Zorica M. Vuković

Supramolecular Route to Well-Ordered Metal Nanofoams

Metal nanofoams with a porosity above 50% v/v have recently attracted great interest in materials science due to their interesting properties. We demonstrate a new straightforward route to prepare such nanofoams using diblock copolymer-based PS-block-P4VP(PDP) supramolecules that self-assemble into a bicontinuous gyroid morphology, consisting of PS network channels in a P4VP(PDP) matrix. After dissolving the PDP, the P4VP collapses onto the PS struts and a free-standing bicontinuous gyroid template of 50-100 μm thickness and interconnected, uniformly sized pores is formed. The hydrophilic P4VP corona facilitates the penetration of water-based plating reagents into the porous template and enables a successful metal deposition. After plating, the polymer is simply degraded by heating, resulting in a well-ordered inverse gyroid nickel foam. Essential to this approach is the removal of only one part of the matrix (i.e., PDP). Therefore, the template accounts for 50% v/v or more. The porosity characteristics (amount, size of pores) can be tuned by selecting the appropriate copolymer and by adjusting the amount of PDP.

THE INFLUENCE OF ACID TREATMENT ON THE COMPOSITION OF BENTONITE

Bentonite from the ‘Bogovina’ coal mine in Serbia, was characterized. The influence of acid treatment on its composition, as well as mathematical descriptions of this influence are reported. The purpose of this work was to correlate the concentration of the acid used for the treatment with the resulting bentonite composition. X-ray diffraction (XRD), infrared spectroscopy and quantitative chemical analysis were employed to define the changes caused by acid treatment.The contents of all the cations, except Si, decreased exponentially with increasing concentration of the HCl used for the treatment of the bentonite. This approach was tested on previously published data and was shown to be valid.The basal reflections of smectite decreased gradually and eventually disappeared after intense treatment, while the other reflections remained in the XRD patterns of all the samples, but decreased slightly with increasing acid strength. In addition, the amount of X-ray amorphous matter formed increased rapidly with increasing acid concentration up to 4.5 M. With further increase in the acid strength, the amount of X-ray amorphous matter remained virtually constant.

Nanoporous Network Channels from Self‐Assembled Triblock Copolymer Supramolecules

Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating.

The Influence of Acid Treatment on the Nanostructure and Textural Properties of Bentonite Clays

The nanostructure and textural properties of acid-activated bentonite clays from the Bogovina coalmine were investigated. The acid activation was performed with HCl in the concentration range 1.5-7.5 M. The atomic force microscopy followed by image analysis was used in order to establish the influence of the acid treatment on the size of bentonite particles. Nitrogen adsorption-desorption isotherms at -196 °C were used to estimate the specific surface area, pore volume and pore size distribution. The acid treatment reduces the size of bentonite particles and increases the specific surface area and pore volume of the investigated bentonites. These effects are improved by increasing the acid concentration up to 4.5 M HCl. Further increase in acid concentration does not result in development of new porous structure.

Effect of Candida antarctica Lipase B Immobilization on the Porous Structure of the Carrier

A series of poly(GMA-co-EGDMA) resins with identical composition but varying particle sizes, pore radii, specific surface areas and specific volumes are studied to assess how Candida antarctica lipase B immobilization affects the porosity of the copolymer particles. Mercury porosimetry reveals a significant change in the average pore size (up to 6.1-fold), the specific surface area (up to 3.2-fold) and the specific volume (up to 2.1-fold) of the epoxy resin. A similar behaviour is observed for glutaraldehyde-modified epoxy resins. The influences of the resin porosity properties on the loading of Candida antarctica lipase B during immobilization and on the hydrolytic activity (hydrolysis of p-nitrophenyl acetate) of the immobilized lipase are studied.

Textural properties of poly(glycidyl methacrylate): acid-modified bentonite nanocomposites

The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modified bentonite (BA) into the reaction system. All samples were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), mercury intrusion porosimetry, and low temperature physisorption of nitrogen. The FTIR and TEM analysis confirmed incorporation of BA into the copolymer structure and the successful formation of nanocomposites. TEM images confirmed formation of nanocomposites having both intercalated and exfoliated acid-modified bentonite in copolymer matrix. A significant increase of specific surface area, pore volume, and porosity of the nanocomposites in comparison to the copolymer were obtained. The difference between textural properties of nanocomposites with different amounts of incorporated acid-modified bentonite was less prominent.

RESPONSE SURFACE OPTIMIZATION FOR ACTIVATION OF BENTONITE USING MICROWAVE IRRADIATION

Microwave irradiation as a means for heating bentonites during acid activation has been investigated in the past but it has never been optimized for industrial applications. The purpose of this study was to apply a factorial 23 experimental design to a Serbian bentonite in order to determine the influence of microwave heating on the acid-activation process. The effect of acid activation under microwave irradiation on the textural and structural properties of bentonite was studied as a model reaction. A mathematical, second-order response surface model (RSM) was developed with a central composite design that incorporated the relationships among various process parameters (time, acid concentration, and microwave heating power) and the selected process response of specific surface area of the bentonite. The ranges of values for the process parameters chosen were: time, 5–21 min; acid concentration, 2–7 M; and microwave heating power, 63–172 W. The effect of individual variables and their interaction effects on the textural and structural properties of the bentonite were determined. Statistical analysis showed that the duration of microwave irradiation was less significant than the other two factors. The model showed that increasing the time and acid concentration improved the textural properties of bentonites, resulting in increased specific surface area. This model is useful for setting an optimum value of the activation parameters for achieving the maximum specific surface area. An optimum specific surface area of 142 m2g−1 was achieved with an acid concentration of 5.2 M, activation time of 7.4 min, and microwave power of 117 W.

Porotic paradox: distribution of cortical bone pore sizes at nano- and micro-levels in healthy vs. fragile human bone

Bone is a remarkable biological nanocomposite material showing peculiar hierarchical organization from smaller (nano, micro) to larger (macro) length scales. Increased material porosity is considered as the main feature of fragile bone at larger length-scales. However, there is a shortage of quantitative information on bone porosity at smaller length-scales, as well as on the distribution of pore sizes in healthy vs. fragile bone. Therefore, here we investigated how healthy and fragile bones differ in pore volume and pore size distribution patterns, considering a wide range of mostly neglected pore sizes from nano to micron-length scales (7.5 to 15000 nm). Cortical bone specimens from four young healthy women (age: 35 ± 6 years) and five women with bone fracture (age: 82 ± 5 years) were analyzed by mercury porosimetry. Our findings showed that, surprisingly, fragile bone demonstrated lower pore volume at the measured scales. Furtnermore, pore size distribution showed differential patterns between healthy and fragile bones, where healthy bone showed especially high proportion of pores between 200 and 15000 nm. Therefore, although fragile bones are known for increased porosity at macroscopic level and level of tens or hundreds of microns as firmly established in the literature, our study with a unique assessment range of nano—to micron-sized pores reveal that osteoporosis does not imply increased porosity at all length scales. Our thorough assessment of bone porosity reveals a specific distribution of porosities at smaller length-scales and contributes to proper understanding of bone structure which is important for designing new biomimetic bone substitute materials.Graphical Abstract

Study of the effect of Mg(II) addition and the annealing conditions on the structure of mesoporous aluminum oxide using Plackett–Burman design

A statistical design was used to investigate the effect of various pro- cessing conditions on the structure of sol-gel derived Mg(II) doped alumina. Six process variables were selected based on the Plackett-Burman design: concentration of magnesium nitrate, time and temperature of alcohol evapor- ation, temperature and time of annealing and heating rate were changed at two levels. For every set of conditions, samples with different specific surface area and degree of crystallinity were obtained. Analysis of the results showed that the annealing temperature, heating rate and concentration of magnesium nitrate were the main factors affecting the average crystallite size of the predominant alumina phase. In the case of the specific surface area, two of selected six variables had pronounced effects; however, the temperature of annealing was more effective than others. The present results showed that the proposed model that uses crystallite size as a response variable is preferable to other research.

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the templates channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.