A correlation for the pressure drop in monolithic silica columns

To gain insight into how the pressure drop in monolithic silica columns is determined by the microscopic details of the pore structure, a series of well-validated computational fluid dynamics simulations has been performed on a simplified model structure, the so-called tetrahedral skeleton column. From these simulations, a direct correlation between the pressure drop and two main structural properties (skeleton thickness and column porosity) of the monolithic skeleton could be established. The correlation shows good agreement with the experimental pressure-drop data available from the literature on silica monoliths, especially when a correction for the flow-through pore size heterogeneity is made. The established correlation also yields a much more accurate representation of the relation between the flow resistance and the bed porosity than does the Kozeny-Carman model, making it much better suited for porosity optimization calculations.     

Characterization of silica-based monoliths with bimodal pore size distribution

Band dispersion was studied and the retention thermodynamics addressed for insulin and angiotensin II on C18 silica monoliths with a bimodal pore size distribution, covering linear mobile-phase velocities up to 1 cm/s and different temperatures. These data suggest that the influence of average column pressure on retention (between 0 and 10 MPa) is not negligible. Plate height curves were interpreted with the van Deemter equation by assuming an independent contribution from mechanical and non-mechanical dispersion mechanisms. This analysis revealed diffusion-limited mass transfer in the mesoporous silica skeleton which, in turn, allowed us to calculate an equivalent dispersion particle diameter (d(disp) = 3 microm) using the C-term parameter of the van Deemter equation. The resulting superposition of reduced plate height curves for monolithic and particulate beds confirmed that this view presents an adequate analogy. The macroporous interskeleton network responsible for the hydraulic permeability of a monolith was translated to the interparticle pore space of particulate beds, and an equivalent permeability particle diameter (d(perm) = 15 microm) was obtained by scaling based on the Kozeny-Carman equation.     

Tailoring the morphology of methacrylate ester-based monoliths for optimum efficiency in liquid chromatography

Methacrylate ester-based monolithic stationary phases were prepared in situ in fused-silica capillaries and simultaneously in vials. The influence of the composition of the polymerization mixture on the morphology was studied with mercury intrusion porosimetry, scanning electron microscopy, and nitrogen adsorption measurements. A high-density porous polymeric material with a unimodal pore-size distribution was prepared with 40 wt % monomers and 60 wt % solvent in the mixture. A low-density material, prepared with a 20:80 ratio of monomers versus pore-forming solvent, showed a bimodal pore-size distribution and a much finer structure than the high-density monolith. The characteristic pore size could be controlled by changing the ratio of pore-forming solvents. With increasing solvent polarity, both the pore size and the dimension of the globules increased. The best efficiency in the CEC mode was obtained with an average pore size of 600 nm. Low-density monoliths exhibited lower A- and C-terms than high-density monoliths. With the optimal monolithic material, a minimum plate height of 5 mum could be obtained. The low-density monolith also performed better in the HPLC mode, giving a minimum plate height of 15 mum and a much higher flow permeability than that of the high-density material.     

Co-continuous monolithic titania prepared by organic polymer monolith as pore template

We achieved preparation of co-continuous titania based monolithic materials using several organic polymer monoliths as pore templates. Firstly, the organic polymer monoliths that had well controlled structures were prepared, and filled the pores of polymer monolith with tetra-n-butyl titanate (titan monomer). The following hydrolysis of the titan monomer resulted in titanium dioxide. The polymer monolith was removed by calcination at elevated temperature. We carefully studied the utility of polymer monolithic template, filling method of the titan monomer, and calcination conditions to realize co-continuous titania monolith. In addition, by the change of domain size (size of a skeleton + size of through a pore) of template, we were able to control domain size of the resulting titania monoliths.     

Performance of monolithic silica capillary columns with increased phase ratios and small-sized domains

Monolithic silica capillary columns for HPLC were prepared from tetramethoxysilane to have smaller sized domains and increased phase ratios as compared to previous materials, and their performance was evaluated. The monolithic silica columns possessed an external porosity of 0.65-0.76 and a total porosity of 0.92-0.95 and showed considerably higher performance and greater retention factors in a reversed-phase mode after chemical modification than columns previously reported. An octadecylsilylated monolithic silica column with the smallest domain size (through-pores of approximately 1.3 microm and silica skeletons of approximately 0.9 microm) showed a plate height of less than 5 microm at optimum linear velocities (u) of 2-3 mm/s in 80% acetonitrile for a solute having retention factors of approximately 1, and approximately 7 microm at u = 8 mm/s. With a permeability similar to that of a column packed with 5-microm particles, the monolithic silica columns were able to attain column efficiencies comparable to that of particulate columns packed with 2-2.5-microm particles, and showed performance in the "forbidden region" for the previous columns. The performance of the monolithic column can be compared favorably with that of a particle-packed column when 15,000-30,000 or more theoretical plates are desired at a pressure drop of 20-40 MPa or lower. The increased homogeneity of the co-continuous structures, in addition to the small-sized domains, contributed to the higher performance as compared to previous monolithic silica columns.     

Assessing the macroporous structure of monolithic columns by transmission electron microscopy

A set of monolithic stationary phases representing a broad span of monomers and porogens have been characterized directly in their capillary chromatographic format by computational assessment of their pore structure from transmission electron micrographs obtained after in situ embedment of the monoliths in contrast resin, followed by dissolution of the fused-silica tubing, further encasement of the resin-embedded monolith, and microtomy. This technique has been compared to mercury intrusion, a more conventional technique for macroporosity estimation. Supplementing the embedding resin by lead methacrylate gave a negative staining, and the resulting micrographs showed a good contrast between the polymeric monoliths and the embedding resin that allowed studies on the pore formation and polymer development. The technique was also applied to a commercial monolithic silica column.     

Use of Synthetic Calcium Aluminosilicate for Immobilization of Radioactive Wastes

Leaching rate, phase composition, specific surface area, pore volume, and pore size distribution of synthetic calcium aluminosilicate (SCAS) promising for immobilization of radioactive wastes was studied. The initial SCAS powder for forming monoliths was prepared by superadiabatic combustion of the charge containing fly ash of thermoelectric power stations and limestone. The monoliths were prepared from SCAS by two procedures: (1) solidification with water under common conditions with subsequent prolonged carbonation in air and (2) cold pressing of air-dry powder material. In the first case, a high-strength monolith was formed by filling of the pore volume with a mixture of calcium carbonate in various crystalline polymorphic modifications, and in the second case, by pozzolanic reaction of active silica with the products of -dicalcium silicate hydration. It was found that, at contact with solution, the pores in the monolithic samples are filled with a calcium hydrosilicate gel decreasing their porosity and, in turn, leaching rate. SCAS matrices exceed special glasses and are close to some ceramic compositions in the safety of immobilization of alkali and alkaline-earth elements.     

Performance of a monolithic silica column in a capillary under pressure-driven and electrodriven conditions

A continuous macroporous silica gel network was prepared in a fused-silica capillary and evaluated in reversed-phase liquid chromatography. Under pressure-driven conditions, the monolithic silica column derivatized to C18 phase (100 microns in diameter, 25 cm in length, silica skeleton size of approximately 2.2 microns) produced plate heights of about 23 and 81 microns at 0.5 mm/s with a pressure drop of 0.4 kg/cm2, and at 4.0 mm/s with 3.6 kg/cm2, respectively, in 90% acetonitrile for hexylbenzene with a k value of 0.7. The separation impedance, E, calculated for the present monolithic silica column was much smaller at a low flow rate than those for particle-packed columns, although higher E values were obtained at a higher flow rate. Considerable dependence of column efficiency on the linear velocity of the mobile phase was observed despite the small size of the silica skeletons. A major source of band broadening in the HPLC mode was found in the A term of the van Deemter equation. The performance of the continuous silica capillary column in the electrodriven mode was much better than that in the pressure-driven mode. Plate heights of 7-8 microns were obtained for alkylbenzenes at 0.7-1.3 mm/s, although the electroosmotic flow was slow. In HPLC and CEC mode, the dependency of plate height on k values of the solutes was observed as seen in open tube chromatography presumably due to the contribution of the large through-pores. Since monolithic silica capillary columns can provide high permeability, the pressure-driven operation at a very low pressure can afford a separation speed similar to CEC at a high electric field.     

Surface-alkylated polystyrene monolithic columns for peptide analysis in capillary liquid chromatography-electrospray ionization mass spectrometry

Macroporous poly(styrene-divinylbenzene) (PS-DVB) monoliths were prepared by in situ polymerization in PEEK, fused silica, or stainless steel tubing having an inner diameter of 75 or 125 microm. A process is described for subsequent alkylation of the flow-contacting surfaces of the monoliths. The process treats all the surfaces including through-pore surfaces of the rigid macroporous monolith with a solution containing a dissolved Friedel-Crafts catalyst, an alkyl halide (1-chlorooctadecane), and an organic solvent. This process produces an improved reversed-phase liquid chromatographic separation of peptides compared to an unmodified monolithic PS-DVB column. The surface octadecylation is not necessary for a reversed-phase separation of proteins since both unmodified and modified columns provide comparable results. Tryptic protein digests, standard proteins, and standard peptides were used to evaluate the monolithic columns by employing electrospray mass spectrometry detection. Potential applications in proteomics studies by mass spectrometry, which use the alkylated monolithic column engaged onto the nanofabricated electrospray ionization chip, are also discussed.     

Multiscale structural characterization of methyltriethoxysilane-based silica aerogels

A series of methyltriethoxysilane-based silica aerogel monoliths were prepared by ambient pressure drying with various volume ratios of water to ethanol (R). The pore volumes and average pore sizes of silica aerogels were obtained by Barrett–Joyner–Halenda (BJH) method from nitrogen adsorption–desorption isotherms. The stress–strain curves of the cylindrical aerogel specimens were measured by performing uniaxial compressive tests. The particle size distributions and the average particle sizes of silica aerogels were also evaluated based on scanning electron microscopic observations. The experimental data revealed that the average particles size increased from 0.115 to 3.08 μm as R varied from 0.7 to 1.5, and that the silica aerogels exhibited two characteristic types of the compressive stress–strain responses. By proposing a multiscale structural model to describe microstructures of silica aerogels, a structural parameter, defined as the slenderness L/D of the cube column length L and the average particle diameter D, was related to the specific volume and the BJH volume of the silica aerogel monoliths, as well as the specific volume of silica. Accordingly, the two types of the compressive stress–strain responses may be distinguished by the critical value (L/D)_c.     

A graphitized-carbon monolithic column

The preparation of a novel carbon monolithic column for high performance liquid chromatography is described. A phenolic resin rod with embedded 10-microm silica beads was prepared by acid-catalyzed polymerization of a resorcinol/iron(III) complex and formaldehyde. This rod was carbonized and graphitized under inert atmosphere with a programmed temperature cycle from room temperature to 1250 degrees C. Subsequently, the silica beads along with iron catalysts were removed, leaving a porous carbon rod. Imaging of this monolithic rod by scanning and transmission electron microscopies revealed a highly interconnected bimodal porous structure. The porosity and pore size distribution of the mesopores were characterized by N2 absorption/desorption. Graphene sheets were found in the TEM images of the carbon rod, and the graphite index was characterized by Raman spectrum and X-ray diffraction. A monolithic column prepared with the aforementioned carbon rod was evaluated using a mixture of alkylbenzenes. It exhibited an excellent separation power and a low hydraulic resistance. The bundle-of-capillaries model was used to characterize the hydrodynamics of this monolith. Its permeability was found to agree well with the theoretical one.     

Moment analysis of mass-transfer kinetics in C18-silica monolithic columns

The moment analysis of elution peak profiles based on new moment equations provides information on the mass-transfer characteristics of C(18)-silica monolithic columns. The flow rate dependence of the HETP data was analyzed using the generalized van Deemter equation, after correction of these data by subtraction of the external mass-transfer contribution to band broadening. Kinetic parameters and diffusion coefficients related to the mass-transfer processes in monolithic columns were derived by taking advantage of the different flow velocity dependence of their contributions to band broadening. At high flow rates, axial dispersion and diffusive migration across the monolithic C(18)-silica skeleton contribute much to band broadening, suggesting that it remains important to reduce the influence of eddy diffusion and the mass-transfer resistance in the stationary phase to achieve fast separations and a high efficiency. Surface diffusion plays a predominant role for molecular migration in the monolithic stationary phase. Although the value of the surface diffusion coefficient (D(s)) depends on an estimate of the external mass-transfer coefficient, D(s) values of the order of 10(-7) cm(2) s(-1) were calculated for the first time for the C(18)-silica monolithic skeleton. The value of D(s) decreases with increasing retention of sample compounds. Analysis of a kind of time constant calculated from D(s) suggests that the "chromatographic corresponding particle size" is approximately 4 microm for the C(18)-silica monolithic stationary phase used in this study. The accuracy of the D(s) values determined was discussed.     

Monolithic porous polymer for on-chip solid-phase extraction and preconcentration prepared by photoinitiated in situ polymerization within a microfluidic device.

Monolithic porous polymers have been prepared by photoinitiated polymerization within the channels of a microfluidic device and used for on-chip solid-phase extraction and preconcentration. The preparation of the monolithic material with hydrophobic and ionizable surface chemistries is easily achieved by copolymerization of butyl methacrylate with ethylene dimethacrylate, or 2-hydroxyethyl methacrylate and [2-(methacryloyloxy)ethyl]trimethylammonium chloride with ethylene dimethacrylate, respectively. The porous properties, and consequently the flow resistance, of the monolithic device are controlled by the use of a mixture of hexane and methanol as a porogenic mixture. This mixture was designed to meet the specific requirements for pore formation within macroporous monoliths useful in the microfluidic formats. The low flow resistance enables high flow rates of up to 10 microL/min, which corresponds to a linear flow velocity of 50 mm/s and far exceeds the flow velocities typical of the common analytical microchips. The function of the monolithic concentration device was first demonstrated using very dilute solutions of Coumarin 519. The performance in a more realistic application was then demonstrated with the enrichment of a hydrophobic tetrapeptide and also of green fluorescent protein for which an increase in concentration by a factor as high as 10(3) was achieved.     

整体型环氧树脂大孔聚合物的制备与表征

用三亚乙基四胺(TETA)作为固化剂,通过双酚A环氧树脂在聚乙二醇(PEG)介质中的聚合反应诱导相分离制备具有三维骨架结构的整体型环氧树脂大孔聚合物。固定PEG1000与PEG2000的质量比为6∶1,分别研究了环氧树脂与PEG的比例关系和TETA的用量对整体型大孔聚合物孔结构的影响,用FT-IR、SEM、BET和MIP对整体型大孔聚合物进行表征并将其用于重金属离子的吸附。结果表明,改变环氧树脂与PEG的比例关系或者TETA的用量都可以调控大孔聚合物的孔结构,其孔径为0.1~1μm。孔径最小的整体型大孔聚合物比表面积最大,约84.4m~2/g,但孔径较大的整体型大孔聚合物对重金属离子(Cu~(2+))的吸附性能更好,吸附量高达113.1mg/g。     

Chiral monolithic columns for enantioselective capillary electrochromatography prepared by copolymerization of a monomer with quinidine functionality. 2. Effect of chromatographic conditions on the chiral separations

The effect of chromatographic conditions on the performance of chiral monolithic poly(O-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroqui nidine-co-ethylene dimethacrylate-co-2-hydroxyethyl methacrylate) columns in the capillary electrochromatography of enantiomers has been studied. The flow velocity was found to be proportional to the pore size of the monolith and both the pH and the composition of the mobile phase. The length of both open and monolithic segments of the capillary column was found to exert a substantial effect on the run times. The use of monoliths as short as 8.5 cm and the "short-end" injection technique enabled the separations to be achieved in approximately 5 min despite the high retentitivity of the quinidine selector. Very high column efficiencies of close to 250000 plates/m and good selectivities were achieved for the separations of numerous enantiomers using the chiral monolithic capillaries with the optimized chromatographic conditions.     

The effect of microstructure on the permeability of metallic foams

Pressure drop was measured across complex and simple structure metallic foams at different velocity ranges using air as working fluid. Darcian and non-Darcian permeability parameters, K and C, were determined by fitting experimental data with widely accepted quadratic model of Hazen-Dupuit-Darcy. Generally, the experimental results are in good agreement with the model. The differences in K and C values between the two types of metallic foams are due to the different microstructure. For the simple structure specimens, permeability K increased whereas non-Darcian permeability C decreased with increasing pore diameter. The effect of pore size on the permeability of complex structure metallic foams seems to be opposite to that observed with the simple structure specimens and to results reported by other researchers on other porous medium. This discrepancy mainly stems from the differences in window concentration in addition to some heterogeneity in the foam that impeded the gas flow on one side of the specimens. The difference in pressure drop observed in the different metallic foams is due to combined effect of K and C. However, for simple structure foams, K and C could be predicted by Ergun-like model using appropriate values for the empirical constants. The permeability K is significantly affected by pore size and porosity. The quadratic term of Hazen-Dupuit-Darcy equation is mainly due to the inertia of the flow and partially to the drag exerted by the microstructure of the metallic foam. For both foams, as the porosity increases, pressure drop decreases and permeability, K, increases. The introduction of the open cross sectional area term enabled better understanding of the permeability of metallic foams with intricate morphologies.     

纯水体系SiO2纳米多孔材料的低成本制备与表征

以低成本工业级硅溶胶为硅源, 水为溶剂, 在常压条件下干燥后制备出纳米多孔SiO₂块体材料。在制备过程中, 采用表面活性剂十六烷基三甲基溴化铵(CTAB)来降低水的表面张力, 减少样品在干燥过程中开裂和收缩, 避免了繁琐的溶剂替换过程。所制备的SiO₂块体密度为150~260 mg/cm³, 比表面积为91~140 m²/g, 平均孔径为15~27 nm, 其室温热导率可达0.048 W/(m·K)。该方法大大缩减了制备SiO₂纳米多孔材料的成本, 并降低了操作工艺难度和危险, 将在很大程度上推动硅纳米孔材料的工业化生产与应用。     

Influence of pore size on tensile strength, permeability and porosity of hyaluronan-collagen scaffolds

Recent investigations have shown the importance of scaffold pore size on the realisation of tissue engineered cartilage which promotes cell adhesion, proliferation and differentiation. The objective of this study was to investigate the influence of pore size on the mechanical properties, the permeability and the porosity of hyaluronan-collagen scaffolds. Hyaluronan-collagen scaffolds with three different mean pore sizes (302.5, 402.5 and 525 microm) have been produced according to a standardised protocol. The maximum stress at rupture, the Young's Moduli, permeability and porosity of the scaffolds were investigated. The permeability was determined both empirically and mathematically. Increased pore sizes indicated a larger stress at rupture as well as increased Young's Moduli. Porosity and permeability were raised by increasing pore sizes. The mathematically calculated permeability showed the same trend. The results indicate a higher mechanical stability for scaffolds with larger pores. The experimental and mathematical experiments both show increased permeability and fluid mobility for larger pores in scaffolds. Morphological changes resulting from the alteration of pore size led to non-correlation between the calculated and the experimental permeability.     

Chiral monolithic columns for enantioselective capillary electrochromatography prepared by copolymerization of a monomer with quinidine functionality. 1. Optimization of polymerization conditions, porous properties, and chemistry of the stationary phase

Monolithic columns for chiral capillary electrochromatography have been prepared within the confines of untreated fused-silica capillaries in a single step by a simple copolymerization of mixtures of O-[2-(methacryloyloxy)ethylcarbamoyl]-10,11-dihydroquinidine , ethylene dimethacrylate, and glycidyl methacrylate or 2-hydroxyethyl methacrylate in the presence of mixture of cyclohexanol and 1-dodecanol as a porogenic solvent. The porous properties of the monolithic columns can easily be controlled through changes in the composition of the binary porogenic solvent. Although both thermal- and UV light-initiated polymerizations afford useful capillary columns, monoliths prepared using the former approach exhibit better chromatographic properties. The ability to control pore size independently of the polymerization mixture composition enables the preparation of monoliths with varying percentages of the chiral monomer and cross-linker, as well as the optimization of their separation properties. Very good separations of model racemate (R,S)-N-3,5-dinitrobenzoylleucine were achieved using an optimized monolithic CEC column, with high efficiencies of up to 74000 plates/m for the retained peaks.     

Fabrication of silica monolithic columns with ordered meso/macropore structure

Recently, much effort has been focused on the materials with ordered meso/macropores, because of their potential applications in catalysis, separations, coatings, microelectronics and electro-optics. In this paper, silica monoliths with well-defined columnar shape more than 1 cm in length are successfully fabricated by using the micelles of triblock copolymer F127 and colloidal crystals composed of polystyrene (PS) latex microspheres as mesopore and macropore template, respectively. The column templated by PS microspheres 870 nm in diameter and 0.5 g F127 (MCL-0.5-870) shows uniform ordered macropores, contact pores connecting macropores together, and assembled and inter-particle pores increasing the BET specific surface area and adsorption capability of the monolithic column. The backpressure curve and hydraulic permeability experiment exhibit its good penetrability and mechanical stability. These excellent characteristics, together with high BET specific surface area (387.4 m² g⁻¹) and porosity (80%), may endow its potential application for chromatography separation. In addition, the size of macropores and mesopores can be easily regulated by changing the diameter of PS spheres and F127 weight, respectively. This indicates that this method is a facile and universal protocol to fabricate the applied monolithic column with ordered meso/macropores.