Synthesis, characterization and modelling of inorganic materials

1) Introduction

The research group has a long tradition in studying different aspects of the chemistry of metal systems. In the past such activity was concentrated on binary and ternary alloy systems involving Rare Earths. Subsequently different classes of materials, besides metallic alloys, became subject of our investigations. 
At present several research lines are active and will be briefly described in the following.


2) Research lines

2A) Phase diagrams and constitutional properties of intermetallic compounds

The experimental investigation of phase equilibria in intermetallic systems is particularly focused on the existence, stability, crystal structure, and physical properties of new compounds, including complex intermetallics (CIMs) characterized by superstructures, modulated, or disordered structures. The accurate determination and analysis of crystal structures are the basis for highlighting regularities and structural relationships useful for rationalizing the growing amount of data on this class of compounds. The knowledge of the crystal structure is also the indispensable starting point for performing electronic structure calculations and analysis of the chemical bond in the real space in the framework of the QTAIM theory (Quantum Theory of Atoms in Molecules), using for example the Electron Localizability Indicator (ELI). These fundamental studies are aimed at evidence relations between composition-structure-bonding-properties useful for novel materials design. Typical ternary systems recently studied are R-{M,T}-{Si, Ge, Sn} and R-T-Mg (R = rare earth metal, T = transition metal, M = s- or p-block metal).
Collaborations include: Max Planck Institute for Chemical Physics of Solids (Dresden), University of Vienna, University of Lisbon, Technical University of Freiberg, Technical University of Munich.
Contact persons for this research line are Adriana Saccone, Serena De Negri, Pavlo Solokha


2B) Physical properties of intermetallics

As far as physical properties are concerned, intermetallic compounds with strong electronic correlation, magnetically frustrated, or systems with quantum phase transitions are studied. The extensive and in-depth knowledge of the constitutional properties deriving from this activity not only contributes to basic research but constitutes an important starting point for the subsequent characterization of the metallic materials studied in view of their technological use (new metallic cryocoolers for adiabatic demagnetization refrigeration, materials for storage of hydrogen, bio-compatible materials, materials with electrocatalytic properties, superalloys, materials for photovoltaic and thermoelectric devices).
Collaboration includes among others: Technical University of Vienna, Centro Atomico Bariloche, University of Presov, University of Johannesburg, Charles University of Prague, University of Cantabria.
Contact person for this research line is Mauro Giovannini.


2C) Thermochemical properties of bulk and nanostructured alloys

The research activity carried out includes the investigation of two or more components alloys both in massive and in nanosized form. The addressed studies include materials with potential application in various sectors of technological interest (i.e. low and high T lead-free solders, structural materials, hydrogen storage systems) without neglecting the important aspect of basic science. In particular, the determination of thermodynamic properties such as formation, mixing and melting enthalpy of alloys, gives the knowledge of the reactivity of the metallic systems and is important for the validation of computational methods (i.e. ab initio methods) and as input data for thermodynamic modeling (i.e. CALPHAD method). The study of metallic materials in massive form, has been joined by the one on nanosized metallic materials trying to optimize the synthesis and determine some interesting properties, with particular reference to their thermal behavior.
Collaborations includes: CNR-ICMATE Genoa, Department of Inorganic Chemistry/Materials Chemistry (Vienna University), Department of Materials Science and Engineering, Robert R. McCormick School of Engineering and Applied Science, Northwestern University, Evanston, IL, USA.
Contact person for this research line are Simona Delsante and Nadia Parodi.


2D) Computational Thermodynamics of Materials (COMAT)

Focus of the COMAT group is to model materials by means of computational techniques possibly supported by experimental investigations in order to improve fundamental knowledge and solve application problems.
Thermodynamic modeling according to the CALPHAD approach is applied to multi-component materials including alloys as well as ceramics in order to predict phase equilibria, thermodynamic properties, phase interactions, etc. Typical subjects recently investigated are:
* Phase transformations in Cobalt superalloys used in turbine blades
* Joining of UHTC (Ultra High Temperature Ceramics) by Ni and Ni-B alloys
* Prediction of single-phase stability ranges in HEAs (High Entropy Alloys) based on the Al-Co-Cr-Fe-Ni with additions of refractory metals.
* Ceramic-metal interfacial interactions between SiC and Al-Ti alloys
* Simulation of superalloy coatings (CoNiCrAlY family) at high temperature.
* High temperature interactions between TBC (Thermal barrier coatings) and CMAS (Calcium-Magnesium-Aluminium Silicates)
Collaborations includes: CNR-ICMATE, Ansaldo Energia, TU Bergakademie Freiberg, Foundry Research Institute Krakow,
Contact person for this research line is Gabriele Cacciamani.


2E) Chalcogenide compounds

Particular interest is devoted to chalcogenide semiconductors for photovoltaic applications, from fundamental to industrial perspectives. This research line encompasses both thermodynamics and kinetics (synthesis, phase stability and compatibility, solid-gas equilibria), as they relate to point defects and device performance, with a special emphasis on extrinsic doping and associated solid state diffusion phenomena. Synthetic and characterization techniques include: thin film electroplating, reactive annealing, chemical vapour transport, liquid ammonia handling and electrochemical photocurrent spectroscopy.
Collaborations includes: University of Bath, University of Luxembourg, Luxembourg Institute of Science and Technology, Max-Planck Institut fuer Eisenforschung, University of Versailles, International Iberian Nanotechnology Laboratory and National Renewable Energy Laboratory.
Contact person for this research line is Diego Colombara.


2F) New materials for different uses

The study of chemical and biochemical methods for the recovery of precious metals and rare earths elements from waste is of great interest for both recovery or remediation purposes. The research focuses on electronic waste (recovery of precious raw materials) and industrial waste water (remediation from inorganic pollutants) by means of new double layer idroxide (LDH). Furthermore these materials are under experimental evaluation as electrode constituent for post lithium battery.
Collaborations includes: Copenhagen University, University of Camerino, Karlsruhe Institute of Technology (KIT).
Contact person for this research line is Anna Maria Cardinale.


3) Recent publications



A Martinelli, S Sanna , G. Lamura, C Ritter, B Joseph, E Bauer and M Giovannini, Structural and magnetic properties of the Yb2Pd2(In1−xSnx) system: a synchrotron x-ray and neutron powder diffraction investigation, J. Phys.: Condens. Matter 31 (2019) 385802.



J.G. Sereni, J. Roberts, F. Gastaldo, M.G-Berisso, M. Giovannini, “Sastry-Sutherland phase formation in magnetically frustrated Ce2Pd2In1-xSnx alloys” Materials Today Proceeding 14 (2019) 80-83.



M. Ostrowska, G. Caacciamani, Critical evaluation and thermodynamic modeling of the Al-Co-Fe system. In JOURNAL OF ALLOYS AND COMPOUNDS vol. 794 pp.553-568.



R. Freccero, S.H. Choi, P. Solokha, S. De Negri, T. Takeuchi, S. Hirai, P. Mele, A. Saccone, “Synthesis, crystal structure and physical properties of Yb2Pd3Ge5” J. Alloys Compd. 783 (2019) 601-607.



R. Freccero, P. Solokha, S. De Negri, A. Saccone, Y. Grin, F.R. Wagner, “Polar-covalent bonding beyond the Zintl picture in intermetallic rare-earth germanides”, Chem. Eur. J. , 25 (2019) 6600 – 6612.



S. Delsante, G. Borzone, R. Novakovic, “Experimental thermodynamics and surface properties of Ag–Cu–Ge solder / braze alloys", Journal of Phase Equilibria and Diffusion, 40 (1) (2019) 115–120.



P. Cristiani, G. Ghiara, G. Tassistro, P. Piccardo, R. Spotorno, S. Delsante, “Dezincification inhibition of a food processing brass OT60 in presence of Pseudomonas fluorescens”, Corrosion Science 157 (2019) 370–381. 10.1016/j.corsci.2019.06.003


Colombara, D. Frank-Turnbull dopant migration may enhance heteroatom diffusivity: Evidence from alkali-doped Cu(In,Ga)Se2. Phys. Rev. Materials 3, 054602 (2019).









A.Martinelli, M. Giovannini, J.G.Sereni and C.Ritter, Suppression of ferromagnetic order by Ag doping: a neutron scattering investigation on Ce2(Pd1−xAgx)2In (x = 0.20, 0.50), J. Phys.: Condens. Matter 30 (2018) 265601.



J. G. Sereni, I. Curlík, M. Giovannini, A. Strydom and M. Reiffers, Physical properties of the magnetically frustrated very-heavy-fermion compound YbCu4Ni, Phys. Rev. B 98 (2018) 094420. https://doi.org10.1103/PhysRevB.98.094420



Curlik, M. Giovannini, F. Gastaldo, A.M. Strydom, M. Reiffers, J.G. Sereni, “Crystal structure and physical properties of the two stannides EuPdSn2 and YbPdSn2” J. Phys. Cond. Matter 30 (2018) 495802.



G. Cacciamani, G. Roncallo, Y. Wang, E. Vacchieri, A. Costa, Thermodynamic modelling of a six component (C-Co-Cr-Ni-Ta-W) system for the simulation of Cobalt based alloys. In JOURNAL OF ALLOYS AND COMPOUNDS vol. 730 (2018) pp.291-310.


Sirio Consani, Tonci Balić-Žunić, Anna Maria Cardinale, Walter Sgroi, Gabriele Giuli and Cristina Carbone, “A novel synthesis routine for woodwardite and its affinity towards light (La,Ce,Nd) and heavy (Gd and Y) rare earths elements” Materials 2018, 11(1), 130.



R. Freccero, P. Solokha , D.M. Proserpio, A. Saccone, S. De Negri, “Lu5Pd4Ge8 and Lu3Pd4Ge4: two more germanides among polar intermetallics”, Crystals 8 (2018) 205.



F. Rosalbino, D. Macciò, G. Scavino, A. Saccone, “Influence of rare earths alloying addition on the corrosion behavior of Zn in neutral aerated sodium chloride solution”, Materials and Corrosion 69 (2018) 1447-1454.



S. Delsante, R. Novakovic, G. Borzone, “Synthesis, characterization and thermal stability of SnAg and SnAgCu nanoparticles”, Journal of Alloys and Compounds, 747 (2018) 385–393.



R. Novakovic, S. Delsante, G. Borzone, “Wetting and interfacial reactions: experimental study of the Sb–Sn–X (X = Cu, Ni) systems” Journal of Mining and Metallurgy, Section B: Metallurgy, 54 (2) B (2018) 251–260.


R. Novakovic, S. Delsante, J. Lee, G. Borzone, “Surface and transport properties of liquid Ag–Sn alloys and a case study of Ag–Sn eutectic solder”, Journal of Materials Science: Materials in Electronics, 29 (2018) 17108–17121.




Colombara, D. et al. Sodium enhances indium-gallium interdiffusion in copper indium gallium diselenide. Nature Communications 9, 826 (2018).


Colombara, D., Gonçalves, A.-M. & Etcheberry, A. Synthesis of K2Se solar cell dopant in liquid NH3 by solvated electron transfer to elemental selenium. Electrochemistry Communications 93, 44–48 (2018).



A. M. Cardinale, N. Parodi, D. Macciò (2018). Alloying behaviour of zinc with rare earth metals: the Er-Pr-Zn system. JOURNAL OF PHASE EQUILIBRIA AND DIFFUSION, vol. 39, p. 908-915.


Cardinale, A. M., Parodi, N. (2018). R–Al–Si systems (R: Pr, Nd) Experimental investigation of phase equilibria in the Al-rich corner. JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, vol. 134, p. 1327-1335.




4) Permanent Staff

CACCIAMANIGabrieleChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03
CARDINALEAnna MariaChimica e Chimica industriale (DCCI)Ricercatore TICHIM/03
COLOMBARADiegoChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03
DELSANTESimonaChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03
DE NEGRISerenaChimica e Chimica industriale (DCCI)Prof. OrdinarioCHIM/03
FRECCERORiccardoChimica e Chimica industriale (DCCI)Ricercatore TD-ACHIM/03
GIOVANNINIMauroChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03
MACCIO'DanieleChimica e Chimica industriale (DCCI)Ricercatore TICHIM/03
PARODINadiaChimica e Chimica industriale (DCCI)Ricercatore TICHIM/03
RIANIPaolaChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03
SOLOKHAPavloChimica e Chimica industriale (DCCI)Prof. AssociatoCHIM/03

5) Postdoctoral Researcher

ROSSIChristianChimica e Chimica industriale (DCCI)CHIM/
PICCINNIMarcoChimica e Chimica industriale (DCCI)CHIM/

6) Ph.D. Students

Michael CasaleChemical Sciences and TechnologiesXXXVIIID. Colombara (DCCI), D. Peddis (DCC)
Lorenzo FenocchioChemical Sciences and TechnologiesXXXVIIG. Cacciamani (DCCI)
Marco FortunatoChemical Sciences and TechnologiesXXXVIA.M. Cardinale (DCCI)

7) ERC sectors of the research group

  • PE3_4 Electronic properties of materials, surfaces, interfaces, nanostructures
  • PE3_5 Semiconductors and insulators: material growth, physical properties
  • PE4_1 Physical chemistry
  • PE4_2 Spectroscopic and spectrometric techniques
  • PE4_8 Electrochemistry, electrodialysis, microfluidics, sensors
  • PE4_13  Theoretical and computational chemistry
  • PE5_1  Structural properties of materials
  • PE5_2  Solid-state materials
  • PE5_3 Surface modification
  • PE5_4 Thin films
  • PE5_6  New materials: oxides, alloys, composite, organic-inorganic hybrid, nanoparticles
  • PE5_12 Chemistry of condensed matter