SESSION B - INDUSTRIAL AND ENVIRONMENTAL APPLICATIONS OF NANOMATERIALS

Given the widespread use of engineered nanoparticles (ENPs) in consumer goods, a large portion of these materials will soon go into the waste stream; potentially, to soil and sediments or added directly to agricultural lands via biosolids. Preliminary data from several research groups have shown that ENPs may have direct impact on food safety and the food chain. However, our knowledge about detection and characterization of ENPs in the environment, especially in terrestrial environments, is still not well understood. Synchrotron techniques are nondestructive analytical tools that can provide information about the crystal structure, elemental (chemical) composition and physical properties of the ENPs. By using the synchrotron facilities at Stanford University, and the European Synchrotron Facility (Grenoble, France), we have obtained clear evidence of the presence of CeO2 NPs soybean (Glycine max). Other XAS studies have shown that TiO2 ENPs are absorbed by the roots and translocated to the leaves in cucumber plants. Our X-ray absorption spectroscopy results demonstrated that CeO2 and TiO2 ENPs are potentially transmitted to the next plant generation, threatening the environmental and human health.

Suggested References:
[1] Servin, A. Castillo-Michel, H., Hernandez-Viezcas, J.A., Peralta-Videa, J.R., Gardea-Torresdey, J.L. 2012. Synchrotron micro-XRF and micro-XANEs confirmation of the uptake and translocation of TiO2 nanoparticles in cucumber (Cucumis sativus) plants. Environmental Science and Technology 46(14), 7637-7643.
[2] Priester, J.H., Ge, Y., Mielke, R.E., Horst, A.M., Cole Moritz, S., Espinosa, K., Gelb, J., Walker, S.L., Nisbet, R.M., An, Y.-J., Schimel, J.P., Palmer, R.G., Hernandez-Viezcas, J.A., Zhao, L., Gardea-Torresdey, J.L., Holden P.A. 2012.Soybean Susceptibility to Manufactured Nanomaterials: Evidence for Food Quality and Soil Fertility Interruption. PNAS 109(37) E2451-E2456.
[3] Hernandez-Viezcas, J.A., Castillo-Michel, H., Andrews, J.C., Cotte, M., Rico, C.M., Peralta-Videa, J.R., Priester, J.H., Holden, P.A., Gardea-Torresdey, J.L. 2012. In situ synchrotron fluorescence mapping and coordination of CeO2 and ZnO nanoparticles in soil cultivated soybean (Glycine max). ACS Nano DOI: 10.1021/nn305196q.

Nanoscale Zero Valent Iron (nZVI) can be protected from rapid oxidation by simple oxidic layer. Such layer allows long-term nZVI storage on air, safe delivery and simple manipulation. On the other hand the material must be activated prior its application. The activation process involves leaving prepared nZVI/water slurry in a concentrated state (usually 20% wt.) for 48 hours. The activation process initiates nZVI reactivity with contaminants and improves mobility as well. In the present research three particles with different oxide shell thickness were compared in order to assess reactivity in water and with Cr6+, a representative contaminant. Results showed a diminution in Cr6+ reduction capacity with the increase of shell thickness in unactivated particles. The activation process was able to create irregularities into the protective oxide shell with thickness <3.4 nm and to increase Cr6+ reduction significantly.

In this study, we present the application of polycrystalline Boron doped diamond (BDD) thin films in the field of water micropollutants degradation. Conventional waste water treatment plants cannot degrade the majority of new types of pollutants. Hence the powerful methods for the decontamination of drugs, psychoactive substances and antibiotics waste have received increasing attention over the past decade. The BDD anode is the best electrode with low adsorption properties, remarkable corrosion stability even in strongly acidic media and extremely high O2, OH radicals evolution. Effective degradation process of the legal and illegal drugs in water (Methamphetamine, Cocaine, Cotinine, Tramadol, Diclofenac, etc.) were presented by LC-MS/MS in waste water from the output of a sewage treatment in Bratislava.
ACKNOWLEDGEMENTS:
This work was financially supported by the grants of No. 1/0785/14, Slovak Research and Development Agency under the contract No. APVV-0365-12.

The aim of this study is the acid dye removal by polyamide 6 nanofibrous membrane (PNM). An apparatus in the continual dead-end mode was applied to evaluate the efficiency of membrane. PNM with areal density 1.3 g/m2 and C. I. Acid Blue 41 were used. The surface morphology of PNM before and after filtration was observed by scanning electron microscope (SEM), the concentration of dye solutions before and after filtration was tested by an UV-Vis spectroscopy. The dye removal capacity and dye removal kinetics of PNM were calculated based on the absorbance of solutions. The results showed that the dye removal rate of PNM was about 99% in the very beginning process. After 10 minutes, the filtration process reached the steady state, and the dye removal rate of PNM was less than 2%. The dye removal capacity of PNM increased as the increase of feed dye solution concentration and adding one more layer PNM.

Activated carbon (AC) from gum kondagogu (GK), a natural tree gum, was prepared by a carbonization/chemical activation process. The nanocomposite fibres contain AC, poly vinyl alcohol (PVA) and GK, which were fabricated by electrospinning. The system and the process parameters of the electrospinning were optimised to obtain smooth and uniform AC-GK/PVA composite nanofibres. The composite nanofibres with a mean diameter of 250±55 nm were obtained after cross-linking with heat treatment. Hydrophobic composite nanofibres of AC-GK/PVA were created using methane plasma treatment. Various microscopic and spectroscopic characterization techniques were used to characterize the composite nanofibres. The adsorption efficiencies of both AC-GK/PVA and GK/PVA composite nanofibres were tested on toxic metal contaminants (Pb2+, Cd2+, Cu2+, Ni2+, Zn2+, total Cr and As) in an aqueous solution and were assessed quantitatively using ICP-AES and ICP-MS. The renaissance and reusability of the composite nanofibres for consecutive operation were evaluated. The large surface area to volume ratio, extremely high stability, multi-functional groups and increased hydrophobic character of the prepared AC-GK/PVA composite nanofibres were found to be the key factors for the high adsorption/removal of toxic metals contaminant from the aqueous environment.

With more than 25 years of experience serving the semiconductor industry, CS CLEAN SYSTEMS is a reliable partner for exhaust gas abatement, with a primary focus on dry bed absorption. At the core of our technology are our proprietary CLEANSORB granulates, which safely convert toxic, corrosive, and pyrophoric gases to stable solid by-products. In addition to the silicon and compound semiconductor industries, we also serve the rapidly-growing photo voltaic and MEMS sectors. More than 5,000 installations worldwide testify to customer confidence in CS CLEAN SYSTEMS‘ unique products and services. CS CLEAN SYSTEMS is a truly global company with research and development, manufacturing and marketing located in dedicated centers of competence located throughout Europe, Japan, USA, and the Far East. CS CLEAN SYSTEMS is serving the nanomaterials world by treating exhaust gas streams of ALD and CVD processes used for the production of e.g. carbon nanotubes, nanodiamonds, 2-D materials like molybdenum disulfide and diselenide.

Multicomponent K-doped Co-Mn-Al mixed oxide deN2O catalysts were prepared by calcination of Co-Mn-Al layered double hydroxide and following impregnation by KNO3. Tuning of the catalyst properties was guided by catalytic tests of N2O decomposition including the effect of water, oxygen and NOx inhibitors, TPR-H2 and in-situ work function measurements. The optimal composition of the catalyst revealed in the laboratory experiments was successfully reproduced in large scale synthesis and shaping. In the pilot plant tests (130 days), high output in N2O removal from the tail gases of the nitric plant was reached.
ACKNOWLEDGEMENTS:
This work was financially supported by the Technology Agency of the Czech Republic (project no. TA 01020336) and by the Ministry of Education, Youth and Sports of the Czech Republic in the “National Feasibility Program I”, project LO1208 “Theoretical Aspects of Energetic Treatment of Waste and Environment Protection against Negative Impacts”.

Biogas production from renewable sources has the greatest potential to guarantee energetic demands of sustainable society. Unfortunately, biogas contains about one third of CO2 and other contaminants. Therefore, an efficient purification is needed to obtain sufficiently pure methane for further use. Recently, polymer mixed matrix membranes (MMMs) with embedded liquid or solid additives are seen as promising candidates for radical improvement in gas separations[1]. The major issue for developing effective gas separation membranes with enhanced performance is successful overcoming of well-known trade-off[2]. An achievement of high permeability and selectivity towards the target gas is crucial.
In this work, performance of (i) unique ex-situ controlled tailor-made tunable nano-additives embedding into polyimide based MMMs and (ii) of PES based MMMs with 75 wt. % of ionic liqud 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]) targeted for CO2/CH4 separation from biogas is presented. Nano additives based on zeolite-imidazole frameworks (ZIF-8), Fe3O4 particles and surface-modified SiO2 hollow spheres were imbedded into 4,4´-oxydiphtalanhydride (ODPA) and 4,4´,4´´-triaminotriphenylmethane (MTA) (1:1 mol/mol). Properties of additives and membranes were tested via gravimetric and time-lag fixed volume pressure increase methods[3].
ACKNOWLEDGEMENTS:
The financial supports of Czech Science Foundation (grant GAČR No. 15-06479S) and Czech Ministry of Education, Youth and Sports - project KONTAKT II - LH14006 and a specific university research MSMT No 20/2015 are greatly appreciated.
REFERENCES:
1. P. Bernardo, E. Drioli, G. Golemme; Ind. Eng. Chem. Res. 48 (2009) 4638.
2. L. M. Robeson, J. Membr. Sci. 320 (2008) 390.
3. A. F. Bushell, et al. J. Membr. Sci. 427 (2013) 48.

Understanding the relationship between properties and performance of nanomaterials has always been a major challenge for Materials Science. Due to the particle size-dependent effects, nanomaterial’s properties can substantially deviate from those of the same substance on a micron- or larger scale, which explains strong interest to nanomaterials as novel building blocks for modern technologies.
Because of its remarkable electronic, mechanical, and optical properties, graphene has generated a significant research interest and attracted a lot of investments in such areas as advanced electronic sensors, displays, transistors, batteries, supercapacitors, fuel cells, as well as photovoltaic (solar) systems for energy generation.
In order to unravel graphene’s performance details and to determine its behavior in real applications, researchers require high-quality materials with reproducible performance characteristics on the scale, which exceeds capabilities of a conventional research laboratory. In general, an efficient transfer of novel technologies from a small research scale to a much large prototype scale and beyond proceeds through intermediate steps, which include an initial scale up, validation, reproducibility studies and final scale up to the manufacturing scale available at Sigma-Aldrich.
The presentation highlights Sigma–Aldrich’s R&D and scale-up capabilities in the area of graphene and other inorganic nanomaterials. It will discuss the current product portfolio focusing on materials for electronic, magnetic and optical applications.

Photoactive nanomaterials are of considerable interest to the scientific community for many years and their importance increases with increasing environmental pollution. This study is focused on ZnO/clay photoactive nanocomposites where ZnO nanoparticles are the photoactive components and the clay serves as a cheap and chemically stable matrix on which the ZnO nanoparticles are anchored. Anchoring nanoparticles on the matrix is often used method allowing easier handling of the nanocomposite (clay particles are of micrometric sizes) in comparison with pure nanoparticles. Moreover, nanoparticles anchored on the matrix do not represent such an environmental and healts risks (due to the reduced mobility) as pure nanoparticles. Two clays were used in this study: kaoline KKAF and Moroccan clay ghassoul, unique mixture of stevensite and sepiolite, from Jbel Ghassoul deposit in Morocco. Photoactive nanocomposites were prepared from ZnCl2 and NaOH precursors using a simple hydrothermal method. Resulting samples were dried and calcined at 600 °C for 1 h. The precursors:clay ratios were chosen so that the nanocomposites contained 50 wt.% of ZnO. Nanocomposites were characterized using X-ray powder diffraction, UV-VIS diffuse reflectance spectroscopy, and scanning electron microscopy techniques. Photodegradation activities were evaluated by discoloration of acid orange 7 aqueous solutions under UV irradiation. Sizes of crystallites and band gap energies were determined. Mutual comparison of the properties of both nanocomposites and also the comparison with pure ZnO nanoparticles were carried out.

ROPLASS company is a Czech producer of plasma sources for plasma modification of various materials. ROPLASS plasma systems are based on the technology of so-called Diffuse Coplanar Surface Barrier Discharge (DCSBD). This type of discharge is suitable for production of plasma systems with different geometry and with different plasma area depending on the application needs.
A special remark should be noted, that the DCSBD plasma systems utilize the visually diffuse non-thermal plasma. This means that the risk of thermal damage of processed substrates is minimized. Moreover, the active plasma layer is of sub-millimetre thickness resulting in unique achieved power densities of more than 100 W/cm3. This enables very fast and efficient plasma processing various materials. Planar surfaces as glasses, ceramics, metals, woods and also woven/non-woven textiles, papers, polymeric foils, rubbers, leather, etc. are only a few examples of materials very suitable for effective plasma modification using presented DCSBD plasma systems.
The overview of DCSBD plasma technology will be presented together with the examples of applications - from research to industry. The typical usage scenarios of DCSBD plasma technology will be given for the nano-modifications of solid surfaces and also for the treatment of solid surfaces before immobilization of different coatings and nanoparticles with emphasis on applications in the field of textile, electrotechnical and construction industry.
Throughout the conference the live exhibitions of plasma treatment of solid surfaces will be presented using easy-to-use hand-held plasma system ROPLASS RPS40-25. So do not forget to visit our exhibition stand!

Adsorption using activate carbon (powdered or granular) is widely used for dye removal from wastewaters. However, it's very expensive because it need regeneration and reactive procedure. In this way our study is focused on characterisation, analysis and application of activated carbon issued from the cryogenic grinding of olive stones.
The first part concerns the determination of the characteristics of activated carbons obtained from the olive stones which were reduced to small grounds by using a cryogenic grinding with liquid nitrogen. Chemical activation of this precursor at 450 °C was adopted by using the phosphoric acid as dehydration agent at 2/1 impregnation ratio. FTIR was carried out to identify the surface groups. The microscopic structure and surface were examined by a SEM/EDX and BET respectively. Results showed surface area and pore volume approaching 1000 m2/g and 1 cm3 respectively. The SEM imaging shows a microcrystalline structure and a highly developed porosity.
In the second part we investigate the feasibility of adsorption of Methylene Blue on the activated carbon prepared from olive stones. The stock solution was prepared by dissolving Methylene Blue in 1000 ml distilled water. The experiments were carried out at ambient temperature, with the initial concentration varying from 5–50 mg/l. The absorbance of dye solution was determined by a spectrophotometer at 665 nm wavelength. The amounts of dye adsorbed were calculated from the concentrations in solutions before and after adsorption.
Activated carbon issued from the cryogenic grinding of the olive stones seems to be a promising adsorbent for removal of the cationic dye Methylene Blue from water. Indeed, 5 g of adsorbent could almost completely decolorize solution of Methylene Blue (50 mg/l).

As X-Ray Microscopy is extended from the Synchrotron community to the laboratory, correlation to other imaging techniques is vital for many reasons. Partly due to the need to show where the technique fits in the landscape of multi length scale imaging and partly to show the efficacy of the application by correlating similar imaging modalities. We will show through various applications from the fields of Materials, Life Science, Geo Science, and Electronics how X-Ray microscopy complements existing technology, not replacing any technique, but adding further information to gain a deeper understanding of the scientific application. The technical possibility to perform in-situ and XRD (X-Ray Diffraction) experiments makes the X-Ray Microscope to a versatile high resolution 3D imaging device.