Guido Cerri

Influence of zeolites on the sintering and technological properties of porcelain stoneware tiles

Low-cost zeolitic rocks are promising substitutes for feldspathic fluxes in ceramic bodies, since their fusibility, modest hardness and high cation exchange capacity (CEC) should improve grinding and sintering. Five large-scale Italian deposits of natural zeolites with different mineralogy were characterised and tested in porcelain stoneware bodies. Their behaviour during processing was appraised and compared with that of zeolite-free bodies. Zeolites increased the slip viscosity during wet grinding, causing a coarser grain size distribution and consequently some drawbacks in both unfired and fired tiles. After overcoming this hindrance by dry grinding of zeolite rocks, the technological behaviour of zeolite-bearing tiles appear to be similar to that of current porcelain stoneware, though with larger firing shrinkage and residual closed porosity.

Methods of determining cation exchange capacities for clinoptilolite-rich rocks of the Logudoro region in Northern Sardinia, Italy

Clinoptilolite-rich materials from widespread pyroclastic and epiclastic deposits of northern Sardinia were investigated to assess their cation exchange properties and to find the most reliable experimental method to determine their cation exchange capacity (CEC). The CECs were evaluated using a cross exchange method (CEM) and a batch exchange method (BEM). The CEM resulted in values 30–35% lower than the theoretical or expected CEC calculated from the chemical analyses of the clinoptilolite-rich materials. The BEM resulted in CECs 6–12% lower than the expected CECs. Various parameters, such as the grain-size of powders (<64 µm and 125–250 µm) and replacement cation (Na+, K+, Li+, Cs+, NH4+, Ca2+, Mg2+, Sr2+) were evaluated in order to optimize the cation exchange process, i.e. enhance complete exchange. The particle size did not affect the exchange process appreciably. The type of replacement cation had a substantial effect on the experimental CEC determined by the BEM. The NH4+ and Cs+ replacement solutions resulted in the best experimental CECs ranging between 75% and 94% of the theoretical CEC with NH4+ as the replacement cation and 79% and 88% of the theoretical CEC with Cs+ as the replacement cation. The exchange efficiency was also measured as a function of ammonium concentration in the replacement solution (0.50, 1.00, 2.00 and 3.00 M). Experimental CECs ranged between 94% (0.5 M NH4Cl solution) and 99% (1 M NH4Cl solution) of the theoretical CEC for one epiclastic rock sample and between 79% (3 M NH4Cl solution) and 87% (2 M NH4Cl solution) of the theoretical CEC for one pyroclastic rock sample.

Solid microparticles based on chitosan or methyl-β-cyclodextrin: a first formulative approach to increase the nose-to-brain transport of deferoxamine mesylate

We propose the formulation and characterization of solid microparticles as nasal drug delivery systems able to increase the nose-to-brain transport of deferoxamine mesylate (DFO), a neuroprotector unable to cross the blood brain barrier and inducing negative peripheral impacts. Spherical chitosan chloride and methyl-β-cyclodextrin microparticles loaded with DFO (DCH and MCD, respectively) were obtained by spray drying. Their volume-surface diameters ranged from 1.77 ± 0.06 μm (DCH) to 3.47 ± 0.05 μm (MCD); the aerodynamic diameters were about 1.1 μm and their drug content was about 30%. In comparison with DCH, MCD enhanced the in vitro DFO permeation across lipophilic membranes, similarly as shown by ex vivo permeation studies across porcine nasal mucosa. Moreover, MCD were able to promote the DFO permeation across monolayers of PC 12 cells (neuron-like), but like DCH, it did not modify the DFO permeation pattern across Caco-2 monolayers (epithelial-like). Nasal administration to rats of 200 μg DFO encapsulated in the microparticles resulted in its uptake into the cerebrospinal fluid (CSF) with peak values ranging from 3.83 ± 0.68 μg/mL (DCH) to 14.37 ± 1.69 μg/mL (MCD) 30 min after insufflation of microparticles. No drug CSF uptake was detected after nasal administration of a DFO water solution. The DFO systemic absolute bioavailabilities obtained by DCH and MCD nasal administration were 6% and 15%, respectively. Chitosan chloride and methyl-β-cyclodextrins appear therefore suitable to formulate solid microparticles able to promote the nose to brain uptake of DFO and to limit its systemic exposure.

Nanocomposite films and coatings using inorganic nanobuilding blocks (NBB): current applications and future opportunities in the food packaging sector

The aim of this review is to provide an in-depth overview on the use of inorganic nano-sized entities for the generation of nanocomposite materials in the form of films and coatings for food packaging applications. According to recent trends toward “green” strategies, special focus has been dedicated to the development of nanocomposite coatings obtained using biopolymers as the main polymer matrix. After a first introductive part, the discussion has been addressed to the use of inorganic fillers, metals and metal-oxides, zeolites, and graphene. For each class of filler, a first ‘in-depth’ description of the most relevant physicochemical properties for the food packaging sector has been followed by case-by-case references to recent developments and envisaged implementations. The technical aspects that may be crucial in the design and end use of (bio)nanocomposite coatings have been covered in the last part of this work, which also includes an updated list of current applications on nano-sized inorganic fillers in the food packaging field.

THERMAL BEHAVIOR OF NATURAL AND CATION-EXCHANGED CLINOPTILOLITE FROM SARDINIA (ITALY)

The thermal behavior of two clinoptilolites from an epiclastic and a pyroclastic deposit of central-northern Sardinia and of their exchanged forms (Li, Na, K, Cs, Mg, Ca, Sr and ammonium) were investigated by differential thermal analysis and thermogravimetry up to 1000°C. Their thermal stability was studied by evaluating the residual crystallinity (expressed as rehydration capacity) after 2 h thermal treatments at 450, 600 and 900°C. The water loss at 1000°C was linearly related to the radius (r) and the charge (z) of the exchangeable cations by the equations r2/z or r3/z, which are proportional to the inverse of the charge density over the surface or to the charge density over the volume of the cations.The cation composition plays a crucial role in determining the thermal behavior of clinoptilolite. The presence of cations such as Cs or K, which have low surface or volume charge densities, was found to increase the thermal resistance. In particular, the crystallinity of Cs- and K-exchanged forms of both clinoptilolites was not affected by thermal treatment at 450°C and was only slightly reduced by thermal treatment at 600°C.Predicting the thermal behavior of natural and cation-exchanged forms of these clinoptilolites can provide useful information for possible applications in catalysis, in the case of high thermal stability, or for thermal transformation into ceramics or lightweight aggregates.

Development of solid nanoparticles based on hydroxypropyl‐β‐cyclodextrin aimed for the colonic transmucosal delivery of diclofenac sodium

Objectives  Nanoparticles were designed for the oral administration and transmucosal colon delivery of drugs.

Self-assembled nanostructured biohybrid coatings by an integrated ‘sol–gel/intercalation’ approach

The combination of sol–gel technology and intercalation was investigated in this study as a strategy to develop bionanocomposite hybrid materials in the form of coatings with specifically intended oxygen barrier properties. To this goal, the exopolysaccharide pullulan was used as the organic phase, whereas tetraethyl orthosilicate (TEOS) and Na+–montmorillonite (MMT) were used as the metal alkoxide precursor and the nanobuilding blocks (NBB) for the sol–gel technology and the intercalation process, respectively. Complementary information from XRD and TEM analyses disclosed a new supramolecular organization arising from the self-assembly of NBB and pullulan, with the latter apparently intercalated between the clay platelets. Although affected by a rise in haze, the hybrid coatings exhibited outstanding oxygen barrier properties, with permeability coefficient values (P′O2) ranging from 0.89 mL μm m−2 (24 h)−1 atm−1 for a filler volume fraction (ϕ) = 0.017 to an impressive 0.15 mL μm m−2 (24 h)−1 atm−1 (ϕ = 0.095) under dry conditions. Modeling of P′O2 suggested a very tight structure under dry conditions, which yielded an apparent clays aspect ratio (α) ∼50, whereas in the hydrated state a more realistic α ∼ 100 was restored. This finding was further supported by SEM analysis, which also highlighted partial embrittlement of the final hybrid coatings.

Zeolitic Tuffs as Raw Materials for Lightweight Aggregates

The aim of this research is to assess the possible use of Italian zeolitic rocks for the production of lightweight aggregates. In particular, both the expansion at high temperature and the technological features of fired products were investigated. Fifteen zeolite-bearing volcanoclastites from Northern Sardinia and three zeolitized tuffs from Campania and Tuscany (Sorano and Campanian ignimbrites and Neapolitan Yellow Tuff) were taken into account. The firing expansion turned out to be mainly dependent on the chemical composition (especially SiO 2 and fluxing oxides such as Fe 2 O 3 , Na 2 O, K 2 O, MgO and CaO) and the water content (largely related to the zeolite amount) of the raw materials. Other relevant parameters were the temperature of maximum expansion (ranging between 1350 and 1500 °C, without additives) and soaking time (between 2 and 5 min). Some products are highly impervious to water (water absorption below 1%) and exhibit a considerable firing expansion (> 100% in volume), a low bulk density (0.5–0.7 g•cm −3 ) and fair technical properties (loose weight and strength of particles). These encouraging results make some of the investigated tuffs interesting raw materials for the production of lightweight aggregates.

The effect of formulative parameters on the size and physical stability of SLN based on “green” components

Abstract Cocoa butter (CB) is a largely used excipient in pharmaceutical field. Aim of this work was to set formulative parameters for the preparation of SLN based on “green” lipid matrix for drug delivery as natural, both human and environmental safe systems. Double emulsion technique (w1/o/w2) was selected for SLN preparation. The effect on the dimensional properties of different surfactants (Tween 80 and PEG 40 monostearate) and co-surfactants (PEG400 monostearate, Emulium® Kappa2 and Plurol®Stearique) at different concentrations was evaluated. Stability tests were performed. SLN dispersions were exsiccated and the effect of the dried process on SLN size was evaluated. The influence of temperature on SLN dimensions was investigated at 37 °C. MTT test was performed on raw materials and formulations. The w1/o/w2 is suitable, rapid and economic technique for the preparation of CB SLN. Tween 80-Plurol Stearique combination gives the best results: particles size less than 400 nm and PI of about 0.4 are obtained when PS 2% is used. Both raw materials and formulations are safe. The importance to evaluate the effect of different surfactant and/or co-surfactant on the dimensional properties of SLN is evident by selecting substances with preferable safety profiles, and favorable environmental properties to develop stable “green” SLN.

Distribution of Industrial Minerals in Sardinia (Italy): Clinoptilolite Bearing Rocks of the Logudoro Region

Volcaniclastic products of Northern Sardinia (Italy) turned out to be affected by diffuse zeolitisation processes. About 130 samples, representative of the identified formations (pyroclastic flows and epiclastic deposits), were collected in order to evaluate the distribution of zeolitic phases. Clinoptilolite was the most widespread zeolite, whereas mordenite and chabazite rarely occured. A quantitative evaluation performed by the Reference Intensity Ratio (RIR) and Rietveld methods indicated that about 30% and 44% of samples from pyroclastic flows and epiclastic deposits, respectively, have a zeolite content higher than 50%.