaces. These morphologies include elongated shape, split-off, and “butterfly” shape. A correlation for critical split-off conditions has been determined. An energy analysis of droplet impingement shows that the normalized surface energy of the droplet is independent of the Weber number if the droplet is elongated or butterfly-shaped.     

Fabrication of Novel Superhydrophobic Surfaces and Droplet Bouncing Behavior — Part 2: Water Droplet Impact Experiment on Superhydrophobic Surfaces Constructed Using ZnO Nanoparticles

When a liquid droplet impacts a solid surface, it spreads up to a point and the kinetic energy is dissipated by viscosity, collision and surface energy during the process. The droplet can retract if the energy dissipation during the impact process which is only partly governed by surface properties is not too large. Otherwise, the droplet would stick to the surface or break into smaller droplets. In this second part, we introduced contact angle hysteresis (CAH) and studied the impact behavior between a water droplet and a superhydrophobic surface both theoretically and experimentally. On our superhydrophobic surface, the contact angle is about 155° , so the kinetic energy of the droplet can be largely transferred to surface energy. Thus, under certain conditions, the droplet can fully bounce. The impact behavior of normal impact was analyzed theoretically. The critical falling heights for rebound (CFHR) were investigated on constructed ZnO–PDMS superhydrophobic surface in both normal and oblique impact conditions, and CFHR was found to increase with the increase of tilt angle. This shows that the normal Weber number (We _n ) is the major factor governing the rebound, while the tangential Weber number (We _t ) also has effect on the phenomenon. Compared to the energy dissipated by collision and viscosity, the influence of surface properties is relatively small. The adhesion number (N _a ) is the parameter determining the energy dissipated by surface tension and N _a has direct relation with contact angle (CA) and CAH.     

Inducing surface porosity in aqueous‐quenched,microporous Nylon 11 and Nylon 12 films

Nylon 11 and Nylon 12 have been studied for many years for the purpose of fabricating microporous films. Unfortunately, these polymers have somewhat unique properties that prevent the films from exhibiting porous surfaces when their solutions undergo thermally induced phase separation by quenching in water. Without surface pores, these films have limited utility as water purification membranes. In this work, application of high temperature diluent coatings to the surface prior to quenching is shown to enable the formation of surface porosity in Nylon 11 and Nylon 12 films. Furthermore, the pore sizes achieved are suitable for ultrafiltration applications. Following successful lab‐scale coating experiments, the effects of coating thickness, temperature, and solvent type on surface morphology are demonstrated over five film extrusion trials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44695.     

Characterization of superhydrophobic a-C:F thin film deposited on porous silicon via laser ablation of a PTFE target

Fluorinated amorphous carbon (a-C:F) thin films are deposited on both flat silicon and porous silicon (PS) surfaces via laser ablation of a polished polytetrafluoroethylene (PTFE). Porous silicon (PS) is prepared by anodic etching of p-type silicon wafers in HF based solution. The film deposited on the flat silicon surface exhibits a highly hydrophobic state with water contact angle (WCA) of ~ 146°. In comparison, the surface of film deposited on PS layer shows a roll-off superhydrophobic state, where the water droplet is seen to roll off without wetting its surface with contact angle hysteresis of ~ 4.5°. Micro-Raman results show that the graphite domain of the film deposited on PS has higher disorder level and lower average gain size. The effect of substrate porosity on chemical composition of deposited films has been investigated by using both Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). It is found that the porous substrate improves the incorporation of the fluorine into the film. Atomic force microscopy (AFM) results revealed that the film deposited on PS has higher surface roughness and lower grain size as compared to the film deposited on flat silicon surface.     

液滴撞击高温梯度表面的动态行为特性

以铜片为基底制备了微方孔结构浸润梯度表面,利用高速摄像技术对液滴撞击高温梯度表面的动态行为特性进行了研究。结果表明：在不同表面温度和韦伯数（We）下,液滴撞击在梯度表面上会出现5种不同的撞击模式,即润湿模式、接触沸腾模式、过渡模式、碎裂模式和反弹模式;当表面温度达到Leidenfrost温度时,液滴进入反弹模式,反弹液滴会沿着梯度能方向发生多次连续弹跳行为,且由于弹跳过程中能量的不断衰减,反弹高度逐渐减小直至趋于零。基于表面物理化学理论分析了液滴的定向弹跳行为,并利用图像处理技术,分析了弹跳液滴的动态特征。进一步地,通过液滴以相同We数撞击不同表面温度实验,研究了液滴在弹跳运动过程中反弹高度、铺展因子和运动的水平加速度变化特征,发现三者随反弹次数的增加具有相似的变化过程,即呈现先快速减小、后逐渐稳定的特征。水平加速度的与铺展因子的变化趋势具有一致性,从而验证了理论分析的合理性。     

Physical evaluation of pure zein films by atomic force microscopy and thermal mechanical analysis

Biodegradable edible films can be made from corn protein, α-zein. Pure zein films are cast from an organic solution of α-zein. This report outlines the surface conditions of such pure zein films. First, the transition temperature, T _t′ of the pure zein film was measured with a thermomechanical analyzer. T _t was between 167.0 and 172.7°C. The thermal elongation of the films depended on the drying conditions used during film preparation. Second, the surface microstructure of pure zein films, produced under several different drying conditions, was observed by atomic force microscopy. The surface had a morphology that showed depressions either with acutely (90–120°) or obtusely (121–180°) angled features depending upon the drying conditions. On the other hand, the surface microstructure after thermal elongation analysis appeared to have a pattern of projections that was repeated every 25 nm. Third, we measured the contact angle of the pure zein films. We found a correlation between surface microstructure and contact angle. Pure zein films with projections smaller than 200 nm in base diameter on the surface had a high contact angle (>70°).     

Full‐physics simulations of spray‐particle interaction in a bubbling fluidized bed

Numerical simulations of a gas‐particle‐droplet system were performed using an Euler‐Lagrange approach. Models accounting for (1) the interaction between droplets and particles, (2) evaporation from the droplet spray, as well as (3) evaporation of liquid from the surface of non‐porous particles were considered. The implemented models were verified for a packed bed, as well as other standard flow configurations. The developed models were then applied for the simulation of flow, as well as heat and mass transfer in a fluidized bed with droplet injection. The relative importance of droplet evaporation vs. evaporation from the particle surface was quantified. It was proved that spray evaporation competes with droplet deposition and evaporation from the particle surface. Moreover, we show that adopting a suitable surface coverage model is vital when attempting to make accurate predictions of the particle's liquid content. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2569–2587, 2017     

Effect of adhesive thickness on the wettability and deformability of polyacrylic pressure‐sensitive adhesives during probe tack test

Effect of adhesive thickness on the wetting and deformation behaviors during probe tack test of pressure‐sensitive adhesive (PSA) was investigated. For this purpose, cross‐linked poly(n‐butyl acrylate‐acrylic acid) [P(BA‐AA)] and poly(2‐ethylhexyl acrylate‐acrylic acid) [P(2EHA‐AA)] random copolymers with an acrylic acid content of 5 wt % and thicknesses in the range of ～15–60 μm were used. Tack was measured using the probe tack test and the fracture energy was calculated from the areas under force–displacement curve recorded during debonding process. From contact time dependence of fracture energy, the rising rate of fracture energy with contact time increased with increasing of adhesive thickness and was P(2EHA‐AA) > P(BA‐AA). The fracture energy was P(BA‐AA) > P(2EHA‐AA) at shorter contact time, whereas it reversed at longer contact time. This was caused by two different interfacial adhesions: the physical wetting of PSA molecules to the adherend surface with contact time and the chemical interaction between the acrylic acid units and the adherend surface. From the force–displacement curve measured under the condition of sufficient interfacial adhesion, both maximum force and displacement—namely, the deformability of PSA during debonding process—increased with adhesive thickness. The degree of increase of deformability was P(2EHA‐AA) > P(BA‐AA). The fracture energy was found to depend on the development of interfacial adhesion during contacting process and the deformability of PSA during debonding process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43639.     

Environmentally Friendly Solvent‐ and Water‐Based Coatings for Mitigation of Crystallization Fouling

The surface properties of solvent‐based (SB) and water‐based (WB) coatings and their impact on fouling during convective heat transfer of CaSO₄ solutions were investigated. Experiments demonstrated that the SB coatings had generally better non‐adhesive characteristics, especially at higher values of the electron donor component since the deposits could easily be washed away. For the SB coatings, a longer induction period compared to those of untreated surfaces was observed and a significant reduction of the fouling rate could be achieved. Further analysis of surfaces revealed that SB coatings enhanced the acid‐base repulsive force and thus reduced the deposit/solid adhesion energy. For the WB coatings, the Liftshitz‐van der Waals attractive force plays a decisive role in the adhesion process due to the higher apolar component of the surface energy.     

Water-assisted formation of honeycomb structured porous films

Honeycomb structured porous materials were formed using four different casting variations of the water droplet templating method. The film quality of the materials generated from these casting techniques (airflow, cold stage, casting on water, and emulsion methods) was investigated by altering the polymer architecture and composition. Linear, star, and comb polystyrene as well as an amphiphilic diblock copolymer comprised of polystyrene-block-poly(dimethylacrylamide) (PS-b-PDMA) were previously synthesized and cast into films via these techniques. While irregular pore distributions were observed for linear polystyrene films generated by every technique screened, increasing the architectural complexity of the polymer yielded more regular films for a broad range of casting conditions for each of the techniques. With the exception of linear polystyrene, the airflow casting technique was shown to be the only technique capable of generating regular porous films for all of the polymeric materials.     

Ag-TiO2多孔薄膜及其非紫外光辐照下的超亲水特性

采用溶胶凝胶法，以钛酸丁酯为前驱体、硝酸银络合物为银源、聚乙二醇2000（PEG2000）作为结构导向剂，制备超亲水多孔Ag-TiO₂复合薄膜。用X射线衍射仪、X射线光电子能谱仪、扫描电镜、原子力显微镜表征薄膜晶相结构、化学成分以及表面形貌。根据静态水接触角、动态润湿时间、超亲水长效稳定性综合评价不同Ag含量及PEG2000添加量薄膜的超亲水性能。研究发现，掺杂Ag与PEG2000对薄膜在非紫外光下的超亲水特性具有协同作用，掺杂Ag明显提高薄膜动态润湿速度及可见光响应，表面粗糙多孔结构有利于避光条件下的长效超亲水特性。Ag含量10%、PEG2000掺杂量5%的Ag-TiO₂复合薄膜在自然光条件下已具备优良的超亲水性能；水滴0.2 s内即可在表面完全铺展到0°；避光条件下保存，超亲水时效性可达到30 d以上。在可见光活化下即可强化超亲水性能，具有良好的防雾效果。     

Study of the correlation between flexible food packaging peeling resistance and surface composition for aluminum-metallized BOPP films aged at 60°C

ABSTRACT

This study investigated the correlation between surface composition and peeling resistance in food packaging films by studying the heat aging of fabricated films over varying periods of time. The films consisted of a layer of aluminum (Al) metallized, biaxially oriented polypropylene (BOPP) bonded with a polyurethane (PU) adhesive onto another polymeric layer of low-density polyethylene (LDPE). The Al metallized films were prepared by physical vapor deposition (PVD) and aged at 60°C for either 5 or 15 days. The resulting aluminum surfaces were analyzed using X-ray photoelectron spectroscopy (XPS) and found to contain aluminum oxide (Al₂O₃) and trihydroxide (Al(OH)₃). The XPS characterization also revealed a 29% increase in the Al(OH)₃ layer thickness of the aged sample relative to a non-aged sample. Atomic force microscopy (AFM) was applied on investigations of possible morphology changes. The aluminum and PU adhesive surface energies were also determined using contact angles measurements and the aluminum surface energy was found to increase by as much as 11.7% compared to the non-aged sample, while the PU adhesive surface energy was at least 65% higher than that of the metallic substrate. The peeling resistance of the laminated aluminum was determined by average peel strength measurements and it was found that the variation in peel strength was related to changes in the Al₂O₃ layer thickness. The delaminated samples were analyzed using scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) and showed the cohesive failure of the aluminum film.