AFM imaging and characterization of latex particles formed by copolymerization of styrene and poly(ethylene oxide) macromonomer

A new type of latex particle was prepared by copolymerization of styrene and poly(ethylene oxide) macromonomer. By controlling the concentration of styrene in reaction mixtures, several latexes with different grain sizes were obtained. The packing patterns of the latex films as well as shapes and sizes of the latex particles were measured with atomic force microscopy (AFM). AFM images revealed that the grain sizes of the latexes increase with increasing concentration of styrene. At a higher styrene concentration (10 wt%), the latex showed a rather homogenous distribution of grain sizes. Lateral force microscopy (LFM) was used to reveal frictional features of latex particles. Contact and non-contact mode AFM were employed to image the same sample of the latex films. The results show that AFM working in non-contact mode can be used to effectively eliminate the horizontal-line-like artifacts, which may obscure AFM images.     

Measurement of mobility of adsorbed colloids by lateral force microscopy

The surface mobility of colloidal latex particles adsorbed on mica was measured by moving the particles with an AFM tip in the lateral force microscopy mode. The same particle was repeatedly scanned while the normal force was gradually increased, until the particle was displaced from its location on the substrate. The lateral (friction) force curve obtained for that scan was then used to determine the force needed to displace the particle. The data accumulated for approximately 100 particles indicate a wide distribution in the lateral force required. However, the data show that the mean lateral force is proportional to the particle diameter, with the effect of electrostatic interactions on the mobility of adsorbed particles seen to be weak. These results are consistent with classical theories of friction in macroscopic systems.     

GIUSAXS and AFM studies on surface reconstruction of latex thin films during thermal treatment

The structural evolution of a single-layer latex film during annealing was studied via grazing incidence ultrasmall-angle X-ray scattering (GIUSAXS) and atomic force microscopy (AFM). The latex particles were composed of a low-Tg (-54 degrees C) core (n-butylacrylate, 30 wt %) and a high-Tg (41 degrees C) shell (t-butylacrylate, 70 wt %) and had an overall diameter of about 500 nm. GIUSAXS data indicate that the q(y) scan at q(z) = 0.27 nm(-1) (out-of-plane scan) contains information about both the structure factor and the form factor. The GIUSAXS data on latex films annealed at various temperatures ranging from room temperature to 140 degrees C indicate that the structure of the latex thin film beneath the surface changed significantly. The evolution of the out-of-plane scan plot reveals the surface reconstruction of the film. Furthermore, we also followed the time-dependent behavior of structural evolution when the latex film was annealed at a relatively low temperature (60 degrees C) where restructuring within the film can be followed that cannot be detected by AFM, which detects only surface morphology. Moreover, compared to AFM studies GIUSAXS provides averaged information covering larger areas.     

Latex film morphology and electrical potential pattern dependence on serum components: a scanning probe microscopy study

Dry films formed by surfactant-stabilized, peroxide-initiated styrene-butyl acrylate latex were examined by atomic and electric force microscopy (AFM and EFM). The effects of latex serum components on the films were observed by subjecting the latex to extensive dialysis prior to film formation, and comparing the results to as-prepared latex. The films formed with the dialyzed latex are smoother (as evidenced by roughness and fractal dimension measurements) than the films from the as-prepared latex, but they display large electric force gradients between neighboring domains. The films made with the as-prepared latex have the highest electric uniformity, with a maximum potential variation lower than 80 mV, while this reaches 200 mV in the dialyzed latex film.     

Layer-by-layer synthesis of multilayer core-shell latex and the film formation properties

Polymer latex particles were synthesized with multilayer core-shell structure via surface cross-linking emulsion polymerization. The latex core is coated with a five-layer shell. The polymerization was done in a semicontinuous fashion monitored by a dynamic laser scattering (DLS). The copolymer in each layer is designed with alternating high and low glass transition temperature (T(g)). Divinylbenzene (DVB) was added as the cross-linking agent in the synthesis of the "hard" layers to prevent the molecular diffusion from the adjacent "soft" layers. The layer-by-layer increment on the latex core is proved by the alternating changes on the film-formation capabilities of different latex emulsions at room temperature in correspondence with the variance in the T(g) of the outermost polymer layer. The detailed morphologies of the films formed by the latex with different number of layers were characterized by atom force microscopy (AFM). The deformation of the latex particles is largely depended on the nature of the polymer in the outermost layer of the latex particles. Further characterization carried out by multifrequency temperature-modulated differential scanning calorimetry (TOPEM-DSC) confirmed the layer-by-layer structure of the particles, although the molecular redistribution and the interlayer structures were observed. The work provides a routine toward the synthesis of multilayer polymer latexes.     

Synthesis of block copolymer poly (n-butyl acrylate)-b-polystyrene by DPE seeded emulsion polymerization with monodisperse latex particles and morphology of self-assembly film surface

Synthesis of poly (n-butyl acrylate)-b-polystyrene (PnBA-b-PSt) with high molecular weight in an environmentally benign medium was carried out in seeded emulsion polymerization, using a novel chain transfer active DPE (1,1-diphenylethylene) agent. Seed latex containing precursor P(nBA-DPE) was prepared first, and the second monomer styrene was swelled into seed latex particles, yielding block copolymer at high conversion. Structures as well as molecular weight of precursor and block copolymer were characterized by FTIR, (1)H NMR, and SEC, respectively. Furthermore, Transmission Electron Microscopy (TEM) observation and Laser Light Scattering (LLS) manifested that monodisperse latex particles were obtained. Self-assembly morphology of block copolymer membrane surface was examined by atom force microscopy (AFM). Phase separation was observed clearly, which was confirmed by the observation of two glass transitions in DSC curve.     

Kinetics of latex formation of PBMA latex in the presence of alkali soluble resin using atomic force microscopy

 The effect of alkali-soluble resin (ASR), poly(ethylene-co-acrylic acid), EAA, postadded to emulsifier-free monodisperse poly(butyl methacrylate) (PBMA) latexes on the kinetics of film formation was investigated using atomic force microscopy (AFM). Corrugation height of latex particles in films was monitored at various annealing temperatures as a function of annealing time. Enhanced polymer diffusion was found in a latex film containing ASR regardless of anneal-ing temperature. With increasing annealing temperature, a much higher rate of polymer diffusion was found in latex films containing ASR. These results can be interpreted that the low molecular weight and low Tg EAA resin adsorbed at the particle surface is more susceptible to diffusion than that of the PBMA in the film formation stage, thus it enhances the mobility of PBMA polymer. Received: 30 October 1997 Accepted: 20 March 1998     

Nanoscale Wetting of Single Viruses

The epidemic spread of many viral infections is mediated by the environmental conditions and influenced by the ambient humidity. Single virus particles have been mainly visualized by atomic force microscopy (AFM) in liquid conditions, where the effect of the relative humidity on virus topography and surface cannot be systematically assessed. In this work, we employed multi-frequency AFM, simultaneously with standard topography imaging, to study the nanoscale wetting of individual Tobacco Mosaic virions (TMV) from ambient relative humidity to water condensation (RH > 100%). We recorded amplitude and phase vs. distance curves (APD curves) on top of single virions at various RH and converted them into force vs. distance curves. The high sensitivity of multifrequency AFM to visualize condensed water and sub-micrometer droplets, filling gaps between individual TMV particles at RH > 100%, is demonstrated. Dynamic force spectroscopy allows detecting a thin water layer of thickness ~1 nm, adsorbed on the outer surface of single TMV particles at RH < 60%.     

Analysis of Contact Interactions between a Rough Deformable Colloid and a Smooth Substrate

A model was developed for the effect of van der Waals interactions between a rough, deformable, spherical colloid and a flat, smooth, hard surface in contact. The model demonstrates the significant effect of colloid roughness on removal force. Small changes in colloid roughness produce large changes in the predicted removal force. Several authors attribute discrepancies in the observed interaction force between particles and surfaces to colloid roughness, and our model supports their hypotheses. Experimental data documenting the force required to remove colloids of polystyrene latex from silica substrates in aqueous solution were collected during AFM studies of this system. When colloid roughness exists, as is the case in this work, our model bounds the observed removal force. The predicted range of removal forces is in better quantitative agreement with our removal force data than are forces predicted by classical DLVO theory. Copyright 2000 Academic Press.     

Latex Surface and Bulk Coagulation Induced by Solvent Vapors

Latex exposure to solvent vapors leads to highly specific changes in latex stability as well as on the morphologies of the particle association products, depending on the latex and solvent used. Examples of solvent vapor-induced aggregation are given: surface films are obtained on two PS latexes; in one case, the film surface is mirror-reflective and very flat, as evidenced by AFM. Another PS latex coagulates under exposure to acetone vapors, and the morphologies of the coagula are highly sensitive to the exposure conditions. This latex yields a highly porous foam-like structure, in which particles are strongly coalesced but form percolating patches around the pores. The same latex but under other conditions produces a coagulum of large numbers of aggregated particles with a raspberry-like morphology. Density centrifugation experiments show that the effect of solvents on different latex fractions is not uniform, and some fractions show larger density changes than others, thus evidencing a variability in their swelling ability. Copyright 2000 Academic Press.     

The influence of electrostatic forces on protein adsorption

In this paper we investigate the importance of electrostatic double layer forces on the adsorption of human serum albumin by UV-ozone modified polystyrene. Electrostatic forces were measured between oxidized polystyrene surfaces and gold-coated atomic force microscope (AFM) probes in phosphate buffered saline (PBS) solutions. The variation in surface potential with surface oxygen concentration was measured. The observed force characteristics were found to agree with the theory of electrical double layer interaction under the assumption of constant potential. Chemically patterned polystyrene surfaces with adjacent 5 microm x 5 microm polar and non-polar domains have been studied by AFM before and after human serum albumin adsorption. A topographically flat surface is observed before protein adsorption indicating that the patterning process does not physically modify the surface. Friction force imaging clearly reveals the oxidation pattern with the polar domains being characterised by a higher relative friction compared to the non-polar, untreated domains. Far-field force imaging was performed on the patterned surface using the interleave AFM mode to produce two-dimensional plots of the distribution of electrostatic double-layer forces formed when the patterned polystyrene surfaces is immersed in PBS. Imaging of protein layers adsorbed onto the chemically patterned surfaces indicates that the electrostatic double-layer force was a significant driving force in the interaction of protein with the surface.     

Adhesion of spherical polyelectrolyte brushes on mica: an in situ AFM investigation

We demonstrate that the adsorption of cationic spherical polyelectrolyte brushes (SPB) on negatively charged mica substrates can be controlled in situ by the ionic strength of the suspension. The SPB used in our experiments consist of colloidal core particles made of polystyrene. Long cationic polyelectrolyte chains are grafted onto these cores that have diameters in the range of 100 nm. These particles are suspended in aqueous solution with a fixed ionic strength. Atomic force microscopy (AFM) in suspension as well as in air was used for surface characterization. In pure water the polymer particles exhibit a strong adhesion to the mica surface. AFM investigations of the dry samples show that the particles occupy the identical positions as they did in liquid. They were not removed by the capillary forces within the receding water front during the drying process. The strong interaction between the particles and the mica surface is corroborated by testing the adhesion of individual particles on the dried surface by means of the AFM tip: after a stepwise increase of the force applied to the surface by the AFM tip, the polymer particles still were not removed from the surface, but they were cut through and remained on the substrate. Moreover, in situ AFM measurements showed that particles which adsorb under liquid in a stable manner are easily desorbed from the surface after electrolyte is added to the suspension. This finding is explained by a decreasing attractive particle-substrate interaction, and the removal of the particles from the surface is due to the significant reduction of the activation barrier of the particle desorption. All findings can be explained in terms of the counterion release force.     

AFM study of the behavior of polystyrene and glass particles during the electrodeposition of copper

In this paper, the behavior of polystyrene and glass particles on a copper electrode during the electrodeposition of copper was studied using an atomic force microscope (AFM). Polystyrene or glass particles glued to the tip of the AFM cantilever were kept in contact with the surface of the electrode. The surface forces between the polystyrene or glass particle and the copper electrode were measured before, during, and after electrodeposition. These experiments revealed that glass particles do not make contact with the electrode, probably due to the repulsive hydration force. Polystyrene particles, on the other hand, make contact with the electrode, due to the attractive hydrophobic force. The AFM experiments were correlated with sedimentation co-deposition experiments of polystyrene and glass particles with copper. It was found that 80% of the polystyrene particles added to the plating solution incorporated with copper, while only 0.25% of the glass particles co-deposited under the same conditions.     

EFFECT OF THE PHASE STRUCTURE EVOLUTION ON THE PROPERTIES OF FILMS FORMED FROM PBA/P(St-co-MMA) COMPOSITE LATEX

A group of heterogeneous latexes poly(butyl acrylate)/poly(styrene-co-methyl methacrylate)(PBA/P(St-co-MMA)) were prepared by a semi-continuous seeded emulsion polymerization process under monomer starved conditions.The glass transition temperature(T_g)and the mechanical properties of the film formed from the composite latex changed with the evolution of the particle morphology.A photon transmission method was used to monitor the phase structure evolution of films which were prepared from core-shell PBA/...     

DOPC/DPPC单层膜中分子间的相互作用及形态特征

利用Langmuir-Blodgett(LB)技术制备了不同表面压力下的1,2-二油酸-甘油-3-磷脂酰胆碱(DOPC)/1,2-二棕榈酸甘油-3-磷脂酰胆碱(DPPC)(摩尔比为1:1)和DOPC/DPPC/Chol(摩尔比为2:2:1)单层膜, 对单层膜内分子间的相互作用进行了热力学分析, 并用荧光显微镜和原子力显微镜对其形态进行了观测.热力学分析表明, DOPC与DPPC分子在单层膜结构中相互作用为排斥力, 诱导单层膜出现相变; DOPC, DPPC与胆固醇(Chol)间的相互作用均为吸引力, 当表面压力(π)大于18 mN/m时, DPPC与胆固醇的作用力大于DOPC.荧光显微镜观测表明, DOPC/DPPC单层膜出现明显相分离现象, 富含DPPC微区成“花形”结构, 且随着表面压力的升高微区逐渐增大, “花瓣”增多; 当胆固醇加入到DOPC/DPPC体系时, 单层膜相态由液相与凝胶相共存转变为液态无序相与液态有序相共存结构, 富含DPPC的微区形状从“花形”转变成“圆形”.原子力显微镜对单层膜的表征验证了荧光显微镜的观测结果, 表明胆固醇加入到DOPC/DPPC体系中对单层膜排列具有明显的影响, 压力和溶液状态等是影响脂膜结构的重要因素.     

In-situ AFM studies of the phase-transition behavior of single thermoresponsive hydrogel particles

The volume phase transition (VPT) behavior of individual thermally responsive poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) hydrogel microparticles was studied by in-situ dynamic mode atomic force microscopy (AFM) and force spectroscopy during heating and cooling cycles. Hydrogel samples were prepared by electrostatic immobilization of microparticles to amine-modified gold surfaces. The AFM studies of particle deswelling were performed by varying the force applied on the particles during imaging as a function of the geometry and material of the AFM probe. Aluminum-coated silicon cantilevers were found to influence substantially the behavior of the particles during the VPT, leading to a significant shape change. Low force impact magnetic excitation of the AFM probe (MAC mode) during dynamic mode measurements resulted in an undisturbed deswelling behavior enabling observation of the expected volume changes of the particles without significant tip-sample interaction. Hence, MAC-mode AFM was determined to be the most suitable technique for in-situ AFM studies on volume and shape changes at single hydrogel particles during VPT. Elasticity measurements performed at single particles at temperatures below and above the VPT revealed a 15-fold increase in the Young's modulus after passing the VPT, indicating the transition from a soft, swollen network to a stiffer, deswollen state.     

Study of bulk morphology of polymer latex films using laser confocal fluorescence microscopy

Ｐｏｌｙｍｅｒｆｉｌｍｆｏｒｍａｔｉｏｎｆｒｏｍｅｉｔｈｅｒｌａｔｅｘｏｒｓｏｌｕｔｉｏｎｉｓｑｕｉｔｅａｎｉｎｔｅｒｅｓｔｉｎｇｂｕｔｃｏｍｐｌｉｃａｔｅｄｓｕｂｊｅｃｔｄｅａｌｉｎｇｗｉｔｈｄｉｆｆｕｓｉｏｎ,ｉｎｔｅｒｐｅｎｅｔｒａｔｉｏｎａｎｄｃｏａｇｕｌａｔｉｏｎｏｆｐｏｌｙｍｅｒｃｈａｉｎｓ,ａｎｄｅｓｐｅｃｉａｌｌｙｃｏｒｒｅｌａｔｅｄｔｏｔｈｅｐｒｏｐｅｒｔｉｅｓｏｆｔｈｅｆｉｎａｌｌｙｆｏｒｍｅｄｆｉｌｍ.Ｍａｎｙｓｔｕｄｉｅｓ[1—3]ｈａｖｅｂｅｅｎｃａｒｒｉｅｄｏｕｔｏｎｌａｔ…     

Interaction between poly(styrene-acrylic acid) latex nanoparticles and zinc oxide surfaces

Latex particles with an average diameter of 70 nm, functionalized at the surface with carboxylic groups, are chemically coated by layer-by-layer deposition onto a spherical probe attached on an atomic force microscope cantilever. The forces between poly(styrene-acrylic acid) latex nanoparticles and differently terminated zinc oxide surfaces are studied by a homemade atomic force microscope based apparatus. The results confirmed a preferred adhesion of the latex particles to zinc-terminated ZnO faces, 0001, compared to oxygen-terminated and apolar faces. The method proposed allows the measurement of the interaction between nanometric particles and planar surfaces, which may be of interest for different applications in surface and colloid sciences.     

PDMS-MDI-PEG多嵌段共聚物涂层表面微相分离行为研究

采用两步溶液聚合方法合成了一系列聚二甲基硅氧烷(PDMS)-4,4′-二苯基甲烷二异氰酸酯(MDI)-聚乙二醇(PEG)多嵌段共聚物.利用轻敲模式原子力显微镜(AFM)观察了嵌段共聚物的表明形貌,研究了退火、共聚物组成以及PEG分子量和不同的官能团对涂层表面微相分离行为的影响,同时对微相分离行为的形成机理也作了相应的探讨.研究表明,该嵌段共聚物即使在PDMS含量大于50wt%时,涂层表面仍呈现出规整有序的纳米级相分离结构,其中疏水相和亲水相分别由PDMS链段和MDI-PEG组分构成.