Crystallography in Bulgaria

This Special Report was published in the IUCr Newsletter, Vol. 19, No. 4 (2011).

The Beginnings

Crystallography began in Sofia U., Bulgaria, in 1893 with the establishment of the Dept. of Natural History by G. Bonchev. Bonchev, the first PhD student in crystallography in Zagreb, Croatia, taught geology, introduced a course in crystallography and published the first books on crystallography in Bulgaria in the 1890s. In 1905 he was appointed Chair of the Dept. of Mineralogy and Petrography.

New minerals found in Bulgaria: Manganilvaite, CaFe2+Fe3+(Mn, Fe2+)(Si2O7)O(OH) (approved by IMA-CNMMN 16-2002; I. Bonev et al., 2005) from the Madan region, Central Rhodopes, Bulgaria.

Academician Prof. Ivan Kostov.

I. Kostov graduated from the Natural Sciences Dept. of Sofia U. 'St. Kliment Ohridski' in 1936. After studying at the Imperial College of Science and Technology in London (1940-1945), he returned to Sofia U. In 1953, as the first Head of the Dept. of Mineralogy and Crystallography, he taught crystallography, organized mineral collections, published Bulgarian, Russian and English editions of his textbooks on Mineralogy and Crystallography, and supervised doctoral studies. In 1967, Kostov was elected to Membership in the Bulgarian Academy of Sciences (BAS), where he served as Head of the Geological Institute, Head of the Sector Mineralogy and Geochemistry, and Director of the National Museum of Natural History. He was a member of the German and Russian Academies of Sciences and an Honorary member of the Bulgarian, Russian and Ukrainian Mineralogical Societies. His successor at the Dept. of Mineralogy and Crystallography V. Breskovska, conducted crystallographic activities with G. Kirov, M. Maleev and S. Petrov.

Mikhail Maleev and Kostadin Petrov discussing in front of a giant quartz crystal during the 2nd National Crystallographic Symposium.

Equipment currently available for crystallographic studies in the Geological Inst. of BAS includes a modern digital image foil Guinier camera (Huber GmbH), older Weissenberg and precession cameras, and the last functional optical (double-circle) goniometer for crystal morphology studies in the country.

The Institute of General and Inorganic Chemistry of the BAS was founded in 1960 by G. Bliznakov whose studies of the effects of impurities on the nucleation, growth and shape of crystals received international recognition. Crystallographic research was initiated in the 1960s with an electron microscope and Debye-Scherrer camera. In 1974, a DRON-1 diffractometer equipped with high- and low-temperature chambers was installed. In 2006, the Institute obtained Bruker D8 equipment, which was successfully upgraded in 2010 with a linear LynxEye detector.

(right) Associate Prof. Daniela Kovacheva with her staff and (left) the new XRD diffractometer (2008) in the Laboratory of Solid State Chemistry and XRD analysis.

Between 1982 and 1985, K. Petrov was Head of the Methodical X-Ray Diffraction Lab at the Center of Chemical Sciences, which consists of 10 institutes. His research activities were in the fields of preparative and applied inorganic solid state chemistry, structural perfection and texture of materials for electronics, superconductors, catalysts, refractory compounds, thin films, diffusion layers and galvanic coatings. He applied X-ray and neutron powder diffraction and Rietveld methods to materials identification, phase analysis and determination of crystallite sizes and microdeformations. His PhD thesis was concerned with polycrystalline inorganic catalysts, and microstructure and topotactic synthesis of materials (K. Petrov, N. Zotov and D. Kovacheva).

Crystallography in the 1980s

In the 1980s, researchers from the BAS and Sofia U. held four meetings to discuss X-ray diffraction methods. The meetings evolved into National symposia held in 1983, 1985, 1987 and 1991. These symposia were attended by over 80 scientists from 30 universities, research institutes and industrial laboratories in Bulgaria who gathered to share experiences and plan future studies. The interest in applying XRD-based methods for study of materials grew among physicists, chemists, geologists, mineralogists and soil researchers. Resulting publications concerned small angle diffraction, X-ray topography, micro-deformations of metal structures, thin layers, fiber composites, textures, and high- and low-temperature experiments.

Institute of Applied Mineralogy

The new X-ray single crystal diffractometer Supernova A (Oxford Diffraction) in the Laboratory of X-ray diffraction analysis, IAM (2010).

The new X-ray powder diffractometer D2 Phaser (Bruker AXS) in the Laboratory of X-ray diffraction analysis, IAM (2009).

The recent staff of the Laboratory of X-Ray Diffraction Analysis (IAM). From left to right: Boris Shivachev, Rositsa Petrova, Luiza Dimova, Yana Tsvetanova, Ognyan Petrov, Vladislav Kostov-Kytin.

The Institute of Applied Mineralogy of the BAS was established in 1984 for research on minerals and their applications in industry and ecology. The Institute housed an XRD laboratory with an Enraf-Nonius CAD-4 single-crystal diffractometer and two powder diffractometers, and Electron Microscopy and Crystal Growth laboratories. More than 100 structures of new crystalline materials were published under the leadership of J. Macicek who also supervised the PhD studies of O. Angelova, T. Todorov, R. Petrova and others. In 1988, the research group obtained a grant from the International Centre for Diffraction Data (ICDD) for production of PDF patterns of new crystalline phases. More than 200 new diffraction patterns were added to the ICDD (simple and double selenates, selenites, hydroselenites, adducts of inorganic salts with organic molecules, and perrhenates with nicotinic and isonicotinic hydrazides). The research included synthesis and determination of structures and corundum numbers (RIRs). Computer programs were developed for calculating RIRs of powder patterns from known structures and characterization of the data according to IUCr guidelines.

Institute of Mineralogy and Crystallography

The Central Laboratory of Mineralogy and Crystallography (CLMC) of the BAS was established in March 1995 to conduct fundamental and applied investigations, provide consultation on and application of analytical methods and training of specialists in mineralogy and crystallography. At the 5th General Assembly of the BAS, the Laboratory was renamed Inst. of Mineralogy and Crystallography 'Acad. Ivan Kostov' (IMC-BAS). Today, IMC consists of well-equipped laboratories, offices and a library, it is supplied with an optical cable and Internet as well as PC for every research associate and specialist. Achievements are presented through Annual Reports (www.clmc.bas.bg), at scientific conferences and exhibitions, in periodicals, and via the mass media.

The laboratories of CLMC and IAM have produced hundreds of scientific papers, conducted dozens of national and international projects, awarded PhD degrees and acquired a new scanning electron microscope (ZEISS EVO LS25), powder diffractometer (D2 Phaser Bruker AXS), single-crystal diffractometer (Oxford Supernova A with temperature control from 80 to 400 K), a micro-FTIR Spectrometer (TENSOR 37 Bruker, MIR and NIR with ATR accessories), and SETSYS Evolution TGA-DTA/DSC/MS up to 2400 K (Setaram).

Bulgarian crystallographers during the 2nd National Crystallographic Symposium.

The Bulgarian National Committee for Crystallography (BNCC) was founded in 1992 as an adhering body of the BAS. The members of the BNCC are specialists in the fields of structural crystallography, crystal chemistry, crystal physics, mineralogy and materials sciences. BNCC coordinates the activities of the Bulgarian crystallographic community and maintains relations with the IUCr and the European Crystallographic Association (ECA). Former Chairmen of BNCC were A. Apostolov (Sofia U., 1992-2000), K. Petrov (Inst. of General and Inorganic Chem., BAS, 2000-2008), and O. Petrov (Central Lab. of Min. and Cryst., BAS, 2009-2010).

The 1st Bulgarian National Crystallographic Symposium organized by the BNCC in Oct. 2009 was attended by 98 participants presenting 68 oral and poster reports. Full papers were published in the Proceedings volume 1st National Crystallographic Symposium (ISSN 1313-9991, Academic Publishing House. M. Drinov, editor; online at http://clmc.bas.bg/symp09/docs/First_Cryst_Symp.pdf).

An assembly to establish the Bulgarian Crystallographic Society (BCS) was held on February 27, 2010, at the Inst. of Min. and Cryst. of the BAS. 47 crystallographers from institutions throughout the country attended the assembly. The Bulgarian Crystallographic Society was officially registered in Bulgaria in April, 2010 with a Board of seven Managers, O. Petrov, President of the Board, and R. Nikolova, Vice-President. They planned to apply for membership of the IUCr at the XXII General Assembly and Congress in Madrid, 2011.

The 2nd Bulgarian National Crystallographic Symposium (www.bgcryst.com/symp10) was organized by the Faculty of Chemistry, Sofia U., chaired by T. Spassov and featured international speakers B. Krebs (U. of Münster, Germany), M. Aroyo (U. of the Basque Country, Spain), B. Mihailova (U. of Hamburg, Germany), and S. Ferdov (U. of Minho, Portugal). The symposium, attended by 78 participants and more than 20 students, covered crystal growth, inorganic and mineral structures, organic and organometallic compounds, nano materials, macromolecules, structure-properties relationships, defects, microstructures and textures, experimental techniques and equipment. There were round-table discussions on state-of-the-art equipment and modern laboratories in Bulgaria, and planning of further activities of the BCS. Outstanding presentations by three young scientists were awarded prizes. The symposium allowed young crystallographers to present their research, exchange ideas and participate in the open discussions.

In the last two years Bulgarian crystallographers have advanced scientifically and organizationally. The crystallographic community in Bulgaria is fully aware of achievements of scientists and specialists in crystallography, crystal chemistry, mineralogy, and materials science and recognize that crystallography is crucial to modern materials sciences and the study of mineral systems, natural resources, biomaterials and nanomaterials. Crystallographic research contributes to technological progress and the quality of life, critically needed at times of economic crisis. The BCS hopes to foster investment of the business community in technologically advanced materials.

Ognyan Petrov ([email protected])