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NATIONAL R&D INSTITUTE FOR NON-FERROUS AND RARE METALS NANOSTRUCTURED MATERIALS LABORATORY

The Nanostructured Materials Laboratory is founder member of the Romanian Technological

Platform for Nanomedicine (RO-NANOMED). The Laboratory was recognised and funded as a Centre for Excellence in the frame of the National Virtual Centre for Nano-bio-technologies CENOBITE.

HISTORY: Founded under the name of Ceramic Materials Group in 1995, the primary objective was to develop new chemical methods for obtaining ceramic nanocrystalline powders by using non-ferrous metals starting from soluble inorganic salts studied in the institute. From 2005 following the accreditation as National Institute the group was enlarged and transformed to Nanostructured Materials Laboratory.

MISSION: Fundamental and applied research and development works in the field of chemical methods for synthesis of ceramic, metal-ceramic and hybrid composite nanomaterials for functional and structural applications with emphasis to the following fields:

nano-bio-materials (ceramics, composites, hybrid inorganic-organic systems) for regenerative medicine and tissue engineering.

thin films and advanced coatings by hydrothermal – electrochemical processes and sol-gel colloidal methods;

functionally graded materials

MAIN AREA OF EXPERTISE: Wet chemical synthesis of nanocrystalline ceramic powders (co-precipitation, sol-gel colloidal from inorganic precursors, hydrothermal); chemical synthesis of new hybrid inorganic-organic nanomaterials by in-situ reactions and functionalisation; development of chemical processing for thin/thick nanocrystalline ceramic films: sol-gel, hydrothermal/electro-depositing processes; synthesis of ceramic matrix composite nanomaterials; synthesis of core/shell structured powders; processing of ceramic and composite powders; fundamental studies on the mechanisms and kinetics of the synthesis processes.

RESEARCH TEAM: A team of 4 senior researchers with complementary expertise in Materials Science and Applied Physical Chemistry, 2 PhD students (Materials Science and Applied Physical Chemistry) one engineer, 2 technicians working jointly together and some students preparing license diploma and master degree in Materials Science, in continuous

interactions with the Institute’s Centre for Technology Transfer in Advanced Materials (CTT AVANMAT) for SMEs driven applications. INTERNATIONAL NETWORKS: The laboratory is member in the following networks:

G5RT-CT-2001-05024 European Network Polar Electronic Ceramics-“POLECER” (2001-2007); COST 525–“Advanced Electroceramics: Grain boundary engineering” (Roxana Piticescu was

member in the management committee 2004-2005); COST D30 -“High Pressure Tuning of Nanomaterials” (Roxana Piticescu and Robert Piticescu

are members in the management committee 2004-2007); ECO-NET (EGIDE) “Functional Nanomaterials”- CNRS/PROMES Font Romeu France, IMNR

Romania, UNIPRESS Warsaw Poland and Inst. Solid State Physics, Univ.Riga, Latvia (2005-2006).

NATIONAL NETWORKS: The nanostructured materials laboratory was member of “Virtual Network of Centres of Excellence in Nanobiotechnologies-CENOBITE” (financed from 2002 to 2005 by National Programme for Advanced Materials, Micro and Nanotechnologies MATNANTECH) and participate in the Research of Excellence Programme CEEX “Integrated research network Nano-biotechnologies for Health - RO-NANOMED” (2005-2008). Other National networks financed by CEEX Programme with the participation of INCDMNR are: “Services network for structuring and characterisation at nanometric scale for converging technologies - NANOSCALE-CONV” and “Advanced nanocomposite materials with antibacterial, self-cleaning and solar energy concentrators applied in building and ambient improvement - NANOAMBIENT”.


PARTICIPATION TO INTERNATIONAL CONTRACTS NATO SfP 974054 “Zirconia Nanomaterials” (2000-2004) European PHARE Technology Transfer and Quality Management 1135 (2000) GRD1-99-1-1008V-1 “Microscale fabrication of graded materials components” (2002-2004) G5ST-CT-2002-50328 Craft METMICOATED (2003-2005) SOLFACE – Optonanos, FP6 Infrastructure Project (2004-2005) IP 026467 “Direct Ultra-precision Fabrication - MANUDIRECT” (2006-2010) Bilateral project “Research and Development of new metal-ceramic composites with core-shell

structure”, IMNR and Politecnico di Torino, Italy (2000-2004) Bilateral project “Hybrid Nanostructured thin films for biosensors”, INCDMNR and INASCO

Athens, Greece (2006-2007)

MAIN EQUIPMENTS

Most of the equipments have been installed in the last 3 years in modernised endowments:

Clean room for the synthesis of new nano-biomaterials; Two clean rooms for the synthesis and processing of ceramic and composite powders

Synthesis and processing equipments: Computer-controlled hydrothermal-electrochemical system for synthesis of nanopowders and

electrodepositing of thin films (Unique in Europe); Sol-gel colloidal synthesis pilot plant and spin-coater equipment. Powders processing equipments: ball milling, hydraulic press, ovens, chamber furnace

CARBOLITE (air/controlled atmosphere) at 18000C, tubular furnace MHI (air/controlled atmosphere/vacuum) at 17400C.

Own specific characterisation equipment: UV-VIS spectrometer PG Instruments T90; Thermal kinetic behaviour characterisation of composite materials by DSC-F3 MAIA Netzsch ; Nanoseizer ZS90 Malvern, viscozimeter, titrator system and soft (measurement of grain sizes, zeta potential, molecular mass); Software for thermodynamic predictions; software for electrochemical studies Collaboration with the chemical and structural characterisation laboratory of the institute (Inductive Coupled Plasma Spectrometer Spectroflame, Germany and Direct Coupled Plasma Spectrometer-Beckman USA; C, N and O analysis LECO Germany, gravimetric chemical analysis)

ACHIEVEMENTS IN THE FIELD OF NANOMEDICINE

Certification of a laboratory for chemical and physical analysis for nano-bio-materials characterization – Acronym NANOBIOMATLAB

Research for Excellence Project no. 199/2006– Module dedicated to the development of research infrastructure and development of accredited characterisation methods (2006-2008) Location: INCDNMR-IMNR, project director Adrian M. Motoc, web page: www.imnr.ro/nanobiomatlab

The project aims to improve the endowment of an analytical laboratory from a national R&D institute by purchasing high performance equipments and subsequently to certify the same laboratory in the filed of chemical analysis (atomic absorption) and structural characterisation (X ray diffraction). The analytical methods will be developed for nano-biomaterials, these products being under the European regulations regarding health: European Directive 93/42/CEE concerning medical devices, modified by Directives 98/78/CE, 2000/70/CE,

2001/104/CE, 2003/12/CE and Regulation 1882/2003 and series of corresponding standards


EN ISO 10993 for Biologic Evaluation of medical devices. The main goals of the project are: adjustment of chemical and structural characterization methods of conventional materials to nanostructured materials; development and optimisation of chemical and structural characterization methods for nanostructured ceramic biomaterials; formation of nano-biomaterials database, based on chemical and phase analysis performed with high accuracy and reproducibility; development of performant equipment base for chemical and structural analysis, specific for the proposed tests; High quality equipments (mainly XRD and AAS) have been installed. This project also deals with designing and implementation of the quality management system for the laboratory according to SR EN ISO/CEI 17025:2005, and RENAR (Romanian Accreditation Association) certification for the proposed chemical and physical analysis; The laboratory will contribute to the development of specific analytical procedures and best practices related to characterization of new metallic, ceramic, metal-ceramic and hybrid inorganic-organic nanomaterials with main applications in regenerative medicine and tissue engineering.

Advanced Technologies for the synthesis and processing of biocompatible nanocomposite powders- Acronym Bionanocom (2003-2005)

MATNANTECH Project 138(306) Participants: IMNR (Project Director Dr. Roxana M. Piticescu), Inst. Macromolecular Chemistry

Petru Poni Iassy, Inst. Chemical Pharmaceutical Research Bucharest, SENCO PLASMA CER srl, RO. The main objectives of the project were the development of non-conventional hydrothermal

methods for obtaining of biocompatible composite nanostructured powders in the system calcium phosphate-polymers, development of biocompatible sintered materials for biocompatibility tests, fundamental researches on the interactions in hybrid systems, studies of the correlations between microstructure and biocompatibility properties. Hybrid organic-inorganic nanocomposites were synthesised in situ in hydrothermal conditions at low temperatures and high pressures. FT-IR analysis revealed the formation of a strength bond between organic phase (sodium maleate copolymer with vinyl acetate) and inorganic phase (hydroxyl apatite) with participation of phosphate and hydroxyl groups from hydroxyl apatite. Nanosized particles of about 100 nm were obtained. Both hydroxyl apatite alone and hybrid nanocomposites synthesised in situ in hydrothermal conditions are biocompatible, but they induce morphological modifications whereof it is not possible yet to define their repercussions on the cellular metabolism. Tests of other cellular markers and cells type are required.

The studies have shown an enhanced biocompatibility of the new hybrid materials compared to pure HAP. A patent demand was deposited by participants. Progresses in high pressure synthesis of nanomaterials with special emphasis on new hybrid organic-inorganic nanomaterials for different applications were reported also in COST D30 workgroup actions. Samples with 20% polymer seem to give the best results concerning pH of the medium, cell density, cell morphology and cell viability.

Integrated technology Research Network in advanced biocompatible

structures for dental implants

Research for Excellence Project CEEX 46 Rete-β-dent (2005-2008) Project web page www.imnr.ro/retebdent Participants: INCDMNR (Project Director Dr. Roxana M. Piticescu), Inst. Macromolecular

Chemistry Petru Poni Iassy, University POLITEHNICA-Centre BIOMAT, Institute for Biochemistry Bucharest, Romanian Academy, University of Medicine and Pharmacy Carol Davila Bucharest, National Institute for Materials Physics Bucharest, SITEX 45 srl.

The aim of the project is to obtain advanced structures based on hybride nanocomposites polymer-calcium phosphate as coating materials for different metallic substrates (Ti, TiAl6Nb7, TiAl5Fe2.5), metallo-ceramics having core-shell structure (stainless steel for the core and alumina for the shell) or doped zirconium dioxide, which will be tested from the point of view of biofunctional performances for dental implants applications. The proposed nanostructures to be obtained in the frame of the project, the substrates to be used and also the deposition techniques (hydrothermal-electrochemical and MAPLE) represent an absolute novelty at national level. The hydrothermal-electrochemical technique is also an European priority.

HAP-polymer composite


The main result of the project is represented by the analysis regarding the compatibility between the inovative deposition techniques (hydrothermal-electrochemical and MAPLE techniques), on the one hand and structure, film properties and the strategy to participate in the frame of the NANOMEDICINE technical platform, on the other hand. Human embryonic kidney (HEK293) cells grown on HA-polymer coatings show excellent biocompatibility behaviour: normal morphology, good adhesion and spreading to the substrate, demonstrated by actin filament organization and prominent focal adhesions.

ZrO2 –Y2O3 substrate is stable in fibroblast cell culture. Their components doesn’t present citotoxicity; cells grow at normal parameters, comparable with control substrate.

Integrated technologies for obtaining nanostructured biocomposites with applications in the regenerative medicine of bone tissue

Research for Excellence Project CEEX 16 TECOREMED (2005-2007) Coordinator National R&D Institute for Chemistry and Petrochemistry ICECHIM. In charge of

Project from INCDMNR Director Dr. Roxana M. Piticescu.

The main objective of the project is to obtain and characterise different binary and ternary hybrid nanostructured biocomposites, comparison of their properties and elaboration of a strategy for development of the research in the field of hybrid materials for regenerative medicine. The main role of Nanostructured Materials Lab is the soft chemical elaboration of hybrid nanomaterials based on calcium phosphates, titanium dioxide, silicates and carbon aerogel with different natural and synthetic polymers by in-situ hydrothermal methodologies.

The morphologic structure of the liophilisated matrices allows both on the surface and in situ conjunctive cells adhesion and proliferation. They are micro porous matrices which contain macro, micro, nano pores, similar to extracellular matrix, they allow penetration of the physiological fluids essential for cell growth. Compared with collagen these hybrids are more thermally stable and they have enhanced mechanical properties.

Hybrid nanostructured materials for biosensors and biobanks In the frame of the CEEX Integrated research network Nano-biotechnologies for Health (RO-

NANOMED) and with the support of Romanian-Greek bilateral project, the Nanostructured Materials Laboratory from INCDMNR develops fundamental and applied research activities in order to get a new generation of self-assembly hybrid materials as sintered membranes and nano-structured transparent thin films with controlled selectivity for biological molecules and also for studying their optical, electrical and/or magnetic properties as function of composition, microstructure and adhesion degree of biological cells, the final task being the development of new biomaterials and biosensors with increased biocompatibility. This includes to study “in-situ” functionalisation of ceramic particles (mainly calcium phosphates, alumina and zirconia-reinforced calcium phosphate

HAP+20% collagen

HAP-polymer deposited on TiAlNb by hydrothermal-electrochemical method

HAP-polymer deposited on TiAlNb by spin coating

HAP-ZrO2 deposited on Ti by RF-sputtering

HAP deposited on Ti by MAPLE technique

X 50 collagen X 100 (COLTER with

HAP/ silicate) X 50 (COLTER HAP/ collagen hydrolised)


and doped zinc oxide nanopowders obtained by hydrothermal crystallization) using copolymers, obtaining hybrid compact nanomaterials used as standard samples for characterization of their electric properties and biocompatibility, developing hybrid nanostructured thin films with controlled porosity and mechanical properties by an innovative method (hydrothermal/electrodeposition and by sol gel method on different metallic substrates. Detailed studies will be performed to reveal the influence of main deposition parameters on the characteristics of the films.

Hybrid Nanostructured thin Films for Biosensors Project no. 26 in the frame of Protocol of the joint Research and Technology Programme between Greece and Romania for years 2006-2007

Hydrothermal methods were proposed for the first time to produce new hybrid inorganic/organic nanomaterials. Starting from these new nanostructures non-invasive biosensors based on thin films can be designed. The measurements of dielectric properties are used to characterise the functional properties of the sensor. In this project, some electrical tests were performed at INASCO-Greece on some samples synthesized, chemically and structural characterized by IMNR. The results were encouraging for the integration of new materials and methods with microelectronic technologies.

Hybrid Nanostructured thin Films for Sensors with potential use in Therapy and Diagnosis

National Programme 4: Research in Partnership (2007-2010) Coordinator National R&D Institute for Non-ferrous and Rare Metals, Project Director Dr. Roxana

M. Piticescu. Project web page www.imnr.ro/hinamasens

The aim of this project consists in: study and development of new hybrid materials based on hydroxyl apatite and organic macromolecular architectures with controlled structures at nanometer level, for sensors with potential applications in diagnosis (dependent on cell type – normal / malign in different stages – which could discriminate against normal cells and transformed cells, especially circulating ones) and therapy (e.g. monitoring restoration of bone tissue after surgical intervention dependent on cell number and ratification of their adhesion on bioactive layer); study and understanding of interactions between hybrid nanostructured material and cell; design and testing of functionality of nanostructured sensors for the measurement of adhesion and cell growth grade in tissue engineering. One of the greatest challenges in the development of analytical means for biology is based on surface design with controlled interactions related to cells. Three innovative directions are developed in the frame of proposed project: structuring of bioactive surface for guided cell growth, integrated studies of biomolecules behaviour at the interaction with nanostructured materials and achievement of sensing element. These directions involve very high risks and they are absolutely new at national level. The main expected results of this project are: fabrication of a device able to control conformation and activity of immobilized biomolecules, development of knowledge in the field of regenerative medicine which covers entirely in all-in-one unit material technology, sensing element and in vitro tests, as well as integration of the activities in the European Technological Platform NANOMEDICINE.

ACHIEVEMENTS IN THE FIELD OF STRUCTURAL CERAMICS Microscale Fabrication of Graded Materials Components

FP5 Contract G1RD-CT2000-00195 Acronym –Micromaking (2002-2004) Coordinator: Prof. Paolo Matteazzi, Consorzio Interuniversitario per lo Svillupo dei Sistemi a Grande Interfase CSGI, Treviso, Italy. In charge of project from IMNR Dr. Robert Piticescu

The general objective of the project can be summarized as to set up a Machine prototype capable of delivering performances in several of the aspects listed below. This was planned to be done by the way of Scientific objectives, Technological Objectives and finally technical achievements. The main objectives of the project are in three different directions, they are as follows. Scientific research objectives: 1) realize nanophased powders materials with particle size in the micron range; 2) conceive a laser/powder head being capable of spatial resolution of better than 50


µm; 3) realize an on-line monitoring system capable of fully control in real time the process variables (temperature and height control); 4) microscale fabrication of materials with gradients resolution in the 10-50 µm range. Technological research objectives: 1) micromaking machine for graded materials and components fabrication, with a productivity in the order of 0.1 g/s; 2) fully dense micromade components with graded materials and functions, and tolerances within the 10 µm range for fabricated volumes in the order of tens to hundreds mm3; Technical achievements: 1) micromade (the top of tool will be micromade) recess tools for the aeronautics fasteners industry, with improved wear resistance and service life; 2) micromade tools inserts (typically around several hundreds mm3) for plastics injection molding, with graded wear resistance, thermal conductivity and cooling channels; 3) process conditions of Micromaking for laser sintering of nanophased powdersProgress in the laser technology, their precision and focused high energy helped the development of new technologies for fabrication of graded materials. The main role of IMNR-Nanostructured Materials Laboratory was to contribute to understanding the role played by initial characteristics of powders, melting and solidification reactions, microstructural evolution, shrinkage behaviour and porosity of final material on the mechanical properties of graded materials for applications in structural applications. Experimental results show that general principles deduced from the sintering theory and experiments have been confirmed and continuous sintered layers based on two powder systems (Fe60-Cu 40 and composite powders 48% Fe-20% Cu-32% Al2O3) could successfully be deposited and sintered with the micromaking laser system on the stainless steel substrates with precision in the range of 50 m required for final applications. Development of new, low cost metal-ceramic composites massive and coating materials, based on PM of ceramic coated metal powders FP 5 CRAFT METMICOATED Project G5ST-CT-2002-50358 (2003-2005) Coordinator: SINTERLOY SpA, Castelamonte, Italy. In charge of project from IMNR Dr. Roxana M. Piticescu

The main objective of the research was to develop new low cost ceramic-coated metal powders with an innovative, versatile and low cost soft chemical technique. These powders with controlled distribution and level of metallic and ceramic components should be used in the manufacturing of composite massive and coating materials with high corrosion, wear and other specific properties for advanced applications. This will help an important number of SMEs from EC members and associated countries involved in the horizontal production of devices and

components to increase their efficiency and profit and face the global market economy. The objectives of IMNR-Nanostructured Materials Group in the project were to develop clean and cost

effective production routes for composite metal ceramic powders, elaborate methods to fabricate composite massive and coating components using cost effective near net shape technologies, obtain micro-uniform dispersion of ceramic reinforcement particles and to study the ways for increasing the wear and corrosion properties of PM materials. Formation of strong chemical bounding between metallic and ceramic phase during synthesis and processing of powders highly improved the adhesion of the ceramic shell to the metallic core, strongly improving mechanical properties of sintered and plasma deposited materials. A kinetic model describing the penetration of Fe into the alumina particles was also proposed to predict the evolution of the spinel layer.

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Research Network for the development of functionally nanostructured graded composites materials for magnetic sensors and thermal barrier coatings

Research for Excellence Project CEEX 290 NANOGRAF (2006-2008) Project web page www.imnr.ro/nanograf Coordinator: INCDMNR (Project Director Dr. Roxana M. Piticescu)

The main objective of the proposed project is to create a research network having as specific objectives: achievement of functionally graded materials for use for thermal barriers coatings (strategic and traditional industries); actuators (microfluide devices for industrial security);elaboration of new synthesis methods in solution at low temperatures and pressures (soft solution processes) to synthesise functionally graded nanostructured composite materials; - elaboration of a feasible technology to process these powders as sintered products;elaboration of the methods for deposition of nanostructured composite powders using TVA technique; elaboration of infiltration technique to synthesise FGNMs with different shapes; elaboration of fast analysis and characterization methods for FGNMs easy to apply for potential end-users; comparative evaluation of the performances of compact materials using the two methods mentioned above (sintering and infiltration technique);evaluation of the performances of the functionally graded materials coatings;the selection of the devices/parts based on functionally graded nanostructured composite materials (structural applications as thermal barriers coatings, magnetic sensors) according to industrial customer requirements; dissemination of the results on the basis of national and international existent partnerships and new ones developed during the project. Composite NiAl5Fe-Al2O3 and NiAl5Co-Al2O3 powders have been synthesised by sol-gel colloidal process after dispersing the intermetallic compound powders and hydrolytic precipitation of alumina in different ratios on their surface, as shown by XRD analysis. These powders are formed from agglomerates of powders with similar sizes as the initial intermetallic ones, bounded by weak bridges of the ceramic component. A small amount of free alumina particles is observed. It was also observed the formation of craters due to the electrostatic repulsion between the particles and electronic current of the microscope. The results show that intermetallic alumina composite particles have been formed during chemical processing and firing. The resemblance between initial intermetallic core and composite particle sizes as well as the small amount of free ceramic particles evidence the formation of a thin nanostructured alumina shell onto the initial intermetallic core particle. The stability of the alumina film onto the NiAl particle surface may be explained by the surface free energy reduction due to the interactions between the surface point defects (in particular substitution of Ni atoms with Al atoms- NiAl and Ni vacancies- VNi) and oxygen atoms from alumina thin nanostructured shell. The project was additionally granted to organise special promotion activities to increase the visibility of Romanian Research in the field of Functionally Graded Materials. (CEEX 117/2006 VIZGRAF< coordinated by Centre for Technology Transfer in Advanced Materials)>

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ACHIEVEMENTS IN THE FIELD OF FUNCTIONAL CERAMICS Zirconia nanomaterials for applications using electrochemical and mechanical

properties NATO Science for Peace Project SfP 97405 (2000-2004). Participants: CNRS/PROMES Font-Romeu France (Project director: Dr. Claude Monty); IMNR RO scientific director Dr. Robert Piticescu); Jozef Stefan Institute, Ljubljana, Slovenia (Prof. Dr. Marija Kosec); Enterprise for Electronic and Electrotechnical Devices IPEE SA Curtea de Arges, RO, Microelectronica SA Bucharest, RO.

The main scientific objective of the proposed project consisted in the development of novel routes for the generation of nanostructured YSZ and zirconia based nanostructured materials with controlled electrochemical and mechanical properties for oxygen and pressure sensors. The most important results obtained were: Modelling and optimization of the hydrothermal synthesis route for obtaining YSZ nanopowders

starting from Zr (IV) soluble complexes; Elaboration of the evaporation-condensation process for obtaining YSZ nanophases in a solar

furnace, establishment of the correlation between initial and final composition of YSZ powders; Obtaining of zirconia reference powders with mean crystallite sizes 4 to 22 nm by

hydrothermal procedures; Development of tape casting for preparation of zirconia membranes; Investigation of the YSZ and YTZP reference materials for ionic conductivity Elaboration of theoretical model based on a new “brick-layer” approach allowing prediction of

ionic conductivity of zirconia nanomaterials vs. grain size. Applications Design of the architecture of oxygen sensors; Design of mechanical pressure sensors; Studies regarding the compatibility of different types of thick film resistors with zirconia

substrates for mechanical pressure sensors. The potential of YTZP nanomaterials resulting from their superior mechanical characteristics was also used in producing pressure gauges with sensitivities 2 times higher than presently alumina sensors.

New perspectives for obtaining knowledge-based nanomaterials and new emerging technologies for a wider field of application have been opened by optimisation of tape casting technology, processing of thin oriented films, densification of nanopowders without significant grain growth. From the scientific point of view, the research lead to a better understanding of complex correlation between the nanostructure and composition of material and their grain size dependant properties and development of new technologies for obtaining thick films of zirconia. Joint Research and Development of barium titanate ceramics for

thermal elements with low energy consumption PHARE Technology Transfer and Quality Management Project 1135 (Jan.-Nov. 2000) Participants: IMNR RO (Project director Dr. Roxana M. Piticescu), CSIC-ICMAB Barcelona (Dr. Xavier Obradors), Enterprise for Electronic and Electrotechnical Devices IPEE SA Curtea de Arges, RO

Soft chemical method based on hydrothermal processes has been used for producing sub-micrometric doped BaTiO3 powders. Standard methods for their processing to sintered ceramic materials and characterisation of semiconducting properties were developed and tested for application to the industrial partner. Mathematical modelling of the synthesis process was used for optimisation of powders composition and microstructure.

TEM of hydrothermal synthesized YTZP

SEM of sintered YTZP materials

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Piezoelectric materials based on perowskite powders and thin films obtained by hydrothermal – electrochemical processes-Acronym CEROPER

MATNANTECH Project 1060180 (2001-2004) Participants: IMNR (Project director Dr. Roxana M. Piticescu), ICPE-CA Bucharest, IPEE SA Curtea de Arges The main tasks of the project were to proposed new methods for obtaining piezoceramic materials

with perowskite structure, experimental works for hydrothermal synthesis of nanopowders and hydrothermal-electrochemical deposition of thin films, development of laboratory methods for nanopowders processing and thin films thermal treatment, characterisation of dielectric properties of some perowskite nanostructured compact materials and thin films and modelling the applications of thin films Nb-doped PZT for possible device integration. The proposed hydrothermal-electrochemical process may be integrated in a feasible way with CMOS electronic technology; the chemical process developed is environmental clean.

Multifunctional materials as thin nanostructured films with controlled

ferroelectric properties - Acronym DEFAZOR. Project web page www.defazor.imnr.ro MATNANTECH Project 4045264 (2004-2006) Participants: IMNR (Project director Dr. Roxana M. Piticescu), IMT Bucharest,

University “Alex Ioan Cuza” Iassy and Sitex 45 srl Bucharest The main objective of the project were the elaboration of an original hydrothermal-electrochemical technology for in-situ deposition of doped nanostrucutred (Ba,Sr)TiO3 with non-linear dielectric / ferroelectric properties under variable electric fields, study the mechanisms, thermodynamic and kinetic prediction of chemical deposition processes, chemical, physical and structural characterization of the BST films, design of the prototype for integration in microwaves applications and elaboration of standard methods for thin films characterisation applicable for end-users (mainly SMEs). Application of hydrothermal-electrochemical deposition process is a European priority in the field of converging technologies for microwave applications.

Crono-amperometry and SEI of PZT thin films deposited

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Research and Services Network for the synthesis of Nanostructures for advanced applications in textile industry, protective coatings and environmental protection

Research for Excellence Project CEEX 69 SINAPS (2006-2008) Project web page www.imnr.ro/sinaps, Coordinator: INCDMNR (Project Director Dr. Radu Robert Piticescu)

The general objectives of the project are: synergic integration between RTD, universities and SMEs to ensure sustaining and acceleration of multidisciplinary researches, scientific services, dissemination and training in the proposed fields, based on the expertise and excellence of participating institutions; concentrating and focussing the research activities in domains with high innovation degree on national level and potential for export; development of connexions outside network with new SMEs and companies using the specific activities of the SINAPS platform (workshops, training courses, brokerage); Sustainable integration of material, human excellences and financial resources by a concentrated strategy for participating in the ETP Advanced Materials (EuMaT) and developing specific projects in the FP7 thematic areas. Main specific objectives: Evaluation of the research facilities and competences in the field of nanopowders synthesis procedures (physical, chemical, mechanical) existing in the Romanian research with high potential for innovation in the fields of interest; Evaluation of the best practice methods for processing of nanopowders with desired properties for the industrial end-users; Elaboration of fast analysis and characterization methods for potential end-users; Establishing the barriers at the moment that affects production, transformation and processing of such knowledge based nanomaterials onto the Romanian market.

Synthesis of Al-doped ZnO

The main expected scientific works in this field are directed toward a new insight in the size dependent ionic transport, electronic and luminescence properties in nanostructured doped zinc oxide materials, ab- initio model for prediction of electronic conductivity, formation of polarons and excitons, luminescence vs. composition of main elements and dopants, intrinsic defects, specific surface, grain size, impurity segregation on the particle surface. From social and economical point of view the research will follow the eco-efficient processes applied for nanomaterials synhtesis. The economic impact is related to the possibilites for transfering new technolgies with improved reproducibility to SMEs using the existing networks. These researches benefits of the support from COST D30 and Fun-Nanos ECO-NET project. The results show that electronic properties of Al-doped ZnO nanopowders are strongly influenced by morphology and this may be controlled by the synthesis method.

TEM and SAED images of (Ba,Sr)TiO3 powders; SEM of (Ba,Sr)TiO3 film

TEM and luminescence spectra of 0.5% Al-doped ZnO obtained by:

a) Hydrothermal and b) solar PVD processes

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Dr. Roxana Mioara PITICESCU, head of Nanostructured Materials Laboratory, graduated Organic Chemical Technology Faculty at the University POLITEHNICA Bucharest in 1983. She started to work in research field moving from rubbers and plastics chemistry to anti-cancer drugs synthesis and finally in 1988 to the Institute for Non-ferrous and Rare Metals. From 1997 she is PhD in Applied Physical Chemistry. Beside coordination of more Projects in the frame of National Programme for Advanced Materials, Micro and Nanotechnologies, she was in-charge of work in more European projects and also member in the

management committee of two European COST projects. From 1999 until now she attended some research stages in Italy, Spain and France, including a NATO Fellowship in the Institute for Materials Science PROMES Font Romeu, France. She published 2 books and more papers in different national and international journals and participated in many conferences and workshops. She is founder member of the Romanian Association for New and Advanced Materials, member of Romanian Ceramic Society and reviewer for Nanotechnology (editor Institut of Physics, Great Britain) and Journal of American Ceramic Society. Her basic background in organic chemistry together with the high level of knowledge received during practical and theoretical approach to ceramic nanomaterials meet together in developing new projects and ideas in the field of regenerative nanomedicine, bringing materials closer to life.

Selected publications 1. R.R. Piticescu, Roxana M. Piticescu, D. Taloi, “Modelling hydrothermal synthesis of ceramic

nanocomposite powders”, Solid State Phenomena, ISSN 10120394, pp.165-170 (2003) 2. Roxana M. Piticescu, R. R. Piticescu, D. Taloi, V. Badilita ”Hydrothermal synthesis of ceramic

nanomaterials for functional applications”, Nanotechnology vol. 14, no. 3, February 2003

3. Roxana M. Piticescu, A. M. Moisin, D.Taloi, V. Badilita, I. Soare, ”Hydrothermal Synthesis of ultradisperse PZT powders for polar ceramics”, J. Eur. Ceram. Soc. 24, pp.931-935 (2004)

4. Roxana M. Piticescu, G.C. Chitanu. M.L. Popescu, W. Lojkowski, A. Opalinska, T. Strachowski, “New hydroxyapatite based nanomaterials for potential use in medical field”, Annals of Transplantation, 9 (1A), 20-25 (2004)

5. Roxana M.Piticescu, G. C. Chitanu, M. Albulescu, M. Giurginca, M.L.Popescu, W.Lojkowski, “Hybrid HAp-maleic anhydride copolymer nanocomposites obtained by in situ Functionalisation”, Reviews on Advanced Materials Science 8[2],164-169 (2004)

6. Roxana M. Piticescu, L. Mitoseriu, M. Viviani, V.M. Poladian, Preparation and Characterisation of Pb(Zr0.52Ti0.48)0.975Nb0.025O3 ceramics, J.Eur.Ceram.Soc.25, 2491-2494 (2005)

7. Roxana M.Piticescu, Gabrielle C. Chitanu, Mihaela Albulescu, Maria Girurginca, Madalina L. Popescu and W. Lojkowski, “Biocompatibility of thin films based on hydrothermal synthesized Hap”, in “From Nanopowders to Functional Materials”,pp.47-56, Trans Tech Publications, ISSN 1012-0394 (2005)

8. R.R. Piticescu, C. Monty and D. Millers, “Hydrothermal synthesis of nanostructured zirconia materials: state of the art and future prospects”, Sensor and Actuators B, vol 109, No. 1, pp102-106 (2005)

9. Roxana M.Piticescu, Paula Vilarinho, Madalina L. Popescu, R.R.Piticescu, „Hydrothermal synthesis of perovskite based materials for microelectronic applications”, J. Optoelectronics and Advanced Materials, vol.8 (2), pp.543-547 (2006)

10. R.R. Piticescu, C. Monty and D. Millers, “Synthesis of Al-doped ZnO nanomaterials with controlled luminescence”, J. Eur.Ceram.Soc., 26, pp. 2979-2983 (2006)

11. Roxana M.Piticescu, Paula Vilarinho, Madalina L. Popescu, R.R.Piticescu, „Perovskite nanostructures obtained by hydrotherma electrochemical process”, J. Eur.Ceram.Soc., 26, pp. 2945-2949 (2006)

12. J. Fidelus, W. Lojkowski, D. Millers, L. Grigorjeva, K. Smits, Radu R. Piticescu, „Zirconia Based Nanomaterials for Oxygen Sensors-Generation, Characterisation and Optical Properties”, Solid State Phenomena, vol.128, pp. 141-150 (2007)

Visit our new web site www.avanmat.imnr.ro for all our services, including CTT AVANMAT e-Newsletters

CONTACT PERSONS: Dr. Teodor VELEA, General Manager, e-mail : [email protected] Dr. Radu Robert PITICESCU, Director CTT AVANMAT, e-mail : [email protected] Phone: 0040-21-3522046; Fax 0040-21-3522045

Started from July 2004 in cooperation with Romanian Chamber of Commerce and Industry and National R&D Institute for Microtechnologies, CTT AVANMAT is ad-hoc member of European Technological Platform for Materials (EuMaT)

Accredited by the Romanian Ministry of Education and Research (Decision 9056/2006 of the President of National Authority for Scientific Research)

CTT AVANMAT aims to implement, consolidate and develop a national pole in the field of advanced nanostructured materials (metals, ceramics, composites) with biocompatible and intelligent properties (sensors, materials with pre-determined corrosion/abrasion characteristics). The main tasks of the center are to give value to all research results in the field and to sustain on long run the economical – social development by reinforcing the segment of small and medium enterprises (SME's) and by establishing new innovative enterprises (SIE's), by increasing the competitiveness of R&D institutes, SME's and SIE's acting in the target field. It also follows the complete integration in the economic European circuit.

MISION of CTT AVANMAT: To realize a fast technological transfer towards SME’s, of the R&D results in the field of

advanced biocompatible and intelligent materials (metallic, ceramic, composite); To identify the technologies, services and products required by the market, in the target field; To assure scientific consultancy and expertise in the field; To assure continuous qualified training in the target field for the specialist acting in SME’s; To provide a profound education in the field of advanced biocompatible and intelligent

materials to students and PhD candidates; To offer consultancy for SME’s to submit project proposals in national and international R&D

competitions – linked with the target field; To consolidate and to develop a specific market for the target domain; To forecast the market demand for medium and long term in order to align applied R&D

activities to the market trend; To develop market activities for the target field; To disseminate knowledge (scientific and technological) related to the target field, especially

for SME’s; To sustain SME’s and other enterprises in the target field to implement European standards

for the characterization of biocompatible and intelligent advanced materials (metallic, ceramic and composites);

To establish networks that will facilitate the contact between R&D specialist and SME’s in this field and to encourage the national and international partnerships;

To develop activities linked with patents and intellectual property rights. In order to achieve its tasks, CTT AVANMAT is open towards any public or private initiative intended to assimilate, to promote, to develop and to transfer technologies to enterprises acting in the field of advanced materials.

Dr. Radu Robert PITICESCU, director of CTT AVANMAT from 2004, graduated the Faculty for Materials Science and Engineering in 1981 and obtained his PhD in Materials Science in 1998. Director of many national and international projects: NATO SfP 974054-Zirconia Nanomaterials (2000-2004), FP5 GRD1-99-1-1008V-1 “Microscale fabrication of graded materials components” (2002-2004), COST D30 -“High Pressure Tuning of Nanomaterials” (member in the management committee 2004-2007) ECO-NET “Functional Nanomaterials” (financed by EGIDE-France). From September 2006 he is member in the FP7-NMP Programme Committee for Romania.

102 Biruintei Blvd, Pantelimon, Ilfov, ROMANIA, PO 077145. Phone: 0040-21-3522046; Fax: 0040-21-3522045

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