Melting of solvents nanoconfined by polymers and networks

Thermoporosimetry is becoming increasingly used to study nanoscale heterogeneity and structure in polymer networks. The starting point for thermoporosimetry is the Gibbs-Thomson (GT) relation between melting point and inverse crystal size. In the case of polymers, the Flory-Huggins (FH) model also predicts that there is a depression of the melting point because of the mixing of the polymer and the solvent molecules, and this needs to be taken into account. The first step in analysis of size heterogeneity using thermoporosimetry and the GT equation requires that there be quantitative agreement between the FH theory and the melting points of the diluent in the uncrosslinked rubber. We find that both benzene and hexadecane exhibit excessive melting point depressions in uncrosslinked polyisoprene. This may imply that the uncrosslinked polymer is divided into ‘nanoheterogeneities’. We further find that the heat of fusion decreases as polymer concentration increases for the benzene, but not for the hexadecane. Finally, we compare pore size distributions obtained for a crosslinked polyisoprene as determined from the melting behavior of n-hexadecane as a diluent, using different references for how the uncrosslinked polymer behaves. While number average distribution is not very different between the different analyses, the weight average distribution is. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3475–3486, 2006     

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.     

Thermoporosimetry

The pore size distributions (PSDs) of microporous glass, which were controlled by acid leaching subsequent to phase separation of CaO-Al₂O₃-B₂O₃-SiO₂ glass, were determined via both mercury porosimetry and thermoporosimetry (thermal porosimetry). As a result, the pore radii, the cumulative pore volumes, and the surface areas determined via thermoporosimetry were in good agreement with those determined via mercury porosimetry. It was revealed that thermoporosimetry could be applied to pore structure analysis for porous materials having pore sizes at least up to 58 nm in radius.     

Ionic cluster size distributions of swollen nafion/sulfated beta-cyclodextrin membranes characterized by nuclear magnetic resonance cryoporometry

Nafion/sb-CD membranes were prepared by mixing 5 wt% Nafion solution with H+-form sulfated beta-cyclodextrin (sb-CD), and their water uptakes, ion exchange capacities (IECs), and ionic cluster size distributions were measured. Gravimetric and thermogravimetric measurements showed that the water uptake of the membranes increased with increases in their sb-CD content. The IECs of the membrane were measured with acid-base titration and found to increase with increases in the sb-CD content, reaching 0.96 mequiv/g for NC5 ("NCx" denotes a Nafion/sb-CD composite membrane containing x wt% of sb-CD). The cluster-correlation peaks and ionic cluster size distributions of the water-swollen membranes were determined using small-angle X-ray scattering (SAXS) and 1H nuclear magnetic resonance (NMR) cryoporometry, respectively. The SAXS experiments confirmed that increases in the sb-CD content of the membranes shifted the maximum SAXS peaks to lower angles, indicating an increase in the cluster correlation peak. NMR cryoporometry is based on the theory of the melting point depression, Delta Tm, of a liquid confined within a pore, which is dependent on the pore diameter. The melting point depression was determined by analyzing the variation of the NMR signal intensity with temperature. Our analysis of the intensity-temperature (IT) curves showed that the ionic cluster size distribution gradually became broader with increases in the membrane sb-CD content due to the increased water content, indicating an increase in the ionic cluster size. This result indicates that the presence of sb-CD with its many sulfonic acid sites in the Nafion membranes results in increases in the ionic cluster size as well as in the water uptake and the IEC. We conclude that NMR cryoporometry provides a method for determining the ionic cluster size on the nanometer scale in an aqueous environment, which cannot be obtained using other methods.     

Enthalpy and interfacial free energy changes of water capillary condensed in mesoporous silica, MCM-41 and SBA-15

The effect of confinement on the solid-liquid phase transitions of water was studied by using DSC and FT-IR measurements. Enthalpy changes upon melting of frozen water in MCM-41 and SBA-15 were determined as a function of pore size and found to decrease with decreasing pore size. The melting point also decreased almost monotonically with a decrease in pore size. Analysis of the Gibbs-Thomson relation on the basis of the thermodynamic data showed that there were two stages of interfacial free energy change after the constant region, i.e., below a pore size of 6.0 nm: a gradual decrease down to 3.4 nm and another decrease after a small jump upward. This fact demonstrates that the simple Gibbs-Thomson relation, i.e., a linear relation between the melting point change and the inverse pore size, is limited to the range not far from the melting point of bulk water. FT-IR measurements suggest that the decrease in enthalpy change and interfacial free energy change with decreasing pore size reflect the similarity of the structures of both liquid and solid phases of water in smaller pores at lower temperatures.     

NMR cryoporometry with octamethylcyclotetrasiloxane as a probe liquid. Accessing large pores

Octamethylcyclotetrasiloxane is presented and investigated as probe liquid for NMR cryoporometry or DSC-based thermoporometry. This compound which may imbibe into both hydrophilic and hydrophobic pores is shown to exhibit a melting point depression that is larger than that for other cryoporometric probe materials such as cyclohexane. The transverse relaxation time differs by more than three orders of magnitude between the solid and liquid states, separated by a sharp phase transition. Hence, as demonstrated in controlled pore glasses, octamethylcyclotetrasiloxane can provide pore size distributions for materials with pore sizes up to the micrometer range.     

Inorganic salt hydrates as cryoporometric probe materials to obtain pore size distribution

The depression of the melting temperature of Zn(NO3)2.6H2O was used to obtain the pore size distributions in controlled pore glasses. Measured by 1H NMR, the average value of the temperature depression DeltaT and the known average pore size yield K=DeltaT.d approximately 116 K.nm as the material-dependent factor for Zn(NO3)2.6H2O in the Gibbs-Thompson equation. The melting temperature is close to room temperature. Hence, this salt hydrate and some related other ones are better materials than water (K approximately 50 K.nm) for cryoporometric studies of systems with hydrophilic pores. The data also provide 46 mN/m for the solid-liquid surface tension of this salt hydrate.     

Nitrocellulose porosity - thermoporometry

Nitrocellulose porosity was investigated by thermoporometry, based on melting point depression of liquid in limited space. Strange behaviour of water-saturated nitrocellulose was observed, which consisted of melting peak shifting of some of liquid. Thermal resistance, connected with limited contact area of nitrocellulose walls and water, is supposed as the source of phenomenon. Water is unable to completely penetrate into pores as nitrocellulose is a hydrophobic material, though prolonged stirring or boiling of mixture improves saturation. Thus total pore volume cannot be estimated correctly. In spite of this pore radius was calculated from obtained DSC curves. The results show good consistency for the same nitrocellulose materials, which proves that thermoporometry is a useful method of nitrocellulose characterisation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mucoadhesive vaginal film of fluconazole using cross-linked chitosan and pectin

A series of silica gels (Si-40, Si-60, Si-100) and related carbon–silica gels, prepared by carbonization of CH₂Cl₂ at a surface of silica gels at 550 °C, characterized using FTIR/PAS, SEM/EDX, and nitrogen adsorption, was investigated upon interactions with polar (water, dimethylsulfoxide), weakly polar (chloroform), and nonpolar (n-hexane, n-decane, benzene, toluene) adsorbates using adsorption and differential scanning calorimetry methods. Features of confined space effects, such as freezing/melting point depression and melting delay, depend strongly on pore sizes, pore wall structure, type and amount of adsorbates, and the degree of pore filling. Melting curves of both polar and nonpolar adsorbates bound in broad pores (Si-60 and Si-100 based materials) can include two–three peaks around melting point, but for Si-40-based materials, a number of similar peaks is smaller. This occurs due to step-by-step melting of frozen structures located in broader pores and the absence of similar effects in narrower pores. The present study shows that complex carbon–silica gel adsorbents can be more effective adsorbents than simple silica gels due to the presence of a number of surface sites of various polarity and structure.

     

Melting of pentaerythritol tetranitrate (PETN) nanoconfined in controlled pore glasses (CPG)

The melting temperature depression of pentaerythritol tetranitrate, nanoconfined in controlled pore glasses (CPG), was systematically studied by differential scanning calorimetry (DSC). The solid–liquid interfacial energy σ _sl was obtained from the Gibbs–Thomson equation fit to melting temperature vs. reciprocal pore diameter. The pore size distribution of the CPG pores was also estimated from the DSC data. Pore sizes obtained from the manufacturer by BET are compared with those determined from the DSC curves using either the curves directly or by assuming spherical shaped confining cavities. The thermal mass vales are in better agreement with the BET estimation.     

Phase transitions of octamethylcyclotetrasiloxane confined inside aluminosilicate and silicate nanoporous matrices

We report the melting behaviour of a dipolar cyclic siloxane liquid: octamethylcyclotetrasiloxane (OMCTS) confined in three mesoporous silica matrices: Al-SBA-15, SBA-15 and CPG glasses, using differential scanning calorimetry and dielectric spectroscopy. We investigate the influence of acid sites on the adsorptive properties of mesoporous silica materials, which were synthesized by applying Pluronic-type polymers as pore-creating agents. Aluminosilicate matrices have been synthesized by direct synthesis procedure using aluminium chloride. These materials characterized by N₂ sorption measurements, and the small-angle X-ray scattering data exhibit the same hexagonal P6 mm structure with a mean mesopores size of 4.6 nm (Al-SBA-15) and 4.9 nm (SBA-15). The controlled pore glasses used in this experiment have pores of mean diameter of 7.5 nm. For all systems studied, the OMCTS melting point in pores has been found to decrease with decreasing pore diameter. This result is in qualitative agreement with that obtained in molecular simulation where the adsorbate-wall interactions are weak compared to the adsorbate–adsorbate interactions.     

Cross-linking of polyolefins: a study by thermoporosimetry with benzene derivatives as swelling solvents.

The solvents o-, m-, p-xylene, p-dichlorobenzene, 1,2,4-trichlorobenzene, and naphthalene were calibrated as condensates used in the thermoporosimetry technique. Exponential relationships were found connecting the pore radii R(p) (in nm) and the freezing-point depression of the swelling solvent deltaT (in degrees C) on the one hand and the apparent energy of crystallization W(a) (in J cm(-3)) and deltaT on the other hand: R(p) = t exp[-1/(c deltaT)]; W(a) = W0 exp(deltaT/f). Pore- or mesh-size distributions can be derived from differential scanning calorimetry results by using the following equation: dV(p)/dR(p) = k{[cY(T)deltaT2]/[W(a)R(p)]}. All the numerical parameters were determined. Polyethylene and polypropylene samples, cross-linked with high-energy electrons or gamma-rays, were submitted to thermoporosimetry study. Relative mesh-size distributions, which depend on the polymer/solvent pair, were calculated for these polyolefins with o-, m-, and p-xylene as solvent and were found to be in the same sequence as those of their degrees of swelling and the irradiation doses received.     

Rapid synthesis of SBA-15 rods with variable lengths, widths, and tunable large pores

Dispersed SBA-15 rods have been synthesized with varying lengths, widths, and pore sizes in a low-temperature synthesis in the presence of heptane and NH(4)F. The pore size of the material can systematically be varied between 11 and 17 nm using different hydrothermal treatment times and/or temperatures. The particle length (400-600 nm) and width (100-400 nm) were tuned by varying the HCl concentration. All the synthesized materials possess a large surface area of 400-600 m(2)/g and a pore volume of 1.05-1.30 cm(3). A mechanism for the effect of the HCl concentration on the particle morphology is suggested. Furthermore, it is shown that the reaction time can be decreased to 1 h, with well-retained pore size and morphology. This work has resulted in SBA-15 rods with the largest pore size reported for this morphology.     

非水反相微乳中NaCl纳米粒子的制备

在乙醇/Brij 30/十六烷反相微乳中利用无水NaAc与HCl反应制备了水可溶性晶态NaCl纳米粒子,平均粒径为 60 nm.与在甲酰胺/AOT/正庚烷反相微乳中制备的粒径约为1 μm的NaCl粒子进行比较,表明在特定条件下,非水微乳可以作为合成水可溶性纳米粒子的有效介质.     

Control of various morphological changes of poly(meth)acrylate microspheres and their swelling degrees by SPG emulsification

Crosslinked poly(meth)acrylate polymers with a variety of morphologies were synthesized with two steps. In the first step, a microporous glass membrane (Shirasu Porous Glass, SPG) was employed to prepare uniform emulsion droplets by applying an adequate pressure to the monomer phase, which was composed of the ADVN initiator, solvent of toluene or heptane or their mixture, and a mixture of (meth)acrylate monomers. The droplets were formed continuously through the membrane and suspended in the aqueous solution, which contained a PVA‐127 suspending agent, SLS emulsifier, and NaNO₂ inhibitor to suppress the nucleation of secondary particles. SPG pore sizes of 0.90, 5.25, and 9.25 μm were used. Then the emulsion droplets were polymerized at 343 K with a rotation rate 160 rpm for 24 h. The (meth)acrylate monomers 2‐ethylhexyl acrylate (2‐EHA), 2‐ethylhexyl methacrylate (2‐EHMA), cyclohexyl acrylate (CHA), methyl methacrylate (MMA), lauryl acrylate (LA), and lauryl methacrylate (LMA) were used in this research. The influences of the ratios of the monomer and crosslinking agent EGDMA, the amount of diluents, the monomer type on the polymer particle morphology, the swelling degree, and the polymer particle size were investigated. It was found that an increase in the concentrations of EGDMA and heptane resulted in higher coarse porous spheres and smaller polymer particle sizes. A coefficient with a variation close to 10%, or a standard deviation of about 4, was obtained. The capacity of these spheres as solvent absorption materials was examined. The highest swelling degrees of heptane and toluene were obtained when LA was employed as the monomer with 30% (by weight) of EGDMA and 70% (by weight) of heptane as an inert solvent. The highest capacity of the solvent absorption was obtained when using a polymer particle size of 4.81 μm, as prepared by SPG pore size 0.9 μm. The polymer particles were able to absorb aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and a mix of aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, such as toluene and heptane. The capacity of solvent absorption for the aromatic hydrocarbon solvents was higher than for the aliphatic hydrocarbon solvents. In addition, the particles did not rupture or collapse after absorption in solvents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4038–4056, 2000     

Melting point depression of ionic liquids confined in nanospaces

A new physical method was proposed to control the liquid properties of room temperature ionic liquids (RT-ILs) in combination with nanoporous materials; the melting point of ILs confined in nanopores remarkably decreases in proportion to the inverse of the pore size.     

2H-solid state NMR and DSC study of isobutyric acid in mesoporous silica materials

Solid state deuterium NMR has been used to study the molecular motion of d(6)-isobutyric acid (d(6)-iBA) in the pure (unconfined) state and confined in the cylindrical pores of two periodic mesoporous silica materials (MCM-41, pore size 3.3 nm and SBA-15, pore size 8 nm), and in a controlled pore glass (CPG-10-75, pore size ca. 10 nm). The line shape analysis of the spectra at different temperatures revealed three rotational states of the iBA molecules: liquid (fast anisotropic reorientation of the molecule), solid I (rotation of the methyl group) and solid II (no rotational motion on the time scale of the experiment). Transition temperatures between these states were determined from the temperature dependence of the fraction of molecules in these states. Whereas the solid I-solid II transition temperature is not affected by confinement, a significant lowering of the liquid-solid I transition temperature in the pores relative to the bulk acid was found for the three matrix materials, exhibiting an unusual dependence on pore size and pore morphology. Complementary DSC measurements on the same systems show that the rotational melting (solid I-liquid) of d(6)-iBA in the pores occurs at a temperature 20-45 K below the thermodynamic melting point. This finding indicated that the decoupling of rotational and translational degrees of freedom in phase transitions in confined systems previously found for benzene is not restricted to molecules with non-specific interactions, but represents a more general phenomenon.     

新型脱硫材料SbSn金属间化合物的制备及其脱硫性能

以Sb、Sn为原料，在氮气氛下采用熔炼法制备出SbSn金属间化合物。正庚烷中加入少量噻吩配制成模拟油品，将模拟油品和汽油分别配制成两种乳状液进行脱硫实验。在密闭反应器中，SbSn和配制好的乳状液按一定比例在常温常压下搅拌反应一定时间即完成脱硫过程。结果表明，较好的SbSn金属间化合物的制备条件为Sb∶Sn质量比为49∶51、950℃、反应60min、Sb粒径<200目和快速冷却。这种新型材料在常温常压下对于模拟油品中噻吩的单程脱除率在15％左右，汽油单程脱硫率为11.8%。选用了三种方法对脱硫后的SbSn进行清洗，结果表明，用甲苯清洗过的SbSn金属间化合物，再次脱硫能力明显好于其他两种方式。材料经甲苯清洗，三次循环脱硫实验结果表明，模拟油品脱硫率可达到32％，汽油脱硫率为27％。