Slot die-coated blue SMOLED multilayers

The key challenge in solution-processing efficient OLEDs is to realize the multilayer device architecture. We demonstrate that slot die coating is applicable to deposit small-molecule (SM) layers on top of each other without dissolving the underlying layer. A stack for a blue SMOLED is chosen comprising slot die-coated PEDOT:PSS, an SM emissive layer (EML) as well as an SM electron transport layer (ETL). The devices are fabricated in a sheet-to-sheet coating process with a slot die table coater under ambient conditions. While keeping the processing parameters constant for PEDOT:PSS and the EML, the composition of the ETL is varied. The choice of solvent for coating the ETL is crucial regarding wetting and dissolution of the underlying layer, solubility, surface roughness, and device efficiencies. Average roughness values down to 0.38 nm and peak to valley values around 10 nm were measured. Comparing device efficiencies of devices with and without ETL, an increase in efficiency with a factor up to 42 was achieved. In total, we show 135 blue SMOLEDs to demonstrate reproducibility.     

Minimum wet thickness for double‐layer slide‐slot coating of poly(vinyl‐alcohol) solutions

A combined slide‐slot coating die, with the slide coating on top, was designed and built to investigate the double‐layer coating of poly(vinyl‐alcohol) solutions. The operating coating windows were examined as a function of flow rates and viscosities of the two coating layers. The top coating layer could be made much thinner as compared to the double‐layer coating so long as a stable thin film could be formed on the slide. A minimum wet thickness of the top layer was found to be as thin as 5 μm or less. A large viscosity ratio of the two layer solutions appears to be helpful in expanding the coating windows. Addition of a small quantity of polymer, such as carboxymethyl cellulose, can further enhance the coating speed and reduce the top layer thickness. A flow visualization technique was employed to observe the coating bead region. It was found to be easier to change the flow direction in the slide‐slot coating die than the double‐layer slot die, resulting in a more stable coating flow and much thinner top layer. POLYM. ENG. SCI., 45:1590–1599, 2005. © 2005 Society of Plastics Engineers.     

精密涂布工艺应用新进展

精密涂布工艺在功能性薄膜生产中起着重要作用。当今材料工业的迅速发展,对涂层提出更薄、更均匀的要求。特别象平板显示器(FPD)中所用的功能性光学薄膜,如防反射膜、防眩光膜等,其涂层厚度往往小于1μm。另外,锂电池电极的涂层则要求采用间歇式涂布方法来生产。本文着重介绍了近年来微凹版涂布和条缝涂布工艺在平板显示器、有机发光二极管(OLED)、锂电池行业中应用的新进展。     

Comparison of large scale coating techniques for organic and hybrid films in polymer based solar cells

Polymer based solar cells (PSC) can be manufactured in a continuous roll to roll process as a low cost regenerative energy source. Coating ink properties and film thicknesses of 30–200 nm are challenging with respect to the manufacturing process, which itself has an important impact on film properties and cell efficiencies. In this paper we compare the large area coating methods: knife coating, slot-die coating, and spray coating with laboratory spin coating. Properties of coating inks and a viscosity model for commercial PEDOT:PSS types are discussed. The significantly smaller viscosity to surface tension ratio, of typical coating inks for PSC compared to conventional coating inks, causes a different behavior during the coating process. Wet film thickness, homogeneity, and process stability and their dependence on process parameters are addressed for each coating method. Hole-conductive and photoactive layers, consisting of polymer-fullerene and polymer-nanoparticle blends, are then compared with respect to homogeneity, AFM topography and absorption spectra. First results indicate that the coating method itself has an impact on polymer-fullerene film morphology and opto-electric properties.     

A review of the operating limits in slot die coating processes

Slot die coating is a pre‐metered process commonly used for producing thin and uniform films. It is an important film fabrication method for applications where precise coating is required. A major concern in slot die coating processes is how to determine the operating limits to set the appropriate range of operating parameters, including coating speed, flow rate, vacuum pressure, coating gap, liquid viscosity and surface tension, etc. Operating limits directly determine the effectiveness and efficiency of the process. In this article, the current state of academic research on operating limits in slot die coating processes is reviewed. Specifically, the theories, mechanisms, and empirical conclusions related to the limits on vacuum pressure, the low‐flow limit, the limit of wet thickness for zero‐vacuum‐pressure cases, the limit of dynamic wetting failure, and the limits of coating speed for a specific flow rate are reviewed. The article concludes with some recommendations for future work. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2508–2524, 2016     

Process limits in two-layer reverse roll transfer

Reverse roll coating in which a thin single layer of liquid is applied onto a substrate has been used in industry for decades and has been extensively analyzed in the literature. Modern coatings, however, are often composed of more than one layer to improve the product performance and to reduce the manufacturing cost. Premetered methods such as slot, slide, and curtain coatings are typically used to produce such multilayer coatings. If the caliper of the substrate to be coated is not constant, then the coating gap and consequently the final film thickness deposited on the web will also be nonuniform. In this study, we focused on the use of reverse roll technique with slot die liquid delivery system to produce a uniform thin two-layer coating. The use of this coating technique to produce such a coating has not been previously explored. The liquid film surface as it is transferred from a rigid steel roll to a deformable urethane-covered roll was visualized to find out how the uniformity of the two-layer coating is affected by the speed ratio between two rolls, layers’ wet thicknesses, and liquid viscosities. The effect of these parameters on the ribbing frequency and amplitude was also investigated. The results show that in the two-layer coating, as in the single layer reverse transfer, there is a critical web speed above which ribbing occurs. The critical speed is determined by the bottom layer viscosity.     

Transient response of two‐layer slot coating flows to periodic disturbances

Coating uniformity requirement is becoming more severe as new products come into the market. Coating processes have to be designed not only based on the steady‐state operation but also taking into account how the flow responds to ongoing disturbances on process conditions. These disturbances may lead to thickness variation on the deposited liquid layers that may be unacceptable for product performance. This study extends available transient analysis of single‐layer slot coating to determine the amplitude of the oscillation of each individual coated layer in two‐layer slot coating process in response to small periodic perturbation on different operating parameters. The predictions were obtained by solving the complete transient Navier–Stokes equations for free surface flows. The results show the most dangerous perturbations and how the deposited film thickness variations of each layer can be minimized by changing the geometry of the die lip and liquid viscosities. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1699–1707, 2015     

Two-layer tensioned-web-over-slot die coating: Effect of operating conditions on coating window

Tensioned-web-over-slot die (TWOSD) coating deploys elastohydrodynamic interaction to control the distance between the moving substrate and the coating die lip surface in order to be able to coat an ultra-thin liquid layer. Dual slot TWOSD coating is designed to deposit two thin uniform liquid layers onto a moving web simultaneously. Like in the fixed-gap dual slot coating, the interlayer separation point needs to be at the downstream corner of the mid lip in order to prevent coating defects. Different flow features, like weeping, bead breakup and feed slot vortices, limit the range of operating parameters that ensures uniform coating, and define the operating window of the process. In this study, we analyze dual slot TWOSD coating flow by solving the Navier–Stokes equation coupled with thin cylindrical shell equation using the finite element method. The boundaries in the parameter space that define the operating window or vortex-free window are automatically computed by a direct tracking method of flow features. The effect of operating conditions, such as liquid viscosity, web tension and web speed, on the critical layer thickness at which the coating becomes non-uniform is determined by this study.     

Influence of support layer and PDMS coating conditions on composite membrane performance for ethanol/water separation by pervaporation

A systematic study was performed on the combination of support properties and polydimethylsiloxane (PDMS) coating conditions for the lab‐scale preparation of a defect‐free, thin film composite membrane for organophilic pervaporation. Support layers having comparable surface porosities were prepared from three polymers with different chemical composition (PVDF, PSF, PI). Their exact role on the deposition of the PDMS coating (i.e., wetting and intrusion) and the final membrane performance (i.e., effect on mass transfer of the permeants) was studied. The crosslinking behavior of dilute PDMS solutions was studied by viscosity measurements to optimize the coating layer thickness, support intrusion and wetting. It was found essential to pre‐crosslink the PDMS solution for a certain time prior to the coating. Dip time for coating the PDMS solution on the supports was varied by using automated dip coating machine. The performance of the synthesized membranes was tested in the separation of ethanol/water mixtures by pervaporation. Both flux and selectivity of the membranes were clearly influenced by the support layer. Resistance of the support layers increased by increasing the polymer concentration in the casting solutions of the supports. Increasing the dip time of the PDMS coating solution led to increased selectivity of the composite membranes. Scanning Electron Microscopy analysis of the composite membranes showed that this leads to a minor increase in the thickness of the PDMS top layer. Top layer thickness increased linearly with the square root of the dip time (t^0.5) at a constant withdrawal speed of the support. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43670.     

Trailing edge formation during slot coating of rectangular patches

Different products, such as adhesives, pharmaceutical patches, batteries, and fuel cell membranes, require coating discrete patches onto moving substrates. For coating rectangular patches, intermittent slot die coating is the preferred method. The patches can be obtained by rapidly starting and stopping the flow out of the coating die. Controlling the flow start-up and shutdown to produce sharp and uniform leading and trailing edges of each patch is challenging. Different ways to control the liquid feeding are used to optimize the process. Even if the start-up and shutdown of the feeding system are well designed, the transient flow in the coating bead contributes to the formation of nonuniform leading and trailing edges of coated patches. In this work, we analyze how the operating conditions, die geometry, and liquid properties affect the coating bead breakup process and the trailing edge configuration. The process is directly related to the contact line dynamics. The results show that the uniformity of the trailing edge of each coated patch can be improved by changing the die shoulder angle and wetting characteristics of the die surface.     

Response of slot coating flows to periodic disturbances

Slot coating is a common method in the manufacture of a wide variety of products. It belongs to a class of coating method known as premetered coating: in a steady-state operation, the thickness of the coated liquid layer is set by the flow rate fed to the die and the speed of the substrate moving past, and is independent of other process variables. Thus premetered methods are ideal for high precision coating. However, even the best designed slot coating operations are subjected to small oscillations on the process conditions, such as flow rate, vacuum pressure and gap fluctuations. These oscillation may lead to unacceptable variation on the thickness of the deposited liquid layer. The effect of process condition disturbances on the coated layer has to be minimized to assure a wet thickness as uniform as possible.The effect of an imposed periodic perturbation on the liquid flow rate or on the gap clearance in the coated layer thickness is explored in this work by computer-aided analysis. The amplitude of the thickness variation is determined at different process conditions and die configurations by solving the transient, two-dimensional, viscous free surface liquid flow in the coating bead. The system of equations, with appropriate boundary conditions, was solved by the Galerkin/finite element method, and an implicit time integration. The results show the response as a function of the imposed perturbation frequency and of the die geometry. They indicate that the die geometry may be optimized in order to minimize the film thickness oscillation of a slot coating operation.     

Experimental study on tensioned‐web slot coating

Tensioned‐web slot coating (TWSC) technology was developed in the early 1980s and was considered an efficient method for thin liquid film coating. An experimental study was carried out to investigate the effects of several key parameters on the minimum wet thickness of TWSC. The experiment was performed on a pilot coater with dilute Newtonian poly(vinyl) alcohol (PVA) solutions as test fluids coating on polyethylene‐terephthalate (PET) substrates. It was found that the minimum wet thickness for TWSC was between 0.5 and 1.5 μm, which is much lower than that obtained using conventional slot die coating. The minimum wet thickness was proportional to the tension number T_N, which is defined as the ratio of fluid viscous force over web tension. Furthermore, on the basis of the experimental data, two additional dimensionless groups: dimensionless pressure P_N and dimensionless surface tension L_N were found to be relevant to the performance of TWSC. A universal correlation involving these dimensionless groups as well as the die geometry was used to predict the minimum wet thickness of TWSC. POLYM. ENG. SCI., 47:841–851, 2007. © 2007 Society of Plastics Engineers     

Wetting behavior of the shear thinning power law fluids

The knowledge of the wetting characteristics of a coating solution is a prerequisite of assuring the final quality of thin films manufactured by the slot die coating process. Because the maximum coating speed is limited by defects, such as air entrainment, which are directly related to film quality, an understanding of the coating limits is critical. Despite the existence of a vast body of literature to understand the occurrence of defects and the coating limits to produce defect-free films, the mechanism of air entrainment is still not well understood, especially for various classes of solutions. In this study, the shape of the upstream meniscus of a mildly shear thinning non-Newtonian coating bead has been studied both numerically and experimentally and subsequently linked to the air entrainment threshold. It has been found that the dynamic contact angle reaches its maximum value at the air entrainment threshold, primarily as a function of the capillary number. In addition, this work suggests that the onset of the dripping and air entrainment boundaries of solutions that follow the power law can be predicted based on the dynamic contact angle as a function of the consistency and power law indices.     

Process-dependent conductivity and film homogeneity of slot-die-coated PEDOT:PSS–PVA composite films

In this study, we investigate the impact of process parameters on homogeneity and electrical conductivity of slot-die-coated PEDOT:PSS–PVA composite films that are doped with DMSO. Due to a strong correlation between conductivity and morphology of PEDOT:PSS films and the latter’s dependency on the processing step itself, we apply slot die coating for maximized process control and systematically evaluate the impact of coating gap, speed, and film thickness. Since the entire coating and drying process is run in batch mode, the setup is optimized regarding steady-state conditions and high homogeneity of the films. Overall, for the films manufactured in batch mode, we obtain a reproducibility film thickness of 99% and a low deviation from the set film thickness (below 8%). In order to analyze the impact of the coating parameters, stable operating points derived from the viscocapillary model are chosen and either the dimensionless gap or the capillary number is varied. Coating gap and film thickness emerged as dominating parameters, leading to an increase in conductivity of 40% and 70%, respectively, or, when changing both simultaneously, of 157%. Only a minor impact of shear forces (increase of 10%) was found.     

单股流布水改性碳钢表面的润湿特性

湿式静电除尘技术收尘极表面的易腐蚀和水膜均布问题是影响该技术连续可靠运行的重要因素。针对这两个问题,对碳素钢冷轧成型板进行了抗腐蚀保护层和在保护层基础上黏附不同附加亲水层的改性。使用称重法和平面成像法进行了单股流布水不同Reynolds数下不同改性表面持液量、表面流量、成膜率、水膜平均厚度等润湿特性的研究。结果表明:抗腐蚀保护层降低基材的润湿特性,附加亲水层中台丽碳纤维布的持液量较基材碳钢表面增加1.0～2.2倍,细沙粒成膜率比基材碳钢增加50%～60%,水膜厚度均在0.3～0.7 mm之间(最大达1.4 mm);玻璃纤维布黏附在环氧树脂表面的疏松程度直接影响表面的润湿特性,涂刷第3层环氧树脂后自然晾晒12 h,120℃加热1 h后敷设玻纤布,自然冷却至固化得到的表面润湿特性最佳,其持液量可达0.014～0.021 g·cm^-2,临界饱和时间 < 3 min,实现完全润湿,成膜率较基材增加34～40倍;改性材料表面布水参数:喷水孔间距≥10 cm、Reynolds数超过2000,此时表面液膜为波动层流,可获得理想冲刷效果。     

Transient response of slot coating flows of shear-thinning fluids to periodic disturbances

Slot coating is a popular coating method, in which the film thickness is precisely controlled by adjusting the flow rate and production speed. When the coating flow undergoes small-scale disturbances generated by rotating elements such as motors, pumps, or uneven rolls, the downstream meniscus fluctuates, which causes film thickness variation in the flow direction. Although most coating liquids including polymeric and particulate solutions exhibit a shear-thinning rheological property, their effect on transient coating flow behaviors is not deeply understood. Here, the effect of shear-thinning property on film thickness variation under different disturbances is investigated using a computer-aided analysis of transient slot coating flow. In this study, the Carreau model is used to describe the shear-thinning property, and four different disturbances are considered.     

Effect of roughness as determined by atomic force microscopy on the wetting properties of PTFE thin films

The influence of film roughness on the wetting properties of vacuum-deposited polytetrafluorethylene (PTFE) thin films has been investigated using atomic force microscopy (AFM) and contact angle goniometry. Surface roughness has been characterized by atomic force microscopy in terms of RMS roughness (R_q) and fractal dimensions. A contact angle correlation with surface roughness, as determined by AFM, is evident from these results, which are discussed on the basis of wetting theory. The results also confirm that the high water contact angles (as high as 150°) recently observed at the surface of a new water repulsive coating material (mixture of PTFE and binder) are because of surface roughness. Such measurements clarify the effect of nanometer-size surface asperities on the wetting properties of hydrophobic coating.     

Coating weight reduction by a carrier layer for tensioned‐web slot coating

The feasibility of using a dilute bottom carrier layer to reduce the thickness of a viscous top layer for tensioned‐web slot coating was examined experimentally. Aqueous poly(vinyl) alcohol solutions were prepared for both the carrier and the top layers. The solutions were coated on poly(ethylene terephthalate) films for observation. The thickness ratio of the two layers has to be in a certain range for stable coating, otherwise different types of coating defects would appear. The effects of viscosity, wrapping angle, surface tension, and web tension were studied. It was found that the viscosity ratio of the top layer to the carrier layer is the most critical factor; a large ratio is more helpful in reducing the thickness of the top layer. Increasing the wrapping angle, web tension, and surface tension of the top layer can also decrease the coating thickness of the top layer. The drying load is reduced substantially owing to the significant reduction of the top layer thickness. It was estimated that 50–90% of the energy required for drying could be saved by introducing a carrier layer in this study. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis of Silica Decorated MWCNTs for Field Emission Property

A novel route to nanocomposites containing surface modified multiwalled carbon nanotubes (MWCNTs) by silica thin film is reported. The effect of chemical oxidation on the surface of MWCNTs by using different acid-treatments is studied.The acidic processes are characterized by Raman spectroscopy, thermogravimetry analysis, scanning electron microscopy, and transmission electron microscopy. MWCNTs can be coated homogeneously with silica film by using tetraethoxysilane (TEOS)as a precursor in a sol-gel process. Varying the shell thickness of amorphous silica coating layers on MWCNTs exhibits excellent thermal stability, reliability, and lifetime of field emission properties, especially down to less than 10 nm.     

Two-layer tensioned-web-over-slot die coating: Effect of die lip geometry

Tensioned-web-over-slot die coating (TWOSD) takes advantage of the elastohydrodynamic interaction between the curved web under tension and the coating liquid to sustain a very small coating gap that enables ultra thin coating at relatively high speed. When the product requires two liquid layers, dual slot TWOSD coating can be used to coat those layers simultaneously. In this case, the liquid pressure along the coating bead sets not only the web configuration and meniscus locations but also the interlayer separation point. An easy way to control the pressure distribution is through the die lip geometry.Here, we analyze the effect of four different die lip geometric parameters, e.g. the downstream lip radius, the mid lip radius, the downstream lip offset and the mid lip apex point, on the coating window of the dual slot TWOSD coating. Using the model proposed by Nam and Carvalho (2009c) and a direct tracking of flow features, the boundaries of the vortex-free operating window, area inside the parameter spaces that ensure a uniform coating without vortex inside the flow, were obtained and compared for each die lip configuration.We found that the mid lip radius is one of the important parameters to control the location of the upstream meniscus. Also the location of the interlayer separation point can be controlled by the lip offset and location of the apex point.