Measurement of mar resistance and study of marring mechanism of polymeric coatings with scanning probe microscope

A scanning probe microscope (SPM) equipped with a custom-made probe, consisting of a diamond tip and rectangular tungsten cantilever, was used to measure the mar resistance of crosslinked polymeric surface coatings at micron and submicron scales. The term “mar” is used to describe the surface damage of coatings, which may not be readily noticeable individually, however, the existence of many mars does degrade the appearance of coatings. Good mar resistance is a requirement for many coatings applications. With the unique high resolution of the SPM, the dimension of the mars can be measured with great accuracy, thus different responses of coatings to the marring stress, i.e., elastic recovery, plastic deformation, and abrasive wear, can be identified quantitatively. In addition, the dynamic process of marring, including viscoelastic creep, strain-hardening, micro-cracking, and surface fatigue, has also been studied with the SPM. Presented at the 77th Annual Meeting of the Federation of Societies for Coatings Technology, on October 18–22, 1999, in Dallas TX. 313 Strong Hall, Ypsilanti, MI 48197.     

Studies of microhardness and mar resistance using a scanning probe microscope

Scanning probe microscopy (SPM) is in a period of rapid development. It shows great promise for characterizing coating surfaces. This paper describes modification of an SPM so that it can be used to mar the surfaces of coatings under controlled conditions and to characterize the mars. Mar resistance of coatings is analyzed in terms of a ‘three response, two mechanism model.' The three responses (fracture, elastic, and plastic) can be measured quantitatively using the SPM. Of the three responses, only two (fracture and plastic deformation) are marring mechanisms – elastic deformations recover instantaneously. In some cases mars resulting from plastic deformation may recover slowly with time or with immersion in water; this phenomenon is attributed to viscoelastic creep. Microhardness is also measured with the modified SPM. Some thermoset coatings appear to be substantially harder near their surfaces than in the mass of material, and such materials may respond quite differently to stress applied at different levels near the surface. This finding has important implications for all coating properties that are strongly influenced by the surface. A quantity called ‘micro mar resistance' is defined. It may be useful for comparing different coatings under specified conditions of marring. However, there can be no single quantity that expresses ‘mar resistance' of a coating under all conditions.     

Evaluation of mar/scratch resistance of a two component automotive clear coat via nano-indenter

Nano-indenter as a technique for characterization and evaluation of mar/scratch resistance of a two component automotive clear coat is used. Different responses of the coatings to the marring stress and critical forces are discussed. The plastic deformation compared to the elastic part and the damage width is decreased by adding nano-silica in the coatings formulation.     

Metrology for characterizing scratch resistance of polymer coatings

Current methods for scratch resistance assessment are often based on “relative but not quantitative” types of measurements, such as visual inspection, gloss changes, and changes in gray scale level or lightness. Most results are used for qualitative assessment purposes, which result in the lack of a repeatable and reliable standardized test method for the polymer materials community. To implement a scientifically based standardized test method for quantifying scratch resistance, it is vital to understand the relationships between material mechanical properties, morphology, and appearance (optical properties) of surface and subsurface deformation. In this article, preliminary results from a scratch testing protocol to identify the “onset” of plastic deformation in poly(methyl methacrylate) and poly(propylene) commercial samples are presented. Recent advances in optical scattering measurements to identify the onset of plastic deformation by analyzing specular and off-specular intensities are also presented. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Calorimetric Measurements of The Heat Generated by The Peel Adhesion Test

The peel test is a simple mechanical test commonly used to measure the adhesion of flexible films bonded to rigid substrates. When the film is deformed elastically during peeling, the peel force is a direct measure of the strength of the interface. However, when plastic deformation takes place, the work of detachment is much larger than the thermodynamic work of forming the fracture surfaces. Simultaneous mechanical and calorimetric measurements of the work of detachment and the heat generated during the peeling of polymeric films from metal substrates and metal films from polymeric substrates have been made. An energy balance for peeling has been proposed. Most of the work of peeling was consumed by plastic deformation. The peeled polymer dissipated approximately one half of the work of peeling as heat and most of the remainder was stored in the peeled material. The peeled metal dissipated most of the work of peeling as heat.     

Study of Materials Deformation in Nanometric Cutting by Large-scale Molecular Dynamics Simulations

Nanometric cutting involves materials removal and deformation evolution in the surface at nanometer scale. At this length scale, atomistic simulation is a very useful tool to study the cutting process. In this study, large-scale molecular dynamics (MD) simulations with the model size up to 10 millions atoms have been performed to study three-dimensional nanometric cutting of copper. The EAM potential and Morse potential are used, respectively, to compute the interaction between workpiece atoms and the interactions between workpiece atoms and tool atoms. The material behavior, surface and subsurface deformation, dislocation movement, and cutting forces during the cutting processes are studied. We show that the MD simulation model of nanometric cutting has to be large enough to eliminate the boundary effect. Moreover, the cutting speed and the cutting depth have to be considered in determining a suitable model size for the MD simulations. We have observed that the nanometric cutting process is accompanied with complex material deformation, dislocation formation, and movement. We find that as the cutting depth decreases, the tangential cutting force decreases faster than the normal cutting force. The simulation results reveal that as the cutting depth decreases, the specific cutting force increases, i.e., “size effect” exists in nanometric cutting.     

Scratch resistance of automobile clearcoats: Chemistry and characterization on the micro-and nanoscale

The scratch resistance of polymeric clearcoats intended for automobile exterior surfaces was tested with scanning 3D nanoindentation and laboratory car wash simulation (AMTEC). It could be shown by using “real world” samples with comparable scratch resistance that the applied methods were suitable for discriminating even small differences in scratch resistance with high accuracy. In the area of physical characterization of scratch resistance, the results of this investigation demonstrate the ability of microscopic, single-contact testing methods to reproduce the macroscopically experienced results. By using a combination of different scratch methods, insight into the fundamentals, e.g., chemistry, that are responsible for good or bad scratch resistance, is achieved. One key for this goal is the imaging and analytical evaluation of the damage pattern after the indent, which leads to additional results and models presented in this article. It was found that an essential key to obtaining scratch resistant surfaces is a strengthening of rubber-like elasticity as well as minimizing interactions between individual polymeric chains.     

Preparation and electrowetting transitions on superhydrophobic/hydrophilic bi-layer structures

A simple method of preparing porous superhydrophobic materials using glass fiber materials, where hydrophobicity is provided by a variety of coatings such as self-assembled alkyl-silane monolayers and fluoropolymers such as Teflon is presented. Fibrous structures of the filter material provide for the modulation of “surface roughness” on the micro- and nano-scale, required for achieving a superhydrophobic state, with advancing contact angle of water on such surfaces close to 150 degrees. Such superhydrophobic structures are effective at separating water-octane mixtures by allowing only low-surface-tension component to go through the thickness of the material, while repelling the water (high-surface-tension component) and preventing it from permeating through the material. In addition, a bi-layer structure that combines a superhydrophobic surface with a highly hydrophilic bulk material is described. It is formed by subjecting superhydrophobic fiber material to a brief oxygen plasma treatment to remove the hydrophobic coating from one side of the material, whereas the opposite side is protected during treatment and remains superhydrophobic. Tunable properties of the superhydrophobic fiber material are demonstrated using electrowetting with PEDOT–PSS conductive polymer core, parylene as a dielectric and Teflon as a hydrophobic coating. Applicability of such bi-layer materials to microfluidic and energy storage micro-devices is discussed.     

Effect of preliminary loading on the deformation and strength properties of high-strength fibres

High-strength, high-modulus polyethylene fibres fabricated with gel technology is similar to low-modulus fibres of the olefin and amide series (Capron, polypropylene) with respect to the character of the correlation of the stress—strain diagrams and curve of accumulation of the residual component of deformation. The residual deformation component is relatively large both for high-strength PE fibre and for p-polyamide fibres. The differences in the character of accumulation of the plastic component in these fibres are due to the fact that the residual strains arising in high-strength PE fibre, as in other flexible-chain polymer fibres (polypropylene, Capron) is initiated by breaking of bonds in the main chain. In p-polyamide fibres (Armos, SVM, Terlon, Kevlar), plastic strains arise due to highly elastic deformation “frozen≓ by hydrogen bonds and orientation of molecular chains. Preliminary deformation affects the strength properties of high-modulus fibres differently: in PE fibres, the strength decreases, it increases for Armos and SVM fibres, and remains unchanged for Terlon fibre. This difference is to a great degree due to the difference in the types of intermolecular interaction in fibres of the olefin and amide series. For all fibres investigated, the character of accumulation of the residual deformation component can be correlated with the type of stress—strain diagram, which will allow creating simpler methods of evaluating residual strains. Translated from Khimicheskie Volokna, No. 3, pp. 30–33, May–June, 1998.     

A new approach to characterize scratch and mar resistance of automotive coatings

Mar damage is a major customer concern of the automotive coatings industry. Our study of mar performance can be separated into two distinct areas, a detailed understanding of the damage formation mechanism, and an investigation of the relationship between the damage morphology and appearance. We have developed a nanoscratch technique that can measure important physical quantities, such as penetration depth, normal force and tangential force during the formation of the scratch. Mar resistance of three coatings was evaluated and compared based on the damage mechanisms: plastic flow and fracture. The different deformation mechanisms result in different damage morphologies and a corresponding change in visual impact of the scratch. Statistical surveys of appearance of well-defined scratches indicate that in very short observation times, scratches where fracture has occurred are much more visible than those made by plastic deformation alone. However, with sufficient time and strong illumination a significant percentage of observers could see plastic deformation as well.     

Scratch resistance behavior of model coating systems

Coatings are often subjected to physical deformations caused by car wash brushes, tree limbs, keys, fingernails, and the like, which may result in mechanical abrasion. The resistance of the coating to scratches imposed by such mechanical abrasions has been studied through the utilization of laboratory tests such as nanoindentors, crockmeters, scanning probe microscopes, and taber abraders. Little emphasis, however, has been placed on the influence of coating attributes on measured scratch resistance. In this study we attempt to relate the effect of coating glass transition temperature, crosslink density, and crosslink type in a series of formulated waterborne polyurethane dispersion clearcoats on resultant scratch resistance. Methods utilized to impart the scratches, e.g., scanning probe microscopy, weighted fingernail, and crockmeter, as well as related coating physical properties measured, e.g., viscoelastic behavior, hardness, and tensile strength, are discussed. The scratch resistance of model coating systems analyzed was found to be dependent upon the base resin T_g, which affected the surface hardness of the coating and the toughness of the crosslinked network, as measured by the method of essential work. Coatings that exhibited both hard surfaces and tough-elastic network integrity afforded the optimized scratch resistance behavior. Presented at the 26th International Waterborne, High-Solids, and Powder Coatings Symposium, February 10–12, 1999, New Orleans, LA. 401 Southfield Rd., P.O. Box 6231, Dearborn, MI 48121-6231.     

Responses of pre-crystallized and crystallized zirconia-containing lithium silicate glass ceramics to diamond machining

This paper reports on the responses of pre-crystallized and crystallized zirconia-containing lithium silicate glass ceramics (ZLS) to diamond machining in simulated dental milling and adjusting processes. Machining mechanics, tool wear and tribological characteristics, and surface and subsurface damage were investigated. Machining forces and coefficients of friction were measured using a force sensor and high-speed data acquisition system. Diamond tool wear and debris adhesion, and machining-induced surface and subsurface damage were examined using field emission scanning electron microscopy. The results show that both tangential and normal forces of crystallized ZLS were significantly higher than those of pre-crystallized ZLS (p < 0.05) while these forces for both materials significantly increased with the material removal rate (p < 0.05). Coefficients of friction in machining of crystallized ZLS were significantly higher than those in machining of pre-crystallized ZLS. In spite of the minimum wear of applied diamond tools in machining both materials, more crystallized ZLS debris adhesion on tool surfaces was observed. The principal removal mechanisms in machining of both materials were primary fracture and minor plastic deformation of pre-crystallized and crystallized ZLS. However, there was more severe fracture in machining of pre-crystallized ZLS than in machining of crystallized ZLS. Although machining-induced subsurface edge chipping damage in both materials remarkably increased with the feed rate (p < 0.05), such damage was significantly severer in pre-crystallized ZLS than in crystallized ZLS (p < 0.05). These microstructure-property-processing relations provide practical guidance of process selection for high-quality fabrication of ZLS materials.     

Structure/property relationships in flexible alkoxysilane automotive coatings

Flexible automotive coatings are susceptible to scratch and mar damage, especially during finishing and assembly operations. One-component (1K) flexible clearcoats exhibit very good scratch and mar resistance, but unfortunately suffer from poor durability and environmental etch resistance. Two-component clearcoats offer improvements in both etch and durability, but at the expense of scratch and mar. In this paper, the concept and properties of 1K flexibilized silane clearcoats for use on automotive plastics will be introduced and their structure/property relationships examined as they apply to scratch and mar. The role of coating crosslink density, toughness, glass transition temperature (T_g), and surface profile on the scratch damage of coated plastic substrates will be described. In addition, a new scratch methodology, termed Scratcho, is utilized to determine relative scratch performance and is compared to conventional scratch resistance testing. Results to date indicate that hardness, as affected by the glass transition temperature, and crosslink density, as it contributes to higher essential work values, both affect resultant scratch propensity of the flexible coatings. The relative ranking of different coating systems employing alternate crosslinkers (e.g., isocyanate and melamine) is also presented and compared to the newly developed silane crosslinked coatings. Presented at the 28th International Waterborne, High-Soids, and Powder Coatings Symposium, Feb. 21–23, 2001, in New Orleans. LA. 377 Fairall St., Ajax, Ont., L1S 1R7, Canada. 401 Southfield Rd., P.O. Box 6231, Dearborn, MI 48121-6231.     

聚合物热黏弹塑性变形微热压成型机理的数值模拟研究

研究了聚甲基丙烯酸甲酯（PMMA）超疏性阵列圆柱微结构特征功能表面的微热压成型技术,通过模拟研究了成型工艺参数对成型过程的影响规律,揭示了其热黏弹塑性变形充填流动机理,明晰了关键调控参数。结果表明,基片材料的弹性模量、成型温度和压力是影响充填成型的关键调控参数,成型压力和变形应力与成型温度呈负关联关系,而充填高度与成型温度呈正关联关系;提高成型温度至高于基片材料的玻璃化转变温度（Tg）,使基片处于黏弹性高弹态,易使基片快速产生明显的热黏弹塑性变形,且可使成型压力和变形应力趋于最小值,这有利于基片避免断裂损伤并加速充模流动。     

High‐solids mar resistant clearcoats prepared from an isophthalate‐based oligoester and a melamine resin. Study and characterization of mar resistance with scanning probe microscopy method

A new series of high‐solids [low‐VOC (volatile organic compound)content] mar resistant clearcoats (CL‐series) were prepared upon crosslinking of a new‐synthesized hydroxyl‐terminated isophthalate‐based liquid oligoester (L‐311) with an hexakis(methoxymethylol)melamine (HMMM) resin, via an acid‐catalyzed etherification reaction. The chemical, physical, and mechanical properties of the CL‐clearcoats were compared to those of a reference clearcoat (CRO). An attempt was made to investigate the effect that the amounts of catalyst and melamine resin had on the clearcoats' physical, chemical, and mechanical properties, and moreover, to correlate these properties to the films chemical structures. The new‐formulated high‐solids clearcoats (CL‐series) presented enhanced processability and higher NVW values (lower VOC content) than the reference clearcoat CRO, and their properties (pencil hardness, knoop hardness, adhesion, impact resistance, solvent and gasoline resistance, mar resistance, and flexibility) were better or comparable to those of the CRO. More specifically, the mar resistance of the CL‐clearcoats series was investigated by applying both the crockmeter test and a novel method that employed a modified scanning probe microscope. In addition, we identified and characterized the different responses of the CRO and certain CL‐clearcoats to marring stress. The experimental data regarding the mar resistance of the new‐formulated clearcoats fully justified our polymer design strategy, verifying our expectations for the possibility of preparing glossy, high‐solids mar‐resistant clearcoats that could present enhanced processability and solvent resistance, relatively high pencil hardness, and at the same time very good elastic recovery to marring stress. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1317–1333, 2002     

Rapid-set, waterborne coatings from polyzwitterionic polymers formulated with a critical solvent combination

Waterborne coatings that rapidly set and become tack-free can be prepared from polymers containing both pendant anionic (acidic, carboxylate, or strong-acid groups such as sulfonate) and cationic functionality (quaternary ammonium groups). This phenomenon is related to anion-cation interactions that function as ionic crosslinks and dramatically enhance the physical properties and water resistance of the coatings. We define this process as “controlled ionic-coacervation.” The best coating properties can only be obtained by using a “critical solvent combination.” The critical solvent combination requires water plus at least two organic solvents: (1) a lower boiling (70 to 134°C) water-soluble organic solvent having at least one hydroxyl group and (2) a higher boiling (135 to about 250°C) organic solvent. Loss of only a small amount of solvent causes a coating to rapidly become tack-free. Ionization of acid functionalities on the polymers by an increase in pH (e.g., through the loss of CO₂) can initiate controlled ionic interactions. The influence of polymer and solvent compositions on coating properties is discussed. 1712 Building, Midland, MI, 48642. Email: rosegd@dow.com.     

Soft Surface Nanostructure with Semi-Free Polyionic Components for Sustainable Antimicrobial Plastic

Surface antimicrobial materials are of interest as they can combat the critical threat of microbial contamination without contributing to issues of environmental contamination and the development drug resistance. Most nanostructured surfaces are prepared by post fabrication modifications and actively release antimicrobial agents. These properties limit the potential applications of nanostructured materials on flexible surfaces. Here, we report on an easily synthesized plastic material with inherent antimicrobial activity, demonstrating excellent microbicidal properties against common bacteria and fungus. The plastic material did not release antimicrobial components as they were anchored to the polymer chains via strong covalent bonds. Time-kill kinetics studies have shown that bactericidal effects take place when bacteria come into contact with a material for a prolonged period, resulting in the deformation and rupture of bacteria cells. A scanning probe microscopy analysis revealed soft nanostructures on the submicron scale, for which the formation is thought to occur via surface phase separation. These soft nanostructures allow for polyionic antimicrobial components to be present on the surface, where they freely interact with and kill microbes. Overall, the new green and sustainable plastic is easily synthesized and demonstrates inherent and long-lasting activity without toxic chemical leaching.     

Fracture toughness of rotationally molded polyethylene and polypropylene

In this work, the fracture toughness of rotationally molded polyethylene (PE) and polypropylene (PP) was measured using J integral methods at static loading rates and at room temperature. Two different commercially available rotational molding grades PE and PP were tested in this study which have been used in various rotationally molded products such as small leisure craft, water storage tanks, and so on. Scanning electron microscope (SEM), optical microscope, differential scanning calorimetry (DSC), solid‐state nuclear magnetic resonance (solid‐state NMR), and X‐ray scattering were used to investigate the microstructure, fracture surfaces, and compare toughness properties of these materials. In PE, higher molecular weight and broader molecular weight distribution, larger amorphous and crystal region thicknesses are found to be related to higher toughness values. High molecular weight favors higher number of entanglements that improve fracture energy and broader distribution increases long chain branching of higher molecular weight fractions which creates higher entanglements at the branch sites. Larger amorphous regions promote microvoiding more easily compared to thinner amorphous regions, leading to greater plastic deformation and energy absorption. Higher crystal thickness also contributes to microvoiding in the amorphous region. For PP, greater plastic deformation observed in the fracture surfaces is related to higher fracture toughness values. POLYM. ENG. SCI., 58:63–73, 2018. © 2017 Society of Plastics Engineers     

纳米结构陶瓷涂层精密磨削表面/亚表面的形貌

用扫描电镜对纳米(以n表示)结构WC／12Co(n-WC／12Co)和Al2O3／13TiO2(n-Al2O3／13TiO2)涂层经立式精密平面磨削后的磨削表面／亚表面的形貌进行观察，测量了n-WC／12Co和n-Al2O3／13TiO2涂层精密磨削的磨削力分力比、比磨削能。结果表明：在大多数磨削条件下，n-WC／12Co磨削的材料去除机理主要是非弹性变形方式，即以塑性变形为主，伴随一定的材料粉末化。材料较少以脆性碎裂去除。n-Al2O3／13TiO2陶瓷涂层磨削的材料去除机理主要是脆性去除，同时也存在一定的材料粉末化以及极少的显微塑性变形。     

Surface characteristics of coating layers formed by coating pigments with different particle sizes and size distribution

The effects of coating color raw material variables were tested on absorbing and non-absorbing base materials. The particle size of the coating pigments was the main variable affecting the gloss of the non-absorbing base materials. Adding binders and increasing the drying temperature has a negative effect on the gloss development of both calendered and uncalendered coating layers. On calendered layers, coating layer films showed more gloss development than for coated papers, especially with coarse particles. Uncalendered calcium carbonate-coated papers have a higher PPS roughness than calendered clay-coated papers. The effectiveness of calendering, as described by “calenderability,” showed an increase in gloss with increasing number of nips, irrespective of size, and size distribution of pigment particles.