STRUCTURE FORMATION OF COATED FILMS WITH DISPERSED PIGMENTS DURING DRYING

ABSTRACT

In the drying of coated films with dispersed pigments, such as floppy disks, the structure of the film is formed during the drying process and depends on the drying condition. It is important to understand the structure formation during drying for the design of the dryer and die better quality of the product. We measured die drying characteristics of the film and determined the structure of dried film experimentally. A qualitative model for the structure formation during drying of the coated film is suggested.     

Delamination behavior of lithium-ion battery anodes: Influence of drying temperature during electrode processing

One essential process step during electrode processing for lithium-ion batteries is the drying of the wet particulate electrode coating. The electrode film solidifies during evaporation of the solvent and a porous film is formed. In this study, we focus on the influence of drying temperature on the internal electrode structure of the dry film. Anode slurries that consist of graphite and an aqueous binder system were coated and subsequently dried. To assure defined and controllable drying conditions, a laboratory set-up with a temperature-controlled substrate carrier and an impingement dryer was used. To facilitate a scale-up to continuously passed dryers, the choice of experimental temperatures was based on a calculation of steady-state temperatures that result from gas temperatures that are commonly applied in industrial drying processes. The delamination behavior of the differently dried electrodes was investigated by means of a 90° peel test. The results show a strong dependency of electrode adhesion on drying temperature. A lower adhesion force at higher temperatures hints at a variation in binder content at the interface between the copper substrate and the coating layer. The formation of a consolidation layer at the air-film interface during drying is identified as a possible explanation and a criterion for consolidation layer formation is suggested.     

Film designed for lubricative coated steel sheets

This paper reports on a film designed for lubricative coated steel sheets which has excellent die galling resistance even during conducting of continuous press forming under severe conditions. Our newly developed film whose self-crosslinked structure was formed with a silanol group can retain a high modulus even up to when a high temperature is attained and that it has excellent die galling resistance even during continuous press forming.     

Formation of Particle Layer Within Coated Slurry Characterized by Thickness Variation

An understanding of the conversion process from slurry to particle layer on a substrate is required for the precise control of the particle alignment and the material distribution in the coated slurry. In this work, variation of coated slurry thickness during drying was applied to evaluate drying and particle layer formation simultaneously. The slurry used consisted of micron-sized silica or poly (methyl methacrylate) particles and an aqueous solution of poly-vinyl alcohol (PVA) possessing differing degrees of hydrolysis. During the drying process, initially the thickness of the coated slurry was observed to decrease at a constant rate in the concentration stage, and subsequently it began to show large fluctuations due to the emergence of particles on the drying surface in the packing stage. In the final fixing stage, the fluctuation of film thickness was restricted because particles were immobilized by highly viscous concentrated PVA or by PVA molecule bridging. Based on the variation and fluctuation of film thickness, we introduced two characteristic dimensionless time ratios: (a) void fraction in a packed particle layer at the end of concentration stage; and (b) the time required to fix particle position after the end of the packing stage. We concluded that the dispersed state and settling velocity of the particle determines the space between particles in a loose packing layer, and we found that the distribution of polymers in a particle layer has a strong influence on the mobility of particles in a tightly packed layer.     

Drying-Induced Cracks in Thin Film Fabricated from Colloidal Dispersions

As a colloidal dispersion is coated and dried on a nonporous rigid substrate, the enormous stresses developing during the drying process can fracture the thin film. The drying-induced cracks can produce serous technological consequences and even destroy the efficacy of coatings, which is not desirable in most industrial cases. Therefore, as the first step of controlling cracks in thin film, understanding of crack properties and cracking mechanisms leading to fracture is of vital significance. Although numerous experiments and models have been proposed for cracking during drying of colloidal dispersions, there is little consensus on even the most basic mechanisms, and the effect of heat transfer on cracks as well as optimization of drying process are rarely taken into account. Additional, the broad employments of nanosuspensions bring both opportunities and challenges for this area. This review will give a comprehensive physical picture of thin film fabrication by drying of colloidal dispersions and cracking phenomenon, present current investigations for drying-induced cracks, and point out some prospects for cracking researches especially for industrial R&D, as well as propose combination of thin film preparation with drying technique for exploring crack-free thin film.     

颗粒表面料层干燥机理

颗粒表面料层干燥是喷雾流化干燥技术的基本环节. 为了探讨喷雾流化干燥机理,着重探讨了物料表面蒸汽分压与物料湿含量的关系,首次建立了单颗粒表面料层干燥的物理模型,并进行了数值计算,计算结果与实验结果吻合较好.分析了惰性载体的密度、比热容、直径及热导率对干燥时间的影响,对喷雾流化干燥的深入研究以及放大、优化设计等具有重要的指导意义.     

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.     

Turbidity study of the process of film formation of thin films of aqueous acrylic dispersions

This study was directed towards determining the factors that define the process of film formation of binder particles in drying aqueous dispersion coatings, based on acrylic polymers. The work described focuses on the infrastructure of drying and ageing thin films of acrylic latices.

In concentrated latices the binder particles are arranged in closely packed structures which cause colored light patterns, the so-called Bragg diffractions. The light waves move within the latex film, where the waves are scattered by the internal structure composed of the spheres and water voids. The pattern of light transmission reveals the internal structure of the latex film. From the change in interference during the drying process of a thin latex film, it is possible to follow the internal movement and deformation of polymer spheres (coalescence process). Further coalescence results in a transparent film. When this film is immersed in water, the remaining internal interfaces between the adhered binder particles swell, thus regenerating the interference pattern. It is expected that during ageing of the film, the proportion of internal interfaces will decrease with time, so that when the aged film is immersed in water the remaining internal interfaces will swell. The resulting interference pattern reveals the decrease in the interfaces between the deformed polymer particles in the dried latex film (auto-adhesion process).     

Biocoatings: challenges to expanding the functionality of waterborne latex coatings by incorporating concentrated living microorganisms

Biocoatings concentrate living, nongrowing microbes in nanoporous adhesive polymer films. Any microbial activity or trait of interest can be intensified and stabilized in biocoatings. These films will dramatically expand the functionality of waterborne coatings. Many microbes contain enzyme systems which are unstable when purified. Therefore, thin polymer coatings of active microbes are a revolutionary approach to stabilize living cells as industrial or environmental biocatalysts. We have demonstrated that some microbes survive polymer film formation embedded in nontoxic adhesive waterborne binders by controlling formulation and drying. Biocoatings can be a single layer of randomly oriented microbes or highly structured multilayer films combining monolayers of different types of microbes on solid, porous, or flexible substrates. They can be formed by drawdown or ink-jet deposition, convective sedimentation assembly, dielectrophoresis, or coated onto or embedded within papers. Controlled drying generates nanoporous microstructure; the pores are filled with a carbohydrate glass which stabilizes the entrapped dehydrated microbes. When the coating is rehydrated, the carbohydrates diffuse out generating nanopores. The activity of biocoatings can be 100s of g L^?1 (coating volume) h^?1 stabilized for 100–1000s of hours, and therefore, they represent a new approach to process intensification (PI) using thin liquid film bioreactors. A current challenge is that many microbes being engineered as environmental, solar, or carbon recycling biocatalysts do not naturally survive film formation. The mechanisms of dehydration damage that occur during biocoating formulation, ambient drying, and during dry storage have begun to be studied. Critical to preserving microbe viability are minimizing osmotic stress, toxic monomers, biocides, and utilizing polymer chemistries that generate strong wet adhesion with arrested coalescence (nanoporosity). Therefore, controlling desiccation, drying rate/uniformity, and residual moisture are important. Optimization of biocoating activity can be affected at multiple stages—cellular engineering prior to coating (preadaptation), formulation, deposition (film thickness), film formation/drying (generates microstructure), dry storage (minimize metabolic activity), and rehydration. Gene induction (activation) leading to enzyme synthesis following rehydration has been demonstrated. However, little is known about gene regulation in nongrowing microbes. Challenges to optimizing biocoating activity include generating stable film porosity, strong wet adhesion, control of residual water content/form/distribution, and nondestructive measurement of entrapped microbe viability and activity. Indirect methods to measure viability include vital staining, enzyme activity, reporter genes, response to light, confocal fluorescent microscopy, and ATP content. Microbes containing stress-inducible reporter genes can be used to monitor cell stress during formulation, film formation, and drying. Future cellular engineering to optimize biocoatings includes desiccation tolerance, light reactivity (photoefficiency), response to oxidative stress, and cell surface-to-polymer or substrate adhesion. Preservation of microbial activity in waterborne coatings could lead to high intensity biocatalysts for environmental cleaning, gaseous carbon recycling, to produce H₂ or electricity from microbial fuel cells, delivery of probiotics, or for biosolar energy harvesting.     

纳米氧化锌对天然胶乳膜干燥及硫化性能影响研究

采用失重法和溶胀法研究了普通氧化锌和纳米氧化锌活化的天然胶乳膜的干燥动力学,以及干燥过程中胶乳膜交联密度变化.结果表明:天然胶乳厚胶膜在成膜后仍含有大量水分并且去除困难.纳米氧化锌活化胶膜的干燥速率明显高于普通氧化锌胶膜.干燥温度对干燥过程影响显著,干燥时间随干燥温度升高明显降低.随着干燥的进行,2种氧化锌活化的胶乳膜的交联密度均迅速上升,在相同条件下,纳米氧化锌活化胶乳膜交联密度均比普通氧化锌的大.纳米氧化锌对天然胶乳膜的干燥及硫化过程均有促进作用.     

IMPINGING JET DRYER

In coating and gravure printing, an impinging jet nozzle with high thermal efficiency for drying of coated film was developed.

Trial production 0f 40 kinds of nozzle enables to develop a high-performance impinging jet nozzle with heat transfer coefficient 1.5 times larger than that of current slit nozzle, through measurement of heat transfer coefficient, visualizations of air flow and heat transfer, and measuremenu of jet velocity and turbulence distribution. The purpose of the trial production was to expand a range of high heat transfer and promote turbulence compared with the current nozzle.

Paying attention to mass transfer within gravure ink coated film, drying characteristic of the film was analyzed by numerical solution of a set of equations governing the drying process in which concentration dependencies 0f the diffusion coefficient and the equilibrium vapor pressure were considered.

Applying these analyses. an industrial scale dryer with excellent drying efficiency has finally been developed.     

Effect of thermal history during drying and curing process on the chain orientation of rod-shaped polyimide

Chain orientation in polyimide (PI) film is influenced by the thermal history during drying and curing process. The amount of residual solvent and the degree of imidization, among other factors, play a major role in determining the chain orientation during the process. In the present study, poly(amic acid), the precursor of PI, coated on the glass substrate was imidized to PI through different drying and curing protocols. On the way of complete imidization, the residual solvent concentration and the degree of imidization were characterized using confocal Raman spectroscopy. The poly(amic acid) began to imidize quickly while retaining more solvent in the film as the initial drying temperature increased. The degree of in-plane chain orientation in fully imidized PI film made by different process protocols was compared using polarized Raman spectroscopy. The fully imidized PI showed the lowest degree of in-plane chain orientation when it was processed by the protocol with the highest drying temperature. The difference in the degree of in-plane chain orientation among different PI films significantly influenced the in-plane thermal expansion coefficient, while no significant change in crystallinity or glass transition temperature was observed.     

天然胶乳胶膜干燥过程及交联结构研究

采用失重法、溶胀法及红外光谱,研究了天然胶乳厚胶膜的干燥动力学过程及干燥过程与橡胶分子链交联密度的关系。结果表明,天然胶乳胶膜的干燥温度和厚度显著影响其干燥过程,通过动力学拟合结果,建立了干燥动力学方程;胶膜干燥开始后,橡胶分子交联密度迅速上升,达到最大交联密度后,交联密度随干燥时间的增加而降低,红外光谱的研究结果也证明了这一规律。干燥过程对天然胶膜的交联结构有明显影响。     

A STUDY OF CLOSED CYCLE DRYING FOR THE COATED FILM WITH ORGANIC SOLVENT ON THE CONTINUOUS SHEET MATERIALS

The conventional drying of the coated film with organic solvent on continuous sheet materials is usually performed in open or one pass drying system using air as the drying medium. The concentration of evaporated organic solvent in the drying system must be low enough to prevent explosion and large volume of off gas from dryer to solvent recovery system is required, resulting in poor heat economy for all the plant

To improve the heat economy of the plant it had been proposed to use a closed cycle drying system, where an inert gas, e.g. nitrogen, is used as the drying medium. High concentration of the organic solvent in the recycle gas mixture may then be used, which results in smaller volume of recycle gas and possibility of applying an inexpensive solvent recovery system of dehumidification. This investigation includes two important problems to realize the closed cycle drying

(1)Measurement of solvent (toluene) evaporation rate from coated film in the gas mixture of toluene andnitrogen over a wide range of toluene/nitrogen ratios (0-1.0) and drying temperature using bench scaleapparatus

(2)Development of a contactless sealing method, using an inert gas, for closed cycle drying of continuoussheet materials. The results of preliminary tests demonstrate its feasibility.     

THERMORADIATION DRYING OF A THIN SURP ACE FILM ON A TRANSLUCENT SUBSTANCE

The paper presents the results of an investiga- tion into thermoradiation drying and film formation of a two-component solution having substantially dif- ferent boiling temperatures of the components, and being applied to a substrate under the conditions of matching the spectral emissive characteristics of the radiator with the spectral thermoradiative properties of the object of drying. The film transmissivity is found to,increase with a decrease in the mass of the solution during drying.     

THERMORADIATION DRYING OF A THIN SURP ACE FILM ON A TRANSLUCENT SUBSTANCE

The paper presents the results of an investiga- tion into thermoradiation drying and film formation of a two-component solution having substantially dif- ferent boiling temperatures of the components, and being applied to a substrate under the conditions of matching the spectral emissive characteristics of the radiator with the spectral thermoradiative properties of the object of drying. The film transmissivity is found to,increase with a decrease in the mass of the solution during drying.     

A STUDY OF CLOSED CYCLE DRYING FOR THE COATED FILM WITH ORGANIC SOLVENT ON THE CONTINUOUS SHEET MATERIALS

The conventional drying of the coated film with organic solvent on continuous sheet materials is usually performed in open or one pass drying system using air as the drying medium. The concentration of evaporated organic solvent in the drying system must be low enough to prevent explosion and large volume of off gas from dryer to solvent recovery system is required, resulting in poor heat economy for all the plant

To improve the heat economy of the plant it had been proposed to use a closed cycle drying system, where an inert gas, e.g. nitrogen, is used as the drying medium. High concentration of the organic solvent in the recycle gas mixture may then be used, which results in smaller volume of recycle gas and possibility of applying an inexpensive solvent recovery system of dehumidification. This investigation includes two important problems to realize the closed cycle drying

(1)Measurement of solvent (toluene) evaporation rate from coated film in the gas mixture of toluene andnitrogen over a wide range of toluene/nitrogen ratios (0-1.0) and drying temperature using bench scaleapparatus

(2)Development of a contactless sealing method, using an inert gas, for closed cycle drying of continuoussheet materials. The results of preliminary tests demonstrate its feasibility.     

IMPINGING JET DRYER

ABSTRACT

In coating and gravure printing, an impinging jet nozzle with high thermal efficiency for drying of coated film was developed.

Trial production 0f 40 kinds of nozzle enables to develop a high-performance impinging jet nozzle with heat transfer coefficient 1.5 times larger than that of current slit nozzle, through measurement of heat transfer coefficient, visualizations of air flow and heat transfer, and measuremenu of jet velocity and turbulence distribution. The purpose of the trial production was to expand a range of high heat transfer and promote turbulence compared with the current nozzle.

Paying attention to mass transfer within gravure ink coated film, drying characteristic of the film was analyzed by numerical solution of a set of equations governing the drying process in which concentration dependencies 0f the diffusion coefficient and the equilibrium vapor pressure were considered.

Applying these analyses. an industrial scale dryer with excellent drying efficiency has finally been developed.     

Slot coating flows of non‐colloidal particle suspensions

Slot coating is used in the manufacturing of functional films, which rely on specific particle microstructure to achieve the desired performance. Final structure on the coated film is strongly dependent on the suspension flow during the deposition of the coating liquid and on the subsequent drying process. Fundamental understanding on how particles are distributed in the coated layer enables optimization of the process and quality of the produced films. The complex coating flow leads to shear‐induced particle migration and non‐uniform particle distribution. We study slot coating flow of non‐colloidal suspensions by solving the mass and momentum conservation equations coupled with a particle transport equation using the Galerkin/Finite element method. The results show that particle distribution in the coating bead and in the coated layer is non‐uniform and is strongly dependent on the imposed flow rate (wet thickness). © 2016 American Institute of Chemical Engineers AIChE J, 63: 1122–1131, 2017     

Film Properties of Glyceryl Esters of Various Octadecadienoic Acids

The effect of cis and trans isomers in isolated and conjugated structures of glyceryl esters of octadecadienoic acids on film formation was examined with respect to drying time, film quality and after-tack. Little difference in the drying rates of the conjugated trans-trans and cis-trans oils was observed. Oils based on octadecadienoic acids with a high content of either conjugated or isolated double bonds dried at a slower rate than blends of these two types. A minimum drying time occurred when 60 ± 5% of conjugated oils were blended with 40 ± 5% of isolated diene oils. This is related to the faster oxygen uptake and peroxide formation of the isolated cis structure. This peroxide acts as the initiator for vinyl-type polymerization. The drying rate of isolated trans diene oils is directly related to the trans content. The development of after-tack appears to be related to the trans content. The conjugated trans-trans esters heat-polymerize more rapidly than the conjugated cis-trans.