AFM Colloidal Probe Research Articles

Coalescence Behavior of a CO2-Resistant Dispersed Particle Gel (SCDPG) in Supercritical CO2

The reservoir heterogeneity and unfavorable oil/gas mobility ratio lead to gas channeling and low CO2 sweep efficiency during CO2 flooding in low-permeability reservoirs. A dispersed particle gel (DPG) could migrate deep into the reservoir and coalesce, which has the potential for CO2 gas channeling control. In this work, a CO2-resistant bulk gel was prepared by a cross-linking reaction of a copolymer with acid-resistant groups and catechol–hexamethylenetetramine, which exhibited excellent CO2 resistance. Subsequently, a CO2-resistant dispersed particle gel (SCDPG) used in supercritical CO2 was successfully prepared from the CO2-resistant bulk gel by a high-speed mechanical shearing method. Meanwhile, the coalescence behavior of the SCDPG particles in supercritical CO2 was systematically investigated from the microstructure, particle size, ζ potential, and mechanical strength. The results showed that the SCDPG particles were dispersed in the liquid phase as a single particle. SCDPG had good dispersion stability during storage and injection. In supercritical CO2, the dispersion stability of SCDPG decreased, and the particles coalesced with each other to form aggregates with a stereostructure instead of degradation. The SCDPG particles maintained high mechanical strength, showing the long-term effectiveness for gas channeling control during CO2 flooding. In addition, the interparticle force of SCDPG particles was measured by an AFM colloid probe based on the reservoir characteristics. The interparticle force of SCDPG particles changed from repulsion to adhesion with increasing salinity. At a salinity of 0.5 mol/L, the adhesion force increased with the increase of temperature and the decrease of the pH value. According to the type of intermolecular force, the adhesion force originated from the hydrogen bond, π–π stacking, and cation−π interaction. This work provides theoretical support for the field application of the dispersed particle gel and promotes the development of utilization of carbon dioxide in oilfields.

Interaction Mechanisms and Predictions of the Biofouling of Polymer Films: A Combined Atomic Force Microscopy and Quartz Crystal Microbalance with Dissipation Monitoring Study.

Biofouling of polymeric membranes is a severe problem in water desalination and treatment applications. A fundamental understanding of biofouling mechanisms is necessary to control biofouling and develop more efficient mitigation strategies. To shed light on the type of forces that govern the interactions between biofoulants and membranes, biofoulant-coated colloidal AFM probes were employed to investigate the biofouling mechanisms of two model biofoulants, BSA and HA, toward an array of polymer films commonly used in membrane synthesis, which included CA, PVC, PVDF, and PS. These experiments were combined with quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The Derjaguin, Landau, Verwey, and Overbeek (DLVO) and the extended-DLVO (XDLVO) theoretical models were applied to decouple the overall adhesion interactions between the biofoulants and the polymer films into their component interactions, i.e., electrostatic (El), Lifshitz-van der Waals (LW), and Lewis acid-base (AB) interactions. The XDLVO model was found to predict better the AFM colloidal probe adhesion data and the QCM-D adsorption behavior of BSA onto the polymer films than the DLVO model. The ranking of the polymer films' adhesion strengths and adsorption quantities was inversely proportional to their γ- values. Higher normalized adhesion forces were quantified for the BSA-coated colloidal probes with the polymer films than the HA-coated colloidal probes. Similarly, in QCM-D measurements, BSA was found to cause larger adsorption mass shifts, faster adsorption rates, and more condensed fouling layers than HA. A linear correlation (R2 = 0.96) was obtained between the adsorption standard free energy changes (ΔGads°) estimated for BSA from the equilibrium QCM-D adsorption experiments and the AFM normalized adhesion energies (WAFM/R) estimated for BSA from the AFM colloidal probe measurements. Eventually, an indirect approach was presented to calculate the surface energy components of biofoulants characterized by high porosities from Hansen dissolution tests to perform the DLVO/XDLVO analyses.

Temperature-dependent slip length for water and electrolyte solution

HypothesisThe temperature dependence of boundary slip at liquid–solid interface is critical both for the fundamental theory and applications of fluid mechanics on micro and nanoscale, such as sustainable cooling of electronic devices. However, there is a controversy on the temperature dependence of boundary slip which lacks experimental evidence, we aim to resolve it by hypothesizing that the temperature dependent slip length depends on the variation in the interfacial energy barrier. ExperimentsHere, we measured ls – T relation of water and NaCl solution on self-assembled FDTS (Perfluorodecyltrichlorosilane) surface using colloidal probe AFM. The transition of ls – T monotonicity is found. For water and 0.1 M NaCl solution, ls is negatively correlated with T, while for 1 M NaCl solution, ls is positively correlated with T. FindingsTogether with molecular dynamics simulations, such observation is quantitatively explained with an analytical model based on rate theory, where the ls – T monotonicity depends on the difference between liquid–solid interfacial energy barrier and liquid internal energy barrier. Our results provide not only solid experimental evidence for the boundary slip being a rate process, but also a basis for the thermal-hydrodynamic design of microfluidic and nanofluidic devices.

Insights and Applications of Composite Electroplating

Composite electroplating is the process of particle incorporation during the electrolytic deposition of metal. This process produces composite films consisting of a metallic matrix containing a dispersion of small particles. The advantages of composite electrodeposition over other coating methods are the uniformity of deposition even for complex shapes, the strong adhesion to the substrate, reduction of waste compared to dipping or spraying techniques, low levels of contamination, the ability to produce functionally-gradient material and to continuously process parts. In addition, this process avoids the problems associated with high temperature or vacuum processing.There are many contradictory experimental results in literature concerning the effects of the electrocodeposition process variables on particle incorporation. The effects of some of the process variables also vary for different particle-electrolyte combinations and cell configurations. Some of the reported contradictions are a direct consequence of incomparable hydrodynamics. The bulk of experimental electrocodeposition research has been conducted using a vertical parallel plate electrode set-up. In this configuration, the particles are maintained in suspension by either stirring the solution, vibrating a perforated plate at the bottom of the cell, bubbling gas, or pumping the suspension through the cell, all of which result in uncontrollable, and hence incomparable hydrodynamics. Other contradictions are due to the fact that the process parameters were evaluated only for a narrow range of experimental parameters and to differences in particle size and purity.This talk discusses the experimental results and mathematical modeling of electrocodeposition of particles in a metallic matrix. The effects of several key parameters, such as current density, particle loading, electrolyte composition, particle surface charge and polarity, on particle incorporation in electrodeposited composite coatings were studied and modeled. All experiments were done utilizing rotating disk electrodes over a wide range of experimental conditions in which the incorporation behavior changes appreciably, yielding reproducible data for better interpretation of process effects and modeling. These studies were combined with colloidal probe AFM experiments and process archeology using pulse plating which helped to understand the codeposition mechanism.

Microstructural probing of phosphonium-based ionic liquids on a gold electrode using colloid probe AFM.

Atomic force microscopy (AFM) with a gold colloid probe modeled as the electrode surface is employed to directly capture the contact resonance frequency of two phosphonium-based ionic liquids (ILs) containing a common anion [BScB]- and differently lengthened cations ([P6,6,6,14]+ and [P4,4,4,8]+). The comparative interfacial studies are performed by creating IL films on the surface of gold, followed by measuring the wettability, thickness of the films, adhesion forces, surface morphology and AFM-probed contact resonance frequency. In addition, the cyclic voltammetry and impedance spectroscopy measurements of the neat ILs are measured on the surface of the gold electrode. The IL with longer cation alkyl chains exhibits a well-defined thin film on the electrode surface and enhanced the capacitance than the shorter chain IL. The AFM contact resonance frequency and force curves reveal that the longer IL prefers to form stiffer ion layers at the gold electrode surface, suggesting the "…anion-anion-cation-cation…" bilayer structure, in contrast, the shorter-chain IL forms the softer cation-anion alternating structure, i.e., "…anion-cation-anion-cation…".

Mapping humidity-dependent mechanical properties of a single cellulose fibre

Modelling of single cellulose fibres is usually performed by assuming homogenous properties, such as strength and Young’s modulus, for the whole fibre. Additionally, the inhomogeneity in size and swelling behaviour along the fibre is often disregarded. For better numerical models, a more detailed characterisation of the fibre is required. Herein, we report a method based on atomic force microscopy to map these properties along the fibre. A fibre was mechanically characterised by static colloidal probe AFM measurements along the longitudinal direction of the fibre. Thus, the contact stress and strain at each loading point could be extracted. Stress–strain curves were be obtained along the fibre. Additionally, mechanical properties such as adhesion or dissipation were mapped. Local variations of the effective fibre radius were recorded via confocal laser scanning microscopy. Scanning electron microscopy measurements revealed the local macroscopic fibril orientation and provided an overview of the fibre topography. By combining these data, regions along the fibre with higher adhesion, dissipation, bending ability and strain or differences in the contact stress when increasing the relative humidity could be identified. This combined approach allows for one to obtain a detailed picture of the mechanical properties of single fibres.Graphic abstract

On the interaction between PEDOT:PSS and cellulose: Adsorption mechanisms and controlling factors

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a conducting polymer frequently used with cellulose, to develop advanced electronic materials. To understand the fundamental interactions between cellulose and PEDOT:PSS, a quartz crystal microbalance with dissipation (QCM-D) was used to study the adsorption of PEDOT:PSS onto model films of cellulose-nanofibrils (CNFs) and regenerated cellulose. The results show that PEDOT:PSS adsorbs spontaneously onto anionically charged cellulose wherein the adsorbed amount can be tuned by altering solution parameters such as pH, ionic strength and counterion to the charges on the CNF. Temperature-dependent QCM-D studies indicate that an entropy gain is the driving force for adsorption, as the adsorbed amount of PEDOT:PSS increased with increasing temperature. Colloidal probe AFM, in accordance with QCM-D results, also showed an increased adhesion between cellulose and PEDOT:PSS at low pH. AFM images show bead-like PEDOT:PSS particles on CNF surfaces, while no such organization was observed on the regenerated cellulose surfaces. This work provides insight into the interaction of PEDOT:PSS/cellulose that will aid in the design of sustainable electronic devices.

Increasing AFM colloidal probe accuracy by optical tweezers.

A precise determination of the cantilever spring constant is the critical point of all colloidal probe experiments. Existing methods are based on approximations considering only cantilever geometry and do not take into account properties of any object or substance attached to the cantilever. Neglecting the influence of the colloidal sphere on the cantilever characteristics introduces significant uncertainty in a spring constant determination and affects all further considerations. In this work we propose a new method of spring constant calibration for ‘colloidal probe’ type cantilevers based on the direct measurement of force constant. The Optical Tweezers based calibration method will help to increase the accuracy and repeatability of the AFM colloidal probe experiments.

Surface charge density and diffuse layer properties of highly defined 2:1 layered silicate platelets

Clays are not only ubiquitous in nature, but they are also used in huge quantities in a broad range of industrial applications, such as thixotropic drilling fluids, ore pelletizers, waste disposal sealants, or fillers in polymer nanocomposites. In order to model environmental processes or to design new materials on a rational base, it is of prime importance to determine and possibly modify the interfacial properties of clay platelets at the solid/electrolyte interface. In this context, the fundamental question rises how far the stoichiometric interlayer charges as determined by the composition of the silicate layer correlates with the diffuse double-layer properties. Here, this question is addressed by means of a series of purposely synthesized sodium 2:1 layered silicates with defined composition and hence interlayer charge densities, respectively. Platelets of layered silicates of large enough diameter to perform AFM colloidal probe measurements were produced by melt synthesis. For comparison also, a natural muscovite mica has been included in this study. The diffuse layer properties in electrolyte solution have been determined by direct force measurements using the colloidal probe AFM technique and by electrokinetic measurements, respectively. We find that the diffuse layer potential decreases with increasing interlayer charge of the 2:1 layered silicates. This counterintuitive finding is attributed to ion adsorption and was further corroborated by determining the quantitative adsorption of polyelectrolytes, namely poly(amidoamine) dendrimers.Graphical abstract

Large Effective Slip on Lubricated Surfaces Measured with Colloidal Probe AFM.

In this work, we study the interfacial boundary conditions at the interface between two immiscible liquids under a laminar flow. We measure the hydrodynamic drainage forces acting on a colloid probe as it approaches a flat and smooth Teflon film coated with silicone oil films, submerged in a sucrose solution using atomic force microscopy. On Teflon substrates, silicone oil films of thickness several hundred nanometers could be stabilized, and we found the effective slip length over these to be of the order of several hundred nanometers which increases with increasing silicone oil film thickness, as expected. The fitted slip length values weakly increased with increasing shear rates. The high values of effective slip length indicate that lubricant-infused surfaces are likely to reduce drag on length scales that approach the macroscopic scales.

Optimized process for the fabrication of PDMS membranes integrating permanent micro-magnet arrays

Here we report on the fabrication of micro-magnet arrays by powder agglomeration in a polymer matrix. The NdFeB@polydimethylsiloxane (PDMS) inner microstructure and the generated magnetic forces were studied, when prepared under two different magnetic field configurations. The initial process uses the classical crosslinking of PDMS mixed with NdFeB powder under a low magnetic field gradient provided by a permanent magnet (LG set-up for low gradient). In contrast, the optimized process uses an intermediate layer, composed of iron microstructures in a PDMS matrix that amplifies and focuses the magnetic field gradient given by the permanent magnet (HG set-up for high gradient). Both processes result in a heterogeneous material that can be described as an array of permanent micro-magnets diluted in a non-magnetic host matrix. The NdFeB@PDMS microstructure was characterized by X-ray tomography and optical microscopy. The magnetic properties were also measured by magnetometry and colloidal probe AFM. Results showed that the HG set-up leads to an array of micro-magnets localized at the surface, with higher compactness and density, resulting in stronger magnetic performances compared to the LG set-up. This technology only implies easy-to-handle and cheap fabrication processes, paving the way for the development of low-cost lab-on-chip devices integrating magnetophoretic trapping functionality.

Preparation and characterization of cellulose acetate membranes with TEMPO-oxidized cellulose nanofibrils containing alkyl ammonium carboxylates

Cellulose acetate (CA) membranes have been widely used for water purification owing to several advantages, e.g., biocompatibility and low fouling rate. However, they suffer from a lower water flux compared to the other polymeric membranes. Therefore, in this study, CA membranes were blended with 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (T-CNFs) containing quaternary alkyl ammonium (QA) carboxylates to improve their water flux. When increasing the alkyl chain length of the QAs, the positron lifetime and intensity of the CA membranes increased and decreased respectively, as revealed via positron annihilation lifetime spectroscopy. This indicated that the CA membranes had larger and fewer pores when using the T-CNFs containing QAs with longer alkyl chains. The pure water flux of these membranes also increased with the alkyl chain lengths of QAs although their rejection rate (Rj) decreased accordingly. However, they revealed a potentiality to be used as ultrafiltration membranes, allowing a 99% Rj for albumin. The tensile strength, strain to failure, and work of fracture of the CA membranes increased when blended with T-CNFs. Force measurements using the AFM colloidal probe technique showed that the adhesion between the membrane constituents depends on their surface chemistry. This indicated that the structural differences observed among the blended membranes may be due to the affinity between CA and T-CNF containing QAs with different alkyl chain lengths. This study demonstrates that the properties of CA membranes can be tailored by the addition of T-CNFs with different surface chemistries.

A simple extension of the commonly used fitting equation for oscillatory structural forces in case of silica nanoparticle suspensions.

Background: The ordering of molecules or particles in the vicinity of a confining surface leads to the formation of an interfacial region with layers of decreasing order normal to the confining surfaces. The overlap of two interfacial regions gives rise to the well-known phenomenon of oscillatory structural forces. These forces are commonly fitted with an exponentially decaying harmonic oscillation as introduced by Israelachvili (Israelachvili, J. N. Intermolecular & surface forces; Academic Press: San Diego, CA, USA, 1985). From the fit three important parameters are obtained, namely wavelength, amplitude and decay length, which are related to the period, the strength and the correlation length of the oscillatory structural forces, respectively. The paper addresses structural forces between a silica microsphere and a silicon wafer across silica nanoparticle suspensions measured with a colloidal probe AFM. Using the simple fitting procedure with three parameters often leads to underestimation of actually measured forces. The deviation of the fit from the experimental data is especially pronounced at small distances of the confining surfaces and at high concentrations of silica nanoparticles. As a consequence, the parameters of the common fit equation vary with the starting point of the fit. Although the wavelength is least affected and seems to be quite robust against the starting point of the fit, all three parameters show distinct oscillations, with a period similar to the wavelength of the oscillatory structural forces themselves. The oscillations of amplitude and decay length, which are of much higher magnitude, show a phase shift of 180° implying not only a dependence on the starting point of the fit but also on each other. The range affected by this systematic deviation of the fit parameters is much larger than the optically perceived mismatch between fit and experimental data, giving a false impression of robustness of the fit.Results: By introducing an additional term of exponentially decaying nature the data can be fitted accurately down to very small separations and even for high silica nanoparticle concentrations (10 wt %). Furthermore wavelength, amplitude and decay length become independent of the starting point of the fit and in case of the latter two of each other. The larger forces at small separations indicate a more pronounced ordering behavior of the particles in the final two layers before the wall. This behavior is described by the proposed extension of the common fit equation.Conclusion: Thus, the extension increases the accessible data range in terms of separation and concentration and strongly increases the accuracy for all fitting parameters in the system studied here.

Polymersomes at the solid-liquid interface: Dynamic morphological transformation and lubrication

Polymersomes are hollow spheres self-assembled from amphiphilic block copolymers of certain molecular architecture. Whilst they have been widely studied for biomedical applications, relatively few studies have reported their interfacial properties. In particular, lubrication by polymersomes has not been previously reported. Here, interfacial properties of polymersomes self-assembled from poly(butadiene)-poly(ethylene oxide) (PBD-PEO; molecular weight 10,400 g mol−1) have been studied at both hydrophilic and hydrophobic surfaces. Their morphology at silica and mica surfaces was imaged with quantitative nanomechanical property mapping atomic force microscopy (QNM AFM), and friction and surface forces they mediate under confinement between two surfaces were studied using colloidal probe AFM (CP-AFM). We find that the polymersomes remained intact but adopted flattened conformation once adsorbed to mica, with a relatively low coverage. However, on silica these polymersomes were unstable, rupturing to form donut shaped residues or patchy bilayers. On a silica surface hydrophobized with a 19 nm polystyrene (PS) film, the polymer vesicles formed a more stable layer with a higher surface coverage as compared to the hydrophilic surface, and the interfacial structure also evolved over time. Moreover, friction was greatly reduced on hydrophobized silica surfaces in the presence of polymersomes, suggesting their potential as effective aqueous lubricants.

Measuring elasticity of wet cellulose beads with an AFM colloidal probe using a linearized DMT model

The mechanical properties of wet cellulose are investigated using an atomic force microscope AFM and calculated using a linearized DMT model.

Colloid-probe AFM studies of the surface functionality and adsorbed proteins on binary colloidal crystal layers

We demonstrate the applicability of colloid-probe AFM to detect different surface chemistries on binary colloidal crystal layers of different chemical and protein patterns.

Effect of Final Monomer Deposition Steps on Molecular Layer-by-Layer Polyamide Surface Properties.

A current challenge to desalination membrane technology is the inability to precisely control the properties of the polyamide selective layer due to the complexity of interfacial polymerization. In this study, we investigate the ability of molecular layer-by-layer (mLbL) assembly, an alternative polyamide fabrication technique, to create polyamide surfaces with tunable chemistry. We explore the influence of terminating monomer, monomer deposition time, monomer size, and the presence of underlying ionizable functional groups on mLbL-derived polyamide surface properties. AFM colloidal probe measurements, contact angle titrations, QCM cesium adsorption experiments, and XPS data show that polyamide films terminated with m-phenylenediamine or trimesoyl chloride for 20-30 s are chemically similar. Increasing terminating monomer deposition time or using a smaller, more reactive monomer results in more distinct colloidal-probe adhesive interactions, contact angle titration curves, negative charge densities, and near surface atomic compositions. By optimizing the final monomer deposition steps, both amine-rich and carboxyl-rich polyamide surfaces can be fabricated, which has implications for the application of mLbL assembly to membrane-based desalination.

Dispersion Control of Liquid Toner by Dispersant and Analysis of Adsorption Structure

Dispersant which is effective for dispersion of liquid toner and adsorption structure of the dispersant were investigated. In order to disperse polyester toner particles in paraffin oil, a basic dispersant was examined. As the adsorbing unit, polyethyleneimine was selected, which can adsorb to carboxylic acid of polyester toner by acid-base interaction. Homopolymer of 12-hydroxystearic acid was selected as the dispersing unit because it has low polarity and it is easy to control molecular weight. Amide dispersants were synthesized by condensation reaction between adsorbing units and dispersing units of different molecular weight. After the evaluation of liquid toner dispersibility with synthesized or commercially available dispersants, it was found that the dispersant with low molecular weight adsorbing units showed better dispersibility than one with high molecular weight adsorbing units. To compare the adsorption structure of dispersants, interaction force between surfaces adsorbed with each dispersant was analyzed by colloidal probe AFM. It was indicated that the adsorbing unit of high molecular weight forms train-loop-tail structure, while that of low molecular weight forms the brush-like layer. In the case of dispersant of high molecular weight, it was suggested that some of the adsorbing unit may adsorb to more than a single particle, which causes cross-linking between particles and leads to bad dispersibility.

Swelling and Surface Interactions of End-Grafted Poly(2-vinylpyridine) Layers in Acidic Solution: Influence of Grafting Density and Salt Concentration.

In previous studies, the authors found that end-grafted layers of the weak polybase poly(2-vinylpyridine) (P2VP) in aqueous solutions do not only swell and collapse if the pH value and salt concentration are varied but also exhibit a pH- and salinity-dependent adhesion to microsized silica spheres. For a better understanding of these effects, in situ force measurements using the AFM colloidal probe technique were applied to end-grafted P2VP layers of different grafting densities in NaCl solutions at pH 2.5. Although a mushroom-to-brush transition could be seen in the dry state, the layers were in the brush regime in aqueous solutions at all NaCl concentrations and grafting densities. We observed an increase of the brush height with increasing grafting density and a salinity-dependent collapse and reswelling of the brushes. The adhesion between the P2VP layer and a silica sphere depended on both grafting density and salinity. At low salt concentrations, the adhesion reached its highest value at the intermediate grafting density and disappeared with denser brushes. Maximum adhesion was obtained for high NaCl concentrations and the lowest grafting density. From a detailed analysis of the experiments, we gained insight into chain stretching and density profiles under complex ionic conditions and into the mechanism of adhesion of polyelectrolytes to solid surfaces.

Tuning the Mechanical Properties of Hydrogel Core-Shell Particles by Inwards Interweaving Self-Assembly.

Mechanical properties of hydrogel particles are of importance for their interactions with cells or tissue, apart from their relevance to other applications. While so far the majority of works aiming at tuning particle mechanics relied on chemical cross-linking, we report a novel approach using inwards interweaving self-assembly of poly(allylamine) (PA) and poly(styrenesulfonic acid) (PSSA) on agarose gel beads. Using this technique, shell thicknesses up to tens of micrometers can be achieved from single-polymer incubations and accurately controlled by varying the polymer concentration or incubation period. We quantified the changes in mechanical properties of hydrogel core-shell particles. The effective elastic modulus of core-shell particles was determined from force spectroscopy measurements using the colloidal probe-AFM (CP-AFM) technique. By varying the shell thickness between 10 and 24 μm, the elastic modulus of particles can be tuned in the range of 10-190 kPa and further increased by increasing the layer number. Through fluorescence quantitative measurements, the polymeric shell density was found to increase together with shell thickness and layer number, hence establishing a positive correlation between elastic modulus and shell density of core-shell particles. This is a valuable method for constructing multidensity or single-density shells of tunable thickness and is particularly important in mechanobiology as studies have reported enhanced cellular uptake of particles in the low-kilopascal range (<140 kPa). We anticipate that our results will provide the first steps toward the rational design of core-shell particles for the separation of biomolecules or systemic study of stiffness-dependent cellular uptake.