Nanoscale Effects of Radiation (UV, X-ray, and γ) on Calcite Surfaces: Implications for its Mechanical and Physico-Chemical Properties

Calcite, the most stable polymorph of calcium carbonate (CaCO3), attracts growing attention due to its wide applications in many fields, such as composite materials, food industry, biomineralization, and dating of archeological and geological objects. Our study shows the influence of UV, X-ray and γ-radiation on the mechanical and physicochemical properties of calcite at the nanoscale. Using nanoindentation technique we observed a clear detriment in the mechanical response (hardness and elastic modulus) of the calcite (104) surface after irradiation, most visible in the case of UV. Changes in mechanical properties were correlated with the accumulation of radiation defects detected using EPR spectroscopy, and information on chemical bonding and composition obtained through XPS analyses. Additionally, the efficiency in generating defects for all three types of radiation was compared, which allowed us to propose a possible mechanism of UV-induced formation of radiation defects in calcite.

[1]  Seung-Woo Lee,et al.  Behavior and characteristics of amorphous calcium carbonate and calcite using CaCO3 film synthesis , 2016 .

[2]  I. Iatsunskyi,et al.  Topographic reconstruction and mechanical analysis of atomic layer deposited Al2O3/TiO2 nanolaminates by nanoindentation , 2016 .

[3]  Zhongyi Jiang,et al.  CaCO3/Tetraethylenepentamine-Graphene Hollow Microspheres as Biocompatible Bone Drug Carriers for Controlled Release. , 2016, ACS applied materials & interfaces.

[4]  M. Dietzel,et al.  Transformation of Amorphous Calcium Carbonate in Air , 2016 .

[5]  V. Uskoković,et al.  Self-Setting Calcium Phosphate Cements with Tunable Antibiotic Release Rates for Advanced Antimicrobial Applications. , 2016, ACS applied materials & interfaces.

[6]  C. Rodriguez-Navarro,et al.  Direct Nanoscale Imaging Reveals the Growth of Calcite Crystals via Amorphous Nanoparticles , 2016 .

[7]  Paul J. M. Smeets,et al.  Structure and Properties of Nanocomposites Formed by the Occlusion of Block Copolymer Worms and Vesicles Within Calcite Crystals , 2016 .

[8]  S. Armes,et al.  Direct observation of mineral–organic composite formation reveals occlusion mechanism , 2016, Nature Communications.

[9]  G. Strzelczak,et al.  Multifrequency EPR study on radiation induced centers in calcium carbonates labeled with 13C , 2015 .

[10]  L. Qian,et al.  Effect of gamma irradiation on the wear behaviour of human tooth enamel , 2015, Scientific Reports.

[11]  V. Pareek,et al.  Synthesis of micro and nano-sized calcium carbonate particles and their applications , 2014 .

[12]  A. Putnis,et al.  Forming Cohesive Calcium Oxalate Layers on Marble Surfaces for Stone Conservation , 2014 .

[13]  Angela S. Wochnik,et al.  TEM preparation methods and influence of radiation damage on the beam sensitive CaCO3 shell of Emiliania huxleyi. , 2014, Micron.

[14]  Faleh Tamimi,et al.  Osseointegration of dental implants in 3D-printed synthetic onlay grafts customized according to bone metabolic activity in recipient site. , 2014, Biomaterials.

[15]  R. Krzyminiewski,et al.  EPR investigation of UV light effect on calcium carbonate powders with different grain sizes. , 2014, Radiation protection dosimetry.

[16]  Christine Ortiz,et al.  Pervasive nanoscale deformation twinning as a catalyst for efficient energy dissipation in a bioceramic armour. , 2014, Nature materials.

[17]  U. Kaiser,et al.  In Situ Observation of Electron Beam-Induced Phase Transformation of CaCO3 to CaO via ELNES at Low Electron Beam Energies , 2014, Microscopy and Microanalysis.

[18]  Piero Baglioni,et al.  Aragonite crystals grown on bones by reaction of CO2 with nanostructured Ca(OH)2 in the presence of collagen. Implications in archaeology and paleontology. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[19]  F. Huang,et al.  Tuning the H/E* ratio and E* of AlN coatings by copper addition , 2013 .

[20]  W. Sekkal,et al.  Nanoscale analysis of the morphology and surface stability of calcium carbonate polymorphs , 2013, Scientific Reports.

[21]  A. O. Yazaydin,et al.  Dehydration-induced amorphous phases of calcium carbonate. , 2013, The journal of physical chemistry. B.

[22]  J. Peloquin,et al.  Evaluation of strengthening mechanisms in calcite single crystals from mollusk shells. , 2013, Acta biomaterialia.

[23]  L. Estroff,et al.  The effect of magnesium substitution on the hardness of synthetic and biogenic calcite , 2012 .

[24]  J. Alcolea,et al.  U-Series Dating of Paleolithic Art in 11 Caves in Spain , 2012, Science.

[25]  Laura M. Hamm,et al.  Revisiting geochemical controls on patterns of carbonate deposition through the lens of multiple pathways to mineralization , 2012 .

[26]  S. Armes,et al.  An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals. , 2011, Nature materials.

[27]  I. Vorona,et al.  NO32− and CO2− centers in synthetic hydroxyapatite: Features of the formation under γ- and UV-irradiations , 2011 .

[28]  Chun-Long Chen,et al.  Engineered biomimetic polymers as tunable agents for controlling CaCO3 mineralization. , 2011, Journal of the American Chemical Society.

[29]  S. Weiner,et al.  Decoupling Local Disorder and Optical Effects in Infrared Spectra: Differentiating Between Calcites with Different Origins , 2011, Advanced materials.

[30]  Paola Fattibene,et al.  EPR dosimetry with tooth enamel: A review. , 2010, Applied radiation and isotopes : including data, instrumentation and methods for use in agriculture, industry and medicine.

[31]  S. Eichhorn,et al.  Bio‐Inspired Synthesis and Mechanical Properties of Calcite–Polymer Particle Composites , 2010, Advanced materials.

[32]  M. Chiesa,et al.  EPR characterization and reactivity of surface-localized inorganic radicals and radical ions. , 2010, Chemical reviews.

[33]  A. Bouville,et al.  UV EFFECTS IN TOOTH ENAMEL AND THEIR POSSIBLE APPLICATION IN EPR DOSIMETRY WITH FRONT TEETH , 2010, Health physics.

[34]  R. Hochleitner,et al.  Mechanical properties of modern calcite- (Mergerlia truncata) and phosphate-shelled brachiopods (Discradisca stella and Lingula anatina) determined by nanoindentation. , 2009, Journal of structural biology.

[35]  A. Freer,et al.  Biomineralization: elemental and organic influence in carbonate systems. , 2008, Chemical reviews.

[36]  V. Fedorov,et al.  Change in the plastic properties of ionic crystals under UV irradiation , 2008 .

[37]  M. Wencka,et al.  Dynamics of CO2− radiation defects in natural calcite studied by ESR, electron spin echo and electron spin relaxation , 2008 .

[38]  A. C. Fischer-Cripps,et al.  Critical review of analysis and interpretation of nanoindentation test data , 2006 .

[39]  R. Krzyminiewski,et al.  Temperature Effects in ESR Spectra of Radical Centres in Dripstone Calcite Samples Used for ESR Dating , 2005 .

[40]  H. Hercman,et al.  EPR Dating of Hydroxyapatite from Fossil Bones. Transient Effects after γ and UV Irradiation , 2005 .

[41]  A. Ganas,et al.  ESR studies on calcite encrustation on Fili neotectonic fault, Greece , 2005 .

[42]  H. Sato,et al.  Spatial distribution and formation of nitrate radical NO32− in Antarctic calcitic evaporates , 2004 .

[43]  D. Murphy,et al.  ESR dating, dosimetry and microscopy for terrestrial and planetary materials , 2004 .

[44]  G. Pharr,et al.  Measurement of hardness and elastic modulus by instrumented indentation: Advances in understanding and refinements to methodology , 2004 .

[45]  Steve Weiner,et al.  Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization , 2003 .

[46]  A. Matthews,et al.  On the significance of the H/E ratio in wear control: a nanocomposite coating approach to optimised tribological behaviour , 2000 .

[47]  Bartoll,et al.  Generation and conversion of electronic defects in calcium carbonates by UV/Vis light , 2000, Applied radiation and isotopes : including data, instrumentation and methods for use in agriculture, industry and medicine.

[48]  G. Villeneuve,et al.  INVESTIGATION OF ELECTRON PARAMAGNETIC RESONANCE PEAKS IN SOME POWDERED GREEK WHITE MARBLES , 1999 .

[49]  G. Vanhaelewyn,et al.  EPR of carbonate derived radicals: Applications in dosimetry, dating and detection of irradiated food , 1998 .

[50]  V. Chumak,et al.  Properties of light induced EPR signals in enamel and their possible interference with gamma-induced signals , 1998 .

[51]  W. Rink Electron spin resonance (ESR) dating and ESR applications in quaternary science and archaeometry , 1997 .

[52]  V. Stepanenko,et al.  Wide scale EPR retrospective dosimetry. Results and problems , 1997 .

[53]  D. Schramm,et al.  Electron spin resonance (ESR), electron nuclear double resonance (ENDOR) and general triple resonance of irradiated biocarbonates , 1996 .

[54]  F. Garcia-Pichel,et al.  Penetration of ultraviolet radiation into shallow water sediments: high exposure for photosynthetic communities , 1996 .

[55]  D. L. Blanchard,et al.  Studies of the calcite cleavage surface for comparison with calculation , 1993 .

[56]  Tyler B. Coplen,et al.  Continuous 500,000-Year Climate Record from Vein Calcite in Devils Hole, Nevada , 1992, Science.

[57]  G. Pharr,et al.  An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments , 1992 .

[58]  R. Bradt,et al.  Microhardness anisotropy of single crystals of calcite, dolomite and magnesite on their cleavage planes , 1992 .

[59]  M. Hochella,et al.  Structure and bonding environments at the calcite surface as observed with X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) , 1991 .

[60]  J. R. Lindsay,et al.  Sputter depth profiling in mineral-surface analysis , 1988 .

[61]  R. Grün,et al.  ESR-dating: Problems encountered in the evaluation of the naturally accumulated dose /AD/ of secondary carbonates , 1984 .

[62]  K. S. Raju Topaz-on neutron irradiation☆ , 1981 .

[63]  D. Briggs,et al.  Handbook of X‐ray Photoelectron Spectroscopy C. D. Wanger, W. M. Riggs, L. E. Davis, J. F. Moulder and G. E.Muilenberg Perkin‐Elmer Corp., Physical Electronics Division, Eden Prairie, Minnesota, USA, 1979. 190 pp. $195 , 1981 .

[64]  K. S. Raju Radiation effects in calcite , 1977 .

[65]  R. C. Hughes,et al.  EPR of CO2− Defects in Calcite: Motional and Nonsecular Contributions , 1970 .

[66]  S. A. Marshall,et al.  Electron Spin Resonance Absorption Spectrum of CO2− Molecule Ions Associated with F− Ions in Single‐Crystal Calcite , 1968 .

[67]  R. A. Serway,et al.  Electron Spin Resonance Absorption Spectra of CO3− and CO33− Molecule—Ions in Irradiated Single‐Crystal Calcite , 1967 .

[68]  D. R. Lewis,et al.  EFFECTS OF GAMMA RADIATION ON THE EXPERIMENTAL DEFORMATION OF CALCITE AND CERTAIN ROCKS , 1957 .

[69]  Dominique Gorse-Pomonti,et al.  A transmission electron microscopy study of radiation damages to β-dicalcium (Ca2SiO4) and M3-tricalcium (Ca3SiO5) orthosilicates , 2016 .

[70]  Benjamin Marie,et al.  Molluscan shell proteins: primary structure, origin, and evolution. , 2008, Current topics in developmental biology.

[71]  Robert F. Cook,et al.  Microhardness, toughness, and modulus of Mohs scale minerals , 2006 .

[72]  E. Huwald Calcium carbonate - pigment and filler , 2001 .

[73]  M. Laurent,et al.  Thermal behaviour of ESR signals observed in various natural carbonates , 1994 .

[74]  A. Bach,et al.  GENERAL PROPERTIES OF THE PARAMAGNETIC CENTRE AT g = 2.0006 IN CARBONATES , 1992 .

[75]  R. Grün,et al.  Potential and problems of ESR dating , 1991 .

[76]  R. Grün,et al.  Electron spin resonance (ESR) dating , 1989 .

[77]  A. Molodkov The problem of long-term fading of absorbed palaeodose on ESR-dating of quaternary mollusc shells , 1989 .

[78]  A. Molodkov ESR dating of quaternary shells: Recent advances , 1988 .

[79]  P. Smart,et al.  ESR signals in a variety of speleothem calcites and their suitability for dating , 1985 .

[80]  D. Regulla,et al.  Effects of sample preparation on the ESR spectra of calcite, bone and volcanic material , 1985 .

[81]  R. Grün,et al.  ESR dating in quaternary geology , 1983 .

[82]  J. Verhoeven,et al.  XPS spectra of Ca, Sr, Ba and their oxides , 1980 .

[83]  S. A. Marshall,et al.  Motional Effects in the Electron Spin Resonance Absorption Spectrum of CO2– Molecule‐Ions in Single‐Crystal Calcite , 1968 .

[84]  R. A. Serway,et al.  Electron Spin Resonance Absorption Spectrum of Orthorhombic CO3− Molecule—Ions in Irradiated Single Crystal Calcite , 1967 .

[85]  R. A. Serway,et al.  Electron spin resonance absorption spectrum of CO2- molecule-ions in single crystal calcite , 1964 .