A Raman spectroscopic method to find binder distribution in electrodes during drying

Lithium ion batteries are used extensively in electronic devices as well as hybrid and electric vehicles. The anode electrode layer in the battery can be fabricated by coating an aqueous dispersion of carbon, binder, and additives, and then drying. During manufacturing, the distribution of the binder through the coating thickness can become nonuniform, which compromises the properties and performance of the battery. In this study, a quantitative method to analyze the binder distribution in the electrode during drying was established. A drying apparatus with an integrated analytic balance and surface-temperature measurement was used to prepare specimens. At specific time points during drying, specimens were removed from the apparatus, quickly frozen, and then freeze-dried. Raman spectroscopy was then used to measure the binder concentration at different points through the cross section of the freeze-dried electrode coating. Scanning electron microscopy was also used to explore the changing microstructure qualitatively. Using a model electrode formulation, the method demonstrated different binder distributions for electrodes dried at 150°C under airflow and room temperature, 20°C, with no airflow. The results also showed continued changes in distribution in the interior of the coating as drying continued.     

Environmentally friendly wooden-based coatings for thermal insulation: Design,manufacturing and performances

The design of an innovative protective and thermal insulating coating is investigated. The coating is composed of two superimposed layers; the innermost layer consists of dried beech dust dispersed in a diluted polyurethane binder, while the outermost layer is a conventional decorative hybrid epoxy-polyester powder coating. Each layer was sprayed on a metal substrate and baked at moderate temperature to consolidate the coatings and establish their full properties. The morphological features, mechanical response, protective and thermal insulating performance of the coatings were experimentally analysed by varying their structure and dried beech dust concentration in the binder. These coatings exhibit high potential in terms of thermal insulation and also show remarkable behaviour in terms of visual appearance, adhesion to the substrate and long lasting.     

The effect of silane layer drying temperature on epoxy coating adhesion on silane-pretreated aluminum substrate

In this study, 3-glycidoxypropiltrimethoxysilane was used as an adhesion promoter to enhance the adhesion strength of epoxy coating on an aluminum (Al) substrate. Silane layer drying temperature was investigated as a factor that has an influence on the adhesion of polymeric coating on metal substrate and also on its performance in wet and corrosive environments. FTIR tests were carried out to study Al/silane interactions. Drying the silane layer at high temperatures formed a condensed siloxane layer that improved the bonding strength as well as the performance of the protective coating in corrosive environments. The highest dry and wet pull-off strengths were obtained at drying temperatures of 100 and 125°C, respectively.     

Drying and cracking of soft latex coatings

The minimum film formation temperature (MFFT) is the minimum drying temperature needed for a latex coating to coalesce into an optically clear, dense crack-free film. To better understand the interplay of forces near this critical temperature, cryogenic scanning electron microscopy (cryoSEM) was used to track the latex particle deformation and water migration in coatings dried at temperatures just above and below the MFFT. Although the latex particles completely coalesced at both temperatures by the end of the drying process, it was discovered that particle deformation during the early drying stages was drastically different. Below the MFFT, cracks initiated just as menisci began to recede into the packing of consolidated particles, whereas above the MFFT, partial particle deformation occurred before menisci entered the coating and cracks were not observed. The spacing between cracks measured in coatings dried at varying temperatures decreased with decreasing drying temperature near the MFFT, whereas it was independent of temperature below a critical temperature. Finally, the addition of small amounts of silica aggregates was found to lessen the cracking of latex coatings near the MFFT without adversely affecting their optical clarity.     

Drying and property studies on protective coatings formed by spontaneous surface polymerization

Drying studies on a protective coating formed by spontaneous polymerization on aluminum are described. The polymer coating studied here was formed from styrene, n-phenyl maleimide (NPMI), bismaleimide (BMI), and 2-(methacryloyloxy) ethyl acetoacetate (MEA). The coating successfully changed into an adherent film through drying in the presence of a coalescing solvent. Drying at a high temperature (> 170°C) enhanced the performance of the coating in terms of corrosion resistance and adhesion. It was found that the drying process involved removal of surface water on the substrate followed by formation of a dense protective layer associated with thermal crosslinking of g -diketone functional groups in the coating. The reaction mechanism, glass transition temperature, adhesion strength to aluminum, and corrosion resistance of these coatings are reported. The resultant coatings show excellent adhesion strength in a torsional test and very good resistance under the ASTM B-117 accelerated salt fog test.     

Formation of hollow granules from liquid marbles: Small scale experiments

Research into formation of hollow granules from liquid marbles is an emerging field in hydrophobic granulation. A liquid marble is formed by a network of self-assembled hydrophobic powder around a droplet, and this paper investigates the conditions required for forming hollow granules from a liquid marble precursor.Single drops of fluid were produced using a syringe and placed onto loosely packed powder beds of hydrophobic powders. Liquid marbles formed from several powder/liquid combinations were dried at several conditions to investigate the drying conditions required for formation of a stable hollow granule.The formation of stable hollow granules was found to depend on drying temperature and binder concentration. For HPMC and PVP binder, formation of hollow granule is proportional to binder viscosity and for HPC binder, this relationship is constant. Different combinations of powder and binder at both drying temperatures - 60 °C and 100 °C - had mixed success rates in forming hollow granules, but generally the success rate was improved by using higher drying temperatures, smaller particles or higher viscosity binder fluids.     

Changes in epoxy-coated aluminium due to exposure to water

An investigation was performed of the changes that occur in a typical epoxy-coated aluminium system due to exposure to water. The adhesion of the epoxy coating upon exposure to water was evaluated for different exposure temperatures and periods. The adhesion test results showed an initial loss of adhesion of the coating but after this the adhesion improved again and even significantly exceeded adhesion prior to exposure. The amount of adhesion improvement and the speed with which adhesion improvement occurred was found to be larger for higher exposure temperatures. The changes that occur in the epoxy-coated aluminium system due to exposure to water were investigated using a number of different analytical techniques. Based on this, a model was proposed for the processes that take place during exposure and which can explain the adhesion test results. First, the adhesion of the epoxy coating is lost upon exposure due to the accumulation of a significant amount of water at the interface. The water at the interface causes formation and growth of a thin oxyhydroxide layer underneath the epoxy coating. After some time, this oxyhydroxide layer re-establishes contact with the epoxy coating and forms a new, water-stable bond, hence explaining the improvement of the adhesion after its initial loss.

The temperature-dependence observed in the adhesion test results is explained by the fact that at a higher exposure temperature, more water accumulates at the interface, the oxyhydroxide layer grows faster and also attains a larger limiting thickness.     

Fatigue strength of diamond coating-substrate interface assessed by inclined impact tests at ambient and elevated temperatures

The effect of two different treatments of cemented carbide substrates, prior to the deposition of a nanocrystalline diamond (NCD) coating, on the film interface fatigue strength was investigated at ambient and elevated temperatures. The first substrate treatment of the cemented carbide substrate was a selective chemical Co-etching and the second one the deposition of a Cr-adhesive layer. Inclined impact tests at 25 °C and 300 °C were performed on the NCD coated specimens. The related imprints were evaluated by confocal microscopy measurements and EDX micro-analyses. The thermal residual stresses developed in the film structure at various temperatures were estimated by Finite Element Method (FEM) calculations. A fatigue damage in the NCD coating interface region was induced by the repetitive impacts. After this damage, the compressive residual stresses in the NCD film are released leading to its lifting from the substrate (bulge formation) and subsequent coating failure. The NCD film-substrate interface fatigue behavior is significantly affected by the test temperature. Based on the attained results at diverse substrate treatments, Woehler-like diagrams were developed for monitoring the fatigue failure of NCD coating interface area at 25 °C and 300 °C. The interfacial fatigue strength worsens as the impact test temperature grows in both examined substrate treatment cases. Moreover, Co-etched substrates compared to coated ones by an adhesive Cr-interlayer possess higher interfacial strength at ambient and elevated temperatures. These phenomena were investigated and related explanations are described in the paper.     

Coating films prepared by photoreactions of the surface‐modified diamond powder and PET film with a binder agent

The surface‐modified diamond and PET film underwent photopolymerization rapidly with a binder agent to afford coating films of interpenetrating network (IPN) structure. The coating films thus formed exhibit higher tensile strength, thermal stability, and adhesion strength to the PET film. The inert surfaces of pristine diamond (PD) and PET film were modified by different chemicals and procedures to introduce epoxide and methacryloyl groups, respectively, on their surfaces. A coating agent consisting of an epoxide group containing modified diamond (called ED), a binder agent, and photoinitiators was prepared. After applying the coating agent to the substrate (a glass plate or a methacryloyl group containing PET film, MMA‐PET) and degassing under reduced pressure, the thin film of the coating agent was exposed to UV light (λ_max; 365 nm) at room temperature to yield a coating film of IPN‐structure. The tensile strength and thermal properties of the ED‐containing free coating film (called free film) increased with the amount of ED embedded, whereas the strength of the PD‐containing free film decreased with the amount of PD embedded. The adhesion strength of the coating film on the MMA‐PET improved significantly by the free radical polymerization of the methacryloyl groups on the MMA‐PET and the acrylate resin in the binder agent. The surface photoreactions of ED and MMA‐PET with the binder agent were confirmed by modeling. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adhesion improvement of diamond coatings on cemented carbide with high cobalt content using PVD interlayer

At present, diamond coating is usually deposited on cemented carbide (WC-Co) tool with low Co content (Co ≤ 6 wt.%). It is more difficult to deposit diamond coating on WC-Co with high Co content because of the strong catalytic effect of Co. However, WC-Co tools with high Co content (Co ≥ 6 wt.%) are more widely used in difficult-to-cut materials machining because of their higher strength and better ductility. In this paper, the research was carried out on the adhesion performance of diamond coating on WC-Co (Co 10 wt.%). The deposition of diamond coating was conducted in hot filament chemical vapor deposition (HFCVD) system with the presence of the strong carbon-forming metallic interlayer (Nb, Cr or Ta), which was prepared using physical vapor deposition (PVD) on WC-Co substrate after chemical etching through a two-step process (Murakami solution and Caro's acid), which is a general way to treat the WC-Co substrate before growth of diamond coating. The results showed that the diamond films grown on the above treated WC-Co substrate have higher nucleation density, purity and adhesion strength than those on WC-Co substrates pretreated only using PVD interlayer or chemical etching. The PVD interlayer restrains the diffusion of Co as a result of high substrate temperature during the diamond film deposition, and consequently prevents the formation of the loosened layer induced by the removal of Co binder phase in the WC-Co substrate. The results also indicated that Nb interlayer leads to the most adhesion improvement of diamond films on the WC-Co inserts among the Nb, Ta and Cr interlayers.     

热镀锌燃气管道外用环氧防腐涂料的制备及性能研究

探讨了不同种类的环氧树脂、不同种类的胺固化剂以及颜基比对热镀锌管基材涂层附着力、铅笔硬度、耐冲击性、耐酸性等性能的影响。研究表明:环氧树脂E-20-聚酰胺125体系可以降低涂层干燥时间,提高涂层在热镀锌管表面耐冲击性能至123.5 cm,同时耐酸试验后耐冲击性能仍达到95.5 cm;当涂层颜基比控制在1.8∶1时,涂层的综合性能达到最佳,耐酸试验前后各项性能均未下降,附着力均达到0级,耐冲击性能均达到162.5 cm。最终选用环氧树脂E-20为基体树脂,聚酰胺125作为固化剂,以1.8∶1的颜基比制备了一种适用于热镀锌燃气管道外用防护涂料,该涂料各项性能均明显优于CGAS001—2016《宽边管件连接涂覆燃气管道技术规程》中对环氧树脂涂料及涂层的技术要求。     

Preparation and characterization of sol–gel Al2O3/Ni–P composite coatings on carbon steel

Ceramic films have been applied to improve the resistance against high temperature oxidation of carbon steels. Alumina film was prepared on carbon steel surface by a dip coating technique. Electroless Ni–P plating film has been pre-deposited as an intermediate layer to improve the adherence of the film to carbon steel substrate. The oxidation kinetics of coated sample was investigated by measuring weight gain at 800 °C for 100 h. The surface and cross-section morphology of samples before and after oxidation were characterized by scanning electron microscopy (SEM). The composition and element distribution at the interface of the coated samples were analyzed by energy dispersive spectroscopy (EDS) and EMAX.The results show that the composite coating is uniform. The alumina coating adhesion strength to the substrate is up to 20 ± 2 N in scratch test because the alumina film presents interdiffusion of nickel and aluminum during heat treatment. The oxidation resistance test indicates higher oxidation resistance of as-coated carbon steel comparing to uncoated ones.     

Drying and collapse of hollow latex

Hollow latex particles are used as white pigments for paints and paper coatings. In the coating dispersion, each hollow particle is filled with water. As the coating dries, water vacates the latex, leaving an air-filled void sized to scatter light (~0.5 μm) within each particle. Examinations of dried coatings reveal that hollow particles can collapse, decreasing their light scattering efficiency. Cryogenic scanning electron microscopy (cryoSEM) was used to characterize the microstructure of coatings containing hollow latex during drying. Images suggest latex voids empty after air invades into the coating interstitial space and collapse occurs late in the drying process. The effects of temperature (10–60°C), humidity (20–80%), and binder concentration (0–30 wt%) on particle collapse were also studied through SEM of dried coating surfaces. High drying temperature, high humidity, and low binder concentrations promoted collapse. For hollow latex particles with porous shell walls, temperature and humidity had little effect, whereas binder increased collapse. From these results, a theoretical model is proposed. During drying, diffusion of water from the particle creates a vacuum inside the latex. The vacuum is either relieved by nucleation of a gas bubble from the dissolved air in the water-filled particle or it causes the particle to collapse by buckling.     

Revealing the effects of aerosol deposition on the substrate-film interface using NaCl coating

Aerosol deposition is a feasible method of fabricating dense ceramic films at room temperature by the impact consolidation of submicron-sized particles on ceramic, metal, glass, and polymer substrates at a rapid rate. Despite the potential usefulness of the aerosol deposition process, there are issues, such as deposition mechanisms and structure of the film-substrate interface, that are not well understood. We have used complementary structural and microstructural analysis to capture the state of the substrate surface after the aerosol deposition process. The results reveal that modification of the substrate surface by the ejected submicron-sized particles is essential for the formation of anchoring layer, thereby, a change in internal residual stress state and surface free energy of the substrate is required to deposit film using AD process. Our analysis also suggests that the adhesion between the metal substrate and ceramic particles is possibly contributed by both physical bonding and mechanical interlocking.     

Coating based on the modified chlorinated polypropylene emulsion for promoting printability of biaxially oriented polypropylene film

In this paper, a polymeric coating based on the modified chlorinated polypropylene (CPP) emulsion was synthesized, methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA) were grafted onto CPP backbone and phase inversion was conducted to obtain waterborne emulsion. Results showed that the concentration of initiator (BPO) had the greatest effect on graft copolymerization. The concentration of emulsifier and temperature influenced the results of phase inversion. Besides, the thermal performances of modified CPP were better than untreated one. In addition, the coating obtained in optimum condition had excellent adhesion to BOPP film, and apparently improved the printing quality of the film. The printability promotion should be attributed to the different movement trend of coating’s polar and un-polar chains during the baking step, as well as the subsequent formations of new coating/substrate and coating/ink interface layer.     

Interplay between adhesion and interfacial properties of diamond films deposited on WC-10%Co substrates using a CrN interlayer

In this study, the effect of deposition temperature on the adhesion of diamond films deposited on WC-10%Co substrates with a Cr-N interlayer is investigated. Diamond films were deposited at different temperatures (550, 650 and 750 °C), using a hot filament chemical vapor deposition reactor. It was found that the optimal adhesion is obtained for the film deposited at 650 °C. The interplay between carbon interfacial diffusion and the adhesion of diamond films deposited at different deposition temperatures were investigated. The combined use of different characterization techniques (Indentation tests, SIMS, XPS, XRD and SEM) shows that the adhesion strength depends on the thickness of Cr-C layer formed at the interface during diamond deposition, which is strongly influenced by the deposition temperature. It is suggested that at the optimum deposition temperature, thickness of the Cr-C layer is too low to introduce a large thermal stress at the interface and sufficiently thick enough to withstand the propagation of indentation induced cracks.     

Film formation of monodispersed polystyrene latex at high temperature

This report discusses the drying behavior of monodispersed polystyrene latex at elevating temperature with particular attention to the relationship between water evaporation rate and morphological evolution during the film formation process. At the first stage, water evaporation rate was less influenced by the skin film formed at the latex/air interface, which was consistent with Croll's model. During this stage, a drying front advanced from the top film toward the bulk dispersion. At the final stage of film formation, the water evaporation rate was less than that of the initial stage, and another drying front developed from the interior region outside the system. Two distinct boundaries corresponding to the opposite directions of the second drying front between completely dried region and wet region were found if the film was peeled off the container surface. Besides, some particular morphologies were found in the completely dried region, which was likely related to preferable coalescence among the particles induced by capillary force because of water evaporation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1835–1840, 2001     

Observation of Phase Transition from Dissolved Organic Semiconducting Materials to Solid Film during Drying

We studied the formation dynamics of low-molecular-weight organic semiconducting molecules of N,N′-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N′-diphenylbenzidine (DNTPD) during solvent evaporation. We dropped the DNTPD–toluene solution on a glass substrate and performed in situ measurements of mass, temperature, scattered light intensity, and photoluminescence (PL). We found that both light scattering and PL measurements were able to detect the onset of solid film formation from dissolved organic semiconducting materials. When a solid thin film forms during drying, sudden changes in scattered light and PL are observed. Furthermore, we also found that a period of time after the onset was necessary for completion of thin solid film formation. Observations and in situ PL measurement during thin-film formation by spin coating revealed that this period of time affected the optical properties of the film. This result indicates that quantitative information on the film formation process is quite important to obtain thin films with desired properties by coating and drying. Our in situ measurements were simple and practical approaches to monitor the formation dynamics of organic thin films during drying.     

Photo-Initiated Lamination of Polyethylene (PE) and Poly(ethylene terephthalate) (PET)

Besides plasma-based processes, photo-initiated surface modifications have an interesting potential for adhesion promotion. This is of special interest with applications ranging from classical finishing to composites. Photo-chemical processes using continuous UV sources — monochromatic as well as broad band — are based on radical activation and ensuing reaction with the atmosphere. Achievable effects are addition of atoms — e.g., introduction of oxygen (photo-oxidation) resulting in increased surface energy — or grafting of functional groups. Both have certain potentials for adhesion promotion in a physico-chemical way. Based on the fundamental scheme of these processes — i.e., a photon-initiated radical reaction at the substrate-atmosphere interface — a direct 'inter-linking' of coating polymer and substrate is presented in this paper. The principal idea is to apply a thin layer of coating polymer on the substrate and irradiate this composite system at certain UV wavelengths. Given a low absorption of the radiation by the thin coating and — at the same time — a high absorption by the substrate, the radiation will penetrate the coating layer and generate radicals at the interface, which will induce cross-linking between the coating polymer and substrate. It is shown that for the example of laminates of polyethylene (PE) film on fabrics made of poly(ethylene terephthalate) (PET), extremely high adhesion strenghths are achieved without any use of additional adhesion promoters.     

Studies on slag deposit formation in pulverized coal combustors. 1. Results on the wetting and adherence of synthetic coal ash drops on steel

As part of a study of slag deposit formation in pulverized-coal-fired boilers, apparent contact angles and adhesion strengths of molten mineral drops contacted with cooler oxidized steel substrates have been investigated. High-speed photography indicated that freezing of the interface between the molten drop and metal surface occurred in milliseconds. Adherence occurred between an oxide film on the metal and the drop, adherence was weak on stainless steels, and particles of oxide film were broken away from the substrate when the drops were sheared off. Higher substrate temperatures gave increased adhesion, with a larger area of strong interaction between the oxide and the drop interface and less area of weak interaction. Addition of compounds to lower the liquidus temperature of the drop gave increased adherence. Pyrite drops were converted to mainly pyrrhotite on melting and showed a high degree of wetting and adherence to the oxidized steel even at low temperatures.