Investigation of the postcure reaction and surface energy of epoxy resins using time-of-flight secondary ion mass spectrometry and contact-angle measurements

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate correlations between the molecular changes and postcuring reaction on the surface of a diglycidyl ether of bisphenol A and diglycidylether of bisphenol F based epoxy resin cured with two different amine-based hardeners. The aim of this work was to present a proof of concept that ToF-SIMS has the ability to provide information regarding the reaction steps, path, and mechanism for organic reactions in general and for epoxy resin curing and postcuring reactions in particular. Contact-angle measurements were taken for the cured and postcured epoxy resins to correlate changes in the surface energy with the molecular structure of the surface. Principal components analysis (PCA) of the ToFSIMS positive spectra explained the variance in the molecular information, which was related to the resin curing and postcuring reactions with different hardeners and to the surface energy values. The first principal component captured information related to the chemical phenomena of the curing reaction path, branching, and network density based on changes in the relative ion density of the aliphatic hydrocarbon and the C₇H₇O⁺ positive ions. The second principal component captured information related to the difference in the surface energy, which was correlated to the difference in the relative intensity of the C_xH_yN_z⁺ ions of the samples. PCA of the negative spectra provided insight into the extent of consumption of the hardener molecules in the curing and postcuring reactions of both systems based on the relative ion intensity of the nitrogen-containing negative ions and showed molecular correlations with the sample surface energy.

Wettability investigation of UV/oand acid functionalized MWCNT and MWCNT/PMMA nanocomposites by contact angle measurement

The dispersion state of individual MWCNT in the polymer matrix influences the mechanical, thermal, and electrical properties of the resulting composite. One method of obtaining a good dispersion state of MWCNT in a polymer matrix is to functionalize the surface of MWCNT using various treatments to enhance the surface energy and increase the dispersibility of MWCNT. In this study, wettability and surface energy of UV/Oand acid-treated multiwall carbon nanotubes (MWCNTs) and its polymethyl methacrylate (PMMA) polymer nanocomposites were measured using contact angle analysis in various solvent media. Contact angle analysis was based on ethylene glycol-water-glycerol probe liquid set and data was further fitted into geometric mean (Fowkes), van Oss-Chaudhury-Good (GvOC), and Chang-Qing-Chen (CQC) models to determine both nonpolar and acid base surface energy components. Analysis was conducted on MWCNT thin films subjected to different levels of UV/Oand acid treatments as well as their resulting MWCNT/PMMA nanocomposites. Contact angle analysis of thin films and nanocomposites revealed that the total surface energy of all samples was well fitted with each other. In addition, CQC model was able to determine the surface nature and polarity of MWCNT and its nanocomposites. Results indicated that the wettability changes in the thin film and its nanocomposites are due to the change in surface chemistry. Finally, electrical properties of nanocomposites were measured to investigate the effect of surface functionality (acid or basic) on the MWCNT surfaces.

Determination of drawbead contacts with variable bead penetration

In stamping operations, the sliding of the sheet metal over the drawbeads is of great importance. The geometry of the drawbead and the degree of penetration both influence material flow and alter the frictional effects between the work and the tool. The effect of drawbead penetration over drawbeads has been studied using the Drawbead Simulator (DBS) test. The contact phenomenon between the sheet and drawbeads was analysed by examining deformed samples with an image fitting technique. The results were compared with an FE simulation and with an approximate geometric analysis. The results give a useful relationship between the rates of change of the contact angle with increasing bead penetration.

Improvement of adhesion of conductive polypyrrole coating on wool and polyester fabrics using atmospheric plasma treatment

In this paper wool and polyester fabrics were pretreated with atmospheric plasma glow discharge (APGD) to improve the ability of the substrate to bond with anthraquinone-2-sulfonic acid doped conducting polypyrrole coating. A range of APGD gas mixtures and treatment times were investigated. APGD treated fabrics were tested for surface contact angle, wettability and surface energy change. Effect of the plasma treatment on the binding strength was analyzed by studying abrasion resistance, surface resistivity and reflectance. Investigations showed that treated fabrics exhibited better hydrophilicity and increased surface energy. Surface treatment by an APGD gas mixture of 95% helium/5% nitrogen yielded the best results with respect to coating uniformity, abrasion resistance and conductivity.

Effects of MWNT nanofillers on structures and properties of PVA electrospun nanofibres

In this study, we have electrospun poly(vinyl alcohol)(PVA) nanofibres and PVA composite nanofibres containing multi-wall carbon nanotubes (MWNTs) (4.5 wt%), and examined the effect of the carbon nanotubes and the PVA morphology change induced by post-spinning treatments on the tensile properties, surface hydrophilicity and thermal stability of the nanofibres. Through differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD) characterizations, we have observed that the presence of the carbon nanotubes nucleated crystallization of PVA in the MWNTs/PVA composite nanofibres, and hence considerably improved the fibre tensile strength. Also, the presence of carbon nanotubes in PVA reduced the fibre diameter and the surface hydrophilicity of the nanofibre mat. The MWNTs/PVA composite nanofibres and the neat PVA nanofibres responded differently to post-spinning treatments, such as soaking in methanol and crosslinking with glutaric dialdehyde, with the purpose of increasing PVA crystallinity and establishing a crosslinked PVA network, respectively. The presence of carbon nanotubes reduced the PVA crystallization rate during the methanol treatment, but prevented the decrease of crystallinity induced by the crosslinking reaction. In comparison with the crosslinking reaction, the methanol treatment resulted in better improvement in the fibre tensile strength and less reduction in the tensile strain. In addition, the presence of carbon nanotubes reduced the onset decomposition temperature of the composite nanofibres, but stabilized the thermal degradation for the post-spinning treated nanofibres. The MWNTs/PVA composite nanofibres treated by both methanol and crosslinking reaction gave the largest improvement in the fibre tensile strength, water contact angle and thermal stability.

Photochromic wool fabrics from a hybrid silica coating

In this work, a photochromic wool fabric has been prepared by applying a photochromic-dye hybrid silica sol-gel onto the surface of fabric. The photochromic fabric was found to have a very quick optical response. Two types of silica were used as the matrix material, and the type of silica had a small effect only on the photochromic performance, the fabric washing fastness, and water contact angle, but affected the fabric handle property considerably. The silica from a precursor containing a long alkyl chain showed very little influence on the fabric handle and better photochromic performance than that containing a phenyl group.

Apatite-inducing ability of titanium oxide layer on titanium surface : the effect of surface energy

In the present study, pure titanium (Ti) plates were firstly treated to form various types of oxide layers on the surface and then were immersed into simulated body fluid (SBF) to evaluate the apatite-forming ability. The surface morphology and roughness of the different oxide layers were measured by atomic force microscopy (AFM), and the surface energies were determined based on the Owens–Wendt (OW) methods. It was found that Ti samples after alkali heat (AH) treatment achieved the best apatite formation after soaking in SBF for three weeks, compared with those without treatment, thermal or H₂O₂ oxidation. Furthermore, contact angle measurement revealed that the oxide layer on the alkali heat treated Ti samples possessed the highest surface energy. The results indicate that the apatite-inducing ability of a titanium oxide layer links to its surface energy. Apatite nucleation is easier on a surface with a higher surface energy.

Superhydrophobic fabrics prepared by silica coating

In this work, a silica sol prepared by co-hydrolysis and co-condensation of TEGS (Tetraethylrthosilicate) and alkyl silane under alkaline condition was applied to polyester, wool, and cotton fabrics. The water contact angle measurement indicated considerable increase in the surface hydrophobicity of the sol-treated fabrics. Five different alky silanes were used, namely methyltritthoxysilane (MTES), pheryl triethoxysilane (PTES), n-octyltricthoxysilane (OTES), hexadecyl trimethoxysilan (HDTMS), and tridecafluorooctyl triethoxysilane (FAS), and the water contact anglc (CA) for the coated fabrics ranged between 1300 and 174°. The alkyl silane used influenced the CA valuc, and the silica coating from FAS, HDTMS and PTES snowed CA value greater than ISO', indicating the formation of superhydrophobicity. The fabric coated by the fluorinated silica (TEOS/FAS) has a water contact angle as high as 174°. The treated polyester fabric showed a slightly higher CA value than the wool and cotton fabrics, under the same coating condition.
The coating surface was characterized by SEM, EDX, TEM, FTlR, XPS and AFM. The results showed that silica nanoparticles with thc sizc in the range of 50-ISOnm werc formed in the cohydrolyzed silica sol, and these particles had a core-shell structure with many alkyl groups gathering on the surface region. The formation of superhydrophobic surface was attributed to the nano-structured surface coating with a low surface energy.

Biomimetic coating on pure titanium submitted to different surface treatments

Titanium (Ti) plates were firstly treated to form various types of oxide layers on the surface and then immersed into simulated body fluid (SBF) to evaluate the apatite forming ability. The surface morphology and roughness of the different oxide layers were measured by atomic force microscopy (AFM), and the surface energies were determined based on the Owens-Wendt (OW) methods. It was found that Ti samples after Alkali-Heat treatment (AH) achieved the best apatite formation after soaking in SBF for 3 weeks, compared to those without treatment, thermal or H₂O₂ oxidation. Furthermore, contact angle measurement revealed that the oxide layer on the alkali-heat treated Ti samples possessed the highest surface energy. The results indicate that the apatite inducing ability of a titanium oxide layer is linked to its surface energy. Apatite nucleation is easier on a surface with a higher surface energy.

具有微纳米结构超疏水表面润湿性的研究

In this paper, advance of wetting behavior research on the superhydrophobic surface with micro- and nano-structures is reviewed, including fabrication methods of superhydrophobic surfaces with micro- and nano-structures, influence of the micro- and nano-structures on wetting behavior, superhydrophobic criterions of surfaces with periodic structures, contact angle hysteresis and functionalization of superhydrophobic surfaces. Problems existed in this research field and possible prospects of superhydrophobic surface with micro- and nano-structures are discussed.

Control over the hydrophobic behavior of polystyrene surface by annealing temperature based on capillary template wetting method

The wetting behavior of water droplets was studied on tunable nanostructured polystyrene (PS) surfaces fabricated by temperature-induced capillary template wetting. The surface morphology of PS varied with the annealing temperature. Contact angle (CA) measurements showed that the wettability of polystyrene surfaces could be tuned from hydrophobic (CA = 104°) to superhydrophobic (CA = 161°) by rendering different morphologies, which could be explained by two distinct wetting modes, i.e., the Wenzel and Cassie–Baxter wetting state. Meanwhile, the critical annealing temperature inducing wetting transition between the Wenzel state and Cassie–Baxter state was obtained. This approach could be easily extended to produce superhydrophobic surfaces on other thermoplastic polymers.

Superhydrophobic polyimide films with a hierarchical topography : combined replica molding and layer-by-layer assembly

Artificial superhydrophobic surfaces with a hierarchical topography were fabricated by using layer-by-layer assembly of polyelectrolytes and silica nanoparticles on microsphere-patterned polyimide precursor substrates followed with thermal and fluoroalkylsilane treatment. In this special hierarchical topography, micrometer-scale structures were provided by replica molding of polyamic acid using two-dimensional arrays of polystyrene latex spheres as templates, and nanosized silica particles were then assembled on these microspheres to construct finer structures at the nanoscale. Heat treatment was conducted to induce chemical cross-linking between polyelectrolytes and simultaneously convert polyamic acid to polyimide. After surface modification with fluoroalkylsilane, the as-prepared highly hydrophilic surface was endowed with superhydrophobicity due to the bioinspired combination of low surface energy materials and hierarchical surface structures. A superhydrophobic surface with a static water contact angle of 160 degrees and sliding angle of less than 10 degrees was obtained. Notably, the polyimide microspheres were integrated with the substrate and were mechanically stable. In addition, the chemical and mechanical stability of the polyelectrolyte/silica nanoparticle multilayers could be increased by heat-induced cross-linking between polyelectrolytes to form nylon-like films, as well as the formation of interfacial chemical bonds.

Superhydrophobic modification of polyimide films based on gold-coated porous silver nanostructures and self-assembled monolayers

We present a facile and effective method for controlling the surface hydrophobicity of polyimide films from sticky to superhydrophobic properties by tailoring their topographies. Nanostructured silver layers were produced on polyimide films by treatment with aqueous KOH and AgNO3, followed by thermal treatment at 200 degrees C or higher temperatures. Further modification of the gold-coated silver layers with n-dodecanethiol led to hydrophobic surfaces. Different morphologies of the silver layers at the micro- and nano-meter scales, which result in the variety of hydrophobicity, can be tailored by controlling the thermal treatment temperature. Surfaces prepared at 320 degrees C showed a sticky property that water drops did not slide off even when the sample was held upside down. Superhydrophobic surfaces were obtained when the temperature was above 340 degrees C. A remarkable superhydrophobicity, as evidenced by a very large water contact angle of 162 degrees and a very small sliding angle of 7 degrees, was achieved by heating the modified polyimide films at 360 degrees C. This is also the first example for superhydrophobic modification of polyimide films.

Anisotropic wetting characteristics on submicrometer-scale periodic grooved surface

Submicrometer-scale periodic structures consisting of parallel grooves were prepared on azobenzene-containing multiarm star polymer films by laser interference. The wetting characteristics on the patterned surfaces were studied by contact angle measurements. Macroscopic distortion of water drops was found on such small-scale surface structures, and the contact angles measured from the direction parallel to the grooves were larger than those measured from the perpendicular direction. A thermodynamic model was developed to calculate the change in the surface free energy as a function of the instantaneous contact angle when the three-phase contact line (TPCL) moves along the two orthogonal directions. It was found that the fluctuations, i.e., energy barriers, on the energy versus contact angle curves are crucial to the analysis of wetting anisotropy and contact angle hysteresis. The calculated advancing and receding contact angles from the energy versus contact angle curves were in good agreement with those measured experimentally. Furthermore, with the groove depth increasing, both the degree of wetting anisotropy and the contact angle hysteresis perpendicular to the grooves increased as a result of the increase in the energy barrier. The theoretical critical value of the groove depth, above which the anisotropic wetting appears, was determined to be 16 nm for the grooved surface with a wavelength of 396 nm. On the other hand, the effect of the groove wavelength on the contact angle hysteresis perpendicular to the grooves was also interpreted on the basis of the thermodynamic model. That is, with the wavelength decreasing, the contact angle hysteresis increased due to the increase in the number of energy barriers. These results may provide theoretical evidence for the design and application of anisotropic wetting surface.