Rheology and curing characteristics of dual-curable automotive clearcoats using thermal radical initiator derived from O-imino-isourea and photo-initiator

The curing characteristics of clearcoats, including a thermal curing initiator (TRI) newly designed from O-imino-isourea and photo-initiator (PI), were investigated by means of different mono-curing and dual-curing pathways. The competitive relationship between TRI and PI on the curing pattern, reacting with acrylate double bonds in a clearcoat was elucidated by altering the UV and thermal sequence in the dual-curing process, through various experimental methods. From the rheological properties of clearcoats along the curing time, two dual-curing methods showed the different evolution of curing patterns. In the UV–thermal dual-curing case, the initial infusion of UV light promoted free radical polymerization during the subsequent thermal curing by generating considerable free radicals, and exhibiting a higher growth rate of elastic modulus during the curing in comparison with the thermal–UV dual-curing case. However, the final modulus value in the thermal–UV dual-curing case was higher due to the suppression of thermal curing by the steric hindrance in the UV–thermal dual-curing. The level of crosslinked networks in clearcoats via different curing steps can be explicitly figured out from the double bond conversion from FT-IR, curing pattern from rigid-body pendulum test, and scratch properties from nano-scratch test.     

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.     

UV- and thermal-curing behaviors of dual-curable adhesives based on epoxy acrylate oligomers

Dual-curable adhesives were prepared using various epoxy acrylate oligomers, a reactive diluent, photoinitiators, a thermal-curing agent and a filler. The UV- and thermal-curing behaviors of the dual-curable adhesives were investigated using photo-differential scanning calorimetry (photo-DSC), Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy, and the determination of the gel fraction, pendulum hardness and adhesion strength.The reaction rate and extent of UV curing were found to be strongly dependent on the concentration of CC bonds in the epoxy acrylate oligomers. The FTIR-ATR absorption peak areas representing the relative concentration of CC bonds in the epoxy acrylate oligomers and trifunctional monomer decreased with increase in UV dose because of photopolymerization. When the dual-curable adhesives were irradiated with UV light, the gel fraction increased with increase in CC bond contents in the epoxy acrylate oligomers. Also, after thermal curing, the gel fraction was highly enhanced due to the cross-linking reaction of the unreacted glycidyl groups in epoxy acrylate oligomers induced by the thermal-curing agent. This cross-linked structure of the dual-curable adhesives affects the pendulum hardness and adhesion strength.     

Scratch resistance of nano-silica reinforced acrylic coatings

Organic–inorganic hybrid coatings were obtained by a dual-curing process combining the sol–gel reaction with the UV-induced polymerization technique by starting from bisphenol A ethoxylate (15 EO/phenol) dimethacrylate (BEMA, as organic network former), methacryloyloxypropyl-trimethoxysilane (MEMO, as coupling agent) and tetraethoxysilane (TEOS, as inorganic silica network precursor). For comparison, TEOS was also substituted with preformed silica nanoparticles. Scratch test was carried out in order to study the scratch resistance of that silica reinforced acrylic resins. Excellent scratch resistant coatings were obtained by UV and sol–gel dual curing process. On the contrary, coatings with very poor scratch resistance were obtained by dispersing preformed nano-silica into the acrylic resin indicating the key role played by the morphology of the inorganic filler and its interaction with the organic matrix.     

Preparation and characterization of UV/thermal dual-curable polyurethane acrylate adhesive for inertial confinement fusion experiment

A new type of polyurethane acrylate (APUE) oligomer, which contains both acrylic and epoxy group in its molecular structure, was synthesized. UV/thermal dual-curable adhesives were prepared using various contents of APUE oligomers, reactive diluent, photoinitiators and thermal-curing agent. The curing behaviors of the dual-curable adhesives were investigated using photo-DSC, on-line FT-IR spectroscopy, the determination of gel fraction and dynamic mechanical thermal analysis (DMTA). The reaction rate and extent of UV curing were studied and found to be strongly dependent on the concentration of C=C bonds in the APUE oligomers. The gel fraction was also evaluated as a function of C=C bond concentration, demonstrating that gel fraction increased with increasing C=C bond contents in the APUE oligomers. Moreover, when the dual-curable adhesive was thermally-cured, the gel fraction was largely improved, due to the thermal-curing agent initiating the unreacted epoxy groups to allow the formation of further crosslinking. The adhesion strength at −196 °C increased with increasing C=C bond content. The latent thermal-curing agent contributed to the enhancement of the adhesion strength.     

Low VOC carbamate functional coatings compositions for automotive topcoats

Polymers and oligomers having carbamate functional groups have been used in a variety of curable coating compositions. Carbamate functional polymers offer many advantages for automotive topcoats, such as outstanding resistance to environmental etching, scratching and marring, humidity, and UV exposure. Hydrophobic carbamate oligomers suitable for crosslinking with standard amino resins were synthesized and formulated into stable one-pack automotive clearcoats with low volatile organic compound (VOC) and excellent physical properties. Because of their unusually steep thermal viscosity curves, these oligomers are particularly adaptable to hot spray techniques that enable coatings in the 85–90% weight solids range to be applied with conventional electrostatic mini-bells. Presented at the 27th Annual International Waterborne, High-Solids, and Powder Coatings Symposium, in New Orleans, LA, March 2000. Automotive Coatings Technical Center, Southfield, MI 48034.     

HMMM cured corrosion resistance waterborne ormosil coating for aluminum alloy

Due to the exceptional advantages of sol–gel process, organically modified silane (ormosil) coating has been applied to study the corrosion protection of aluminum alloy. In the present work, GPTMS/MTMS sol–gel solution was prepared by hydrolysis and condensation of 3-glycidoxypropyltrimetoxysilane (GPTMS) and methyltrimethoxysilane (MTMS) in aqueous solution of 0.05 M acetic acid in molar ratios 3:1. To prepare the ormosil coating solutions, a crosslinking agent hexamethoxymethylmelamine (HMMM) and a blocked acid catalyst p-toluenesulphonic (p-TSA) were combined with the sol–gel solution. Aluminum substrates were dip coated and cured at 130 °C for 45 min. Effectiveness of HMMM as a crosslinking agent was analyzed by evaluating corrosion resistance, chemical resistance and hydrophobicity of coating using potentiodynamic polarization method, immersion test and water contact angle, respectively. UV stability of sol–gel solution, ormosil coating formulation and coated substrate was also studied using UV–vis spectroscopy and UV-weatherometer to see performance of coating in outdoor application. Thermal behavior of ormosil was characterized using TGA and DSC. Surface morphology and structural characteristics were also characterized using SEM, AFM and FT-IR-RAS (reflection absorption spectroscopy). Pencil hardness, impact test and bend test were carried out to determine the adhesion, hardness and flexibility of coating.     

Effect of polysiloxane additives on the scratch resistance of an acrylic melamine automotive clearcoat

Many attempts have been carried out to increase the scratch resistance of clearcoats using various appropriate additives. These additives may increase surface hardness or surface slippage, and/or enhance the bulk mechanical strength of the clearcoat. In the present study, the influence of various added loads of three differently structured polysiloxane additives on the scratch resistances of an acrylic melamine clearcoat was investigated. A series of analytical instruments, such as a laboratory carwash simulator, a scanning electron microscope, an optical microscope and an attenuated total reflectance Fourier transform infrared spectroscope, and others were used to compare the effects of the various added contents of polysiloxane additives on changes in the viscoelastic properties and scratch morphologies of the resultant clearcoats. The results illustrated that all polysiloxane additives improve the scratch resistance of such clearcoats, yet the optimum load varied for each individual additive. There is also a good indication that polyether-modified polysiloxanes improve scratch resistance by increasing surface hardness, while the fluorocarbon-modified polysiloxane tends to change the viscoelastic properties of the clearcoats. It was also found that scratch resistance varied linearly with Micro-Vickers’ hardness for brittle clearcoats.     

Study of fullerene-containing epoxy membranes with tunable ultraviolet light-filtering properties

Fullerene-containing epoxy membranes with tunable ultraviolet (UV) optical properties were prepared by adding various amounts of aminated-fullerene derivatives into an epoxy resin/ethylenediamine system. The influences of content and chemical structure (e.g., amine kind and addition degree) of aminated-fullerene on the mechanical, optical and thermal properties of the cured epoxy membranes were investigated systematically. Dynamic mechanical analysis (DMA) indicates that the aminated-fullerene participates in the epoxy curing process and that a star-like crosslinking structure is formed. A higher cross-link density results in a higher glass transition temperature and storage module. The UV–Vis absorbance spectra reveal that the cutoff wavelength λ_c of the aminated-fullerene/epoxy membranes can be changed over almost the entire UV region simply by varying the fullerene derivative content. The charge-transfer complexes formed between the fullerene derivatives and the epoxy-amine complex may be responsible for the UV light-filtering behaviors. The result of thermogravimertic analyses (TGA) reveals that a higher amount (0.48 wt%) of fullerene derivative obviously leads to the better thermal stability of the cured epoxy membrane.     

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.     

多重交联UV固化水性聚氨酯木器涂料的研制

通过UV固化和有机硅交联改性及多官能度扩链剂的引入,研制了多重交联UV固化水性聚氨酯木器涂料。形成的涂膜在UV固化前即具有较好的涂膜强度和机械性能,耐沾污;经UV固化后,涂膜具有更加优异的耐水性、耐醇性、耐磨性和耐干热性,以及良好的硬度和装饰效果。     

Investigation of synergistic effect of nano sized Ag/TiO2 particles on antibacterial,physical and mechanical properties of UV-curable clear coatings by experimental design

The synergistic effect of nano titanium dioxide (10 and 30 nm) and nano silver (10 nm) as antibacterial agents were investigated on UV curable clear coating. Antibacterial and physical–mechanical properties of coating were optimized using experimental design in response surface method. Twenty different samples of nano Ag and nano TiO₂ were prepared in this method. Antibacterial properties on Gram-negative bacteria (Escherichia coli) were investigated. The results revealed that using equal amounts of two sizes of nano TiO₂ promote the antibacterial activity of nano Ag. So, the coating shows strong activity against E. coli. Physical–mechanical properties such as surface hardness, abrasion resistance, scratch resistance and gloss of the coating were evaluated. The results depicted appropriate physical–mechanical properties. Also, scanning electron microscope (SEM), atomic force microscope (AFM) and Fourier transform infrared (FT-IR) spectroscopy were used to study the effect of nano particles on coating properties.     

Characterization of clearcoats containing phosphoric acid-functionalized acrylic polyols for automotive precoated metal sheet coatings

In this study, the various physical and mechanical properties of clearcoats prepared through a new crosslinking method were investigated. The method was aimed at developing clearcoat systems to improve the deep-draw processing and formability performance in precoated metal (PCM) sheets for automotive applications. From phosphoric acid-functionalized acrylic polyols (PAFAPs) first synthesized in this study and glycidyl methacrylate-modified acrylic copolymer (GMAMAC), phosphoric acid-GMA modified acrylic polyols (PAGMAPs) were newly prepared as new binders in automotive clearcoats. Several clearcoats were formulated with different molecular weights and hydroxyl contents from PAFAPs and GMAMAC. Using clearcoats themselves, the crosslinking reactions for these clearcoats were compared by evaluating the curing behaviors with a rigid-body pendulum test (RPT) and the changes of chemical structures via attenuated total reflectance FTIR spectroscopy. The mechanical properties of the clearcoats were systematically characterized, using dynamic mechanical analysis (DMA) and universal testing machine analysis (UTM). Also, various tests were carried out using PCM sheets by depositing clearcoats above the same PCM-based primers and basecoat layers on galvanized steel. The fracture and deformation patterns related to surface damages on the clearcoat surface were visualized using a nano-scratch test, in association with atomic force microscopy. In particular, deep-draw processing tests, based on forming process simulations, were employed to scrutinize the effect of clearcoats developed in this study on the forming feature in PCM sheets. From the results of RPT, DMA, and UTM tests, the primary crosslinking networks of PAGMAPs from the synthesized PAFAPs and GMAMAC, and also succeeding secondary crosslinking networks between PAGMAPs and blocked isocyanates, were closely correlated with the degree of crosslinking (X _c), in accordance with the molecular weight between crosslinks (M _c), and glass transition temperature (T _g). As a result, the presented clearcoats with a long pendulum period, a low rubbery modulus, and a large tensile strain value, which are the significant factors for developing automotive PCM sheet technology, have truly demonstrated more superior formability during the deep-draw process. It is confirmed that properties of clearcoats with toughness and flexibility could be optimally controlled by PAGMAPs for automotive coatings.     

The Effect of Radiation Dosages and UV/EB Radiation on the Properties of Nanocomposite Coatings

The aim of this study was to compare the effects of ultraviolet (UV) and electron beam (EB) radiation on the properties of cured nanocomposite coatings. Surface hardness increased with increasing radiation dosages (number of passes) for all samples. This was due to the increase in crosslinking with increasing radiation dosages. Pendulum hardness, gel content, and thumb twist results were analyzed to choose the appropriate curing dosage for both curing techniques. The selected dosages were then used to cure coatings for scratch and abrasion resistance tests. It was found that the UV curing produced coatings with better abrasion resistance, whereas EB curing was more suitable for producing scratch-resistant coatings.     

A Fast Thermal-Curing Nanoimprint Resist Based on Cationic Polymerizable Epoxysiloxane

ABSTRACT: We synthesized a series of epoxysiloxane oligomers with controllable viscosity and polarity, and developed upon them a thermal-curable nanoimprint resist that was crosslinked in air at 110 oC within 30 seconds if pre-exposed to ultraviolet (UV) light. The oligomers were designed and synthesized via hydrosilylation of 4-vinyl-cyclohexane-1,2-epoxide with poly(methylhydrosiloxane) with tunable viscosity, polarity and crosslinking density. The resist exhibits excellent chemical and physical properties such as insensitivity toward oxygen, strong mechanical strength and high etching resistance. Using this resist, nanoscale patterns of different geometries with feature sizes as small as 30 nm were fabricated via a nanoimprint process based on UV-assisted thermal curing. The curing time for the resist was on the order of 10s of seconds at a moderate temperature with the help of UV light pre-exposure. This fast thermal curing speed was attributed to the large number of active cations generated upon UV exposure that facilitated the thermal polymerization process.     

UV curing and matting of acrylate coatings reinforced by nano-silica and micro-corundum particles

For UV curable coatings, the effect of the type of photoinitiator and of the photoinitiator content on surface properties has been studied. Increasing photoinitiator concentrations yielded higher acrylate conversion but a lowering of surface hardness. Thus, curing under oxygen-free conditions with 2 wt.% photoinitiator should be applied rather than 6 wt.% photoinitiator for irradiation in air. Compared to nanocomposite materials, UV-cured polyacrylate coatings reinforced by silica nanoparticles and corundum microparticles exhibit markedly improved scratch and abrasion resistance. By using various grades of corundum, a synergetic effect between nano- and microparticles has been observed. These nano/micro-hybrid composite materials are recommended as clear coat for parquet and flooring applications.     

Synthesis and curing behaviors of a crosslinkable polymer from cashew nut shell liquid

In the present study, we have oxidatively polymerized cashew nut shell liquid (CNSL), whose main component is cardanol, a phenol derivative having a meta substituent of a C15 unsaturated hydrocarbon chain with one to three double bonds as the major, and examined the curing behaviors of the resulting polymer. Fe-salen efficiently catalyzed the polymerization in bulk at room temperature to give a soluble crosslinkable polymer in a good yield. Various metal complexes also catalyzed the polymerization at 80 °C, although their catalytic activity was lower than that of Fe-salen. The curing by cobalt naphthenate catalyst or thermal treatment took place to give the crosslinked film (artificial urushi) with high hardness and gloss surface. In the curing of polyCNSL by the thermal treatment, the crosslinking behaviors and properties of the resulting film were similar to those of a commercially available CNSL-formaldehyde resin.     

Photocrosslinkable modified vegetable oil based resin for wood surface coating application

An acrylated epoxidized linseed oil (AELO) was synthesized from epoxidized linseed oil through ring opening of the oxirane group using acrylic acid as ring opening agent. The occurrence of the acrylate group and the ring opening of oxirane group was monitored using FT-IR spectroscopy. The AELO was mixed with three different photoinitiators at two different concentrations. Wood surfaces were coated with the mixtures, subsequently cured under UV light and the resulting surface properties of the coated samples gloss, scratch resistance, solvent resistance, and coating adhesion were characterized. The efficiency of the photoinitiators and the influence of their concentration on the rate and the extent of the curing were studied by curing the AELO mixtures under a monochromatic wavelength of 365 nm and measuring absorption spectra during the cure by real time FT-IR spectroscopy. The decrease of absorption in the measured spectra at 1406 cm⁻¹ was used to calculate the conversion of acrylic double bonds with increasing time of UV light exposure to obtain information on the cure kinetics for each photoinitiator and concentration.     

Surface mechanical properties of transparent poly(methyl methacrylate)/zirconia nanocomposites prepared by in situ bulk polymerization

Poly(methyl methacrylate)/zirconia (PMMA/ZrO₂) nanocomposites with ZrO₂ content as high as 15 wt% were prepared by modifying non-aqueous synthesized ZrO₂ nanoparticles with methacryloxypropyltrimethoxysilane (MPS) in tetrahydrofuran, dispersing MPS-functionalized ZrO₂ nanoparticles in MMA and following in situ bulk polymerization with controlled pre-polymerization time. The MPS-functionalized ZrO₂ nanoparticles showed an efficient crosslinking role in the polymerization, leading to a complete gel of PMMA at 5 wt% of ZrO₂ content. Homogeneous dispersion of the ZrO₂ nanoparticles at primary particle size level was observed in all nanocomposites, which results in good clarity of the obtained nanocomposites. Hardness tests (pendulum hardness tests and indentation tests) and anti-scratch tests (abrasion tests and nano scratch tests) were employed to probe the surface mechanical properties of the nanocomposites. The properties of nanocomposites as a function of ZrO₂ content, revealing from various characterization techniques, are not consistent and discussed in detail. At low ZrO₂ content, the mechanical properties are enhanced by the formed crosslinking structure. However, remarkable improvements of hardness and scratch resistance of PMMA were achieved when 15 wt% of ZrO₂ content was embedded.     

Mechanical properties and thermal stability of ambient-cured thick polysiloxane coatings prepared by a sol–gel process of organoalkoxysilanes

Ambient-curable polysiloxane coatings were prepared by pre-hydrolysis/condensation of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) in the presence of ammonia solution and subsequently mixing with aminopropyltriethoxysilane (APS). The mechanical properties of coatings were thoroughly examined at both macro- and micro-level and the thermal stability of coatings was characterized by thermogravimetic analysis, both of which were correlated with coating composition and the hydrolysis/condensation degree of polysiloxane oligomer. It was found that pro-hydrolysis step is essential for fabrication of thick crack-free coatings (18–35 μm). Higher DMDMS molar ratio, more APS dosage and lower hydrolysis/condensation degree of polysiloxane oligomer favor enhancing the hardness. Excellent impact resistance (50 cm kg) of coatings was obtained at 5% and 10% APS dosage, despite of the type and structure of polysiloxane oligomer. Whatever, the best scratch resistance of coatings was attained using the polysiloxane oligomer, prepared at PTMS-to-DMDMS molar ratio of 2:8 and water-to-precursor molar ratio of 1:1, and 5% APS dosage. The polysiloxane coatings exhibit high thermal stability, however, which strongly depends on the coating composition.