Nucleation of Calcium Silicate Hydrate in Aqueous Solution and the Influence of Biomolecules on Cement Hydration

Total Page:16

File Type:pdf, Size:1020Kb

Nucleation of Calcium Silicate Hydrate in Aqueous Solution and the Influence of Biomolecules on Cement Hydration Nucleation of calcium silicate hydrate in aqueous solution and the influence of biomolecules on cement hydration. Dissertation Erlangung des akademischen Grades ‚Doktor der Naturwissenschaften‘ am Fachbereich Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität Mainz Nina Krautwurst geboren in Mainz Mainz, Juni 2017 1 Dekanin: Prof. Dr. Angelika Kühnle Gutachter/in: 1. Prof. Dr. Wolfgang Tremel 2. Priv. Doz. Ute Kolb 3. Prof. Dr. Karl W. Klinkhammer 2 Declaration Hereby, I declare that I have composed this work on my own and using exclusively the quote references and resources. Literally or correspondingly adapted material has been marked accordingly. Erklärung Hiermit erkläre ich, dass ich die vorliegende Arbeit selbstständig und nur mit den angegebenen Quellen und Hilfsmitteln angefertigt habt. Wörtlich oder sinngemäß übernommenes Gedankengut habe ich als solches kenntlich gemacht. Ort, Datum Nina Krautwurst 3 4 Preface/Acknowledgement Diese Arbeit entstand im Zeitraum von April 2014 bis März 2017 an verschiedenen Forschungseinrichtungen in Deutschland, England und Frankreich. Begonnen im April 2014 an der Universität Mainz am Instit für Anorganische und Analytische Chemie folgte ein Forschungsaufenthalt an der Universität York in England sowie eine Messreise an die European Synchrotron Radiation Facility in Grenoble. Die Doktorarbeit ist ein von der BASF ins Leben gerufenes Projekt über die Kristallisationskontrolle von C-S-H. Es ist ein Kooperationsprojekt zusammen mit der Arbeitsgruppe Paulsen des Instituts für Allgemeine Botanik der Universitä Mainz sowie der BASF Construction Chemicals in Trostberg. Viele Menschen haben mich während dieser Zeit unterstützt, wofür ich Ihnen an dieser Stelle danken möchte. Zuallererst möchte ich ganz herzlich Herr Prof. Wolfgang Tremel danken für sein Vertrauen in meine Arbeit und seine Unterstützung und Betreuung wie auch für all die Diskussionen, die wir in den letzten 3 Jahren hatten und die mich stark weitergebracht haben. Vor allem will ich ihm aber dafür danken, dass er immer hinter mir stand, besonderns in schwierigen Zeiten voller Zweifel und Ärger, die es wahrscheinlich in jeder Arbeit gibt. Großer Dank geht an Niklas Loges und Michael Dietzsch von der BASF CC in Trostberg zur Betreuung der Doktorarbeit. Sie waren immer da, falls Rückfragen auftraten und gaben vorallem viele wertvolle Hinweise während unserer unzähligen Meetings. Weiterhin bedanke ich mich ganz herzlich bei Luc Nicoleau (ehemals BASF CC) für die detaillierten, harten aber immer auch ergiebigen und konstruktiven Diskussionen, welche die Forschungsarbeit entschieden vorangetrieben haben. Weiterer Dank geht an Alexandro Fernandez-Martinez und Alexander E.S. Van Driessche für die fachliche Unterstützung unserer Forschungsreise in Grenoble sowie Christophe Labbez in Dijon, der durch konstruktive Diskussionenen zu C-S-H Simulationen noch deutlich mehr aus unseren Ergebnissen rausholen konnte. Im Laufe dieser Doktorarbeit wurde eine große Anzahl von Methoden verwendet, welche ohne die Hilfe von internen aber auch externen Kooperationen in solcher Weise nicht möglich gewesen wäre. Besonderer Dank geht an Karl Fischer (Universität Mainz) für seine Hilfe während der SLS und DLS Experimente sowie Ingo Lieberwirth (MPI-P Mainz) und Bastian Barton (Universität Mainz) für cryo TEM sowie STEM EDX.Bedanken möchte ich mich an dieser Stelle bei Frau Prof. Angelika Kühnle (Uni Mainz) für die Bereitstellung ihrer Labore für Titrationsexperimente, wodurch die Reproduizierbarkeit der Ergenisse deutlich erhöht werden konnte. Stefanie Maier (BASF CC) und Thomas Wohlhaupter (BASF CC) danke ich für ihre große Hilfsbereitschaft und Gewissenhaftigkeit bei unzählige IC und 5 ICP-OES Messungen. Dank geht an Christian Zerfaß (ehemals AG Paulsen) für seine Hilfe bei der Durchführung des Coomassie Assays sowie SDS-PAGE. Meiner Arbeitsgruppe möchte ich danken für das angenehme Arbeitsklima, welches immer wieder durch Blödeleien, nette Abende und vorallem Durakrunden aufgelockert wurde. Dank geht an Romina Schröder, Laura Besch, Sebastian Leukel und Mirko Montigny als Mitglieder der Kleingruppe Biomingruppe. Besonderer Dank geht an Sebastian Leukel für die Begleitung der durchgeführten Messreisen nach York, Didcot und Grenoble, bei welchen seine große Begeistung und sein Engagement für mich immer eine große Unterstützung dargestellt haben. Ein herzlicher Dank geht an meine Freunde, die mir die Zeit an der Universität Mainz unvergessen machen lassen und besonders auch an meine Familie, die jederzeit für mich da war und mich unterstützt hat, wo immer es auch nur ging. 6 Table of Contents 1 List of abbreviations ................................................................................................... 13 2 General background .................................................................................................. 15 2.1 Introduction and scope...................................................................................... 16 2.2 Classical and non-classical crystallization ........................................................ 20 2.2.1 Classical nucleation theory ................................................................... 20 2.2.2 Two-step nucleation.............................................................................. 22 2.2.3 Heterogeneous nucleation ................................................................... 24 2.2.4 Experimental methods .......................................................................... 25 2.3 Biosilification ...................................................................................................... 27 2.4 Fundamentals of cement chemistry .................................................................. 29 2.4.1 The different mineral phases of ordinary portland cement .................. 29 2.4.2 The hydration of ordinary portland cement .......................................... 31 2.4.3 The nanostructure of C-S-H .................................................................. 33 2.4.4 Accelerating admixtures ....................................................................... 37 2.4.5 Optimum sulphate level ........................................................................ 37 2.4.6 Biocement ............................................................................................. 38 2.5 Potentiometric measurement ............................................................................ 40 2.5.1 Potentiometry ........................................................................................ 40 2.5.2 Ion-sensitive electrode .......................................................................... 42 2.6 Turbidity measurement ...................................................................................... 43 3 Nucleation of C-S-H and the impact of polymers ....................................................... 46 3.1 Nucleation of C-S-H ........................................................................................... 47 3.1.1 Objecives .............................................................................................. 47 3.1.2 Results and Discussion ........................................................................ 49 3.1.3 Conclusion and outlook ........................................................................ 57 3.2 Influence of polymers ........................................................................................ 63 3.2.1 Objectives ............................................................................................. 63 3.2.2 Data evaluation ..................................................................................... 64 3.2.3 Results and discussion ......................................................................... 65 3.2.4 Conclusion ............................................................................................ 74 4 Influence of biomolecules on cement hydration ........................................................ 75 4.1 Enzyme screening ............................................................................................. 76 4.1.1 Objectives ............................................................................................. 76 4.1.2 Results and discussion ......................................................................... 77 4.1.3 Conclusion and outlook ........................................................................ 81 4.2 The effect of the cysteine protease papain ....................................................... 83 7 4.2.1 Objectives ............................................................................................. 83 4.2.2 Results and discussion ......................................................................... 84 4.2.3 Conclusion and outlook ........................................................................ 90 5 Conclusion and Outlook ............................................................................................ 92 6 Authors contributions ................................................................................................. 95 7 Appendix .................................................................................................................... 96 8 References ................................................................................................................120 9 List of Figures ...........................................................................................................124 10 List of Tables
Recommended publications
  • Tobermorite Supergroup: a New Nomenclature
    Mineralogical Magazine, April 2015, Vol. 79(2), pp. 485–495 The tobermorite supergroup: a new nomenclature CRISTIAN BIAGIONI*, STEFANO MERLINO AND ELENA BONACCORSI Dipartimento di Scienze della Terra, Universita` di Pisa, Via Santa Maria 53, 56126 Pisa, Italy [Received 10 July 2014; Accepted 30 September 2014; Associate Editor: S. J. Mills] ABSTRACT The name ‘tobermorites’ includes a number of calcium silicate hydrate (C-S-H) phases differing in their hydration state and sub-cell symmetry. Based on their basal spacing, closely related to the degree of hydration, 14, 11 and 9 A˚ compounds have been described. In this paper a new nomenclature scheme for these mineral species is reported. The tobermorite supergroup is defined. It is formed by the tobermorite group and the unclassified minerals plombie`rite, clinotobermorite and riversideite. Plombie`rite (‘14 A˚ tobermorite’) is redefined as a crystalline mineral having chemical composition Ca5Si6O16(OH)2·7H2O. Its type locality is Crestmore, Riverside County, California, USA. The tobermorite group consists of species having a basal spacing of ~11 A˚ and an orthorhombic sub-cell symmetry. Its general formula is Ca4+x(AlySi6Ày)O15+2xÀy·5H2O. Its endmember compositions correspond to tobermorite Ca5Si6O17·5H2O(x =1andy = 0) and the new species kenotobermorite, Ca4Si6O15(OH)2·5H2O(x =0andy = 0). The type locality of kenotobermorite is the N’Chwaning II mine, Kalahari Manganese Field, South Africa. Within the tobermorite group, tobermorite and kenotobermorite form a complete solid solution. Al-rich samples do not warrant a new name, because Al can only achieve a maximum content of 1/6 of the tetrahedral sites (y = 1).
    [Show full text]
  • The Hydrated Calcium, Silicates Riversideite, Tobermorite, and Plombierite
    293 The hydrated calcium, silicates riversideite, tobermorite, and plombierite. By J. D. C. McCoNNELL,M.Sc. 1)epartment of Mineralogy and Petrology, University of Cambridge. [Conmmnicated by Prof. C. E. Tilley, F.R.S., read March 26, 1953] ] NTRODUCTION. N a recent paper Taylor has shown that three distinct hydration I levels exist within the" calcium silicate hydrate (l)' group of artificial preparations (Taylor, 1953a, p. 168). The individual hydrates may be distinguished from the position of the 002 reflection in X-ray powder photographs. The d spacings corresponding to the three hydrates of this group examined during the present investigation are 1~'6, 11"3, and 9"6 ,A.. These hydrates have 1-[20 : SiO 2 molar ratios of approximately 2-0, 1.0, and 0"5 respectively. A recent examination of the minerals crestmoreite and riversideite (Taylor, 1953b) has shown that both these nfinerals are intimate inter- :growths of members of the above hydrate series with the mineral wilkeite. Both the artificial preparations and the crestmoreite-riversideite inter- growths have failed to provide material suitable for detailed optical study. During a mineralogical investigation of rocks from a dolerite-chalk contact at Ballycraigy, Larne, County Antrim, a mineral was examined and subsequently identified, from X-ray powder photographs, with the 11"3 .~. hydrate referred to above. Optical and X-ray studies on single crystals of this mineral were made and subsequently both the 14.6 and 9-6 A. hydrates were prepared from this material experimentally. X-ray powder photographs of a gelatinous material collected at Ballycraigy showed that this m~tteria] could also be identified with the 'calcium silicate hydrate (f)' group.
    [Show full text]
  • Phillipsite and Al-Tobermorite Mineral Cements Produced Through Low-Temperature Water-Rock Reactions in Roman Marine Concrete Sean R
    Western Washington University Western CEDAR Geology Faculty Publications Geology 2017 Phillipsite and Al-tobermorite Mineral Cements Produced through Low-Temperature Water-Rock Reactions in Roman Marine Concrete Sean R. Mulcahy Western Washington University, [email protected] Marie D. Jackson University of Utah, Salt Lake City Heng Chen Southeast University, Nanjing Yao Li Xi'an Jiaotong University, Xi'an Piergiulio Cappelletti Università degli Studi di Napoli Federico II, Naples See next page for additional authors Follow this and additional works at: https://cedar.wwu.edu/geology_facpubs Part of the Geology Commons Recommended Citation Mulcahy, Sean R.; Jackson, Marie D.; Chen, Heng; Li, Yao; Cappelletti, Piergiulio; and Wenk, Hans-Rudolf, "Phillipsite and Al- tobermorite Mineral Cements Produced through Low-Temperature Water-Rock Reactions in Roman Marine Concrete" (2017). Geology Faculty Publications. 67. https://cedar.wwu.edu/geology_facpubs/67 This Article is brought to you for free and open access by the Geology at Western CEDAR. It has been accepted for inclusion in Geology Faculty Publications by an authorized administrator of Western CEDAR. For more information, please contact [email protected]. Authors Sean R. Mulcahy, Marie D. Jackson, Heng Chen, Yao Li, Piergiulio Cappelletti, and Hans-Rudolf Wenk This article is available at Western CEDAR: https://cedar.wwu.edu/geology_facpubs/67 American Mineralogist, Volume 102, pages 1435–1450, 2017 Phillipsite and Al-tobermorite mineral cements produced through low-temperature k water-rock reactions in Roman marine concrete MARIE D. JACKSON1,*, SEAN R. MULCAHY2, HENG CHEN3, YAO LI4, QINFEI LI5, PIERGIULIO CAppELLETTI6, 7 AND HANS-RUDOLF WENK 1Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah 84112, U.S.A.
    [Show full text]
  • Microstructural and Compressive Strength Analysis for Cement Mortar with Industrial Waste Materials
    Available online at www.CivileJournal.org Civil Engineering Journal Vol. 6, No. 5, May, 2020 Microstructural and Compressive Strength Analysis for Cement Mortar with Industrial Waste Materials Zahraa Fakhri Jawad a, Rusul Jaber Ghayyib a, Awham Jumah Salman a* a Al-Furat Al-Awsat Technical University, Najaf, Kufa, Iraq. Received 06 December 2019; Accepted 02 March 2020 Abstract Cement production uses large quantities of natural resources and contributes to the release of CO2. In order to treat the environmental effects related to cement manufacturing, there is a need to improve alternative binders to make concrete. Accordingly, extensive study is ongoing into the utilization of cement replacements, using many waste materials and industrial. This paper introduces the results of experimental investigations upon the mortar study with the partial cement replacement. Fly ash, silica fume and glass powder were used as a partial replacement, and cement was replaced by 0%, 1%, 1.5%, 3% and 5% of each replacement by the weight. Compressive strength test was conducted upon specimens at the age of 7 and 28 days. Microstructural characteristic of the modified mortar was done through the scanning electron microscope (SEM) vision, and X-ray diffraction (XRD) analysis was carried out for mixes with different replacements. The tests results were compared with the control mix. The results manifested that all replacements present the development of strength; this improvement was less in the early ages and raised at the higher ages in comparison with the control specimens. Microstructural analysis showed the formation of hydration compounds in mortar paste for each replacement. This study concluded that the strength significantly improved by adding 5% of silica fume compared with fly ash and glass powder.
    [Show full text]
  • Atomistic Modeling of Crystal Structure of Ca1.67Sihx
    Cement and Concrete Research 67 (2015) 197–203 Contents lists available at ScienceDirect Cement and Concrete Research journal homepage: http://ees.elsevier.com/CEMCON/default.asp Atomistic modeling of crystal structure of Ca1.67SiHx Goran Kovačević a, Björn Persson a, Luc Nicoleau b, André Nonat c, Valera Veryazov a,⁎ a Theoretical Chemistry, P.O.B. 124, Lund University, Lund 22100, Sweden b BASF Construction Solutions GmbH, Advanced Materials & Systems Research, Albert Frank Straße 32, 83304 Trostberg, Germany c Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS-Université de Bourgogne, BP 47870, F-21078 Dijon Cedex, France article info abstract Article history: The atomic structure of calcium-silicate-hydrate (C1.67-S-Hx) has been investigated by theoretical methods in Received 13 February 2014 order to establish a better insight into its structure. Three models for C-S-H all derived from tobermorite are pro- Accepted 12 September 2014 posed and a large number of structures were created within each model by making a random distribution of silica Available online xxxx oligomers of different size within each structure. These structures were subjected to structural relaxation by ge- ometry optimization and molecular dynamics steps. That resulted in a set of energies within each model. Despite Keywords: an energy distribution between individual structures within each model, significant energy differences are Calcium-Silicate-Hydrate (C-S-H) (B) Crystal Structure (B) observed between the three models. The C-S-H model related to the lowest energy is considered as the most Atomistic simulation probable. It turns out to be characterized by the distribution of dimeric and pentameric silicates and the absence of monomers.
    [Show full text]
  • Thermodynamics of Cement Hydration
    UNIVERSITY OF ABERDEEN DEPARTMENT OF CHEMISTRY Thermodynamics of Cement Hydration by Thomas Matschei Dipl.-Ing., Bauhaus University Weimar A Thesis presented for the degree of Doctor of Philosophy at the University of Aberdeen Aberdeen, 06 December 2007 Declaration This Thesis is submitted to the University of Aberdeen for the degree of Doctor of Philosophy. It is a record of the research carried out by the author, under the supervision of Professor F.P. Glasser. It has not been submitted for any previous degree or award, and is believed to be wholly original, except where due acknowledgement is made. Thomas Matschei Aberdeen, December 2007 Abstract 3 Abstract The application of thermodynamic methods to cement science is not new. About 80 years ago, Bogue wrote a series of equations describing the relationship between clinker raw meal chemical composition and the mineralogy of the finished clinker. These enabled the amounts of minerals to be calculated from a bulk chemical composition. Fundamental to the equations was a precise description of the high temperature equilibrium achieved during clinkering. Bogue admitted four oxide components into the calculation; lime, alumina, silica and ferric oxide and assumed that equilibrium was attained (or very nearly attained) during clinkering. This approach, which is, with modifications, still a widely used tool to quantify cement clinkering, was one of the main motivations of this work. Thus the overall aim of this Thesis is to provide a generic toolkit, which enables the quantification of cement hydration. The use of thermodynamic methods in cement hydration was often doubted, as the water-cement system was considered to be too complex.
    [Show full text]
  • Brownmillerite Ca2(Al, Fe )2O5 C 2001-2005 Mineral Data Publishing, Version 1
    3+ Brownmillerite Ca2(Al, Fe )2O5 c 2001-2005 Mineral Data Publishing, version 1 Crystal Data: Orthorhombic. Point Group: mm2. As square platelets, to about 60 µm; massive. Physical Properties: Hardness = n.d. D(meas.) = 3.76 D(calc.) = 3.68–3.73 Optical Properties: Semitransparent. Color: Reddish brown. Optical Class: Biaxial (–). Pleochroism: Distinct; X = Y = yellow-brown; Z = dark brown. Orientation: Y and Z lie in the plane of the platelets; extinction in that plane is diagonal. α = < 2.02 β = > 2.02 γ = > 2.02 2V(meas.) = n.d. Cell Data: Space Group: Ibm2. a = 5.584(5) b = 14.60(1) c = 5.374(5) Z = 2 X-ray Powder Pattern: Near Mayen, Germany. 2.65 (vs), 7.19 (s), 2.78 (s), 1.93 (s), 2.05 (ms), 3.65 (m), 1.82 (m) Chemistry: (1) (2) (3) TiO2 1.5 1.9 Al2O3 17.2 22.3 13.1 Fe2O3 30.5 27.6 41.9 Cr2O3 0.1 n.d. MgO n.d. n.d. CaO 46.2 44.8 43.7 insol. 4.0 LOI 0.5 Total 94.4 100.3 100.6 (1) Near Mayen, Germany; by semiquantitative spectroscopy. (2) Hatrurim Formation, Israel; corresponds to Ca1.99(Al1.09Fe0.86Ti0.05)Σ=2.00O5. (3) Do.; corresponds to Ca1.95(Fe1.31Al0.64 Ti0.06)Σ=2.01O5. Occurrence: In thermally metamorphosed limestone blocks included in volcanic rocks (near Mayen, Germany); in high-temperature, thermally metamorphosed, impure limestones (Hatrurim Formation, Israel). Association: Calcite, ettringite, wollastonite, larnite, mayenite, gehlenite, diopside, pyrrhotite, grossular, spinel, afwillite, jennite, portlandite, jasmundite (near Mayen, Germany); melilite, mayenite, wollastonite, kalsilite, corundum (Kl¨och, Austria); spurrite, larnite, mayenite (Hatrurim Formation, Israel).
    [Show full text]
  • Effect of Mineralogical Changes on Mechanical Properties of Well Cement
    ARMA 19–1981 Well integrity of high temperature wells: Effect of mineralogical changes on mechanical properties of well cement TerHeege, J.H. and Wollenweber, J. TNO Applied Geosciences, Utrecht, the Netherlands Marcel Naumann Downloaded from http://onepetro.org/ARMAUSRMS/proceedings-pdf/ARMA19/All-ARMA19/ARMA-2019-1981/1133466/arma-2019-1981.pdf/1 by guest on 02 October 2021 Equinor ASA, Sandsli, Norway Pipilikaki, P. TNO Structural Reliability, Delft, the Netherlands Vercauteren, F. TNO Material Solutions, Eindhoven, the Netherlands This paper w as prepared for presentation at the 53rd US Rock Mechanics/Geomechanics Symposium held in New Y ork, NY , USA , 23–26 June 2019. This paper w as selected for presentation at the symposium by an ARMA Technical Program Committee based on a technical and critical review of the paper by a minimum of tw o technical reviewers. The material, as presented, does not necessarily reflect any position of ARMA, its of ficers, or members. ABSTRACT: Wells used for steam-assisted gravity drainage (SAGD), for cyclic steam stimulation (CSS), for hydrocarbon production in areas with anomalous high geothermal gradient, or for geothermal energy extraction all are operated in high temperature environments where maintaining long term wellbore integrity is one of the key challenges. Changes in cement mineralogy and associated mechanical properties may critically affect the integrity of high temperature wells. In this study, the relation between changes in mineralogy and mechanical properties of API class G cement with 40% silica flour was investigated by exposing samples for 1-4 weeks to temperatures of 60-420°C. The effect of mineralogical changes on mechanical properties was investigated using a combination of chemical and microstructural analysis and triaxial strength tests at confining pressures of 2-15 MPa.
    [Show full text]
  • Evolution of Geochemical Conditions in SFL 3-5
    SE0000146 R-99-15 Evolution of geochemical conditions in SFL 3-5 Fred Karlsson Svensk Kambranslehantering AB Maria Lindgren, Kristina Skagius, Marie Wiborgh Kemakta Konsult AB Ingemar Engkvist Barseback Kraft AB December 1999 Svensk Karnbranslehantering AB Swedish Nuclear Fuel and Waste Management Co Box 5864 SE-102 40 Stockholm Sweden Tel 08-459 84 00 +46 8 459 84 00 Fax 08-661 57 19 +46 8 661 57 19 J> ISSN 1402-3091 SKB Rapport R-99-15 Evolution of geochemical conditions in SFL 3-5 Fred Karlsson Svensk Karnbranslehantering AB Maria Lindgren, Kristina Skagius, Marie Wiborgh Kemakta Konsult AB Ingemar Engkvist Barseback Kraft AB December 1999 Keywords: geochemical conditions, deep repository, near-field chemistry, concrete, evolution, LILW. Abstract The evolution of geochemical conditions in the repository for long-lived low- and intermediate-level waste, SFL 3-5, and in the vicinity of the repository are important when predicting the retention of radionuclides and the long-term stability of engineered barriers. In this study the initial conditions at different repository sites at 300 - 400 m depth, the influence of repository construction and operation, the expected conditions after repository closure and saturation, and the evolution in a long-term perspective are discussed. Groundwaters that are found at these depths have near-neutral pH and are reducing in character, but the composition can vary from saline to non-saline water. The water chemistry in the near-field will mainly be influenced by the composition of the groundwater and by the large amounts of cementitious material that can be found in the repository.
    [Show full text]
  • Crystal Structure of the High-Pressure Phase of Calcium Hydroxide, Portlandite: in Situ Powder and Single-Crystal X-Ray Diffraction Study
    American Mineralogist, Volume 98, pages 1421–1428, 2013 Crystal structure of the high-pressure phase of calcium hydroxide, portlandite: In situ powder and single-crystal X-ray diffraction study RIKO IIZUKA,1,2,3,* TAKEHIKO YAGI,1,3 KAZUKI KOMATSU,2 HIROTADA GOTOU,1 TAKU TSUCHIYA,3 KEIJI KUSABA,4 AND HIROYUKI KAGI2 1Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, 277-8581, Japan 2Geochemical Research Center, Graduate School of Science, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-0033, Japan 3Geodynamics Research Center, Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577, Japan 4Department of Materials Science, Nagoya University, Nagoya, 464-8603, Japan ABSTRACT The crystal structure of a high-pressure phase of calcium hydroxide, Ca(OH)2 (portlandite), was clarified for the first time using the combination of in situ single-crystal and powder X-ray diffraction measurements at high pressure and room temperature. A diamond-anvil cell with a wide opening angle and cell-assembly was improved for single-crystal X-ray diffraction experiments, which allowed us to successfully observe Bragg reflections in a wide range of reciprocal space. The transition occurred at 6 GPa and the crystal structure of the high-pressure phase was determined to be monoclinic at 8.9 GPa and room temperature [I121; a = 5.8882(10), b = 6.8408(9), c = 8.9334(15) Å, β = 104.798(15)°]. The transition involved a decrease in molar volume by approximately 5.8%. A comparison of the structures of the low- and high-pressure phases indicates that the transition occurs by a shift of CaO6 octahedral layers in the a-b plane along the a-axis, accompanied by up-and-down displacements of Ca atoms from the a-b plane.
    [Show full text]
  • Bentorite Ca6(Cr, Al)2(SO4)3(OH)12 • 26H2O C 2001-2005 Mineral Data Publishing, Version 1
    Bentorite Ca6(Cr, Al)2(SO4)3(OH)12 • 26H2O c 2001-2005 Mineral Data Publishing, version 1 Crystal Data: Hexagonal. Point Group: 6/m 2/m 2/m. As stout hexagonal prisms, {1010}, {1011}, {0001}, to 0.25 mm; commonly in fibrous masses, granular aggregates, and thin films. Twinning: On {1010} as composition plane. Physical Properties: Cleavage: {1010}, perfect; {0001}, distinct. Hardness = 2 D(meas.) = 2.025 D(calc.) = 2.021 Optical Properties: Transparent. Color: Bright violet. Streak: Very pale violet. Luster: Vitreous. Optical Class: Uniaxial (+). Pleochroism: O = nearly colorless; E = pale violet. Absorption: O < E. ω = 1.478(2) = 1.484(2) Cell Data: Space Group: P 63/mmc. a = 22.35 c = 21.41 Z = 8 X-ray Powder Pattern: Hatrurim Formation, Israel. 9.656 (100), 5.592 (40), 1.942 (20), 3.60 (10), 3.23 (10), 2.772 (10), 3.89 (8) Chemistry: (1) SO3 14.99 CO2 6.70 SiO2 2.50 Al2O3 1.01 Fe2O3 0.10 Cr2O3 7.48 MgO 0.00 CaO 29.90 H2O 37.70 Total 100.38 (1) Hatrurim Formation, Israel; by AA, SO3 by gravimetric analysis, CO2 and H2O by TGA; after deduction of CaO and CO2 as calcite and CaO, SiO2, H2O as truscottite, the remainder 3+ • (about 80%) corresponds to Ca5.88(Cr1.61Al0.32Fe0.02)Σ=1.95(S1.02O4)3.00(OH)11.97 28.06H2O. Mineral Group: Ettringite group. Occurrence: In low-temperature hydrothermal veins in black calcite–spurrite marble. Association: Calcite, thaumasite, truscottite, vaterite, jennite, tobermorite, brownmillerite, mayenite, melnikovite, “chlorite”. Distribution: In a marble quarry in the Hatrurim Formation, near the Arad-Sodom road, Negev Desert, Israel.
    [Show full text]
  • Mayenite Ca12al14o33 C 2001-2005 Mineral Data Publishing, Version 1
    Mayenite Ca12Al14O33 c 2001-2005 Mineral Data Publishing, version 1 Crystal Data: Cubic. Point Group: 43m (synthetic). In rounded anhedral grains, to 60 µm. Physical Properties: Hardness = n.d. D(meas.) = 2.85 D(calc.) = [2.67] Alters immediately to hydrated calcium aluminates on exposure to H2O. Optical Properties: Transparent. Color: Colorless. Optical Class: Isotropic. n = 1.614–1.643 Cell Data: Space Group: I43d (synthetic). a = 11.97–12.02 Z = 2 X-ray Powder Pattern: Near Mayen, Germany. 2.69 (vs), 4.91 (s), 2.45 (ms), 3.00 (m), 2.19 (m), 1.95 (m), 1.66 (m) Chemistry: (1) (2) (3) SiO2 0.4 Al2O3 45.2 49.5 51.47 Fe2O3 2.0 1.5 MnO 1.4 CaO 45.7 47.0 48.53 LOI 2.2 Total 95.1 99.8 100.00 (1) Near Mayen, Germany; by semiquantitative spectroscopy. (2) Hatrurim Formation, Israel; by electron microprobe, corresponding to (Ca11.7Mg0.5)Σ=12.2(Al13.5Fe0.25Si0.10)Σ=13.85O33. (3) Ca12Al14O33. Occurrence: In thermally metamorphosed limestone blocks included in volcanic rocks (near Mayen, Germany); common in high-temperature, thermally metamorphosed, impure limestones (Hatrurim Formation, Israel). Association: Calcite, ettringite, wollastonite, larnite, brownmillerite, gehlenite, diopside, pyrrhotite, grossular, spinel, afwillite, jennite, portlandite, jasmundite (near Mayen, Germany); melilite, wollastonite, kalsilite, brownmillerite, corundum (Kl¨och, Austria); spurrite, larnite, grossite, brownmillerite (Hatrurim Formation, Israel). Distribution: From the Ettringer-Bellerberg volcano, near Mayen, Eifel district, Germany. Found at Kl¨och, Styria, Austria. In the Hatrurim Formation, Israel. From Kopeysk, Chelyabinsk coal basin, Southern Ural Mountains, Russia. Name: For Mayen, Germany, near where the mineral was first described.
    [Show full text]