Nanofibrillar cellulose aerogels

Highly porous aerogels consisting of cellulose nanofibrils were prepared by dissolution/regeneration of cellulose in aq. calcium thiocyanate followed by regeneration and carefully controlled drying. The influence of drying method (regular freeze drying, rapid freeze drying, and solvent exchange drying) on resulting porosity was studied by electron microscopy and nitrogen adsorption. While regular freeze drying caused significant coalescence of microfibrillar units, solvent exchange drying gave highly porous aerogel composed of approx. 50 nm-wide cellulose microfibrils. Correspondingly, specific surface area of the solvent-exchange-dried aerogels ranged 160–190 m²/g, in contrast to 70–120 m²/g of regular freeze-dried materials. Rapid freeze technique using liquid nitrogen-cooled metal plate gave aerogel sheets with asymmetrical porosity, with the face contacted by copper having porous structure similar to those of solvent-exchange dried material.     

Effective preparation of crack-free silica aerogels via ambient drying

Effective ambient-drying techniques for synthesizing crack-free silica aerogel bulks from the industrial waterglass have been developed. Silica wet gels were obtained from aqueous colloidal silica sols prepared by ion-exchange of waterglass solution (4–10 wt% SiO₂). Crack-free monolithic silica aerogel disks (diameter of 22 mm and thickness of 7 mm) were produced via solvent exchange/surface modification of the wet gels using isopropanol/trimethylchlorosilane/n-Hexane solution, followed by ambient drying. The effects of the silica content in sol and the molar ratio of trimethylchlorosilane/pore water on the morphology and property of final aerogel products were also investigated. The porosity, density, and specific surface area of silica aerogels were in the range of 92–94%, 0.13–0.16 g/cm³, and ∼675 m²/g, respectively. The degree of springback during the ambient drying processing of modified silica gels was 94%.     

Direct observation of cellulose dissolution in subcritical and supercritical water over a wide range of water densities (550–1000 kg/m<Superscript>3</Superscript>)

Direct observations of the heating of microcrystalline cellulose (230 DP) in water at temperatures up to 410 °C and at pressures up to 700 MPa were made with a batch-type microreactor. Cellulose particles were found to dissolve with water over temperatures ranging from 315 to 355 °C at high pressures. Dissolution temperatures depended on water density and decreased from about 350 °C at a water density of 560 kg/m³ to a minimum of around 320 °C at a water density of 850 kg/m³. At densities greater than 850 kg/m³, the dissolution temperatures increased and reached a value of about 347 °C at 980 kg/m³. The cellulose dissolution temperatures were independent of heating rates for values ranging from 10 to 17 °C/s. The low dependence of dissolution temperatures on the heating rates is strong evidence for simultaneous dissolution and reaction of the cellulose. Different phenomena occurred depending on water density. At low densities, particles turned transparent and seemed to dissolve into the aqueous phase from the surface. From 670 to 850 kg/m³, the cellulose particles visibly swelled just before completely collapsing and dissolving into the aqueous phase. The swelling probably increased water accessibility and particle surface area and thus lead to the lower dissolution temperatures observed. From 850 to 1000 kg/m³, the particles required longer times to dissolve and many fine brown-like particles were generated as the particles dissolved. FT-IR spectra of the residues were analyzed. Residues formed from heating cellulose at high densities still retained some cellulose character whereas those as low densities had little cellulose character, especially in the O–H stretching vibration region.     

Physical Properties of Silica Aerogels Prepared with Polyethoxydisiloxanes

Silica aerogels were made by sol-gel techniques using industrial silicon derivatives (polyethoxydisiloxanes, E-40), followed by supercritical drying with ethanol. The morphology and microstructure of the silica aerogels were investigated by using specific surface area, S_BET, SEM, TEM and the pore size distribution techniques. The thermal conductivity was also measured as a function of air pressure. The results show that the diameter of the silica particles is about 13 nm and the pore size of the silica aerogels is 20–80 nm. The specific surface area of the silica aerogel is about 470 m²/g and the thermal conductivity of the silica aerogel prepared with E-40 is 0.014 w m^–1 K^–1 at room temperature and 1 atm.     

Ambient pressure dried tetrapropoxysilane-based silica aerogels with high specific surface area

In the present paper, we report the synthesis of tetrapropoxysilane (TPOS)-based silica aerogels with high surface area and large pore volume. The silica aerogels were prepared by a two-step sol-gel process followed by surface modification via a simple ambient pressure drying approach. In order to minimize drying shrinkage and obtain hydrophobic aerogels, the surface of the alcogels was modified using trichloromethylsilane as a silylating agent. The effect of the sol-gel compositional parameters on the polymerization of aerogels prepared by TPOS, one of the precursors belonging to the Si(OR)₄ family, was reported for the first time. The oxalic acid and NH₄OH concentrations were adjusted to achieve good-quality aerogels with high surface area, low density, and high transparency. Controlling the hydrolysis and condensation reactions of the TPOS precursor turned out to be the most important factor to determine the pore characteristics of the aerogel. Highly transparent aerogels with high specific surface area (938 m²/g) and low density (0.047 g/cm³) could be obtained using an optimized TPOS/MeOH molar ratio with appropriate concentrations of oxalic acid and NH₄OH.     

Cellulose–silica composite aerogels from “one-pot” synthesis

Cellulose–silica composite aerogels were prepared via “one-pot” process: aqueous solutions of cellulose–8 wt% NaOH and sodium silicate were mixed, coagulated and dried with supercritical CO₂. The system was studied both in the fluid and solid (dry) states. Cellulose and sodium silicate solutions were mixed at different temperatures and concentrations; mixture properties were monitored using dynamic rheology. The gelation time of the mixture was strongly reduced as compared to that of cellulose–NaOH solutions; we interpret this phenomenon as cellulose self-aggregation inducing partial coagulation due to competition for the solvent with sodium silicate. The gelled cellulose/sodium silicate samples were placed in aqueous acid solution which completed cellulose coagulation and led to in situ formation of sub-micronic silica particles trapped in a porous cellulose matrix. After drying with supercritical CO₂, an organic–inorganic aerogel composite was formed. The densities obtained were in the range of 0.10–0.25 g/cm³ and the specific surface area was between 100 and 200 m²/g. The silica phase was shown to have a reinforcing effect on the cellulose aerogel, increasing its Young’s modulus.     

The effect of heat-treatment on the physico-chemical properties of silica aerogel prepared by sub-critical drying technique

Synthesis of transparent and crack-free monoliths of silica aerogel by sub-critical drying technique is reported in the present article. Silane ageing with 50% tetraethylorthosilicate:ethanol followed by solvent exchange using ethanol was adopted. The effect of heat-treatment on the textural and physical characteristics of silica aerogel was evaluated. The chosen composition resulted in a high surface area silica aerogel of 1,000 m² g⁻¹ and a pore volume of 1.4 cm³ g⁻¹ at room temperature. The aerogel heat-treated at 900 °C possessed a surface area of 450 m² g⁻¹ with a pore volume of 0.4 cm³ g⁻¹. The decrease in surface area and pore volume was associated with the sintering process. The present technique seems advantageous in preserving the high surface area of the material at high temperatures. The XRD studies showed that the amorphous nature of aerogel matrix was retained till 1,400 °C, beyond which it crystallized to phase pure crystoballite.     

Silica–titania aerogel monoliths with large pore volume and surface area by ambient pressure drying

Ambient pressure drying has been carried out for the synthesis of silica–titania aerogel monoliths. The prepared aerogels show densities in the range 0.34–0.38 g/cm³. The surface area and pore volume of these mixed oxide aerogels are comparable to those of the supercritically dried ones. The surface area for 5wt% titania aerogel has been found to be as high as 685 m²/g with a pore volume of 2.34 cm³/g and the 10wt% titania aerogel has a surface area of 620 m²/g with a pore volume of 2.36 cm³/g. Some gels were also made hydrophobic by a surface treatment with methyltrimethoxysilane and trimethylchlorosilane. The surface modified aerogels possess high surface areas in the range of 540–640 m²/g, and are thermally stable in terms of retaining hydrophobicity up to a temperature of 520 °C. The pore size distribution of the aerogels clearly indicates the preservation of the aerogel structure. High Resolution Transmission Electron microscopy has been employed to characterise the aerogels and Fourier Transform infrared spectroscopy to study the effect of titania addition to silica and the surface modification. X-ray diffraction patterns were recorded to verify the molecular homogeneity of the aerogel.     

Surface modification of cellulose with plant triglycerides for hydrophobicity

Hydrophobic cotton was achieved by surface modification of the cellulose with triglycerides from several plant oils including soybean, rapeseed, olive and coconut oils. These oils were delivered to the cellulose substrates in homogeneous solutions of ethanol or acetone as well as aqueous emulsions. Surface modification was facilitated by solvent evaporation followed by heating between 110 and 120 °C for 60 min. All oils, except for coconut, produced hydrophobic and less water-absorbing cotton, supporting the desirable role of higher unsaturation in the fatty acids to achieve crosslinked network. The most hydrophobic surfaces were obtained by the reaction with 1% soybean oil in acetone. On both bleached and scoured cotton, a water contact angle of 80° and water absorption value of 0.82 μL/mg were achieved. The acquired hydrophobicity was not only retained after water washing but also improved with subsequent exposures to elevated temperatures. The surface tension of scoured cotton cellulose was lowered from 63.81 mJ/m² to 25.74 mJ/m² when modified by soybean oil delivered in acetone, which is lower than that of poly(ethylene terephthalate). An aqueous emulsion of soybean oil also rendered the scoured cotton hydrophobic, which shows promise for a green chemistry and bio-based approach to achieve water repellency on cellulosic materials.     

草甘膦锆:干燥方法对微形貌的影响及甲醛吸附行为

本文运用扫描电子显微镜、X射线粉末衍射仪等手段对在不同干燥方法下得到的层状材料草甘膦锆分子聚集体的形貌及其对甲醛吸附性能进行了深入研究,探讨了干燥条件对材料形态的影响以及化合物形态对甲醛吸附不同的内在因素。研究结果表明:干燥方法不同,所得草甘膦锆的形貌有明显差别,应用超临界干燥技术得到的产物是具有大比表面(445m2·g-1)和大比孔容(5.32cm3·g-1)的三维网状结构,应用冷冻干燥技术得到的产物具有介孔结构,而使用喷雾干燥技术得到的产物为微孔与介孔共存微球。在对4种不同干燥产物对甲醛吸附性能的研究发现,甲醛分子在不同形态载体上的吸附能力差距很大,超临界干燥得到的草甘膦锆对甲醛吸附最大百分率(被吸附甲醛的质量占吸附组装体的百分含量)达到7.8%,且甲醛被吸附后热稳定性较好,具有较好的应用前景。     

Aerocellulose: Aerogels and Aerogel-like Materials made from Cellulose

Summary: Cellulose aerogels have been prepared starting from cellulose-NMMO solutions via the classical aerogel-path. Different cellulosic materials have been tested and their influence on the properties of the product aerogels has been studied. Other parameters that have been varied include solution composition as well as the way of cellulose regeneration (solvent and temperature). More than 300 different samples were prepared and analysed. Their density is in a typical range from 0.02 g/cm³ to 0.2 g/cm³ and their internal surface area ranges from 100 m²/g to 400 m²/g. Another property investigated in detail beside density and internal surface area was the shrinkage of the cellulosic bodies during the production process.     

Morphological and structural development of hardwood cellulose during mechanochemical pretreatment in solid state through pan-milling

Mechanochemical pretreatment of hardwood cellulose was conducted by our self-designed pan-mill equipment which has an unique and smart structure and can exert strong shear forces and pressure on materials in between and break them down. The structure transformations, including particle size, powder morphology, molecular structure, crystalline structure during milling were investigated by Laser Diffraction Particle Size Analyzer, SEM, FT-IR and WAXD, respectively. Compared with standard method of ball-milling, the pan-mill shows a much higher efficiency in mechanochemical pretreatment of hardwood cellulose. The average particle size reduced to 21 μm and the specific surface area increased to 0.8 m²/g after 40 milling cycles. Mechanical milling also led to collapse of hydrogen bonds and reduction of crystallinity. The crystallinity index of cellulose powder decreased from its original 65 to 22, after milling for 40 cycles. Thermal analysis and solubility testing illustrated that pan-milled cellulose has lower thermal stability and higher solubility in aqueous alkali.     

Preparation and Characterization of Modified Cellulose Adsorbents with High Surface Area and High Adsorption Affinity for Hg(II)

Cellulose was modified via chlorination using phosphorous oxychloride followed by functionalization with amine and thiol moieties. The obtained modified cellulose samples were investigated by means of FTIR, TGA, TEM, and nitrogen-adsorption surface area (BET). The BET measurements showed a remarkable increase in the surface area of Cell-N-S (477.7 m²/g) and Cell-N (706 m²/g). The resins gave an uptake capacities of 38 and 7.2mmol/g for Cell-N-S and Cell-N, respectively toward Hg(II) from its solutions. These values are considered much better compared with other reported resins. Regeneration of the resins was achieved effectively using acidified thiourea.     

Drying of a cellulose II gel: effect of physical modification and redispersibility in water

The agglomeration of cellulosic materials upon drying, often called hornification, causes a reduction of water retention, among other undesired effects. It is one of the main issues in industrial cellulose processing, especially with regard to nanocelluloses. As a consequence, high transportation and storage costs arise since nanocelluloses need to remain in aqueous suspensions unless trade-offs in reactivity, redispersibility and surface properties are accepted. In this study, different drying strategies for TENCEL^® gel, a nanostructured gel derived from the Lyocell process consisting of spherical particles, are compared and evaluated. First, freeze-drying with consideration of the influence of freezing temperature and the use of tert-butanol as cryo-protectant, and second, simple oven-drying at 60 °C. Surprisingly, oven-dried xerogels showed higher water retention values and also better colloidal stability than the cryogels. This is in stark contrast to cellulose nanofibrils for which freeze-drying has been shown to be significantly superior to oven drying in terms of redispersibility. For the TENCEL^® gel, oven-drying was thus selected and the influence of additives on the redispersibility of the cellulose II gel was studied by means of the common water retention value, particle size, colloidal stability, appearance of the redispersed gel and viscosity. The addition of the polysaccharides carboxymethyl cellulose or xanthan showed the most promising results with regard to redispersibility. Also sucrose and ammonium bicarbonate provided higher colloidal stabilities than that of the untreated TENCEL^® gel. The redispersibility of the cellulose II xerogels could thus be significantly improved by simple and cost-efficient mixing with additives prior to drying.     

Isolation and characterization of nanocrystalline cellulose from flaxseed Hull: A future onco-drug delivery agent

Cellulose is a polysaccharide composed of D-glucopyranose linked by 1,4 β-glycoside bond with three hydroxyl groups. These hydroxyl groups in cellulose have an important role in the compactness of crystalline structure and in determining the physical properties of cellulose. Cellulose in nanometers size range from 10 nm to 350 nm is known as nano cellulose, which has a variety of applications due to the unique properties such as low density, biodegradable, and good mechanical properties. In the present study, we present the isolation of the nano cellulose from flaxseed hull for the first time. The isolated nano cellulose was characterized by techniques such as UV–Vis, FT-IR, BET, XRD SEM, and TEM. The nano cellulose obtained was found to be crystalline in nature with a crystallinity index of 46% and the surface area of 5 cm²/g with excellent thermal stability.     

Improvement of mechanical and oxygen barrier properties of cellulose films by controlling drying conditions of regenerated cellulose hydrogels

Mechanical, thermal and oxygen barrier properties of regenerated cellulose films prepared from aqueous cellulose/alkali/urea solutions can be markedly improved by controlling the drying conditions of the films. By pre-pressing followed by vacuum drying under compression, the tensile strength, Young’s modulus, coefficient of thermal expansion and oxygen permeability of the dried films reached 263 MPa, 7.3 GPa, 10.3 ppm K⁻¹ and 0.0007 ml μm m⁻² day⁻¹ kPa⁻¹, respectively. Thus, films produced in this way show the highest performance of regenerated cellulose films with no orientation of cellulose chains reported to date. These improved properties are accompanied by a clear increase in cellulose II crystallinity from 50 to 62% during pre-pressing/press-vacuum drying process. At the same time, the film density increased from 1.45 to 1.57 g cm⁻³, and the moisture content under equilibrium conditions decreased from 14.1 to 9.8%. Hence, the aqueous alkali/urea solvent system has potential applications in producing new and environmentally friendly cellulose films with high performances through control of the drying conditions.     

Characterization of Hydrophobic SiO2 Powders Prepared by Surface Modification on Wet Gel

Hydrophobic porous silica has been prepared by surface modification of TEOS (tetraethylorthosilicate) wet gel with 6 and 12 vol.% of TMCS (trimethylchlorosilane). We characterized the products by using FT-IR, TGA, DTA, N₂ adsorption/desorption, contact angle and SEM. Surface silanol groups of the gel were widely replaced by–Si(CH₃)₃ to result in a hydrophobic SiO₂ powder as confirmed by contact angle measurements with H₂O, 1-butanol and ethanol. The modified dried gels had a surface area of 950–1000 m²/g (average pore size 120 Å), compared to the non-modified surface which had a surface area of 690 m²/g (average pore size 36 Å). The adsorption/desorption isotherm curves indicated they had similar pore characteristics as aerogels prepared by the supercritical drying process.     

Acidity of Alginate Aerogels Studied by FTIR Spectroscopy of Probe Molecules

Supercritical drying of alginate gels is an efficient way to prepare aerogels with high surface area (>300 m² · g⁻¹). FTIR spectroscopy allows to monitor the adsorption of NH₃ from the gas phase onto the acid sites of the alginate. Free carboxylic groups are effective Brønsted sites, whereas the divalent cations used in the ionotropic gelation present the properties of Lewis sites. The ratio between Brønsted and Lewis sites provides infomation on the role of pH in alginate gelation and suggests that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process.     

The preparation and characterization graphene-cross-linked phenol–formaldehyde hybrid carbon xerogels

A new synthesis route based on polycondensation of phenol and formaldehyde cross-linked by graphene oxide (GO) was developed. Wet gel after gelation was converted into an organic xerogel by ambient pressure drying to obtain GO-cross-linked phenol–formaldehyde (PF) organic xerogels (GOCPFOX). Graphene-cross-linked PF carbon xerogels (GCPFCX) were produced by carbonization. The morphology and chemical structure of GOCPFOX and GCPFCX were analyzed. The electrochemical behavior of GCPFCX as an electrode material in electric double-layer capacitors (EDLCs) was investigated. Results show that the high mechanical strength of GO increased the gel skeleton strength; thus, organic xerogels exhibit very low drying shrinkage. Scanning electron micrographs indicated that addition of GO altered the gel structure. Thus, when GO was added into the PF solution, the PF molecular chains were anchored on the surface of GO by chemical and physical interaction. The GCPFCX-10 sample achieved the highest specific surface area, mesoporous volume, and specific capacity with 378 m²/g, 0.56 cm³/g, and 116 F/g, respectively. Hence, GCPFCX is a potential material for EDLCs owing to its low production cost and ability to avoid supercritical drying.     

Characterization of Highly Porous Materials from Cellulose Carbamate

Highly porous cellulose was formed by gelation of cellulose carbamate solutions in caustic soda. Two methods for gel preparation were optimized for the formation of beads and bulky materials – the chemical precipitation from dilute sulfuric acid and the thermal gelation by annealing at elevated temperatures. Various methods were used for characterizing of the pores of low density materials: scanning electron microscopy, small angle X-ray scattering, mercury intrusion and nitrogen sorption. These methods were optimized and used for characterizing the complete pore system from micro to macro pores. The effects of different preparation (cellulose carbamate concentration in caustic soda) and processing (precipitation, drying and pyrolysis) on the pore structure were studied by the set of complementary methods. Aerocell samples with a minimum density of 0.06 g/cm³ were prepared from cellulose carbamate. They are characterized by a broad pore size distribution ranging from 0.5 nm to 1 mm, specific internal surfaces of up to 660 m²/g and total pore volumes of up to 18 cm³/g.