The Influence of Physical Mixing and Impregnation on the Physicochemical Properties of Pine Wood Activated Carbon Produced by One-Step ZnCl2 Activation.

In this study, two different sample preparation methods to synthesize activated carbon from pine wood were compared. The pine wood activated carbon was prepared by mixing ZnCl2 by physical mixing, i.e., "dry mixing" and impregnation, i.e., "wet mixing" before high temperature carbonization. The influence of these methods on the physicochemical properties of activated carbons was examined. The activated carbon was analyzed using nitrogen sorption (surface area, pore volume and pore size distribution), XPS, density, Raman spectroscopy, and electrochemistry. Physical mixing led to a slightly higher density carbon (1.83 g/cm3) than wet impregnation (1.78 g/cm3). Raman spectroscopy analysis also showed that impregnation led to activated carbon with a much higher degree of defects than physical mixing, i.e., ID/IG = 0.86 and 0.89, respectively. The wet impregnated samples also had better overall textural properties. For example, for samples activated with 1:1 ratio, the total pore volume was 0.664 vs. 0.637 cm3/g and the surface area was 1191 vs. 1263 m2/g for dry and wet mixed samples, respectively. In the electrochemical application, specifically in supercapacitors, impregnated samples showed a much better capacitance at low current densities, i.e., 247 vs. 146 F/g at the current density of 0.1 A/g. However, the physically mixed samples were more stable after 5000 cycles: 97.8% versus 94.4% capacitance retention for the wet impregnated samples.

Co-exfoliation and fabrication of graphene based microfibrillated cellulose composites - mechanical and thermal stability and functional conductive properties.

The excellent functional properties of graphene and micro-nanofibrillated cellulose (MNFC) offer plenty of possibilities for wide ranging applications in combination as a composite material. In this study, flexible graphene/microfibrillated cellulose (MFC) composite films were prepared by a simple method of co-exfoliation of graphite in an MFC suspension by high-shear exfoliation. We show that pristine graphene, without any chemical treatment, was homogeneously dispersed in the MFC matrix, and the produced composites showed enhanced thermal, electrical and mechanical properties compared to a non-co-exfoliated control. The film properties were studied by XPS, XRD, Raman, SEM, FTIR, TGA, nitrogen sorption, UV-vis spectroscopy, optical and formation analysis tests. At 0.5 wt% loading, the specific surface area of graphene/MFC composites increased from 218 to 273 m2 g-1 while the tensile strength and Young's modulus for the graphene/MFC composites increased by 33% and 28% respectively. Thermal stability was enhanced by 22% at 9 wt% loading and the composites showed a high electrical conductivity of 2.4 S m-1. This simple method for the fabrication of graphene/MFC composites with enhanced controlled functional properties can prove to be industrially beneficial, and is expected to open up a new route for novel potential applications of materials based largely on renewable resources.

Assessing the reactivity of cellulose by oxidation with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidinium cation under mild conditions.

The accessibility and reactivity of cellulose are key parameters in its conversion into various products. Several indirect measures, such as water retention value (WRV), fiber saturation point (FSP) and specific surface area (SSA), are often used to characterize cellulosic samples for their reactivity. In this paper, we report on using oxidation with 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxo-piperidinium cation (4-AcNH-TEMPO+) as a probe reaction for the reactivity of cellulose in mild conditions (pH 9, room temperature). 4-AcNH-TEMPO+ is able to selectively convert hydroxymethyl groups into carboxylate groups. The time dependence of the conversion was monitored by iodometric quantification of the residual 4-AcNH-TEMPO+. Soluble substrates, such as 1-propanol and maltose, were quantitatively oxidized in ca. 1min while 3-16% of cellulose was oxidized in ca. 15min depending on its origin. Extrapolation of the slow residual oxidation to zero time allowed quantification of the easily reactive or accessible cellulose. The 4-AcNH-TEMPO+ reactivity was correlated with several pulp characteristics, including WRV, FSP, SSA, chemical composition, crystallinity, the pulping process and the drying history.

From colloidal spheres to nanofibrils: extensional flow properties of mineral pigment and mixtures with micro and nanofibrils under progressive double layer suppression.

Suspensions of mineral pigment and cellulose fibrillar derivatives are materials regularly found in the forest products industries, particularly in paper and board production. Many manufacturing processes, including forming and coating employ flow geometries incorporating extensional flow. Traditionally, colloidal mineral pigment suspensions have been considered to show little to no non-linear behaviour in extensional viscosity. Additionally, recently, nanofibrillar materials, such as microfibrillar (MFC) and nanofibrillar cellulose (NFC), collectively termed MNFC, have been confirmed by their failure to follow the Cox-Merz rule to behave more as particulate material rather than showing polymeric rheological properties when dispersed in water. Such suspensions and their mixtures are currently intensively investigated to enable them to generate likely enhanced composite material properties. The processes frequently involve exposure to increasing levels of ionic strength, coming either from the weak solubility of pigments, such as calcium carbonate, or retained salts arising from the feed fibre source processing. By taking the simple case of polyacrylate stabilised calcium carbonate suspension and comparing the extensional viscosity as a function of post extension capillary-induced Hencky strain on a CaBER extensional rheometer over a range of increasing salt concentration, it has been shown that the regime of constriction changes as the classic DLVO double layer is progressively suppressed. This change is seen to lead to a characteristic double (bimodal) measured viscosity response for flocculated systems. With this novel characteristic established, more complex mixed suspensions of calcium carbonate, clay and MNFC have been studied, and the effects of fibrils versus flocculation identified and where possible separated. This technique is suggested to enable a better understanding of the origin of viscoelasticity in these important emerging water-based suspensions.