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Aqueous processes yielding hybrid or composite materials are widespread in natural environments and their control is fundamental for a multiplicity of living organisms. Their design and in vitro engineering require knowledge about the spatiotemporal evolution of the interactions between the involved liquid and solid phases and, especially, the interphases governing the development of adhesion during solidification. The present study illustrates the effects of distinct proteins on the precipitation of sodium chloride encompassing the size, shape and distribution of halite crystals formed during the drying of droplets containing equally concentrated saline protein solutions. The precipitates obtained from aqueous sodium chloride formulations buffered with tris(hydroxymethyl)aminomethane (Tris) contained either bovine serum albumin (BSA), fibrinogen or collagen and were characterized with respect to their structure and composition using optical and electron microscopy as well as x-ray analysis. The acquired findings highlight that depending on the protein type present during droplet drying the halite deposits predominantly exhibit cubic or polycrystalline dendritic structures. Based on the phenomenological findings, it is suggested that the formation of the interphase between the growing salt phase and the highly viscous saline aqueous jelly phase containing protein governs not only the material transport in the liquid but also the material exchange between the solid and liquid phases.

We present a versatile and highly substrate-independent approach for preparing multisandwich layers based on thermally reduced Graphene Oxide (rGO) which gets strongly attached by bio-interfactants using a layer-by-layer (LBL) aqueous dipping and rinsing process. The process allows for the deposition of homogeneous ultra-thin films (∼5.5 nm) in distinct surface topographies, thicknesses and compositions by varying the bio-interfactant layer(s). The layers formed on quartz or other semi conductive material are electrically conductive, flexible, and transparent. The here-developed approach could be applied for the fabrication of wearables, sensors, and antistatic transparent films.

Composite materials are commonly used in many branches of industry. One of the effective methods to join CFRP parts is the adhesive bonding. There is a search of effective methods for quality assurance of bonded parts. There is a need for pre- and post-bond inspection to ensure proper bonding and verify its quality. Research reported here focuses on post-bond inspection of bonded CFRP parts. In this paper we report investigations of samples that were modified with contamination that can be encountered during the manufacturing process of the CFRP parts. The contaminations were introduced before adhesive bonding, and the effect of the contamination on the quality bond is studied. First of the investigated cases was release agent contamination prepared by dip-coating of clean CFRP plates. The release agent is used during the production of composite elements and can contaminate the surface to be bonded. The second case was the moisture contamination. It was obtained by conditioning of the samples in humid conditions. Moisture contamination can be gained from water-coupled ultrasonics or during transportation of unprotected parts. The third type of contamination had more local character. It simulated fingerprints. Artificial sweat was used. The fingerprint contamination can be caused by improper handling of the parts. Apart from single contamination, also mixed contamination cases were studied, as well as curved samples. The samples were studied in non-destructive approach. It was shown that for some of the cases the detection is possible.

Composite materials are commonly used in many branches of industry. One of the effective methods to join CFRP parts is to use adhesives. There is a search of effective methods for quality assurance of bonded parts. There is a need for pre- and post-bond inspection to ensure proper bonding and verify its quality. Research reported here focuses on post-bond inspection of bonded CFRP parts. In this paper we report investigations of samples that were modified in order to simulate the conditions that can be encountered during the bonding repair processes. The modifications were made before adhesive bonding, and their effect on the quality of the bond is studied. The first case was the thermal treatment. It was made by exposure of samples to elevated temperatures. This case accounts for parts that may be exposed to external heat source or lightening impact. Second of the investigated cases was deicing fluid contamination prepared by dip-coating of clean CFRP plates. When cleaning the aircraft for a repair this fluid can be transported to bonding areas and weaken the joint. The third type of modification was faulty curing of the adhesive. It was prepared by local pre-curing of the adhesive. Pre-curing causes irregularities in the curing of the adhesive joint. Apart from single modifications, also mixed cases were studied, as well as scarf bonding. The samples were studied in non-destructive approach. It was shown that for some of the cases the detection is possible.

The aim of this work was to synthesize a non-isocyanate poly(dimethylsiloxane) hydroxyurethane with biomimetic terminal catechol moieties, as a candidate for inorganic and metallic surface modification. Such surface modifier is capable to strongly attach onto metallic and inorganic substrates forming layers and, in addition, providing water-repellent surfaces. The non-isocyanate route is based on carbon dioxide cycloaddition into bis-epoxide, resulting in a precursor bis(cyclic carbonate)-polydimethylsiloxane (CCPDMS), thus fully replacing isocyanate in the manufacture process. A biomimetic approach was chosen with the molecular composition being inspired by terminal peptides present in adhesive proteins of mussels, like Mefp (Mytilus edulis foot protein), which bear catechol moieties and are strong adhesives even under natural and saline water. The catechol terminal groups were grafted by aminolysis reaction into a polydimethylsiloxane backbone. The product, PDMSUr-Dopamine, presented high affinity towards inhomogeneous alloy surfaces terminated by native oxide layers as demonstrated by quartz crystal microbalance (QCM-D), as well as stability against desorption by rinsing with ethanol. As revealed by QCM-D, X-ray photoelectron spectroscopy (XPS) and computational studies, the thickness and composition of the resulting nanolayers indicated an attachment of PDMSUr-Dopamine molecules to the substrate through both terminal catechol groups, with the adsorbate exposing the hydrophobic PDMS backbone. This hypothesis was investigated by classical molecular dynamic simulation (MD) of pure PDMSUr-Dopamine molecules on SiO2 surfaces. The computationally obtained PDMSUr-Dopamine assembly is in agreement with the conclusions from the experiments regarding the conformation of PDMSUr-Dopamine towards the surface. The tendency of the terminal catechol groups to approach the surface is in agreement with proposed model for the attachment PDMSUr-Dopamine. Remarkably, the versatile PDMSUr-Dopamine modifier facilitates such functionalization for various substrates such as titanium alloy, steel and ceramic surfaces.

Surface engineering of magnesium alloys requires adequate strategies, processes and materials permitting corrosion protection. Liquid formulations containing corrosion inhibitors often are to be optimized according to the demands of the respective substrate and following the service conditions during its application. As an interdisciplinary approach, a combination of several techniques for instantly monitoring or elaborately analyzing the surface state of magnesium was accomplished in order to characterize the performance of new adsorbing sustainable amphiphilic polymers which recently were developed to facilitate a multi-metal corrosion protection approach. The application of established techniques like Contact Angle measurements and X-ray Photoelectron Spectroscopy investigations was supplemented by introducing related and yet faster online-capable and larger-scale techniques like Aerosol Wetting Test and Optically Stimulated Electron Emission. Moreover, an inexpensive setup was configured for scaling the inset and the extent of degradation processes which occur at local electrochemical circuits and lead to hydrogen bubble formation. Using these analytical tools, changes of the surface state of emeried AM50 samples were investigated. Even in contact with water, being a moderate corrosive medium, the online techniques facilitated detecting surface degradation of the unprotected magnesium alloy within some seconds. In contrast, following contact with a 1 weight% formulation of a polymeric corrosion inhibitor, surface monitoring indicated a delay of the onset of degradation processes by approximately two orders of magnitude in time. Mainly based on the spectroscopic investigations, the corrosion inhibiting effects of the investigated polymer are attributed to the adsorption of a primary polymer layer with a thickness of a few nanometers which occurs within some seconds. Immersion of magnesium for several hours brings up a protective film with around ten nanometers thickness.

Quality assured surface pre-treatment may greatly enhance adhesive interactions and, thus, the performance and durability of material joints. This holds true as well for substrates used in coating processes as for adherents introduced into bonding processes. Wettable polymeric wetting agents—shortly called polymeric interfactants—contribute to modifying surfaces and governing the properties of interphases. This is demonstrated for amphiphilic polymers directing the adsorption of graphene oxide (GO) nano-sheets from aqueous dispersion on alumina surfaces. In this contribution, contact angle measurements as well as X-ray photoelectron spectroscopy and scanning force microscopy investigations are applied for the characterization of thin films. GO is adsorbed either from a buffered dispersion on pristine aluminum oxide surfaces or on alumina modified with a few nanometers thin layer of a polymeric interfactant. Laterally extended nanoparticles and GO nano-sheets are preferentially found on interfactant layers whereas on pristine aluminum oxide smaller adsorbates dominate. The driving forces directing the GO attachment are discussed using a phenomenological model based on polymer/substrate interactions governing the sticking probabilities of GO nano-sheets with different sizes.

Made available in DSpace on 2018-12-11T16:46:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-01-01 The formation of nano-scale biofilms on hydrophilic silica surfaces from aqueous polypeptide/polysaccharide mixtures containing laccase and maltodextrin was investigated in situ with quartz crystal microbalance with dissipation monitoring (QCM-D). Surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), optically stimulated electron emission (OSEE) and atomic force microscopy (AFM) were applied for characterizing the resulting layers obtained after periods varying from a few seconds to several hours of contact between the substrate and the biopolymers formulation. The biofilm formation in contact with the aqueous laccase/maltodextrin suspension was studied at pH level 4.75, under conditions close to the isoelectric point of the enzyme. The few nanometers rough biofilms obtained were composed of a laccase/maltodextrin mixture, and their thickness was observed to steadily increase during 4 h of contact with the aqueous mixture of biopolymers. Remarkably, the still adhesive films obtained after 1 h of contact with aqueous polypeptide/polysaccharide mixture resisted a 30 min rinsing with acetate buffer. The biofilms growing process was monitored using OSEE, due to the effected attenuation of the UV-induced electron emission from the SiO2/Si substrate, which was found to be more pronounced than the attenuation of the photoelectrons from the substrate which contribute to the XPS signals. Layers as thin as 1 nm were detected by the OSEE. Pós-Graduação em Ciência e Tecnologia de Materiais (POSMAT) São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01 Fraunhofer Institute for Manufacturing Technology and Advanced Materials (IFAM), Wiener Straße 12 Federal University of Ceará, Av. Da Universidade 2853 São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01 Pós-Graduação em Ciência e Tecnologia de Materiais (POSMAT) São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01 São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01

Made available in DSpace on 2018-12-11T16:46:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-01-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Magnesium and its alloys are the lightest metallic materials used for structural applications. Tuning the surface functionalization of magnesium alloys may contribute to increasing their durability. Dry or wet processes may be effective for the modification of magnesium alloy surfaces. The resulting layers may cover surface inhomogeneities and separate the substrate surface from molecular films. This work demonstrates the feasibility and effectiveness of the concepts and techniques comprising laser or plasma based pretreatment processes or dipping procedures that involve synthetic amphiphilic polymers or biopolymers. In detail, the effects of barrier layers that have been applied by the deposition of siliceous polymer coatings in low pressure plasma processes, by laser surface treatments in controlled gas atmospheres or by dipping in liquid formulations containing a recently developed polymeric inhibitor or a mixture of the enzyme laccase and the polysaccharide maltodextrin are monitored. In this respect, a time-resolved hydrogen bubble formation test is performed, revealing interactions between water films and the modified surfaces. The surface modification is shown with X-ray photoelectron spectroscopy investigations and, in addition, the alloy surface and grain structure is characterized using energy dispersive X-ray analysis, scanning electron microscopy and scanning force microscopy. These investigations reveal that the thus established layer/substrate and layer/environment interphases differ in their composition as a result of the non-centrosymmetric layer concepts for surface functionalization applied here. Department of Adhesive Bonding Technology and Surfaces Fraunhofer Institute for Manufacturing Technology and Advanced Materials IFAM, Wiener Straße 12 Department of Chemistry Federal University of Santa Catarina (UFSC) Campus Universitário Trindade Department of Materials UEPG State University of Ponta Grossa, Avenida de General Carlos Cavalcanti 4748 Pós-Graduacao em Ciência e Tecnologia de Materiais (POSMAT) São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01 National Nanotechnology Laboratory LANOTEC Centro Nacional de Alta Tecnología, 1.3 km, Norte de la Embajda de EE.UU. Pavas Pós-Graduacao em Ciência e Tecnologia de Materiais (POSMAT) São Paulo State University (UNESP), Av. Eng. Luiz Edmundo Carrijo Coube 14-01

A refined flexible all-atom model for a room temperature ionic liquid, 1-n-butyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf2N]), is reported here. Extensive molecular dynamics simulations were performed to check the validity of this model. We found that the thermodynamic and dynamic properties such as density, isobaric expansivity, isothermal compressibility, and self-diffusion coefficient described by the present model are in good agreement with experimental observations. Based on the calculated results, there has been a considerable improvement in the force field with respect to the previous model by Lopes et al. [15,16].

Classical molecular dynamics were carried out in order to obtain insights into proper conditions to perform chemical fixation of carbon dioxide (CO2) with epoxide molecules into cyclic carbonates. Two different molecules containing epoxide groups were investigated: 1,2–Epoxybutane (EB), called linear aliphatic epoxide molecule, and 3-Ethyl-7-oxabicyclo(4.1.0)heptane (EC), called cycloaliphatic epoxide molecule. The reaction systems involving carbon dioxide additionally were catalyzed by tetraethylammonium bromide (TEAB). The dynamics of the molecular groups were studied by taking into account known reaction mechanisms to investigate whether the optimal reaction conditions were observed. Radial distribution functions and self-diffusion coefficients were calculated and revealed that in case of the systems with cycloaliphatic epoxide groups as reagent the CO2 molecules were located far away from the agglomerate formed by the dispersed tetraethylammonium bromide catalyst and epoxide groups (EC), and they do not present enough mobility to overcome the long distances to react. Additionally, it was observed that, in the case of the linear aliphatic epoxide groups (EB), the dynamics of the groups tends to facilitate the reaction mechanisms by presenting a considerable amount of available CO2 molecules in the neighborhood of the epoxy rings. Thus, via the Molecular Dynamics insights, the systems containing linear aliphatic epoxide groups presented a much more accessible condition for the subsequent reaction steps of the carbon dioxide fixation to occur as compared to systems containing cycloaliphatic epoxide groups. The simulation results are in agreement with the experimental findings, which showed via infrared spectroscopy the successful conversion of epoxy rings from linear aliphatic epoxide molecules into five-membered cyclic carbonates after reacting with carbon dioxide.

The present work describes pretreatment processes of thermoplastic polyurethane elastomer (TPU) material, used as an adhesive in powder form, that results in the increased peeling resistance of joints. The TPU in powder form is an environmentally friendly adhesive and provides safer bonding conditions in the shoe manufacturing industry. TPU particles are soft and require an anti-blocking agent to prevent agglomeration. However, particles covered by such an anti-blocking agent may account for a low peeling resistance in the resulting joints. To overcome this disadvantage, two pretreatment processes for the TPU adhesive were evaluated. The results of a two-step wet washing process, representing a conventional solvent-based procedure that involves both the application of a solvent and a powder separation step, are compared to the performance of a one-step dry plasma treatment process. The process type did not affect the size and agglomeration behavior of the particles, and both processes were effective in improving joint strength according to peeling test results. Spectroscopic investigation of the particle surface after washing or plasma treatment indicated some zinc concentration, which is interpreted to result from the anti-blocking agent. The crystallinity of the TPU, investigated by thermal analysis, was higher after pretreatment. The obtained results indicate that TPU in powder form is a versatile adhesive for the shoe industry with a safer application compared to solvent based adhesive systems.