单分散聚苯乙烯乳液高温成膜过程的形态观察

单分散乳液指微粒具有相同化学组成、粒径及界面性质等特征的分散体系 ,因其颗粒均一 ,结构可调 ,赋予了其很多独特性质 ,广泛应用于计量、电子、生物、分析、医学、化工和信息等领域 .同时 ,单分散微粒体系作为研究原子或分子结晶过程的模型物 [1] ,在凝聚态物理中具有重要作用 .单分散乳液在一些条件下能排列成最大密堆积规整结构 ,从而赋予乳胶膜更优异的性能 [2 ] .因此 ,研究单分散乳液的成膜过程 ,在基础理论和实际应用中具有重要意义 .软的乳胶微粒玻璃化温度在室温附近 ,它们在常温下就可形变融合成膜 ,此时水蒸发速度较慢 ,乳液中…     

Drying dip-coated colloidal films

We present the results from a small-angle X-ray scattering (SAXS) study of lateral drying in thin films. The films, initially 10 μm thick, are cast by dip-coating a mica sheet in an aqueous silica dispersion (particle radius 8 nm, volume fraction ?(s) = 0.14). During evaporation, a drying front sweeps across the film. An X-ray beam is focused on a selected spot of the film, and SAXS patterns are recorded at regular time intervals. As the film evaporates, SAXS spectra measure the ordering of particles, their volume fraction, the film thickness, and the water content, and a video camera images the solid regions of the film, recognized through their scattering of light. We find that the colloidal dispersion is first concentrated to ?(s) = 0.3, where the silica particles begin to jam under the effect of their repulsive interactions. Then the particles aggregate until they form a cohesive wet solid at ?(s) = 0.68 ± 0.02. Further evaporation from the wet solid leads to evacuation of water from pores of the film but leaves a residual water fraction ?(w) = 0.16. The whole drying process is completed within 3 min. An important finding is that, in any spot (away from boundaries), the number of particles is conserved throughout this drying process, leading to the formation of a homogeneous deposit. This implies that no flow of particles occurs in our films during drying, a behavior distinct to that encountered in the iconic coffee-stain drying. It is argued that this type of evolution is associated with the formation of a transition region that propagates ahead of the drying front. In this region the gradient of osmotic pressure balances the drag force exerted on the particles by capillary flow toward the liquid-solid front.     

Drying of films formed by ordered poly(ethylene oxide)-poly(propylene oxide) block copolymer gels

The drying of hydrogel films formed by poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers (Pluronic P105 and Pluronic L64) is investigated at various air relative humidity (RH) conditions in the range 11-94%. These amphiphilic block copolymers self-assemble to form a variety of ordered (lyotropic liquid crystalline) structures as the water content decreases. The amount of water lost increases linearly with the drying time initially (constant rate region, stage I). After this linear region, a falling rate is observed (stage II). The drying rate increases with decreasing RH, thus greatly shortening the drying time. A decrease of the initial film thickness or a decrease in the initial water content shortens the drying time; however, the drying mechanism remains the same. Analysis of the experimental data shows that the hydration level in the Pluronic hydrogel mainly determines the drying rate, rather than the type of ordered structure formed. Two distinct regions (liquid/gel and solid/crystalline) are observed in the drying isotherm for PEO-PPO block copolymers and homopolymer poly(ethylene glycol)s. A model for one-dimensional water diffusion is used to fit the experimental drying results at different RH, initial film thickness, and initial water content conditions. The model accounts for the shrinkage of the film during drying and for a water diffusion coefficient that is a function of the water concentration in the film. For the experimental conditions considered here, the Biot number (Bi) is less than unity and the drying is mainly limited by evaporation at the film surface. The diffusion model is used to obtain information for cases where Bi > 1.     

Drying rate variations of latex dispersions due to salt induced skin formation

Film formation from latex dispersions with varying concentrations of sodium dodecylsulfate (SDS) and sodium persulfate (NaPS) was studied with a sorption balance. The drying rate decreased significantly at a critical volume fraction of polymer (phi pc). Under constant drying conditions the phi pc varied due to differences in particle stabilization. In SDS containing samples, the droplets wetted larger areas, the film thicknesses decreased and, consequently, the initial evaporation rate was decreased. The decrease in the initial evaporation rate first continued with increasing SDS concentration but leveled off at an apparent critical micelle concentration (CMC). Samples containing NaPS had different types of film formation mechanisms with large variations in phi pc and the total drying time, which could be explained by differences in the electrostatic stabilization. For dialyzed dispersions containing no NaPS, phi pc was close to 0.7. In samples with medium high NaPS concentration a skin was formed at the air interface causing an early shift in the evaporation rate, resulting in 0.25相似文献   

Formation of Polymeric Nanocubes by Self‐Assembly and Crystallization of Dithiolane‐Containing Triblock Copolymers

Template‐free fabrication of non‐spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self‐assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self‐assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol‐ or photo‐induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored.     

Water evaporation on highly viscoelastic polymer surfaces

Results are reported for a study on the evaporation of water droplets from a highly viscoelastic acrylic polymer surface. These are contrasted with those collected for the same measurements carried out on polydimethylsiloxane (PDMS). For PDMS, the evaporation process involves the expected multistep process including constant drop area, constant contact angle, and finally a combination of these steps until the liquid is gone. In contrast, water evaporation from the acrylic polymer shows a constant drop area mode throughout. Furthermore, during the evaporation process, the drop area actually expands on the acrylic polymer. The single mode evaporation process is consistent with formation of wetting structures, which cannot be propagated by the capillary forces. Expansion of the drop area is attributed to the influence of the drop capillary pressure. Furthermore, the rate of drop area expansion is shown to be dependent on the thickness of the polymer film.     

Auto-stratification in drying colloidal dispersions: a diffusive model

The mechanism by which the particles in a drying film come into close packing during solvent evaporation has an important role to play in the final film morphology. During drying the particles can develop non-uniform concentrations across the vertical height of the film, depending on their diffusion rate. By applying the principles of classical diffusion mechanics to a hard sphere system, a theory for this novel method of stratification during drying of a two component film has been derived. The model is dependent on the particle Peclet numbers and when one is above unity and the other below, maximum stratification is observed.     

Effect of the acrylic acid content on the permeability and water uptake of poly(styrene-co-butyl acrylate) latex films

In this contribution, a theoretical modeling of the latex film formation is presented and compared to experimental results: water vapor permeability and latex film capacitance are studied as a function of acrylic acid content in poly(styrene-co-butyl acrylate) latex films. It has been shown that both water uptake and water vapor permeability are mainly affected by film morphology which in turn is defined by intercolloidal interaction and drying rate.     

Effect of soluble polymer binder on particle distribution in a drying particulate coating

Soluble polymer is frequently added to inorganic particle suspensions to provide mechanical strength and adhesiveness to particulate coatings. To engineer coating microstructure, it is essential to understand how drying conditions and dispersion composition influence particle and polymer distribution in a drying coating. Here, a 1D model revealing the transient concentration profiles of particles and soluble polymer in a drying suspension is proposed. Sedimentation, evaporation and diffusion govern particle movement with the presence of soluble polymer influencing the evaporation rate and solution viscosity. Results are summarized in drying regime maps that predict particle accumulation at the free surface or near the substrate as conditions vary. Calculations and experiments based on a model system of poly(vinyl alcohol) (PVA), silica particles and water reveal that the addition of PVA slows the sedimentation and diffusion of the particles during drying such that accumulation of particles at the free surface is more likely.     

Distribution of water-soluble and surface-active low-molecular-weight species in acrylic latex films

Monodisperse core-shell latices were synthesized, differing in the acrylic acid (AA) content in the particle shell (1 or 4 wt%) and the Tg of the acrylic core (around -40 or 10 degrees C). In a first step, the drying mechanisms of the dialyzed latices were studied by confocal Raman spectroscopy. It was shown that, besides some unexpected features (briefly described in the article), drying occurred in a rather classical way, i.e., simultaneously from top to bottom and from edge to center. Then, the distributions of sulfate ion (SO4) (from sodium sulfate) and sodium dodecyl sulfate (SDS) in the dry latex films were established by confocal Raman spectroscopy and attenuated total reflectance (ATR). The two techniques were complementary. SO4 and SDS distributions were quite different, although presenting some common characteristics. In both cases, repartition of the low-molecular-weight species in the film was even less homogeneous when the AA content was lower and the particle core softer. However, SO4 showed enrichment at the film-substrate interface and depletion at the air side, whereas SDS showed concentration maxima at both interfaces. Interpretations stress the importance of desorption from the particle-water interface, transport by water, size effects, and diffusion.     

生物质热反应机理与活化能确定方法Ⅰ.干燥段研究

干燥段是生物质热解的第一个过程.采用热分析仪研究了杉木木屑干燥段质量和热量的变化,推导了非等温干燥动力学模型,探讨了热质传输机理.结果表明,随着温度的升高,木屑含湿量迅速下降,80℃左右出现一个明显的失重峰;非等温干燥动力学Page模型能很好地模拟木屑干燥过程,木屑干燥活化能为12.6 kJ/mol;水分传输与热量传递...     

Why do drying films crack?

Understanding the mechanism by which films fail during drying is the first step in controlling this natural process. Previous studies have examined the spacing between cracks with predictions made by assuming a balance between elastic energy released with a surface energy consumed. We introduce a new scaling for the spacing between cracks in drying dispersions. The scaling relates to the distance that solvent can flow, to relieve capillary stresses, as a film fails. The scaling collapses data for a range of evaporation rates, film thicknesses, particle sizes, and materials. This work identifies capillary pressures, induced by packed particle fronts travelling horizontally across films, as responsible for the failure in dried films.     

Temperature and relative humidity dependency of film formation of polymeric latex dispersions

Thermogravimetric analysis and a synchrotron small-angle X-ray scattering technique were employed to characterize the structural evolution of a polymeric latex dispersion during the first three stages of film formation at different temperatures and relative humidities. Three intermediate stages were identified: (1) stage I*, (2) stage I**, and (3) stage II*. Stage I* is intermediate to the conventionally defined stages I and II, where latex particles began to crystallization. The change of drying temperature affects the location of the onset of ordering, whereas relative humidity does not. Stage I** is where the latex particles with their diffuse shell of counterions in the fcc structure are in contact with each other. The overlapping of these layers results in an acceleration of the lattice shrinkage due to a decrease of effective charges. Stage II* is where the latex particles, dried well above their T(g), are deformed and packed only partially during film formation due to incomplete evaporation of water in the latex film. This is because of a rapid deformation of the soft latex particles at the liquid/air interface so that a certain amount of water is unable to evaporate from the latex film effectively. For a latex dispersion dried at a temperature close to its minimum film formation temperature, the transition between stages II and III can be continuous because the latex particles deform at a much slower rate, providing sufficient surface area for water evaporation.     

Latex Film Formation in the Environmental Scanning Electron Microscope

Summary: Environmental scanning electron microscopy (ESEM) was used to study the film formation mechanisms and extent of coalescence of three acrylic latex compositions with different glass transition temperatures (T_g), here defined as standard-low T_g, standard-high T_g (both carboxymethyl cellulose- stabilised) and novel (stabilised with a novel polysaccharide derived from agricultural waste). The ESEM analysis revealed that the microstructure of the standard – low-T_g system consisted of individual particles in dispersion and upon evaporation a continuous film formed, whereas in the case of the standard - high T_g latex particle deformation was not observed, but particle aggregation resulted in the formation of crystal-like structures that have formed via the formation of stacking faults. However, in the case of the novel system the microstructure consisted of individual particles and clusters and during evaporation a discontinuous film formed with voids present within its structure and some of the clusters accumulating on the surface of the specimens.     

Effect of a solvent on self-organization in nanofilms: Modeling by the dissipative particle dynamics method

Mesoscopic simulation of processes of drying and swelling of thin copolymer films on a solid substrate is performed. Structural rearrangements in films of symmetric and asymmetric diblock copolymers are studied by the dissipative particle dynamics method in the presence of both nonselective and selective solvents. The plasticizing effect of a solvent is favorable for formation of lamellar and hexagonal mesophases. Owing to evaporation of the solvent from a film or its absorption from the external volume, flows along the normal to the film surface arise. These flows exert an orienting effect on the microdomain structure.     

The influence of sodium ethene sulphonate comonomer on the film formation process of poly(vinyl acetate) dispersions

Various latex dispersions from vinyl acetate/sodium ethene sulphonate (sodium vinyl sulphonate) copolymers, stabilised by a constant amount of Hostapal BV, a surfactant with poly(ethylene oxide) groups, were investigated by a variety of solid and liquid state nuclear magnetic resonance methods. In order to investigate the influence of sodium ethene sulphonate on the film formation process, the serum and polymer were analysed separately. The stoichiometric monomer composition of the copolymer in the aqueous phase and in the hydrophobic particles was obtained. The ionic comonomer is enriched at the particle surface via its proximity to the applied surfactant by two-dimensional exchange NMR. For investigations of the film formation process, latex dispersions were prepared and dried to form spatially homogeneous films at different defined solid contents. Depending on the chemical composition of a chosen dispersion, NMR allows the investigation of the drying process of the water. The drying process is a function of the ionic strength of the dispersion and the hydrophilicity of the polymer. It is correlated to the drying mechanism of the water within the film. A not fully dried film contains external water outside the particles, water at ionic and non-ionic groups at surfactants in the polymer water interface and, additionally, water in the swollen and mobilised polymer. The distribution of water to these environments is markedly changed by the ionic comonomer, especially close to the end of the drying process.     

致密储层束缚水干化反应及干化效应差异分析与评价

通过向致密储层中注入干化剂,使其与地层水发生干化反应能够消耗地层水、降低储层含水饱和度,从而提高气体渗流能力。以致密气藏干化原理为基础,对所选干化剂进行原理性干化实验发现,干化剂实际耗水量大于理论耗水量。分析认为,干化剂实际干化效果还受化学反应热效应的影响。本文以热化学理论为基础,研究了干化剂与水反应的热效应及其对干化效果的影响。并考虑到实际地层往往处于不同的温度和压力条件下,故对干化反应热效应随体系温度和压力的变化情况做了研究。结果表明,所选干化剂与水反应能够放出约5.28k J/g的热量,放出的热量能够使反应速率加快和使部分水分子蒸发成气相从而提高干化效率;干化剂化学反应热随温度和压力的升高而增加,但增加速率较小;温度和压力的变化对热蒸发耗水量影响较小。     

Diffusion in mesoporous materials and polymers swelling: a transient calorimetric approach

The diffusion of water and benzene has been followed by DSC using the thermoporosimetry (TPM) approach. The diffusion of water has been observed during the drying of a water impregnated mesoporous silica gel at 40 degrees C under dry air. It was found that the confinement affects the evaporation rate of water. The diffusion of benzene has been observed during the drying and the swelling of a cross linked PDMS sample. The mesh size distributions (MSD) of the elastomer, during swelling and drying, have been calculated at various times using the TPM formalism. Extrapolating the mean mesh size of the polymeric network, it was found that the dry polymer has an average mesh of about 2.5 nm.     

Film formation from monodisperse acrylic lattices 2. Influence of drying temperature on the film formation process

The influence of drying temperature on the properties of latex films was investigated by gravimetry, turbidimetry (i.e., analysis of transmission spectra and interference), atomic force microscopy and measurement of water vapor permeability. Several pitfalls in the determination of water content of dried films that absorb water after being submerged in it have been proposed, such as fading boundaries, remaining water after drying and change of particle sizes. At moderately higher temperatures film formation is improved. This improvement follows from the formation of smoother film surfaces (AFM), lower water vapor permeabilities and smaller values for delta lambda(min). On the other hand, defects as cracks and channels also are created, especially at high temperatures. It appears, however, that these channels do not run from the one surface of a film to the other.