Mechanical properties of films prepared from model high‐glass‐transition‐temperature/low‐glass‐transition‐temperature latex blends

The mechanical properties of films prepared from model high‐glass‐transition‐temperature (T_g)/low‐T_g latex blends were investigated with tensile testing and dynamic mechanical analysis. Polystyrene (PS; carboxylated and noncarboxylated) and poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA); noncarboxylated] were used as the model high‐T_g and low‐T_g latexes, respectively. Carboxyl groups were incorporated into the PS latex particles to alter their surface properties. It was found that the presence of carboxyl groups on the high‐T_g latex particles enhanced the Young's moduli and the yield strength of the PS/P(BMA/BA) latex blend films but did not influence ultimate properties, such as the stress at break and maximum elongation. These phenomena could be explained by the maximum packing density of the PS latex particles, the particle–particle interfacial adhesion, and the formation of a “glassy” interphase. The dynamic mechanical properties of the latex blend films were also investigated in terms of the carboxyl group coverage on the PS latex particles; these results confirmed that the carboxyl groups significantly influenced the modulus through the mechanism of a glassy interphase formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2788–2801, 2002     

Mechanical properties of thermally sprayed porous alumina coating by Vickers and Knoop indentation

Depending on the thermal spraying conditions, coatings obtained can present different defects, like pores, cracks and/or unmelted particles, and different surface roughnesses, that can affect the determination of the hardness and elastic modulus. The present work investigates the mechanical properties, determined by means of Knoop and Vickers indentations, of a plasma as-sprayed alumina coating, obtained with a nano-agglomerated powder sprayed using a PTF4 torch, in order to highlight how the surface defects interfere into the indentation process. As a main result, Knoop indentation compared to Vickers one gives less dispersive results (15% and 33%, respectively), that are, in addition, more representative of the coating properties. The mean values obtained are 110 ± 40 GPa for the elastic modulus and 1.75 ± 0.42 GPa for the hardness. In addition, and for the two indenter types used, multicyclic indentation has been performed because it allows a more appropriate characterization of such heterogeneous coatings due to the representation of the mechanical properties as a function of the indentation load and/or the penetration depth, leading to more reliable results according to the depth-variability of the coating microstructure.     

Mechanical characterization of ultra-thin fluorocarbon films deposited by R.F. magnetron sputtering

Fluorocarbon films were deposited on silicon substrate by R.F. magnetron sputtering using a polytetrafluoroethylene (PTFE) target. Structure of the deposited films was studied by X-ray photoelectron spectroscopy (XPS). Hardness, elastic modulus and scratch resistance were measured using a nanoindenter with scratch capability. -CF_x (x = 1, 2, 3) and C-C units were found in the deposited fluorocarbon films. The hardness and elastic modulus of the films are strongly dependent on the R.F. power and deposition pressure. The film hardness is in the range from 0.8 GPa to 1.3 GPa while the film elastic modulus is in the range from 8 GPa to 18 GPa. Harder films exhibit higher scratch resistance. Differences in nanoindentation behavior between the deposited fluorocarbon films, diamond-like carbon (DLC) films and PTFE were discussed. The fluorocarbon films should find more applications in the magnetic storage and micro/nanoelectromechanical systems.     

Effect of polymer composition on performance properties of maleate-vinyl ether donor-acceptor UV-curable systems

The effect of unsaturated polyester backbone composition on the properties of donor-acceptor-UV-cured coatings was explored. The polyesters were designed with similar molecular weights and levels of unsaturation, but with otherwise widely varying backbone compositions. UV-curable coatings were formulated with stoichiometric levels of triethylenglycol divinyl ether and a photoinitiator. The resulting coatings had a broad range of properties, which were found to correlate with the properties and compositions of the polyester backbone polymers. A relatively flexible backbone resulted in lower glass transition temperatures (T_g). The polymer T_g was found to influence the conversion of double bonds achieved during UV curing. Reaction kinetics were evaluated for the coating systems and the results confirmed that the T_g of the systems influenced the double bond conversion. Thermal stability and König pendulum hardness were also found to vary with the backbone composition of the constituent polyester.     

Morphology of hybrid coatings based on polyester, melamine resin, and silica and the relation with hardness and scratch resistance

The morphology of hybrid coatings based on polyester, melamine resin, and various amounts of silica has been investigated, and the hardness and scratch resistance were determined. By increasing silica content, an increase of silica particles in size and number was observed. Small silica particles were preferentially present at the surface. The influence of the silica content on the K?nig hardness, indentation hardness, and elastic modulus was minor. The improved scratch resistance determined for a hybrid coating with 11.4 wt% silica, compared to a similar organic coating without silica, was attributed to small silica particles preferentially present at the surface. Presented at the 26th International Waterborne, High-Solids, and Powder Coatings Symposium, February 10–12, 1999, New Orleans, LA. Dept. of Polymer Chemistry and Coatings Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands. Materials Division, Dept. of Materials Chemistry and Coatings, P.O. Box 595, 5600 AN Eindhoven, The Netherlands.     

Evaluation of mechanical properties and hydrophobicity of room-temperature,moisture-curable polysilazane coatings

Polysilazane coatings have a broad need in real-life applications, which require low processing or working temperature. In this work, five commercially available polysilazanes have been spin-coated on polycarbonate substrates and cured in ambient environment and temperature to obtain transparent, crack-free, and dense films. The degree of crosslinking is found to have a significant impact on the hardness and Young's modulus of the polysilazane films but has a minor influence on the film thickness and hydrophobicity. Among all five polysilazane coatings, the inorganic perhydropolysilazane-based coating exhibits the largest hardness (2.05 ± 0.01 GPa) and Young's modulus (10.76 ± 0.03 GPa) after 7 days of curing, while the polyorganosilazane-derived films exhibit higher hydrophobicity. The molecular structure of polysilazanes plays a key role in mechanical properties and hydrophobicity of the associated films, as well as the adhesion of coatings to substrates, providing an intuitive and reliable way for selecting a suitable polysilazane coating material for a specific application.     

Mechanical properties of sol–gel prepared nanocomposite coatings in the presence of titania and alumina-derived nanoparticles

Hybrid nanocomposite coatings were prepared by sol–gel method using silica, titania and alumina nanoparticles derived from their alkoxides precursors; in the presence of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) on 1050 aluminium alloy substrate. The effect of type and ratio of nanoparticles on mechanical behaviour of the coatings were investigated by dynamic mechanical thermal analysis (DMA) and nanoindentation experiments. DMA results demonstrated that the values of the glass transition temperature (T_g) and the temperature at maximum tan (δ), (T_t) as well as the storage modulus of the hybrid samples depend mainly on the silane content and titania to alumina molar ratio of nanoparticles in the coating composition. In addition, nanoindentaion experiments were performed to study the mechanical properties such as hardness, elastic modulus and E/H ratio for the nanocomposite hybrid coatings. Nanoindentation results indicate that the homogenous reinforced structure was formed in the surface of nanocomposite coating with incorporation of titania and alumina-derived nanoparticles. The incorporation of TiO₂ in comparison with AlOOH nanoparticles in the GPTMS-based coatings showed an improving effect on E/H ratio.     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Self‐Healing Latex Containing Polyelectrolyte Multilayers

Self‐healing paints would have the potential benefit of protecting the underlying substrate and extending the coating's service life. As a step toward those types of coatings, this work examines layer‐by‐layer films of branched poly(ethylene imine)/poly(acrylic acid) with the inclusion of various types of latex particles with different T_g and different compositions. Due to high mobility of the polyelectrolyte chains when plasticized with water, water enabled self‐healing of these films is demonstrated, as well as steam enabled self‐healing. The films with various latex particles show different swelling ratios, surface hydrophilicity, as well as varying ability to self‐heal scratches. This self‐healing property is studied as a function of temperature. Also, the mechanical properties such as hardness and modulus of the films are measured.     

Macromechanical and micromechanical properties of polymers with reduced density of entanglements

The macromechanical and micromechanical properties of polypropylene, polylactide, and polystyrene with different entanglement densities and different crystallinities were tested. The mechanical properties were characterized by macroscale compression tests and microindentation hardness measurements. The entanglement density modified the mechanical properties only in the high-deformation region, above the yield point, when the strain-hardening occurred, and ca 10% lower stresses were measured for disentangled polymers. In the low-deformation region, the influence of the entanglement density was negligible. The stiffness of semicrystalline polymers increased with their crystallinity and the stiffness of amorphous polymers increased with their glass transition temperature. For example, the elastic modulus was equal to 1.59 MPa for entangled polylactide, 1.68 MPa for partially disentangled polylactide, and 2.20 MPa for semicrystalline, disentangled polylactide. The stiffness-related properties in both macroscale (compressive modulus, E, and yield stress, Y) and microscale (indentation modulus, E_IT and indentation hardness, H_IT) showed very similar trends, which was in perfect agreement with theoretical predictions and confirmed the reliability of our results. The supplementary, viscosity-related properties from microindentation experiments (indentation creep, C_IT, and elastic part of indentation work, η_IT) supported the above-mentioned conclusions in the sense that also these two low-deformation region properties were independent on the entanglement density.     

Elastic properties of adhesive polymers. II. Polymer films and bond lines by means of nanoindentation

Seven different polymers used frequently as adhesives and/or matrix polymers in wood, wood composites, and natural fiber‐reinforced composites were studied by uniaxial tensile tests and nanoindentation. It was shown that the elastic modulus, the hardness, the creep factor, and the elastic‐, plastic‐, and viscoelastic work of indentation of the seven different polymers is essentially the same regardless whether the polymers were tested in the form of pure films or in situ, i.e., in an adhesive bond line with spruce wood. An excellent correlation was found between the elastic modulus measured by tensile tests and the elastic modulus measured by nanoindentation. In spite of the good correlation, the elastic modulus measured by nanoindentation is significantly higher than the elastic modulus measured by tensile tests. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1234–1239, 2006     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Synthesis and characterization of flexible polyester coatings for automotive pre-coated metal

An automotive pre-coated metal system has investigated to remove the wet coating process, such as pre-treatment, dip coating and spray coating for environmental regulations. However, automotive pre-coated metal sheets must have high flexibility and formability to overcome the harsh conditions such as cutting, press and stamping process. For these reasons, flexible polyester coatings were designed to control flexibility using polycarbonatediol. The characteristics, curing behavior and viscoelastic property of the resins were measured by FT-IR, GPC, rheometer, DSC, RPT and DMA. The flexibility was evaluated using a texture analyzer. A nano-scratch tester, equipped optical microscope can measure the scratch resistance of coatings and the scratched surface morphology.With increasing polycarbonatediol content, the final frequency and the storage modulus increased and the T_g of the coatings decreased. This is related to the high mobility of the chain segment in polycarbonatediol. In terms of the flexibility and scratch resistance, CP-3 had high elongation value and good scratch resistance resulting from optimized stamping, pressing and cutting process in automotive pre-coated metal system. Therefore, polycarbonatediol is a powerful factor affecting the flexibility and scratch resistance of polyester coatings.     

Determination of the elastic moduli of silicone rubber coatings and films using depth-sensing indentation

Depth-sensing indentation (DSI) has been used to determine the elastic moduli of silicone rubber coatings on substrates and freestanding films at micro-penetration depth. Complete elastic behavior for rubber-like films was observed for the first time. Substrate effects are hardly observed when the indentation displacement is less than 10% of the total coating thickness. The calculated elastic moduli of the silicone rubber films from the DSI measurements are in good agreement with those measured by dynamic mechanical analysis (DMA), showing that the DSI technique is a reliable and convenient tool for an accurate estimation of the elastic modulus of a rubber-like coating/film.     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

The effect of nitrogen flow rate on TiBN coatings deposited on cold work tool steel

TiBN coatings have high hardness and high adhesion. Due to these excellent properties there has been increasing interest in TiBN coatings. In this study, TiBN coatings were deposited on AISI D2 cold work tool steel and silicon wafers by closed field unbalanced magnetron sputtering (CFUBMS). The structural, mechanical and adhesion properties of these coatings were analysed by X-ray diffraction, scanning electron microscopy, microhardness test, indentation test and scratch tests. TiBN coatings produced by magnetron sputtering exhibited a dense and columnar structure. These results indicate that TiB₂, TiN and h-BN exist in crystalline forms at all coatings. The highest hardness was obtained at the lowest nitrogen flow rate. Very few cracks were observed at the edge of the indentation marks at the highest nitrogen flow rate. The highest critical load obtained with scratch test was identified as 102?N.     

Mechanical surface characterization: A promising procedure to screen organic coatings

Two ductile coating ma-terials were subjected to a combined indentation and scratch test procedure de-signed to screen a predetermined pattern of many small sample surfaces in a limited time. The screening of 50 surface spots ordered in a matrix pattern on the surface was carried out in 4.5 hr. The test provides reproducible data in terms of indentation modulus, elastic recovery, scratch penetration depth, and scratch residual depth, and also offers the possibility of detecting critical mechanical transitions such as rupture. The presented procedure produces sufficient data in a limited time scale to fulfill the requirements for a fast method to screen coating compositions. Dept. Polymer Technology, SE-100 44 Stockholm, Sweden. Jaquet-Droz 1, CH-2007 Neuchatel, Switzerland.     

Multi-response optimization of mechanical properties for ZrWN films grown using grey Taguchi approach

ZrWN nitride films are prepared using direct current (dc) reactive magnetron sputtering. Grey Taguchi analysis is used to determine the effect of deposition parameters (substrate plasma etching time, N₂/(N₂+Ar) flow rates, deposition time, and substrate temperature) on the microstructure and the tribological properties. An orthogonal array, signal-to-noise ratio and analysis of variance are used to determine the effects of deposition parameters. The substrates are pretreated using oxygen plasma etching. The resulting ZrWN coatings are homogeneous, very compact and completely adhered to the substrate. In the confirmation runs, using grey Taguchi analysis, the coefficient of friction decreases from 0.45?±?0.02 to 0.35?±?0.02, the corrosion potential increases from ??0.201?±?0.01 to ??0.072?±?0.01?V, the Vickers hardness increases from 23.63?±?0.07 to 24.65?±?0.05?GPa, and reduced modulus increases from 115.82?±?1.13 to 136.17?±?1.18?GPa. The ZrWN films are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rockwell C indentation and scratch testing. The TEM pattern for the ZrWN films corresponds to the (111), (200) and (220) planes of the face center cubic structure. Samples with a ZrWN film coating are classified as HF1 and exhibit good adhesive strength. The signal of friction and the associated acoustic emission signal are analyzed, and the scratch profile is analyzed using an optical microscope. Results show that the adhesive force for the critical load Lc2 is about 76.2?±?0.5?N.     

连续刚度法对单晶硅片的力学性能的表征

利用纳米压痕仪通过连续刚度测量法对单晶硅片在压入过程中的接触刚度、硬度、弹性模量进行了连续测量.结果表明:当接触深度在20～32 nm左右时,单晶硅片的接触刚度与接触深度成直线关系,硬度和弹性模量基本保持不变,此时所测得的是单晶硅片表面氧化层的硬度和弹性模量,分别约为10.2 GPa和140.3 GPa.当接触深度在32～60 nm左右时,单晶硅片的接触刚度与接触深度成非直线关系,硬度和弹性模量随接触深度急剧增加,表明单晶硅片表面氧化层的硬度和弹性模量受到了基体材料的影响.当接触深度在60 nm以上时,单晶硅片的接触刚度与接触深度成直线关系,硬度和弹性模量基本保持不变,测得值为单晶硅的硬度和弹性模量,分别约为12.5 GPa和165.6 GPa.     

Surface damage resistance and yielding of chemically strengthened silicate glasses: From normal indentation to scratch loading

We report on surface elasticity, plastic deformation and crack initiation of chemically strengthened soda-lime silicate and sodium aluminosilicate glasses during lateral indentation and scratch testing. Instrumented indentation using a normal indenter set-up corroborated previous findings on the effects of chemical strengthening on surface Young's modulus, hardness, and indentation cracking. Using lateral indentation in the elastic-plastic regime, we find a pronounced increase in the scratch hardness as a result of chemical strengthening, manifest in higher work of deformation required for creating the scratch groove. Thereby, the glass composition is found to play a stronger role than the absolute magnitude of surface compressive stress. Using a blunt conical stylus for instrumented scratch testing reveals three distinct modes of scratch-induced surface fracture, which occur during scratching or after unloading. Occasional micro-cracking caused by pre-existing surface flaws at low scratching load can be completely suppressed through chemical strengthening. The intrinsic defect resistance to microcracking is reduced as a result of ion stuffing, depending on the initial glass composition, whereas the resistance to abrasive yielding is enhanced by several hundred MPa.