Porous carbon xerogels with texture tailored by pH control during sol-gel process

Despite commonly accepted ideas, evaporative drying does not always completely destroy the pore texture of phenolic gel. This work shows that very porous carbon materials can be synthesized by evaporative drying and pyrolysis of aqueous resorcinol-formaldehyde gels provided that the operating variables are correctly chosen. Moreover, in this manner monoliths can be easily produced. The pore texture of the materials was studied before and after pyrolysis in order to determine which synthesis and/or pyrolysis variables have an influence on the final texture of the carbon. Results show that it is possible to tailor the morphology of these materials by varying the initial pH of the precursors solution in a narrow range. Micro-macroporous, micro-mesoporous, microporous or totally non-porous carbon materials were obtained. The specific surface area is independent from the initial pH whereas the total void volume varies from 0.4 to 1.4 cm³/g when the initial pH decreases from 6.25 to 5.45. These materials can be used as catalysts supports or for electrochemical applications, the texture control being an interesting advantage.     

Requirements of organic gels for a successful ambient pressure drying preparation of carbon aerogels

In this paper, we investigated the requirements of organic gels for a successful ambient pressure drying by analyzing the role of the strength, the pore size and the surfactant of organic gels in decreasing the drying shrinkage of organic aerogels. Experimental results showed the effect of the decrease of the surface tension, resulting from the surfactant, on the drying shrinkage was very small and negligible. The drying shrinkage depended strongly on the strength and the pore size. Subsequently, the respective role of the strength and the pore size was evaluated. It can be found that the strength plays a greater role than the pore size.     

Towards the production of carbon xerogel monoliths by optimizing convective drying conditions

Resorcinol-formaldehyde hydrogels prepared at various resorcinol/sodium carbonate ratios, R/C, were convectively air dried. The influence of the drying operating conditions, i.e. air temperature and velocity, on the pore texture, shrinkage and cracking of the dried gels were investigated. Shrinkage was found to be isotropic. The shrinkage behaviour and the textural properties of the gels are independent of the drying operating conditions, but are completely determined by the value of the synthesis variables. The analysis of the drying kinetics shows two main drying periods. During the first phase, shrinkage occurs and the external surface of the material remains completely wet: heat and mass transfers are limited by external resistances located in a boundary layer. When shrinkage stops, the second period begins: the evaporation front recedes inside the solid and internal transfer limitations prevail. The drying time can be reduced by increasing the air temperature and/or velocity, but the temperature increase is limited when monolithicity is required, especially when the pores are small. For example, at a temperature of 160 °C and a velocity of 2 m/s, about 1 h is needed to dry a 2.8 cm in diameter and 1 cm in height cylinder containing macropores (pore width > 50 nm after drying). The same cylinder presenting small mesopores (pore width = 10-15 nm after drying) requires 20 h at 30 °C and 2 m/s to reach complete dryness without the development of cracks.     

Synthesis of transition metal-doped carbon xerogels by solubilization of metal salts in resorcinol–formaldehyde aqueous solution

The pore texture of carbon materials obtained from evaporative drying and pyrolysis of resorcinol–formaldehyde aqueous gels is controlled by the initial pH of the precursors solution. In order to produce transition metal-containing carbons with tailored texture, various metallic salts were dissolved in the precursors solution. When necessary, a complexing agent (HEDTA or DTPA) was added to render the metal ions soluble. Ni, Fe and Pd loaded carbon xerogels were synthesized and their pore texture was studied after evaporative drying and after pyrolysis. The carbon texture was also studied with regard to the nature of the metal and the amount of complexing agent. The solubilization of transition metal salts in the resorcinol–formaldehyde aqueous solution does not prevent the texture regulation, even though this texture control is influenced: the limits of the pH interval leading to micro–mesoporous carbon materials can slightly differ when a metal salt and/or a complexing agent are added. The pH range shift depends mainly on the amount and nature of the complexing agent, but also slightly on the nature of the metal ion. Nevertheless, the metal particles obtained are rather big (diameter > 15 nm). For catalytic applications, the metal dispersion must be enhanced, especially in the case of expensive metals.     

Characterization of hyperporous polyurethane-based gels by non-intrusive mercury porosimetry

Evaporative drying of polyurethane-based gels produces xerogels. Supercritical drying after replacement of interstitial liquid by supercritical CO₂ produces aerogels. SEM micrographs show that both materials are made up of small size particles gathered up in filament-shaped, strongly cross-linked aggregates. Density measurements show that they both have a large pore volume.When submitted to mercury porosimetry, the behavior of these materials is similar to that of inorganic aerogels, as previously observed. Mercury does not penetrate the pore network, but the whole material is densified. The usual Washburn equation cannot be used to analyze the mercury porosimetry. A well-suited equation based on a buckling model of filament-shaped aggregates has been developed in order to determine the pore volume distribution of mineral dried gels. This equation is also valid for analyzing the texture of organic hyperporous materials like polyurethane dried nanoporous gel.     

掺加橡胶颗粒混凝土材料的性能研究

本文研究橡胶尺寸对橡胶水泥基材料性能的影响,选择三组粒径为6～8mm,3～5mm和0～2mm的橡胶代替骨料制备混凝土,研究制备混凝土材料的稠度和密度、孔径结构、机械强度和干燥收缩性能。结果表明,混凝土材料的稠度和密度随橡胶粒径的增加而降低;对于孔径结构来说,孔体积随着橡胶颗粒粒径尺寸的减小而增加,其中橡胶颗粒粒径尺寸对中孔(50 nm)体积的影响不如橡胶含量因素条件显著;混凝土材料的机械强度随着橡胶颗粒粒径的减小而降低;而混凝土材料干燥收缩率随着橡胶颗粒粒径的减小而增加。     

Nano porous structure of resorcinol–formaldehyde xerogels and aerogels: effect of sodium dodecylbenzene sulfonate

In the past two decades, resorcinol?Cformaldehyde (RF) gels have found widespread applications owing to their low density and adjustable pore size. They are usually prepared through sol?Cgel polymerization of the monomers in an aqueous media followed by evaporative or supercritical drying. In this study, RF gels were synthesized via sol?Cgel polymerization in the presence of sodium dodecylbenzene sulfonate (NaDBS) followed by ambient and supercritical drying. Dimensional measurements along with N₂ sorption analysis and Scanning electron microscopy (SEM) micrographs revealed that pore structure of the gel is chiefly affected by NaDBS. In all samples (xerogels and aerogels), maximum densities were observed at a critical NaDBS concentration (~1?w/v%), whereas considerable pore size increments and pore size distribution broadenings were found at higher concentrations of NaDBS (??5?w/v%). The most increased mesopore volumes were detected in xerogels (133% for acetone-dried and 67% for water-dried samples), while concerning aerogels, the pore sizes enlargement to macropore regime was observed at 5?w/v% of NaDBS. SEM micrographs, in agreement with porosity analysis, depicted that very large pore volumes could be obtained when supercritical drying was employed. However, in the case of xerogels, a more dense structure with smaller pores (micro and mesopores) exists which can only be altered slightly when using large amounts of NaDBS. The results showed that the RF gel pore texture, independent of drying technique, was strongly influenced by the addition of NaDBS, which should be taken into account when using this surfactant in the gel formulation for a wide variety of applications.     

Effect of aging temperature on the porosity characteristics of subcritically dried silica aerogels

Silica aerogels were synthesised by subcritical drying technique which involves controlled solvent exchange and aging of the wet gel in silane solution followed by drying under controlled conditions. Effect of temperature of aging in silane solution on the porosity characteristics of silica aerogels and the thermal pore stability of the resultant gels were investigated. Aging in silane solution leads to an increased degree of condensation reactions, siloxane crosslinking and the dissolution and reprecipitation of silica monomers to the gel structure and enhances the total strength of the gel. Thermal aging of the wet gel have a pronounced effect on bulk density, linear drying shrinkage, surface area and pore volume. As the temperature of aging increases the bulk density decreases whereas the surface area and pore volume were found to increase. We could achieve a surface area of 1040 m²/g, pore volume 1.2 cc/g and an average pore size of 49 Å corresponding to an aging temperature of 70 °C. Thermal pore stability of the gel was found to be up to 700 °C above which densification of SiO₂ gel starts. The novel findings will help in tailoring the process parameters to prepare mesoporous oxides from sol–gel precursors with specific pore features.     

Physical changes accompanying drying of western US lignites

Experiments have been performed to measure the effect of drying procedures of different degrees of severity on the physical properties of four North Dakota lignites. Moisture desorption-readsorption behaviour was relatively reversible in some cases and irreversible in others. Shrinkage measurements commonly showed volume loss greater than that calculated from moisture loss. The shrinkage was always irreversible, even when drying was relatively incomplete; only ≈ 80% of original volume was regained upon reswelling in water. Severity of drying had a significant effect on measured N₂ surface areas, and on pore size distributions throughout most ranges of pore sizes. All the results are consistent with the view that low-rank coals are essentially colloidal gels, many of whose properties are irreversibly altered by drying.     

Determination of porosity change from shrinkage curves during drying of food material

Based on a very simple model of mass conservation, three experimental properties (solid density, liquid density and initial bulk density) and the simultaneous acquisition of the reduced moisture content and the volume shrinkage during drying, a simple method is proposed to calculate the bulk porosity of a material during drying. This model allows a graphical interpretation to visualize the porosity change by comparing the experimental shrinkage curve with an ideal shrinkage curve. In the present work, several examples were taken from the literature to illustrate the application of this method to foodstuffs (apple, banana, carrot, garlic, pear, potato and sweet potato) with two different processes (convective drying, freeze-drying) and different drying conditions. Porosity calculations including error estimations showed a good agreement with experimental values reported in the literature.     

Examining the relationship between the microstructure of calcium silicate hydrate and drying shrinkage of cement pastes

Cement paste undergoes a volumetric contraction called drying shrinkage when placed in a low relative humidity (RH) environment. Only a portion of this shrinkage is reversible upon rewetting. In order to understand better the mechanisms responsible for the irreversible portion of drying shrinkage, a quantitative comparison was made between shrinkage values and microstructural properties of cement pastes. Drying shrinkage, surface area and pore volume were manipulated using curing temperature and chemical admixtures. It was observed that total and irreversible drying shrinkage increase with surface area and pore volume as measured by nitrogen (1-40 nm pore radius range), when degree of hydration and water-to-cement ratio (w/c) are held constant (0.55 and 0.45, respectively).     

真空冷冻干燥制备TiO2粉体

异丙醇钛为钛源,采用溶胶-凝胶法合成TiO2湿凝胶,以真空冷冻干燥方法干燥处理,得到纳米TiO2冻干胶,并用X-射线衍射(XRD)、扫描电镜(SEM)、BET氮气吸附脱附法、TG-DSC综合热分析仪、激光纳米粒度仪对样品表征,制备的TiO2冻干胶中比表面积最大为301.47 m2/g,其总孔容与平均孔径分别为0.189 cm3/g、2.503 nm。     

水醇淀粉凝胶的形成及多孔淀粉的制备

以木薯淀粉为原料,水和乙醇为混合介质,利用溶胶-凝胶法及超临界CO₂干燥制备多孔淀粉,分别考察了水醇比、糊化时间、固含量、冷藏时间、乙醇置换用量、置换时间等对凝胶体积收缩率和质量损失率的影响,通过扫描电子显微镜、比表面积及孔径分布测试仪、X射线衍射仪表征了多孔淀粉形貌及孔结构,并考察了多孔淀粉的吸油性能。结果发现,水醇比为19∶1,固含量为13%,糊化时间为30min,冷藏时间为5天,醇置换量为5mL/g,置换时间为30min,水醇凝胶的体积收缩程度和质量损失相对较小,多孔淀粉的比表面积为122m²/g,平均孔径为25.6nm,大豆油的吸附率可达457%（质量比）。研究结果表明,适当调整固含量,能改善凝胶的三维网孔密度,增大多孔淀粉的比表面积及孔容;水醇淀粉凝胶中的淀粉分子能形成一定结晶结构的网络骨架,利于维持水醇凝胶的骨架稳定性。     

Water Vapor Emission From Rigid Mesoporous Materials during the Constant Drying Rate Period

It has long been thought that the evaporation rate from mesoporous materials during the constant drying rate period (CDRP) is equal to that of a free-water surface, due to the presence of a liquid film covering the surface of the material. In this article we review several early articles and demonstrate that the experimental scrutiny this hypothesis has received is insufficient. Further, we report a set of evaporative drying experiments on eight building materials whose results also do not confirm such hypothesis. Indeed, the drying rate during the CDRP is not equal either among the tested materials or between these and the free-water surfaces. To explain the differences in drying rate, we have looked at the influence of surface texture and porosity. We have concluded that surface texture, which could increase the effective surface area of the materials, did not have a relevant effect on the CDRP drying rate. However, we have found a good correlation between the CDRP drying rate and capillary porosity. This is consistent with the hypothesis that drying occurs at the pore level during the CDRP. Further, it contradicts the suggestion that there is a film of water covering the surface of the materials during this period.     

Effects of carbonization conditions on the properties of coal-based microfiltration carbon membranes

Carbon membranes, a novel porous inorganic membrane, have considerable potential applications in many industrial fields owing to their better stability in aggressive and adverse environments. However, the high cost of precursor materials has hampered their wide applications on commercial scale. In this study, coal, a cheap material, is used to prepare the tubular microfiltration carbon membranes. The effects of carbonization conditions on the properties of coal-based carbon membrane were investigated by the variation of the weight loss, shrinkage ratio of tube size and pore structure characteristics during carbonization. The results show that carbonization conditions greatly affect the properties of coal-based carbon membranes. The carbon membranes carbonized in the inert gases have more “open” porous structure and high gas flux compared to those carbonized in vacuum which makes the carbon membrane possess smaller pores and low gas flux. The carbonization temperature plays an important role in the determination of the pore structure and densification of carbon matrix. At the temperature below 600°C, the pore structure and carbon matrix of carbon membrane are formed with more than 95% of the total weight loss and only 48% of the total size shrinkage ratio. The matrix of carbon membrane gets more compact with the temperature increasing from 600°C to 900°C, in which the size shrinkage ratio is up to 52% with only 5% of the total weight loss. The low heating rate should favor the preparation of the carbon membranes with small average pore size and narrow pore size distribution, and the high gas flow rate can produce the carbon membranes with large average pore size and high porosity.     

Cryo-FIB–SEM and MIP study of porosity and pore size distribution of bentonite and kaolin at different moisture contents

Clays often constitute the main component of poultices used for salt extraction from porous materials in conservation intervention. Knowledge of the evolution in porosity and pore size of clay based poultices, due to shrinkage during drying, is of crucial importance for the selection of the most suitable poultice.We have studied the porosity and pore size distribution of kaolin and bentonite based poultices at different moisture contents. Both Mercury Intrusion Porosimetry (MIP) measurements on freeze-dried samples and cryo-FIB–SEM observations on wet samples are employed.The results show that these complementary techniques provide complete information on the porosity, pore size and pore structure of clay materials at different moisture contents. Both kaolin and bentonite poultices show a change of their total porosity and pore size distribution during drying: the changes are moderate in the case of kaolin, whereas the changes are very significant in the case of bentonite. These findings underline the necessity, when selecting a desalination poultice, of taking into account possible changes in its pore size distribution during drying, since these changes may affect the effectiveness of the salt extraction. Our results indicate that the good desalination efficiency of kaolin on substrate of pore size between 1 and 10 μm observed in practice is related to the presence in the poultice of pores that are very effective in capillary transport (0.2–2 μm) and to the relatively constant pore size distribution of the poultice during drying.     

USE OF X-RAY MICROTOMOGRAPHY TO FOLLOW THE CONVECTIVE HEAT DRYING OF WASTEWATER SLUDGES

X-ray microtomography is proposed as a new tool to investigate the evolution of size, shape and texture of soft materials during a drying operation. This study is focused on the drying of mechanically dewatered sludges from a secondary wastewater treatment. The shrinkage phenomenon is shown to play a crucial role in the control of the drying process. The shrinkage curves are determined by analysing the shape and size of cross sectional microtomographic images of sludge extrudates at different levels of drying. The observation of drying and shrinkage curves allows us to determine 3 critical water content values, which define different drying zones where extragranular, intragranular or mixed limitations prevail. When drying is externally controlled, the decrease of the drying rate observed during experiments can be related to the reduction of the external area of the sample, i.e., to shrinkage. When drying is internally controlled, resistances inside the solid govern the process. Between these two extreme situations, the drying rate reduction is the result of both the external area decrease and the development of internal resistances limiting drying. A multizone model is proposed to describe quantitatively these observations. The analysis of the internal texture of the sludge extrudates reveals crack formation at the end of the drying process. The onset of crack formation is clearly related to the appearance of internal transfer limitations, i.e., humidity and temperature gradients inside the material.     

Role of Drying Techniques on the Development of Porosity in Silica Gels

Silica gel has been prepared by the hydrolysis of TEOS under three different pH conditions. These gels have been subjected to drying in an air oven, under humidity, and also by exposure to microwaves, followed by further calcination at 500°C under slow heating schedule (3°C/min). Silica samples thus obtained are characterised by B.E.T. specific surface area and pore volume data. The thermal decomposition behaviour of the precursor gels are also reported. The adsorption isotherms of these samples indicate different behaviour related to the method of synthesis. Increase in pH of hydrolysis of the TEOS from 3 to 8 results in increase in specific surface area in tune with the earlier reports. However more significant observation is the variation in pore size distribution as evidenced from adsorption isotherms related to method of drying. Silica gels prepared at pH 3 show Type I behaviour irrespective of the method of drying. However gel prepared at pH 6 shows Type II behaviour when dried under microwave with specific surface area as high as 635 m₂/g and pore volume 0.9733 cc/g. The precursor gels prepared at still higher pH exhibit Type IV behaviour when subjected to microwave drying. The pH conditions of synthesis of precursor gels along with drying techniques appear to affect not only the surface areas and porosities but also the resultant adsorption isotherms, in sol-gel silica.     

Theoretical and Experimental Study of Freeze-Drying of “loco” (Concholepas concholepas)

The “loco” is a mollusk somewhat similar to abalone that exists exclusively in Chile and Peru. Given the high commercial value of loco, preservation through freeze-drying seems economically viable. In this work, the freeze-drying process of loco meat was analyzed theoretically and experimentally. The effects of particle size, freeze-drying pressure, and intermittent use or not of microwave in the secondary drying stage, on the extent of the freeze-drying period, rehydration properties, shrinkage and texture were investigated by using a 2³ factorial design. Drying and rehydration kinetics were adjusted to phenomenological models in order to determine mass transfer parameters.

Freeze-drying pressure significantly affects the extent of the drying process. Freeze-drying pressure results in shrinkage, while microwave produces a volume increase. The effective moisture diffusivity (D_eff) estimated form drying curves fluctuated between 10^?10 and 10^?11 (m²/s), agreeing with values reported for other meat products. The adjustment of the rehydration kinetics to the Constant Diffusivity Model gave the best fit, resulting in D_eff in the order of 10^?10 (m²/s). Particle size and freeze-drying pressure significantly affected rehydration capacity.     

含湿多孔介质的干燥特性

基于含湿多孔介质的水分蒸发过程及其内部毛细管水分的蒸发特性，分析了含湿多孔介质在干燥过程中发生体积收缩的原因．讨论了多孔介质的物性和外部干燥条件对其体积收缩特性的影响。