Measuring local viscoelastic properties of complex materials with tapping mode atomic force microscopy

Tapping mode atomic force microscopy is a technique to measure the topography and properties of surfaces involving a micro-cantilever with a tip at one end that is excited into an oscillation near its resonance frequency. The phase lag between the excitation signal and the observed oscillation is sensitive to local mechanical properties under certain experimental conditions. We have found that by using silicon as an internal standard reference surface we can unambiguously relate the phase lag to local viscoelastic properties of a polymeric material. A model describing this relation has been built, validated with experimental data and finally inverted such that it can be used to determine local properties. This allows us to measure high frequency local viscoelastic properties on length scales as small as several nanometers. This technique works well for relatively compliant polymer surfaces with a shear modulus less than about 1 GPa.     

Latex characterization by atomic force microscopy

Ways, benefits and limitations of extracting the form and size of single latex particles or particle size distributions out of the surface topography of non-coalesced latex films obtained by atomic force microscopy (AFM) are discussed. The general ways to generate the desired information out of topographical information in terms of height, surface curvature and lateral extensions are shown for idealized particles and measurement conditions. The different sources of information are evaluated for practical use and the analysis of particle size distributions is demonstrated by practical examples. The information content in lateral particle dimensions is shown to be the most advantageous for practical use. Determination of latex particle size distributions by AFM is shown to be an interesting alternative to the arsenal of available methods with respect to exactness of results, time consummation and instrumentation costs.     

Nanomechanical mapping of glass fiber reinforced polymer composites using atomic force acoustic microscopy

In this work, a dual‐frequency resonance tracking (DFRT) method was applied on atomic force acoustic microscopy (AFAM) and high‐resolution, quantitative nanomechanical mapping of a glass fiber–reinforced polymer composites (GFRP) was realized. Results show that even using the single‐frequency AFAM, the fiber, and epoxy can give very good contrast in amplitude images. The modulus mapping result on GFRP by DFRT AFAM was compared with that by dynamic nanoindentation, and it is found that DFRT AFAM can map the elastic modulus with high spatial resolution and more reliable results. The interface of GFRP was especially investigated using a 2 μm × 2 μm scanning area. Finite element analysis was implemented to investigate the effect of tip radius and the applied pressing force on the interface measurement using a sharp “interface”. By setting a linear‐modulus‐varied interface with finite width in finite element analysis (FEA), similar comparison between FEA and AFAM experimental results was also implemented. The average interface width is determined to be 476 nm based on the high‐resolution modulus image, indicating that AFAM is a powerful method for nanoscale interface characterization. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39800.     

Crystal growth of faujasite observed by atomic force microscopy

Atomic force microscopy (AFM) was employed to reveal the crystal growth mechanism of faujasite. The seeded growth of faujasite in dilute aluminosilicate solutions was observed. Two solutions were prepared: one was near equilibrium with the seed and the other was in growth mode for the seed. Morphological changes during the seeded growth were observed along with the growth period at the same position on the seed (ex situ observation). These observations showed the rough surface of the seed changing into a well-ordered (1 1 1) face in the solution that was near equilibrium with the seed. This surface ordering proceeded by thermodynamic stabilization of the top-surface structure via the mutual transfer of aluminosilicate species between the solution and solid phases, and/or by the dissolution of the amorphous matter on the seed. In growth mode, most of the top surfaces of the seeded crystals were terminated by double six-membered rings (D6Rs), while some were by complete or incomplete sodalite cage. These results showed that aluminosilicate species equal to or smaller than 6R contributed to the crystal growth.     

A study of adhesion forces by atomic force microscopy

An atomic force microscope (AFM) was used to investigate Si₃N₄ tip interactions with various materials in four different liquid media (water, ethanol, ethylene glycol, and formamide). The adhesion forces calculated using surface energies and the values measured experimentally were compared. For all materials, the calculated adhesion force closely correlated with AFM measurements, except in water. In the case of water, the AFM experiments showed strong adhesion, whereas theoretically (van Oss-Chaudhury-Good model) repulsion is predicted. The difference observed is discussed in terms of the chemical interactions between Si₃N₄ and water.     

Cellulosic nanocomposites. II. Studies by atomic force microscopy

Dissolving‐grade wood pulp fibers were partially esterified by mixed p‐toluene sulfonic/hexanoic acid anhydride in a nonswelling suspending agent. A biphasic morphology was revealed by atomic force microscopy (AFM) for the compression‐molded, partially modified pulp fibers. The AFM phase images indicated distinct periodicity on the scale of several 10's of nanometers. Surface etching with cellulolytic enzymes of the modified pulp fibers produced height images that had virtually the same periodicity. These results indicate that the modified pulp fibers are nanocomposites comprising unmodified cellulose and cellulose hexanoate. Regenerated lyocell fibers (from N,MMNO solvent) subjected to the same esterification system as applied to pulp fibers, by contrast, exhibited AFM phase images that indicated a high level of surface (skin) versus core reactivity. Modified lyocell fibers with an average diameter of about 12 μm and having an overall DS of 0.6 had surface layers that were approximately 1 μm thick. The latter represented a transitional phase in which the chemical composition and the physical properties were intermediate between a highly substituted surface (skin) and an unsubstituted core. When a compression‐molded sheet of the modified lyocell fibers was analyzed by microthermal analysis, the thermoplastic matrix on the lyocell fiber surface was revealed to have an apparent T_g of 75°C corresponding to cellulose hexanoate, whereas no significant thermal transition was determined for the (unmodified) fiber core. These results suggest that both partially modified lyocell fibers and partially modified pulp fibers are capable of producing composites with morphologies that have grossly different scales. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2254–2261, 2000     

Surface crystalline characteristics of polyurethane investigated by atomic force microscopy

A polyester—urethane was synthesized by the reaction of 2,4-toluylene diisocyanate (TDI) with poly(butylene glycol adipate) (PBGAD) using 1,4-butanediol (BDO) as a chain extender. Atomic force microscopy was employed to examine the surface morphologies of polyurethane (PU) films formed by heat treatment as well as at room temperature. At both conditions the surface of the PU film appeared as a spherulitic structure with a varied diameter and vertical height. Furthermore, the crystalline structure of heat-treated film was denser than that of the film formed at ambient. © 1996 John Wiley & Sons, Inc.     

Understanding weathering of oil sands ores by atomic force microscopy

Effect of weathering on colloidal interactions between bitumen and oil sands solids was studied by atomic force microscopy (AFM). The change in bitumen chemistry due to weathering was found to have a negligible effect on the interactions of bitumen with solid particles. However, the increase in solid surface hydrophobicity due to ore weathering reversed the long‐range interaction forces between bitumen and solids from repulsive to attractive with a corresponding increase in adhesion force. The measured force profiles between bitumen and various solids can be well fitted with the extended DLVO theory by considering an additional attractive force. The attractive long‐range force and increased adhesion force make the separation of bitumen from solids more difficult and the attachment of fine solids on liberated bitumen easier, thereby leading to poor bitumen liberation and lower aeration efficiency. Such changes account for the observed poor processability of the weathered ores. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Single polymer chain rubber elasticity investigated by atomic force microscopy

A method, which is called as ‘nanofishing’, enabled us to stretch a single polymer chain adsorbed on an Au(111) substrate with picking it at its two thiol-modified termini using atomic force microscope equipped with a gold-coated probe. A force-extension curve obtained for a single polystyrene chain in a Θ solvent (cyclohexane) showed a good agreement with a so-called worm-like chain model, and thus gave microscopic information about entropic elasticity. Solvent effects on the statistical properties of single polymer chains were also investigated. For example, the second virial coefficient in cyclohexane was determined at a single polymer basis, which was almost comparable with a simple Flory's lattice model.     

Self‐assembled multilayer films based on diazoresins studied by atomic force microscopy/friction force microscopy

The layer‐by‐layer self‐assembled NDR‐PSS (nitro‐containing diazoresin‐polysodium p‐styrenesulfonate) films were fabricated. The crosslinking structure formed from the conversion of ionic bond to covalent bond after UV irradiation, confirmed by small angle X‐ray diffraction. The roughness and microtribological properties of NDR‐PSS films were investigated by atomic force microscopy/friction force microscopy. The ordered multilayer films after photoreaction are better in microtribological performance than that of the monolayer film. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 631–638, 2000     

New applications in studies of waterborne coatings by atomic force microscopy

Atomic force microscopy (AFM) is rapidly emerging as an important tool for coatings characterization. We report several new applications of AFM of particular value to the development of improved waterborne coatings systems. First, an AFM method was developed to quantitatively assess the extent of coalescence and film formation for latex films by measurement of particle number density of protruding (uncoalesced) particles in dried coatings. Second, the use of topographic imaging to evaluate environmental (temperature) effects on film formation was investigated for a waterborne latex system. Finally, specular gloss of waterborne epoxy coatings was studied by AFM and optical measurements, and topographic features analyzed using power spectral density calculations were found to correlate with optical gloss measurements. Mechanisms for gloss reduction over time (particularly in early pot life coatings) were elucidated in the studies. Further applications in coatings studies will be driven by the development of new modes of AFM (friction force, force modulation, and phase contrast) that can be used to map mechanical properties (friction, stiffness, and adhesion) while simultaneously imaging topography. Examples of the use of the phase contrast mode to identify chemically different domains in early pot life waterborne epoxy coatings are presented.     

Nanoindentation behavior of ultrathin polymeric films

Measurement of the mechanical properties of nanoscale polymeric films is important for the fabrication and design of nanoscale layered materials. Nanoindentation was used to study the viscoelastic deformation of low modulus, ultrathin polymeric films with thicknesses of 47, 125 and 3000 nm on a high modulus substrate. The nominal reduced contact modulus increases with the indentation load and penetration depth due to the effect of substrate, which is quantitatively in agreement with an elastic contact model. The flow of the nanoscale films subjected to constant indentation loads is shear-thinning and can be described by a linear relation between the indentation depth and time with the stress exponent of 1/2.     

Morphology of extruded high-density polyethylene pipes studied by atomic force microscopy

Atomic force microscopy (AFM) was used to study the structure of extruded polyethylene (PE) pipe. During extrusion, the outer surface of the pipe was cooled with water. Two cross sections, parallel and transverse to the extrusion direction, were examined in order to spatially follow the structural development during extrusion. The morphology revealed was spherulitic, and the spherulites had a mostly banded appearance when viewed under the AFM. We were not able to distinguish an oriented skin layer at the surface of the pipe, either by AFM or polarizing microscopy. The changes in the pipe's structure resulting from the cooling conditions were found to be rather gradual, and no clearly defined zones were observed. A slight orientation towards the extrusion direction was detected only in the area of the pipe crystallized under the lowest degree of undercooling. Measured spherulitic size, band period, and lamellae thickness showed a gradual increase in their values from the cooled to the noncooled surface of the pipe. Transmission electron microscopy (TEM) was used to verify the band period and lamellae thickness measurements done by AFM. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 515–523, 1997     

Conductive-probe atomic force microscopy characterization of silicon nanowire

The electrical conduction properties of lateral and vertical silicon nanowires (SiNWs) were investigated using a conductive-probe atomic force microscopy (AFM). Horizontal SiNWs, which were synthesized by the in-plane solid-liquid-solid technique, are randomly deployed into an undoped hydrogenated amorphous silicon layer. Local current mapping shows that the wires have internal microstructures. The local current-voltage measurements on these horizontal wires reveal a power law behavior indicating several transport regimes based on space-charge limited conduction which can be assisted by traps in the high-bias regime (> 1 V). Vertical phosphorus-doped SiNWs were grown by chemical vapor deposition using a gold catalyst-driving vapor-liquid-solid process on higly n-type silicon substrates. The effect of phosphorus doping on the local contact resistance between the AFM tip and the SiNW was put in evidence, and the SiNWs resistivity was estimated.     

Adhesion force measurement of a DPI size pharmaceutical particle by colloid probe atomic force microscopy

The method to determine the adhesion characteristics of fine drug particles for dry powder inhalation (DPI) was established using a colloid probe which mounted a 1-3 μm drug particle on a commercial atomic force microscope (AFM) cantilever. A new preparation system of colloid probes for fine particles smaller than 2.5 μm in diameter was developed with the aid of a micromanipulator and a video microscope. Using this colloid probe, adhesion force distribution between a spherical polycrystalline drug particle and a plate of lactose monohydrate representing for DPI carrier materials or stainless steel for device wall materials was measured. Atmospheric humidity as well as the material and surface roughness of a target plate affected the determined adhesion force. With increasing surface roughness of a lactose plate, the adhesion force between a drug particle and the plate distributed more widely and their mean value decreased. Adhesion force increased meaningfully with atmospheric humidity. Adhesion force for stainless steel was higher than that for lactose.     

Probing polymer interdiffusion in carboxylated latices with force modulation atomic force microscopy

Interdiffusion of polymer chains between latex particles is a prerequisite for the development of good mechanical strength and homogeneity in a latex film. This process may be retarded in carboxylated latices if the particles are surrounded by a hard cell wall consisting of ionic groups on the particle surface. The presence of an ionic cell wall can be indirectly detected by atomic force microscopy (AFM) because surfactant migration to the film/air interface is retarded compared with a non-ionic case. In this paper we have used force modulation atomic force microscopy to directly probe the relative polymer density across the film surface during annealing thereby qualitatively monitoring the interdiffusion process. The applicability of this method to study polymer interdiffusion will be discussed.     

Morphological analysis of linear low density polyethylene films by atomic force microscopy

Atomic force microscopy has been used to investigate the morphology of hexene linear low density polyethylene (LLDPE) blown film in the undrawn and drawn states. The morphology of the undrawn film, which is biaxially oriented due to the nature of the extrusion process, is composed of crystallites, which consist of aggregates of lamellae. Elongation of the film caused these crystallites to undergo deformation, resulting in the gradual formation of a fibrillar structure in the draw direction. The transformation of these crystallites into fibrils corresponded with an initial increase in the surface roughness, until 250% elongation. Further extension of the film to 450% caused the surface roughness to reach a plateau. The changes observed in the surface roughness and morphology indicate that drawing of the film caused the crystallites to tilt and slip, rupturing crystalline blocks, which then develop into a fibrillar structure. Further extension of these initial fibrillar structures resulted in a more oriented fibrillar morphology. Wide‐angle x‐ray scattering clearly showed the orientation of the crystals with respect to the draw direction throughout the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 777–784, 2002     

Lamellar morphology of random metallocene propylene copolymers studied by atomic force microscopy

Four sets of propylene based random copolymers with co-units of ethylene, 1-butene, 1-hexene and 1-octene, and a total defect content up to ∼9 mol% (including co-unit and other defects), were studied after rapid and isothermal crystallization. Etched film surfaces and ultramicrotomed plaques were imaged so as to enhance contrast and minimize catalyst and co-catalyst residues. While increasing concentration of structural irregularities breaks down spherulitic habits, the formation of the gamma polymorph has a profound effect on the lamellar morphology. Lamellae grown in the radial axis of the spherulite and branches hereon are replaced in γ-rich copolymers with a dense array of short lamellae transverse or tilted to the main structural growth axis. This is the expected orientation for γ iPP branching from α seeds. Spherulites are formed in copolymers with non-crystallizable units (1-hexene and 1-octene) up to ∼3 mol% total defect content and were observed up to ∼6 mol% in those with partially crystallizable comonomers (ethylene and 1-butene). However, lamellae were observed in all the copolymers analyzed, even in the most defective ones, highlighting the important role of the gamma polymorph in propagating lamellar crystallites in poly(propylenes) with a high concentration of defects. Long periods measured from AFM and SAXS are comparatively analyzed.     

bOptimizing atomic force microscopy for characterization of diamond-protein interfaces

Atomic force microscopy (AFM) in contact mode and tapping mode is employed for high resolution studies of soft organic molecules (fetal bovine serum proteins) on hard inorganic diamond substrates in solution and air. Various effects in morphology and phase measurements related to the cantilever spring constant, amplitude of tip oscillations, surface approach, tip shape and condition are demonstrated and discussed based on the proposed schematic models. We show that both diamond and proteins can be mechanically modified by Si AFM cantilever. We propose how to choose suitable cantilever type, optimize scanning parameters, recognize and minimize various artifacts, and obtain reliable AFM data both in solution and in air to reveal microscopic characteristics of protein-diamond interfaces. We also suggest that monocrystalline diamond is well defined substrate that can be applicable for fundamental studies of molecules on surfaces in general.     

Optimizing atomic force microscopy for characterization of diamond-protein interfaces

Atomic force microscopy (AFM) in contact mode and tapping mode is employed for high resolution studies of soft organic molecules (fetal bovine serum proteins) on hard inorganic diamond substrates in solution and air. Various effects in morphology and phase measurements related to the cantilever spring constant, amplitude of tip oscillations, surface approach, tip shape and condition are demonstrated and discussed based on the proposed schematic models. We show that both diamond and proteins can be mechanically modified by Si AFM cantilever. We propose how to choose suitable cantilever type, optimize scanning parameters, recognize and minimize various artifacts, and obtain reliable AFM data both in solution and in air to reveal microscopic characteristics of protein-diamond interfaces. We also suggest that monocrystalline diamond is well defined substrate that can be applicable for fundamental studies of molecules on surfaces in general.