Surface tension evolution during early stages of drying of sol–gel coatings

Striation defects in spin-coated thin films have been blamed on unfavorable capillary forces that occur due to solvent evaporation commonly experienced during coating deposition. Solvent evaporation during spinning causes predictable composition changes at the surface and these can either stabilize or de-stabilize the surface with respect to convective motions within the coating solution. The present work examines the surface tension changes while adding the most volatile component rather than removing it. This is then a “reverse drying” process, but it provides us with the slope of the surface tension change during normal coating drying. We have examined coating solutions for a case where a specific solvent addition has previously been shown to prevent the formation of striation defects. By measuring both the starting solution (one that produces bad striation defects) and the co-solvent-modified solution (that produces much flatter coatings), we are able to demonstrate the correlation between surface tension changes during spinning and the striation defect formation (or prevention). For the present case, an aluminum-titanate sol–gel recipe, the solvent that eliminated the striation defects is also responsible for a continuous, gradual, reduction in surface tension during the spin-on process, consistent with a model proposed earlier (D. P. Birnie, J Mater Res 16:1145–1154, 2001).     

Synthesis of indium nanoparticles: digestive ripening under mild conditions

Here we report the synthesis of monodispersed indium nanoparticles by evaporation/condensation of indium shot using the solvated metal atom dispersion (SMAD) technique, followed by digestive ripening in low boiling point (BP 38 °C) methylene chloride and in a high boiling point (BP 110 °C) toluene solvent. The as-prepared SMAD indium nanoparticles are polydispersed with particle size ranging from 25 to 50 nm, but upon digestive ripening (heating of colloidal material at the boiling point of solvent in presence of excess surface active ligands) in methylene chloride, a remarkable reduction of particle size was achieved. In higher boiling solvent (toluene), where the indium nanoparticles at reflux temperature are probably melted, it does not allow the best result, and less monodispersity is achieved. We employed different surface active ligands (amine, phosphine, and mixed ligands) to passivate these indium nanoparticles. The temporal evolution of the surface plasmon of indium nanoparticles was monitored by in situ UV-vis spectroscopy, and particles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The merits of this synthesis procedure are the use of bulk indium as starting material, tuning the particle size in low boiling point solvent, particle size adjustment with the choice of ligand, and a possible scale up.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part 1, concept

If a sample evaporates by flash vaporization in an empty injector insert, the solute material is well mixed with the expanding solvent vapors and the maximum injection volume is determined by the requirement that no vapors must leave the vaporizing chamber. If evaporation occurs from a surface (e.g., of Tenax packing), however, the solvent evaporates first. The site of evaporation is cooled to the solvent's boiling point, and the cool island formed in the hot injector retains solutes of at least intermediate boiling point (visually observed for perylene). Solvent vapors, free from such solutes, may now expand backwards from the injector insert and leave through the septum purge exit. When solvent evaporation is complete, the site of evaporation warms up, causing the high boiling solutes to evaporate and to be carried into the column by the carrier gas. The technique somewhat resembles PTV injection, but is performed using a classical vaporizing injector.     

Thermodynamic modeling and investigation of the formation of electrospun collagen fibers

Electrospun type I collagen fibers are very promising materials for tissue scaffold applications, but are typically fabricated from toxic solvents. Recently, electrospinning of type I collagen fibers by using environmentally friendly phosphate buffer saline (PBS)/ethanol solution has been explored. PBS/ethanol solvent systems offer better cell compatibility, but the high surface tension and high boiling point of the solvent system make the collagen difficult to electrospin and can cause inferior fiber morphology. In this study, the influence of solvent surface tension on the morphology of electrospun collagen fibers has been experimentally investigated and analyzed from a thermodynamics perspective. The analytical results indicate that solvents with high surface tension drive the formation of beads along the smaller, thinner fibers. In addition, beads with relatively small angular eccentricity were thermodynamically favorable. The experimental results presented herein corroborate the theoretical analysis and conclusions drawn from this study. The surface tension of the solvent has significant influence on the bead formation, especially in an aqueous system. The environmental humidity for the electrospinning process and the collagen concentration were also investigated. These parameters may result in variations of the evaporation-solidification rates, which consequently impact the formation and morphologies of electrospun collagen fibers. According to the thermodynamic analysis, uniform electrospun collagen fibers without beads can be obtained by manipulating solvent surface tension during the electrospinning process.     

Sample evaporation in conventional split/splitless GC injectors. Part 3: Retaining the liquid in the vaporizing chamber

As most sample liquids tend to pass through an empty injector insert at a speed which is too high to enable complete evaporation, movement of the liquid must be arrested before it reaches the column entrance. Stopping the liquid means deposition on to a surface; this, however, is possible only after the temperature of the surface has been cooled to (or below) the boiling point of the liquid (solvent). The performance of different means of stopping the liquid has been tested visually (by the method described in Part 2). Baffles on the wall of the injector insert had hardly any effect on evaporation: the band of liquid leaving the syringe needle performed a perfect slalorn around them. The inverted cup proved more efficient, but the best performance was obtained from a light plug of glass wool: owing to its low thermal mass, the first fibers to be met by the liquid are immediately cooled to the solvent boiling point, allowing the liquid to wet it. The sample liquid is sucked up by the glass wool, from where the sample evaporates relatively slowly, often over a period of several seconds.     

Controlling the surface composition of PCBM in P3HT/PCBM blend films by using mixed solvents with different evaporation rates

The surface composition of poly(3-hexylthiophene-2,5-diyl) and fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (P3HT/PCBM) blend films could be changed by controlling the film formation process via using mixed solvents with different evaporation rates. The second solvent, with a higher boiling point than that of the first solvent and much better solubility for PCBM than P3HT, is chosen to mix with the first solvent with a lower boiling point and good solubility for both PCBM and P3HT. The slow evaporation rate of the second solvent provides enough time for PCBM to diffuse upwards during the solvent evaporation. Thus, the weight ratio of PCBM and P3HT (m _PCBM/m _P3HT) at surface of the blend films was varied from ca. 0.1 to ca. 0.72, i.e., it increases about seven times by changing from single solvent to mixed solvents. Meanwhile, the mixed solvents were in favor to form P3HT naonofiber network and enhance phase separation of P3HT/PCBM blend films. As a result, the power conversion efficiency of the device from mixed solvents with slow evaporation process was about 1.5 times of the one from single solvents.     

Concurrent solvent evaporation for on-line coupled HPLC-HRGC

A technique is proposed which allows introduction of very large volumes of liquid (10 ml were tested) into capillary columns equipped with short (1–2 m long) retention gaps. It is based on concurrent solvent evaporation, i.e. evaporation of the solvent during introduction of the sample. The technique presupposes high carrier gas flow rates (at least during sample introduction) and column temperatures near the solvent boiling point. The major limitation of the method is the occurrence of peak broadening for solutes eluted up to 30°, in some cases up to 100°, above the injection temperature. This is due to the absence of solvent trapping and a reduced efficiency of phase soaking. Therefore, use of volatile solvents is often advantageous. Application of the concurrent solvent evaporation technique allows introduction of liquids which do not wet the retention gap surface. However, the method is still not very attractive for analysis of aqueous or water-containing solutions (reversed phase HPLC).     

To inhibit coffee ring effect in inkjet printing of light-emitting polymer films by decreasing capillary force

Coffee ring effects of inkjet printed poly(spirobifluorene) films were restrained by decreasing the capillary force due to volatility/viscosity match.     

Column temperature during eluent transfer with concurrent eluent evaporation in coupled HPLC-HRGC

Concurrent solvent evaporation is suited for coupled HPLC-HRGC if solutes elute at intermediate to high column temperatures—otherwise retention gap techniques are more appropriate. Concurrent eluent evaporation using a loop-type interface requires that the GC oven temperature during eluent introduction be above the eluent boiling point at the carrier gas inlet pressure applied. An experimental background is given for facilitating selection of the appropriate column temperature.     

Rapid development of hydrophilicity and protein adsorption resistance by polymer surfaces bearing phosphorylcholine and naphthalene groups

In order to provide a protein adsorption resistant surface even when the surface was in contact with a protein solution under completely dry conditions, a new phospholipid copolymer, poly (2-methacryloyloxyethyl phosphorylcholine (MPC)- co-2-vinylnaphthalene (vN)) (PMvN), was synthesized. Poly(ethylene terephthalate) (PET) could be readily coated with PMvN by a solvent evaporation method. Dynamic contact angle measurements with water revealed that the surface was wetted very rapidly and had strong hydrophilic characteristics; moreover, molecular mobility at the surface was extremely low. When the surface came in contact with a plasma protein solution containing bovine serum albumin (BSA), the amounts of the plasma protein adsorbed on the dry surface coated with PMvN and that adsorbed on a dry surface coated with poly(MPC-co-n-butyl methacrylate) (PMB) were compared. Substantially lower protein adsorption was observed with PMvN coating. This is due to the rapid hydration behavior of PMvN. We concluded that PMvN can be used as a functional coating material for medical devices without any wetting pretreatment.     

含无规共聚组分的两嵌段聚合物A-b-(B-r-C)的合成以及自组装

通过原子转移自由基(ATRP)方法合成了其中一个嵌段是由2种单体无规共聚的两嵌段聚合物——聚丙烯酸肉桂酸乙酯-b-(聚苯乙烯-r-聚丙烯酸叔丁酯),(记为PCEA-b-(PtBA-r-PS)).讨论了聚合过程中影响分子量分布以及分子量控制的各种因素.通过氢核磁(1H-NMR)确定各嵌段的重复单元数分别为50,111,138.通过透射电镜(TEM)观察,研究了该嵌段聚合物在选择性溶剂1-氯癸烷以及环戊烷中的自组装行为,发现该嵌段聚合物在环己烷中直接分散可以形成有聚集倾向的短棒状或球形胶束,而在1-氯癸烷中直接分散得到的胶束,在膜表面随着1-氯癸烷溶剂的缓慢挥发可以组装得到具有规则微纳结构的相互连接的柱状胶束.     

Concurrent solvent recondensation large sample volume splitless injection

Concurrent Solvent Recondensation Large Sample Volume (CRS‐LV) splitless injection overcomes the limitation of the maximum sample volume to 1–2 μL valid for classical splitless injection. It is based on control of the evaporation rate in the vaporizing chamber, utilization of a strong pressure increase in the injector resulting from solvent evaporation, and greatly accelerated transfer of the sample vapors from the injector into the inlet of an uncoated precolumn by recondensation of the solvent. The sample vapors are transferred into the column as rapidly as they are formed in the injector (concurrent transfer). 20–50 μL of liquid sample is injected with liquid band formation. The sample liquid is received by a small packing of deactivated glass wool positioned slightly above the column entrance at the bottom of the vaporizing chamber. Solvent evaporation strongly increases the pressure in the injector (auto pressure surge), provided the septum purge outlet is closed and the accessible volumes around the vaporizing chamber are small, driving the first vapors into the precolumn. Transfer continues to be fast because of recondensation of the solvent, obtained by keeping the oven temperature below the pressure‐corrected solvent boiling point. The uncoated precolumn must have sufficient capacity to retain most of the sample as a liquid. The experimental data show virtually complete absence of discrimination of volatile or high boiling components as well as high reproducibility.     

Spontaneous formation of linearly arranged microcraters on sol-gel-derived silica-poly(vinylpyrrolidone) hybrid films induced by Bénard-Marangoni convection

Complex, sophisticated surface patterns on micrometer and nanometer scales are obtained when solvent evaporates from solutions containing nonvolatile solutes dropped on a solid substrate. Such evaporation-driven pattern formation has been utilized as a fabrication process of highly ordered patterns in thin films. Here, we suggested the spontaneous pattern formation induced by Bénard-Marangoni convection triggered by solvent evaporation as a novel patterning process of sol-gel-derived organic-inorganic hybrid films. Microcraters of 1.0-1.5 μm in height and of 100-200 μm in width were spontaneously formed on the surface of silica-poly(vinylpyrrolidone) hybrid films prepared via temperature-controlled dip-coating process, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. Such highly ordered micropatterns were achieved by Bénard-Marangoni convection activated at high temperatures and the unidirectional flow of the coating solution on the substrate during dip-coating.     

Loop-type interface for concurrent solvent evaporation in coupled HPLC-GC. Analysis of raspberry ketone in a raspberry sauce as an example

Presently, two coupling techniques are used for directly introducing HPLC fractions into capillary GC: The retention gap technique (involving negligible or partially concurrent solvent evaporation) and fully concurrent solvent evaporation. While the former involves use of a conventional on-column injector, it is now proposed that concurrent solvent evaporation technique be carried out using a switching valve with a built-in sample loop. The technique is based on the concept that the carrier gas pushes the HPLC eluent into the GC capillary against its own vapor pressure, generated by a column temperature slightly exceeding the solvent boiling point at the carrier gas inlet pressure. Further improvement of the technique is achieved by flow regulation of the carrier gas (accelerated solvent evaporation) and backflushing of the sample valve (improved solvent peak shape). Concurrent solvent evaporation using the loop-type interface is easy to handle, allows transfer of very large volumes of HPLC eluent (exceeding 1 ml), and renders solvent evaporation very efficient, allowing discharge of the vapors of 1 ml of solvent through the column within 5–10 min.     

Surface Skin Development and Rupture During Sol-Gel Spin-Coating

Spin coating is one of the standard methods for depositing sol-gel, nanocomposite, or polymer coatings onto flat substrates (silicon wafers, glass plates for displays, sensor substrates, etc.). Our recent research has been focused at understanding a wide variety of defect formation mechanisms and looking for ways to prevent these defects. A key aspect of spin-coating is the solvent evaporation that happens at the top surface of the coating fluid during spinning--even while the fluid is moving rapidly, radially, outward on the substrate. As the fluid gets physically thinner, concentration gradients can develop within the fluid as a result of the evaporation. The enrichment of the precursors at the top surface can cause premature gelation there, in other words a “skin” may form. This skin layer is also more resistant to stretching than the underlying fluid and can retard radial fluid motions as well as further solvent evaporation. It is even possible for the stretching forces to be large enough that fracture or tearing of the skin occurs. These surface ruptures create wispy locations of significantly thinner coating or small randomly located linear rips, but they do not typically result in complete penetration through the coating. The occurrence of these defects depends to a large degree on the volatility of key solvents used in the sol-gel process, with less volatile solvents being less likely to result in surface ruptures.     

Effect of a thin spreading solvent film on the efficiency of the hexadecan-1-ol monolayer deposited for water evaporation retardation

The influence of a thin spreading solvent film (ethanol, diethyl ether, and three fractions of petroleum ether boiling at 30–60 °C, 60–90 °C, and 90–120 °C) on the properties of hexadecan-1-ol (C₁₆H₃₃OH) monolayers at the air—water interface was studied. The specific evaporation resistance and the surface pressure were determined to describe the spreading behavior of the C₁₆H₃₃OH monolayers. The physical properties of the solvents and the images obtained in an atomic force microscope were examined. The time of establishing the equilibrium spreading surface pressure of monolayers can be reduced using a more volatile solvent with a lower boiling point and a lower relative density. The influence of the monolayer nature on water evaporation corresponds to the order of changing the solvent spreading rate: petroleum ether (30–60 °C) > diethyl ether > ethanol > petroleum ether (60–90 °C) > petroleum ether (90–120 °C). The monolayers formed upon petroleum ether (30–60 °C) spreading form a film with a less deficient and relatively planar surface. When ethanol is used as a spreading solvent, water evaporation is accelerated rather than retarded, while petroleum ether (30–60 °C) is more appropriate for this purpose.     

Particle dynamics and particle heat and mass transfer in thermal plasmas. Part II. Particle heat and mass transfer in thermal plasmas

This paper is concerned with a review of heat and mass transfer between thermal plasmas and particulate matter. In this situation various effects which are not present in ordinary heat and mass transfer have to be considered, including unsteady conditions, modified convective heat transfer due to strongly varying plasma properties, radiation, internal conduction, particle shape, vaporization and evaporation, noncontinuum conditions, and particle charging. The results indicate that (i) convective heat transfer coefficients have to be modified due to strongly varying plasma properties; (ii) vaporization, defined as a mass transfer process corresponding to particle surface temperatures below the boiling point, describes a different particle heating history than that of the evaporation process which, however, is not a critical control mechanism for interphase mass transfer of particles injected into thermal plasmas; (iii) particle heat transfer under noncontinuum conditions is governed by individual contributions from the species in the plasma (electrons, ions, neutral species) and by particle charging effects.     

Particle Injection in Direct Current Air Plasma Spray: Salient Observations and Optimization Strategies

External injection of high-melting point low thermal conductivity ceramics orthogonal to a typical direct current thermal plasma jet plays a vital role in determining the in-flight state of the particles and the process downstream. The interactions between low density ceramic particles and high temperature plasma jet is quite complex, which influences the spray process and associated deposition. Detailed in-flight particle diagnostics as well as spray stream visualization have significantly enhanced our capability to diagnose and control the process. In this paper we present some salient observations on the role of key variables on particle injection. A number of experiments were conducted using a 7MB torch (Sulzer Metco, Westbury, NY) with both Ar–H₂ and N₂–H₂ plasma gases, where the carrier gas flow to inject Yttria Stabilized Zirconia (YSZ) was varied systematically and the resulting in-flight particle state was captured using an array of particle and spray stream sensors arranged in a 3D set-up. A notable observation is the existence of a “sweet-spot” in the plasma jet where the particle temperatures and velocities achieved a maximum. This sweet-spot can be characterized by the plume position (location of centroid of the spray stream) rather than carrier gas flow rate and is independent of primary gas flows and other process/material conditions. This result suggests a possible approach to optimize particle injection independent of plasma-forming-torch-parameters. Controlling particle injection at this sweet-spot has shown to benefit the overall process efficiency (in terms of melting) and process reliability (both in-flight measurement and coating build-up) with concomitant application benefits.     

Minimum column temperature required for concurrent solvent evaporation in coupled HPLC-GC

Concurrent solvent evaporation using the loop-type HPLC-GC interface requires that the GC oven temperature be above the eluent boiling point at the given carrier gas inlet pressure in order to prevent eluent flowing into the GC capillary column. Corresponding oven temperatures representing minimum oven temperatures for eluent transfer were experimentally determined for solvents and solvent mixtures of interest for use as HPLC eluents. Evaluation of eluents for concurrent evaporation is discussed. Recommended lengths of uncoated column inlets (pre-columns) are derived from the mechanisms involved in solvent evaporation. Temperatures listed as minimum column temperatures for concurrently evaporating HPLC eluents are also useful for estimating maximum applicable column temperatures when working with the conventional retention gap or partially concurrent solvent evaporation techniques in coupled HPLC-GC.     

Ultrathin film deposition by liquid CO2 free meniscus coating-uniformity and morphology

Ultrathin organic films of sucrose octaacetate (SOA) were deposited on 12.5 cm diameter silicon wafer substrates using high-pressure free meniscus coating (hFMC) with liquid CO2 (l-CO2) as a coating solvent. The dry film thickness across the wafer and the morphology of deposited films were characterized as a function of coating conditions-withdrawal velocity, solution concentration, and evaporation driving force (deltaP). When no evaporation driving force was applied (deltaP = 0), highly uniform films were deposited with thickness in the range of 8-105 angstroms over the entire concentration range (3-11 wt%). Uniform films were also obtained at low concentrations (3-5 wt%) with a low evaporation driving force (deltaP = 0.0138 MPa). However, films deposited at medium to high concentrations (7-11 wt%) were thicker (110-570 angstroms) and less uniform, with larger nonuniformities at higher applied evaporation driving forces. Optical microscopy and atomic force microscopy (AFM) were used to characterize film morphology including drying defects and film roughness. Films deposited without evaporation had no apparent drying defects and very low root-mean-square (RMS) roughness (1.4-3.8 angstroms). Spinodal-like dewetting morphologies including holes with diameters in the range of 100-300 nm, and surface undulations were observed in films deposited at medium concentration (7 wt%) and low deltaP (0.0138-0.0276 MPa). At higher concentrations and higher evaporative driving forces, spinodal-like dewetting morphologies disappeared but concentric ring defect structures were observed with diameters in the range 20-125 microm. The film thickness and morphology of SOA films deposited from 1-CO2 hFMC were compared to those deposited from toluene and acetone under normal dip coating. Films deposited from l-CO2 hFMC were much thinner, more uniform, and exhibited much fewer drying defects and lower RMS roughness.