Analysis of scratch characteristics of automotive clearcoats containing silane modified blocked isocyanates via carwash and nano-scratch tests

The aim of this study was to investigate the scratch characteristics of automotive clearcoats based on an acrylic polyol resin, with butylated melamine and silane modified blocked isocyanates, using car-wash and nano-scratch tests.To scrutinize the effect of silane modified blocked isocyanate on the chemical and mechanical properties of clearcoats, with respect to changes in the crosslinking networks inside the clearcoats due to the curing reaction, dynamic mechanical analysis (DMA) and FT-IR analysis were performed. The scratch behaviors were analyzed via Amtec–Kistler car-wash and nano-scratch tests, accompanied with scratch images simultaneously visualized using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The basic properties of various automotive clearcoats such as impact resistance, pencil hardness, solvent resistance, and stone-chip resistance, were also compared. The results showed that a close correlation existed between the scratch resistance data obtained from the car-wash and nano-scratch tests for clearcoats made from acrylic polyol resin, with melamine and silane modified blocked isocyanates. Also, all the mechanical properties, including scratch resistance, noticeably improved due to the increased crosslinking networks via the formation of urethane bonds, when the portion of silane modified blocked isocyanates was increased. This was verified from the surface profiles and images of the scratched clearcoats captured using AFM and SEM.     

Correlation between the wear resistance, and the scratch resistance, for nanocomposite coatings

The nanoscratch test, used in this study, quantitatively characterizes the scratch behaviour of coatings. Some of the obtained parameters are plastic and elastic deformation, critical load to start the scratch, chipping or other change in the scratch mechanism of the coating. The knowledge of the scratch mechanism allows the optimisation of the material behaviour. In the present study the scratch resistance with the wear resistance has been correlated for nanocomposite coatings. Knowledge of mechanical properties extracted from the scratch test, supports the optimization of the coating against wear. The study was applied to nanocomposite coatings with different polymer matrices, different percentages and nature of nanoparticles.     

Dual-curing behavior and scratch characteristics of hydroxyl functionalized urethane methacrylate oligomer for automotive clearcoats

UV–thermal dual-curable, hydroxyl- and methacrylate-functionalized urethane oligomers with different contents of unsaturated double bonds and hydroxyl groups have been synthesized and incorporated into automotive clearcoats to investigate their curing and scratch behaviors. Dynamic mechanical analyses (DMA) and FT-IR analyses were performed to observe the variation of the crosslinking networks that resulted from the chemical reactions by UV and thermal dual-curing operations with varying curing conditions, such as UV dose, thermal curing time, thermal curing temperature, and curing sequence. The scratch behaviors of dual-cured automotive clearcoats were analyzed via nano-scratch tests, accompanied with scratch images simultaneously visualized using scanning electron microscopy (SEM). The mechanical and chemical properties, such as impact resistance, pencil hardness, acid-etch resistance, and stone-chip resistance, of dual-curable clearcoats were also compared with those of UV mono-cure and 1 K thermal-cure clearcoats. The results clearly showed that the dual-curing process induced a considerably higher degree of crosslinking for the cured clearcoats prepared from the dual-curable oligomers, melamine crosslinkers, and photoinitiators. Their mechanical properties including scratch resistance were also noticeably improved via the UV–thermal curing sequence, which led to an increased conversion rate of double bonds compared with clearcoats produced using the thermal–UV curing sequence. The best conditions for high crosslinking density as well as high hardness and modulus were 2400 mJ/cm² at 150 °C for 10 min in the UV–thermal curing process. This result was corroborated from the reaction kinetics and surface images of the scratched clearcoats captured by SEM.     

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.     

Acrylic oligomer for high solid automotive top coating system having excellent acid resistance

Acrylic oligomers containing siloxy groups were synthesized using trimethylsiloxyethyl methacrylate (TMSEMA) which have lower polarity and lower viscosity than those containing naked hydroxyl groups, and developed as high solid automotive top coatings by application of the crosslinking reaction between the siloxy groups and isocyanate groups or by the hybrid crosslinking reaction using the siloxy groups, epoxy groups, acid anhydride groups and hydrolyzable silyl groups. The hybrid crosslinked films show excellent acid resistance and scratch resistance.     

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.     

Viscoelastic effects on the scratch resistance of polymers: relationship between mechanical properties and scratch properties at various temperatures

Scratch durability of polymer surfaces and coatings is becoming critical for the increasing use of these materials in new applications, replacing other materials with harder surfaces.

Scratch resistance of polymers has been the subject of numerous studies, which have led to specific definitions for plastic deformation characterization and fracture resistance during scratch testing. Viscoelastic and viscoplastic behavior during a scratch process have been related to dynamic mechanical properties that can be measured via dynamic nano-indentation testing. Yet, the understanding of the origin of the fracture process of a polymer during scratch remains approximate. Parameters like tip shape and size, scratch velocity and loading rate, applied strain and strain rates, have been considered critical parameters for the fracture process, but no correlation has been clearly established.

The goal of this work is to define and analyze scratch parameters that relate to mechanical properties. The evolution of scratch resistance parameters as a function of temperature and strain rate, compared to the evolution of dynamic mechanical properties obtained from indentation and uniaxial tensile tests over a range of temperature for poly(methyl methacrylate) (PMMA) helped in identifying a correlation between the tensile stress–strain behavior and scratch fracture toughness.

This correlation brings a new understanding of the origin of the fracture mechanisms during a scratch process. In particular, it is demonstrated that the characteristic strain applied by the indenter is a most relevant parameter to describe the fracture resistance during a scratch process, independently of the indenter geometry.     

Relation between the scratch resistance and the chemical structure of organic–inorganic hybrid coatings

Organic–inorganic hybrid materials can be defined as materials combining organic and inorganic domains in a nanometric scale. The development of these organic–inorganic hybrids has achieved properties from both organic and inorganic materials.     

Scaling behavior in the scratching of automotive clearcoats

The scratch resistance of four clearcoat formulations was evaluated using a CSM nano-scratch tester, an AMTEC-Kistler simulated carwash tester, and a laboratory scale macro-scratching tester. Significant differences in the rank-order of all the clearcoats were found when comparing the scratch and mar behavior using macro-scratching, nano-scratching, and AMTEC-Kistler testing. Field vehicles were also examined where the mean and median widths of scratches found on vehicles were 237 and 141 μm, respectively. The range of loads associated with events with the potential to create real-world scratches was found to be significantly higher (5–35 N) than the forces needed to make scratches of the same mean size as those seen in the field (7–10 N). These results indicated that a significant improvement in the scratch resistance of these clearcoats would be needed before customers would notice improvements in their paint finish’s scratch resistance.     

A new approach to investigate scratch morphology and appearance of an automotive coating containing nano-SiO2 and polysiloxane additives

Attempts have been carried out to verify whether gonio-spectrophotometry could be utilized as a new scratch testing approach to investigate scratch morphology and its effect on appearance of an acrylic-melamine clearcoat separately containing nano-silica or polysiloxane additives. The results of gonio-spectrophotometry/colorimetry illustrated that this new approach is capable of differentiating between plastic and fracture types scratches. Furthermore, this approach was found to be suitable for analyzing the self healing abilities of such coatings. The accuracy and reproducibility of such results were checked against the results of scanning electron microscope (SEM) and illustrated great potential as a new approach for such studies.     

Temperature-variant scratch deformation response of automotive paint systems

Painted systems are complex and most automotive car paints consist of up to five different paint layers. The way in which the paint system responds to contact can be strongly influenced by the temperature, which, in service, can vary between −20 °C and +50 °C depending on the weather conditions. This paper compares the scratch response of an automotive system at temperatures ranging from −80 °C to +80 °C made using a specially designed scratch test apparatus. The changes in the deformation modes at various temperatures have been investigated using environmental scanning electron microscopy. It was found that the deformation mechanism at all temperatures was ductile tensile cracking behind the stylus. At temperatures below room temperature the response of the paint was less ductile in nature, and the coefficient of friction was low. Above room temperature the penetration of the stylus into the sample increased rapidly and the coefficient of friction also increased dramatically. The scratch test critical load and scratch hardness were both found to decrease as the temperature increased. The results show the importance of testing at a range of temperatures and the use of scanning electron microscopy in assessing the scratch damage in order to fully evaluate the scratch resistance of paint systems.     

Linear viscoelasticity of polymer blends with co-continuous morphology

The co-continuous morphology of polymer blends has received much attention not only because of its potential promotion of mechanical or electrical properties of polymer blends, but also due to its importance in phase separation by spinodal decomposition. Compared to the recent advances in the characterization of co-continuous structure, the rheology of co-continuous blends has not been understood clearly. In this work, a rheological model is suggested to correlate the linear viscoelasticity and the structural information of co-continuous blends. The dynamic modulus of co-continuous blends is composed of the contribution from components and the interface. The interfacial contribution, which is most important in the rheology of blends, is calculated from a simplified co-continuous structure. This model has been compared satisfactorily with available experimental results, which proves a reasonable connection between the co-continuous structure and linear viscoelasticity of blends.     

Friction and multiple scratch behavior of polymer+monomer liquid crystal systems

We have studied in turn: polystyrene (PS), styrene/acrylonitrile (SAN) and Polyamide 6 (PA6), adding each time to the polymer 1, 3, 5, 7 or 10 wt% of 4,4′-dibutylazobenzene (LC1) which is a monomer liquid crystal (MLC). LC1 reduces both static and dynamic friction of PS and SAN against stainless steels or polytetrafluoroethylene (PTFE). By contrast, friction values are lower for pure PA6 than for PA6 modified with various MLCs or with MoS₂.Multiple scratching tests were carried out with a micro scratch tester on every system between 2.5 and 15 N. The presence of LC1 in PS reduces penetration depth and residual depth and increases the viscoelastic recovery. So far PS was the only polymer, which does not show strain hardening in multiple scratching. The present results confirms this, but it also shows that only 1 wt% of LC reduces the brittleness of PS so that strain hardening appears. This effect is maintained at all higher concentrations of LC1 investigated as well. For SAN or PA6, additions of LC1 reduce penetration depth values with respect to pure polymers, but do not have a significant effect on viscoelastic recovery. Scanning electron microscopy (SEM) was used to study the deformation and wear mechanisms, and to relate the data obtained in multiple scratch sliding wear tests. For PS we see in SEM that increasing the LC1 concentration causes a more ductile behavior, with less crack nucleation. For SAN the debris accumulation in sliding wear is mitigated by the presence of the liquid crystalline lubricant. No debris formation is observed in PA6, with or without a lubricant.     

Plasma sprayed graphene/carbon nanotube reinforced lanthanum-cerate hybrid composite coating

Lanthanum cerate (LC: La₂Ce₂O₇) is a potential material for thermal barrier coating, whose improved toughness is a crucial necessity for the pathway of its industrialization. Herein, we demonstrated a promising approach to develop graphene/carbon nanotube hybrid composite coating using a large throughput and atmospheric plasma spraying method. Graphene nanoplatelets (GNP: 1 wt %) and carbon nanotube (CNT: 0.5 wt %) reinforced lanthanum cerate (LCGC) hybrid composite coatings were deposited on the Inconel substrate. Addition of 1 wt % GNP and 0.5 wt % CNT in LC matrix has significantly increased its relative density, hardness, and elastic modulus up to 97.2%, 2–3 folds, 3–4 folds, respectively. An impressive improvement of indentation toughness (8.04 ± 0.2 MPa m^0.5) was observed on LCGC coating, which is ～8 times higher comparing the LC coating. The toughening was attributed to the factors: such as the distribution of GNPs and CNTs in the LC matrix, synergistic toughening offered by the GNPs and CNTs; (i) GNP/CNT pull-out, (ii) crack bridging and arresting, (iii) splat sandwiching, mechanical interlocking, etc. Finally, this improved toughness offered an exceptional thermal shock performance up to 1721 cycles at 1800 °C, without any major failure on the coating. Therefore, the GNP and CNT-reinforced LC hybrid composite coating can be recommended to open a path for turbine industries.     

Visual appearance and scratch resistance of high performance thermoset and thermoplastic powder coatings

A comparative evaluation of electrostatic spray and ‘hot dipping’ fluidized bed to deposit two different organic paints belonging to the class of thermoplastic (PPA571, an alloy of acid modified polyolefins) and thermoset (TGIC-free transparent pigmented bronze polyester) powders was performed. Visual appearance of the investigated coatings was evaluated by colour, gloss and coating thickness measurements as well as by the determination of the surface morphologies. Micro-mechanical performance of the coatings was assessed by progressive load scratch tests.     

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.     

Effect of pyrocarbon texture on the mechanical and oxidative erosion property of SiC coating for protecting carbon/carbon composites

SiC coating was conducted on C/C composites with rough laminar (RL) or smooth laminar (SL) pyrocarbon matrix separately. The residual stress, elastic modulus and microhardness of RL-SiC (RLS) and SL-SiC (SLS) coatings were investigated. The results showed that compared with SLS, RLS coating possessed smaller residual stress and higher hardness and elastic modulus, which was beneficial for its resistance to cracking and then contributed to the anti-oxidation performance improvement. At temperatures of 300–1400 °C, its mass loss was only 2.41%. At 1500 °C, it showed good self-sealing ability and could provide C/C composites against oxidation at least 120 h.     

Siliconization elimination for SiC coated C/C composites by a pyrolytic carbon coating and the consequent improvement of the mechanical property and oxidation resistances

Carbon/carbon (C/C) composites have a wide application as the thermal structure materials because of their excellent properties at high temperatures. However, C/C composites are easily oxidized in oxygen-containing environment, which limits their potential applications to a great degree. Silicon carbide (SiC) ceramic coating fabricated via pack cementation (PC) was considered as an effective way to protect C/C composites against oxidation. But the mechanical properties of C/C composites were severely damaged due to chemical reaction between the molten silicon and C/C substrate during the preparation of SiC coating by PC. In order to eliminate the siliconization erosion, a pyrolytic carbon (PyC) coating was pre-prepared on C/C composites by the chemical vapor infiltration (CVI) prior to the fabrication of SiC coating. Due to the retardation effect of PyC coating on siliconization erosion, the flexural strength retention of the SiC coated C/C composites with PyC coating increased from 46.27 % to 107.95 % compared with the specimen without PyC coating. Furthermore, the presence of homogeneous and defect-free PyC coating was beneficial to fabricate a compact SiC coating without silicon phase by sufficiently reacting with molten silicon during PC. Therefore, the SiC coated C/C composites with PyC coating had better oxidation resistances under dynamic (between room temperature and 1773 K) and static conditions in air at different temperatures (1773?1973 K).     

Towards thermal barrier coating application for rare earth silicates RE2SiO5 (RE= La,Nd, Sm,Eu, and Gd)

Rare earth (RE) silicates X1-RE₂SiO₅ (RE = La, Nd, Sm, Eu, and Gd) are comprehensively investigated as promising thermal barrier coating candidates. The mechanical, thermal, and corrosion resistance properties are evaluated by theoretical exploration and experimental measurement. Mechanical properties and corrosion resistance to calcium-magnesium alumino-silicates (CMAS) melts of X1-RE₂SiO₅ are linearly correlated with ionic radius of RE elements. Elastic moduli increase with the decrease of ionic radius of RE³⁺. X1-RE₂SiO₅ with larger RE³⁺ exhibits better resistance to molten melts corrosion. For thermal properties, they are not obviously sensitive to RE species. All X1-RE₂SiO₅ demonstrate low thermal conductivities and their magnitudes are significantly modified by concentration of defects. Thermal expansion coefficients of X1-RE₂SiO₅ are more or less close and are compatible with the value of superalloy. The results highlight X1-RE₂SiO₅ as potential thermal barrier coating candidates with overall properties.     

Effect of trifunctional cross-linker triallyl isocyanurate (TAIC) on the surface morphology and viscoelasticity of the acrylic emulsion pressure-sensitive adhesives

Acrylic pressure sensitive adhesive (PSA) latexes were synthesized via a starved monomer-seeded semi-continuous emulsion polymerization process with butyl acrylate (BA), methyl methacrylate, acrylic acid (AA), 2-hydroxyethyl acrylate and trifunctional cross-linker, triallyl isocyanurate (TAIC). Influences of TAIC on the resultant latex and PSA properties were comprehensively investigated. The results indicated that latex particle size was independent of the amount of TAIC in the pre-emulsion feed, while the viscosity of the latex increased remarkably with TAIC content increased. Thermal gravimetric analysis result showed that the thermal stability of the polymers was improved significantly with the addition of TAIC. Besides, with the increase in TAIC content, gel content of the polymer increased significantly, while molecular weight between cross link points (M_c) and sol molecular weight (M_w, M_n) of the polymer decreased remarkably. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the sacrifice of loop tack and peel strength, when compared with the uncrosslinked counterparts. Finally, dynamic mechanical analysis and atomic force microscopy were also used to evaluate the viscoelastic properties and surface morphology of the acrylic emulsion PSA film, respectively.