Dynamic Ink Oil Absorption in a Pigmented Porous Coating Medium Studied by Near-Infrared Diffuse Reflectance Spectroscopy

The rate of absorption (both long and short timescale) of typical heatset offset printing ink oils, namely mineral and linseed oil, has been studied on model ground calcium carbonate coating pigment tablets containing various amounts of either styrene–acrylic or styrene–butadiene binder. The pore structure characteristics of the tablets were determined using mercury intrusion porosimetry. The movement of the oils both on the surface of and within the porous structure of the pigment/binder tablets was studied under the influence of pressure-less capillary flow with subsequent diffusion through the connected void volume of the tablet. The wetting was analyzed by near-infrared (NIR) diffuse reflectance spectroscopy both as a single probe measurement and by hyperspectral imaging. The results showed that the rate of oil filling the structure was strongly dependent on the binder amount in the structure as well as the binder chemistry (oil- or non-absorbing binder), which supports previous findings. The liquid properties, and especially the viscosity of the liquid (oil), influenced the absorption rate. The gradients in absorbance indicated the presence of latex blocking access to some pores and reducing connectivity.     

Effective Thermal Conductivity of Liquid-Saturated Coatings and Their Liquid Vaporisation Behaviour

The effective thermal conductivity is an important element in understanding the thermal response to heating of a paper coating, e.g. during drying in heatset web-offset, and thus it not only affects the drying efficiency but also affects print quality detriments like web fluting. This study examines both the effective thermal conductivity of liquid-saturated ground calcium carbonate coating structures as well as the vaporisation behaviour from these structures. The liquids used for saturation were mineral oil and water in order to resemble ink and fountain solution, respectively, both of which are present in the traditional heatset web-offset process. The effective thermal conductivities of liquid-saturated coating structures are discussed in regard to the corresponding unsaturated systems by using a Lumped Parameter Model. It is shown that the liquid saturation has a dominant effect in determining the effective thermal conductivity. Since this effect is not fully captured by the model, other mechanisms like an apparent pigment–pigment connectivity increase by liquid bridging and the role of liquid in changing the contact resistance during the measurement of thermal conductivity are discussed. In addition, the transformation of three-dimensional structures to an equivalent two-dimensional modelling is evaluated. The vaporisation behaviour of mineral oil and water is studied by a thermogravimetric analysis. By following the changes in maximum evaporation temperatures and evaporation rates, the addition of binder is seen to lead to a reduction in the vaporisation rate of both liquids. Since there is little to no interaction between the liquids and the binder, the confinement caused by the geometry change induced by binder addition is identified as the mechanism resulting in elevated vapour pressure within the structure.     

Influence on Pore Structure of Micro/Nanofibrillar Cellulose in Pigmented Coating Formulations

Nano and microfibrillated cellulose (NFC and MFC, respectively, collectively termed MNFC) is known to interact strongly with water, related to its high polarity and surface area. The swelling behaviour acts to form a gel with high water retention properties. The observation that nanocellulose could possibly be used in paper or other coating formulations, as a co-binder, for example, raises a question about the possible effects it could have on coating pore structure. In this study, we analyse the pore structure of pigmented coatings, liquid absorption and permeability, in respect to the influence of partially substituting traditional co-binder carboxymethyl cellulose with MNFC. The contrast between polar water and non-polar liquid, such as alkane, is used to probe the water interactive and extractable in-coating (internal) gel-formation properties of the nanocellulosic materials. These contrasting liquids are important in many processes, such as offset printing, but also in respect to exposure of coatings in general to environmental factors in application. Results show that permeability to liquid water is dramatically reduced when nanocellulosic material is present, though water can permeate by diffusion through the nanocellulose gel network. Long timescale exposure to water during absorption leads to extraction of any soluble salts remaining after the chemical treatment of the fibrillar material during production. Inert alkane, on the other hand, can absorb and permeate freely without interactive hindrance from the nanocellulose, with no extractive effect. Such a construct could in principle be considered for use as an oil-water differential membrane or for slow release concepts in aqueous systems by loading soluble deliverable materials within the nanocellulosic gel.     

Relating Liquid Location as a Function of Contact Time Within a Porous Coating Structure to Optical Reflectance

Refractive index differences between a first and a second fluid can be utilised to obtain information about the location and amount of the fluids in a porous medium in the case where the light absorption coefficient of the skeletal material is small and the light scattering coefficient high using optical measurement methods. An example of such a medium is an air-filled paper coating, and the fluid that of a printing ink liquid phase absorbing into the coating during printing. We examined capillary absorption of mineral oil, used in offset printing ink, into model coatings compressed from dispersed mineral pigments with a range of latex binder levels, and established a porosity-normalised relationship for light reflectance change as a function of absorbed mass of the liquid established at a given time after initial contact with the liquid. The results suggest a significant change in reflectance due to the absorption, and progressive absorption behaviour of the liquid in the coatings can be monitored by the change in reflectance following a newly established relationship derived from the observational data. The findings support the concept of a preferred pathway flow for the wetting front, defined by differential pore size and connectivity, and a longer time saturation front flow lagging behind the wetting front, which theoretically at the limit of infinite time coincides with the wetting front, the time constant of the approach being related to the permeability of the porous network.     

The effect of dissolved polymers on the rheological properties of coating colours

Coating colours used for the coating of paper and board consist mainly of a mineral pigment, which is very often clay, a synthetic binder such as a styrenebutadiene latex, dispersion agents and water retention aids. The latter are often water soluble polymers. These polymers have a very strong influence on the rheological properties of the coating colours, both on the strain rate dependence of the apparent viscosity and on the viscoelasticity. The effects of two different grades of carboxymethylcellulose (CMC) and one grade of hydroxyethylcellulose (HEC), on the rheological properties at room temperature of a clay-based coating colour at pH 8, have been investigated. It is concluded that the high values of the dynamic modulus of the colours are due to interactions between the cellulose derivatives and the solid particles, i.e. mainly the clay particles. For HEC this interaction is associated with adsorption of the polymeric molecules on the clay particles. In the case of CMC, the adsorption is strongly retarded by the presence of the dispersant (a polyacrylate salt). It is suggested that the marked elasticity of the CMC-containing colour in addition to a possible polymer adsorption may be due to charge interactions and/or depletion flocculation. The effect of CMC and HEC on the water-retention properties of the colour is also discussed.     

Pore-Scale Monitoring of Wettability Alteration by Silica Nanoparticles During Polymer Flooding to Heavy Oil in a Five-Spot Glass Micromodel

It is well known that the oil recovery is affected by wettability of porous medium; however, the role of nanoparticles on wettability alteration of medium surfaces has remained a topic of debate in the literature. Furthermore, there is a little information of the way dispersed silica nanoparticles affect the oil recovery efficiency during polymer flooding, especially, when heavy oil is used. In this study, a series of injection experiments were performed in a five-spot glass micromodel after saturation with the heavy oil. Polyacrylamide solution and dispersed silica nanoparticles in polyacrylamide (DSNP) solution were used as injected fluids. The oil recovery as well as fluid distribution in the pores and throats was measured with analysis of continuously provided pictures during the experiments. Sessile drop method was used for measuring the contact angles of the glass surface at different states of wettability after coating by heavy oil, distilled water, dispersed silica nanoparticles in water (DSNW), polyacrylamide solution, and DSNP solution. The results showed that the silica nanoparticles caused enhanced oil recovery during polymer flooding by a factor of 10%. The distribution of DSNP solution during flooding tests in pores and throats showed strong water-wetting of the medium after flooding with this solution. The results of sessile drop experiments showed that coating with heavy oil, could make an oil-wet surface. Coating with distilled water and polymer solution could partially alter the wettability of surface to water-wet and coating with DSNW and DSNP could make a strongly water-wet surface.     

Achieving Rapid Absorption and Extensive Liquid Uptake Capacity in Porous Structures by Decoupling Capillarity and Permeability: Nanoporous Modified Calcium Carbonate

Porous media with rapid absorption properties are greatly sought after in the fields of super absorbers and catalysts. Natural materials, such as diatomite, or synthetic zeolite feature strongly in industrial reaction processes. Most, or all, of such materials, however, are surface acidic. A novel rapidly absorbing alkaline porous structure, with a high absorption capacity, is presented here. As in the case of diatomite or zeolite, the pigment design incorporates strong capillarity within a highly permeable packed medium. A model is proposed for general use with highly absorbing media that can be proven microscopically to have separate domains of micro- or nano-capillarity embedded within a permeable matrix. The new pigment morphology, based on natural ground calcium carbonate (gcc), exhibits this property using special surface structure modifications. It is contrasted with standard gcc by using consolidated tablet blocks made from a suspension of the pigment and chosen mixtures thereof. The blocks are characterised after drying by mercury porosimetry, and the absorption dynamic of a selected liquid is studied. It is shown that using a self-assembly method of discrete pore structures provides a much faster absorption rate and a liquid capacity for up to 10 times more fluid than a conventional homogeneously distributed pore concept. In such unique discrete network systems, the mercury intrusion curve provides a separable analysis of permeability and capillarity in respect to the inflection point of the cumulative intrusion curve. The discrete decoupled properties each follow the absorption behaviour predicted by previous modelling (Ridgway and Gane, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 206(1–3), 2002). The absorption driving force is shown to be determined by the proportion of fine pores present up to a size equal to a Bosanquet inertially-defined optimum within the timescale of absorption. Combining the wetting force, from the capillarity-controlled fine pore structure, with the experimental flow resistance of the sample, consisting of the assembly of particles, it is possible to predict the trends in absorption dynamic using the pore and throat model Pore-Cor.* Use of this model allows existing materials as well as new synthetic designs to be modelled prior to manufacture. The novel alkaline material is compared with independent absorption data for diatomite and shown to be comparable. *Pore-Cor is a software product name of the Environmental and Fluid Modelling Group, University of Plymouth, Devon PL4 8AA, U.K.     

Spontaneous Inertial Imbibition in Porous Media Using a Fractal Representation of Pore Wall Rugosity

Considering the separable phenomena of imbibition in complex fine porous media as a function of timescale, it is noted that there are two discrete imbibition rate regimes when expressed in the Lucas–Washburn (L–W) equation. Commonly, to account for this deviation from the single equivalent hydraulic capillary, experimentalists propose an effective contact angle change. In this work, we consider rather the general term of the Wilhelmy wetting force regarding the wetting line length, and apply a proposed increase in the liquid–solid contact line and wetting force provided by the introduction of surface meso/nanoscale structure to the pore wall roughness. An experimental surface pore wall feature size regarding the rugosity area is determined by means of capillary condensation during nitrogen gas sorption in a ground calcium carbonate tablet compact. On this nano size scale, a fractal structure of pore wall is proposed to characterize for the internal rugosity of the porous medium. Comparative models based on the Lucas–Washburn and Bosanquet inertial absorption equations, respectively, for the short timescale imbibition are constructed by applying the extended wetting line length and wetting force to the equivalent hydraulic capillary observed at the long timescale imbibition. The results comparing the models adopting the fractal structure with experimental imbibition rate suggest that the L–W equation at the short timescale cannot match experiment, but that the inertial plug flow in the Bosanquet equation matches the experimental results very well. If the fractal structure can be supported in nature, then this stresses the role of the inertial term in the initial stage of imbibition. Relaxation to a smooth-walled capillary then takes place over the longer timescale as the surface rugosity wetting is overwhelmed by the pore condensation and film flow of the liquid ahead of the bulk wetting front, and thus to a smooth walled capillary undergoing permeation viscosity-controlled flow.     

Improved Interpretation of Mercury Intrusion and Soil Water Retention Percolation Characteristics by Inverse Modelling and Void Cluster Analysis

This work addresses two continuing fallacies in the interpretation of percolation characteristics of porous solids. The first is that the first derivative (slope) of the intrusion characteristic of the non-wetting fluid or drainage characteristic of the wetting fluid corresponds to the void size distribution, and the second is that the sizes of all voids can be measured. The fallacies are illustrated with the aid of the PoreXpert^® inverse modelling package. A new void analysis method is then described, which is an add-on to the inverse modelling package and addresses the second fallacy. It is applied to three widely contrasting and challenging porous media. The first comprises two fine-grain graphites for use in the next-generation nuclear reactors. Their larger void sizes were measured by mercury intrusion, and the smallest by using a grand canonical Monte Carlo interpretation of surface area measurement down to nanometre scale. The second application is to the mercury intrusion of a series of mixtures of ground calcium carbonate with powdered microporous calcium carbonate known as functionalised calcium carbonate (FCC). The third is the water retention/drainage characteristic of a soil sample which undergoes naturally occurring hydrophilic/hydrophobic transitions. The first-derivative approximation is shown to be reasonable in the interpretation of the mercury intrusion porosimetry of the two graphites, which differ only at low mercury intrusion pressures, but false for FCC and the transiently hydrophobic soil. The findings are supported by other experimental characterisations, in particular electron and atomic force microscopy.     

The Impact of Pore Water Chemistry on Carbonate Surface Charge and Oil Wettability

Water chemistry has been shown experimentally to affect the stability of water films and the sorption of organic oil components on mineral surfaces. When oil is displaced by water, water chemistry has been shown to impact oil recovery. At least two mechanisms could account for these effects, the water chemistry could change the charge on the rock surface and affect the rock wettability, and/or changes in the water chemistry could dissolve rock minerals and affect the rock wettability. The explanations need not be the same for oil displacement of water as for water imbibition and displacement of oil. This article investigates how water chemistry affects surface charge and rock dissolution in a pure calcium carbonate rock similar to the Stevns Klint chalk by constructing and applying a chemical model that couples bulk aqueous and surface chemistry and also addresses mineral precipitation and dissolution. We perform calculations for seawater and formation water for temperatures between 70 and 130°C. The model we construct accurately predicts the surface potential of calcite and the adsorption of sulfate ions from the pore water. The surface potential changes are not able to explain the observed changes in oil recovery caused by changes in pore water chemistry or temperature. On the other hand, chemical dissolution of calcite has the experimentally observed chemical and temperature dependence and could account for the experimental recovery systematics. Based on this preliminary analysis, we conclude that although surface potential may explain some aspects of the existing spontaneous imbibitions data set, mineral dissolution appears to be the controlling factor.     

Chemical Compositions in Salinity Waterflooding of Carbonate Reservoirs: Theory

Higher oil recovery after waterflood in carbonate reservoirs is attributed to increasing water wettability of the rock that in turn relies on complicated surface chemistry. In addition, calcite mineral reacts with aqueous solutions and can alter substantially the composition of injected water by mineral dissolution. Carefully designed chemical and/or brine flood compositions in the laboratory may not remain intact while the injected solutions pass through the reactive reservoir rock. This is especially true for a low-salinity waterflood process, where some finely tuned brine compositions can improve flood performances, whereas others cannot. We present a 1D reactive transport numerical model that captures the changes in injected compositions during water flow through porous carbonate rock. We include highly coupled bulk aqueous and surface carbonate-reaction chemistry, detailed reaction and mass transfer kinetics, 2:1 calcium ion exchange, and axial dispersion. At typical calcite reaction rates, local equilibrium is established immediately upon injection. In SI, we validate the reactive transport model against analytic solutions for rock dissolution, ion exchange, and longitudinal dispersion, each considered separately. Accordingly, using an open-source algorithm (Charlton and Parkhurst in Comput Geosci 37(10):1653–1663, 2011. https://doi.org/10.1016/j.cageo.2011.02.005), we outline a design tool to specify chemical/brine flooding formulations that correct for composition alteration by the carbonate rock. Subsequent works compare proposed theory against experiments on core plugs of Indiana limestone and give examples of how injected salinity compositions deviate from those designed in the laboratory for water-wettability improvement.

     

涂层低表面能各分量降低流体噪声的试验研究

水下航行在高速运动时,由于物体和流体的相互作用、边界层中产生了速度和压力脉动鸸 流体噪声。针对低表面能涂层改变流体边支的状态,考察了其在水洞中的降噪效果。涂层表面具有很好的疏水性和低的表面能色散分量与水相互作用力分量,使边界是层增厚,降低由于壁面与流体界面的作用所产生的偶极子声源,从而达到降人氏流体噪声的效果。     

Numerical Calculation of Effective Diffusion in Unsaturated Porous Media by the TRT Lattice Boltzmann Method

Numerical models that solve transport of pollutants at the macroscopic scale in unsaturated porous media need the effective diffusion dependence on saturation as an input. We conducted numerical computations at the pore scale in order to obtain the effective diffusion curve as a function of saturation for an academic sphere packing porous medium and for a real porous medium where pore structure knowledge was obtained through X-ray tomography. The computations were performed using a combination of lattice Boltzmann models based on two relaxation time (TRT) scheme. The first stage of the calculations consisted in recovering the water spatial distribution into the pore structure for several fixed saturations using a phase separation TRT lattice Boltzmann model. Then, we performed diffusion computation of a non-reactive solute in the connected water structure using a diffusion TRT lattice Boltzmann model. Finally, the effective diffusion for each selected saturation value was estimated through inversion of a macroscopic classical analytical solution.     

An investigation of hydraulic fracturing. Part II: two-phase flow model

In the previous work presented in Part I (Theoret. Appl. Fracture Mech. 18, 89–102 (1993)), hydraulic fracture in an infinitely large saturated porous medium is analyzed under an assumption of one-phase flow in the medium. The investigation is extended in this paper to the case of a two phase saturated immiscible flow of oil and water in the porous medium. The medium is initially saturated with oil. Flow in the medium is induced by diffusion of water injected into the fracture. The quasi-static growth of the fracture for a prescribed injection rate is analyzed based on the assumptions that the pressure in the fracture is uniform and that the permeating flow in the medium is unidirectional. The constant fracture toughness criterion for plane strain deformation is employed and the effect of capillary pressure is neglected. Empirical formulas are used for the permeabilities of the oil and water phases. It is seen that the distributions of water saturation and pore pressure in the medium are governed by two nonlinear partial differential equations. Numerical solutions are obtained by a finite difference scheme with iterations. It is found that the injected water is restricted within a layer near the surface of the fracture whose thickness is small compared with the length of the fracture. Thus the flow in the medium is governed essentially by the oil phase. To compare our problem with the corresponding problem of one-phase flow, we find that the difference in crack growth in these two problems is small for the ration of kinematic viscosities of the oil and water phases within the practical range. Hence our study confirms the validity of the one phase flow assumption used in the previous work for prediction of hydraulic fracture growth.     

孔隙渗流对环面复层含油轴承润滑性能的影响

含油轴承基体中油液的渗流特性对轴承油膜润滑性能影响显著. 以不同孔隙率分布的环面复层含油轴承为研究对象,利用达西定律建立复层含油轴承基体中流体渗流的控制方程,在极坐标下建立环面复层含油轴承系统渗流润滑模型,研究复层环面副系统中油膜压力分布规律,分析轴承结构参数及孔隙渗流行为对油膜润滑性能的影响. 结果表明:复层含油轴承的流体动压力主要发生在环形摩擦面间,从摩擦界面到轴承底面,流体压力逐渐由外缘向圆心部位传导,流体动压力作用面积逐渐增大,压力峰值逐渐降低;随着倾角增大,摩擦界面间的油膜动压效应增强,油膜润滑性能变好;随着表层渗透率或厚度减小,摩擦界面间的油膜的渗流效应减弱,油膜润滑性能提高;与普通单层含油轴承相比,含致密表层的复层含油轴承能降低整体孔隙率,防止过多轴承间隙油液渗入多孔介质,提高轴承润滑性能. 研究工作为明晰环面复层含油轴承渗流行为及润滑机理提供一定理论依据.      

Measurement of 3D pore-scale flow in index-matched porous media

We present the experimental analysis of fluid flow at the pore-scale of a transparent porous medium with matched refractive indices of the solid and liquid phases. The planar laser-induced fluorescence (PLIF) technique described is the first to simultaneously visualize the 3D pore-scale flow of two immiscible liquid phases in porous media. Through the application of a highly precise index matching method and the employment of up-to-date CCD imaging hardware, the system features a high spatial resolution and sampling rate. The method was used to study the dispersion of a tracer dye in single-phase flow and the displacement of oil by water in an imbibition process.     

Effect of Efflorescence Formation on Drying Kinetics of Porous Media

We study experimentally the evaporation of an aqueous NaCl solution with efflorescence formation in hydrophilic or hydrophobic two-dimensional model porous media. The efflorescence formation only marginally affects the invasion patterns but greatly modifies the drying kinetics compared to pure water. Two mechanisms are identified for explaining the impact of efflorescence formation on drying kinetics. It is shown that the efflorescence contributes to increase the evaporation rate compared to drying with pure water, a surprising result since the water activity is reduced in the presence of dissolved salt. This effect is explained by the efflorescence liquid capillary pumping effect associated with the porous nature of the efflorescence. Then, we identify a second phase where the efflorescence dries out and acts as a vapour diffusion barrier, leading to a dramatic reduction of evaporation rate.     

Rheological behavior of filled propylene/ethylene copolymers

A new family of propylene-ethylene copolymers developed by The Dow Chemical Company has narrow molecular weight distributions for industrial polymers and broad chemical composition distributions. This molecular architecture makes possible high filler loadings while maintaining good processability. To provide a fundamental understanding of the lower than expected viscosity, a study of the shear rheological behavior of two series of composites was performed. The composites consist of stearate-coated calcium carbonate particles suspended in a propylene-ethylene copolymer. The matrix in one series was a new copolymer, and in the other series, it was a traditional metallocene copolymer. For both systems, the viscosity increases dramatically with increasing filler loading; however, the viscosity is lower in the case of the composites of the new copolymer. The stearate coating on the calcium carbonate particles decreases the adhesion of the polymer to the filler surface, allowing particle-matrix interfacial slip. A high temperature atomic force microscopy study has indicated the existence of ethylene-enriched zones in the matrix immediately surrounding the particles in the new copolymer. We hypothesize that these high ethylene content chains around the particle surface enhance particle-matrix interfacial slip resulting in the lower composite viscosity.     

Effect of Organosilicon-Acrylic Emulsion Treatment on Wettability of Porous Media

To investigate the influence of the organosilicon-acrylic on wetting properties of porous media, contact angle tests were performed on two different sandstones. In addition, the effectiveness of the emulsion on wettability alteration of porous media was validated by capillary rise and spontaneous imbibition tests. The results of wettability tests showed that the wettability of two sandstones was altered from water-wet to gas-wet after treatment with the emulsion. The principle that the critical radius of pore throats and wettability of porous media affect liquids flow was derived analytically and verified experimentally. Coreflood results demonstrated that the latex resulted in increasing the water permeability through altering the rock wettability to gas-wetting, then decreasing the friction drag between liquids and rocks surface. Thereby, the emulsion treatment could increase the flowback rate of trapped liquids. Experimental results were in good agreement with the theoretical analysis. In conclusion, all results indicated that the emulsion could alter the wettability from water-wet to intermediate gas-wet and enhance water permeability in porous media. It was extrapolated that the emulsion had the tremendous potential to be applied in field conditions, enhancing gas productivity through the cleanup of trapped water in the vicinity of the wellbore.