Decalcification shrinkage of cement paste

Decalcification of cement paste in concrete is associated with several modes of chemical degradation including leaching, carbonation and sulfate attack. The primary aim of the current study was to investigate the effects of decalcification under saturated conditions on the dimensional stability of cement paste. Thin (0.8 mm) specimens of tricalcium silicate (C3S) paste, white portland cement (WPC) paste, and WPC paste blended with 30% silica fume (WPC/30% SF) were decalcified by leaching in concentrated solutions of ammonium nitrate, a method that efficiently removes calcium from the solid while largely preserving silicate and other ions. All pastes were found to shrink significantly and irreversibly as a result of decalcification, particularly when the Ca/Si ratio of the C–S–H gel was reduced below ¨1.2. Since this composition coincides with the onset of structural changes in C–S–H such as an increase in silicate polymerization and a local densification into sheet-like morphologies, it is proposed that the observed shrinkage, here called decalcification shrinkage, is due initially to these structural changes in C–S–H at Ca/Si ¨1.2 and eventually to the decomposition of C–S–H into silica gel. In agreement with this reasoning, the blended cement paste exhibited greater decalcification shrinkage than the pure cement pastes due to its lower initial Ca/Si ratio for C–S–H gel. The similarities in the mechanisms of decalcification shrinkage and carbonation shrinkage are also discussed. D 2005 Published by Elsevier Ltd.

[1]  R. Cabrillac,et al.  Long-term behaviour of cement pastes used for nuclear waste disposal: review of physico-chemical mechanisms of water degradation , 1998 .

[2]  H. Taylor,et al.  Solubility and structure of calcium silicate hydrate , 2004 .

[3]  H. Taylor,et al.  Microstructural and microanalytical studies of sulfate attack. II. Sulfate-resisting Portland cement: Ferrite composition and hydration chemistry , 1994 .

[4]  C. M. Hunt,et al.  Reaction of Hardened Portland Cement Paste With Carbon Dioxide , 1962 .

[5]  Franz-Josef Ulm,et al.  POROPLASTIC PROPERTIES OF CALCIUM-LEACHED CEMENT-BASED MATERIALS , 2003 .

[6]  Jeffrey J. Thomas,et al.  Effects of Decalcification on the Microstructure and Surface Area of Cement and Tricalcium Silicate Pastes | NIST , 2004 .

[7]  G. Escadeillas,et al.  Use of ammonium nitrate solution to simulate and accelerate the leaching of cement pastes due to deionized water , 1997 .

[8]  P. Gegout,et al.  Effect of pH on the durability of cement pastes , 1992 .

[9]  Paul F. McMillan,et al.  Structure of Calcium Silicate Hydrate (C‐S‐H): Near‐, Mid‐, and Far‐Infrared Spectroscopy , 2004 .

[10]  Franz-Josef Ulm,et al.  Mechanical properties of calcium-leached cement pastes: Triaxial stress states and the influence of the pore pressures , 2001 .

[11]  J. Marchand,et al.  Water attack of a cement paste: towards an improved accelerated test? , 1998 .

[12]  G. Scherer Mechanics of syneresis I. Theory , 1989 .

[13]  M. Kumagai,et al.  29Si MAS NMR Study on Structural Change of Silicate Anions with Carbonation of Synthetic 11Å Tobermorite , 1992 .

[14]  E. Lesniewska,et al.  Investigation by atomic force microscopy of forces at the origin of cement cohesion. , 2001, Ultramicroscopy.

[15]  G. Litvan Volume instability of porous solids , 1984 .

[16]  Å. Grudemo An electronographic study of the morphology and crystallization properties of calcium silicate hydrates , 1955 .

[17]  R. Feldman,et al.  Length change characteristics of Ca(OH)2 compacts on exposure to water vapour , 2007 .

[18]  H. Taylor,et al.  Microstructural and microanalytical studies of sulfate attack. I. Ordinary portland cement paste , 1992 .

[19]  A. Prebus,et al.  Crystal Chemistry of Hydrous Calcium Silicates: III, Morphology and Other Properties of Tobermorite and Related Phases , 1958 .

[20]  F. Adenot,et al.  Leaching of cement: Study of the surface layer , 1996 .

[21]  P. Colombet,et al.  Nuclear magnetic resonance spectroscopy of cement-based materials , 1998 .

[22]  H. Taylor,et al.  Microstructural and microanalytical studies of sulfate attack. IV. Reactions of a slag cement paste with sodium and magnesium sulfate solutions , 1996 .

[23]  I. Richardson Tobermorite/jennite- and tobermorite/calcium hydroxide-based models for the structure of C-S-H: applicability to hardened pastes of tricalcium silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume , 2004 .

[24]  Raoul François,et al.  MODELLING THE LOSS OF STRENGTH AND POROSITY INCREASE DUE TO THE LEACHING OF CEMENT PASTES , 1999 .

[25]  C. Brinker Sol-gel science , 1990 .

[26]  S. Nagasaki,et al.  Silicate Anion Structural Change in Calcium Silicate Hydrate Gel on Dissolution of Hydrated Cement , 2002 .

[27]  J. Young,et al.  Effects of pH on precipitation of quasi-crystalline calcium silicate hydrate in aqueous solution , 2000 .

[28]  A. Nonat,et al.  C-S-H Structure Evolution with Calcium Content by Multinuclear NMR , 1998 .

[29]  A. M. Dunster,et al.  An investigation of the carbonation of cement paste using trimethylsilylation , 1989 .

[30]  E. G. Swenson,et al.  Mechanism of the carbonatation shrinkage of lime and hydrated cement , 2007 .

[31]  N. Lequeux,et al.  Extended X‐ray Absorption Fine Structure Investigation of Calcium Silicate Hydrates , 2004 .

[32]  X. Cong,et al.  29Si MAS NMR study of the structure of calcium silicate hydrate , 1996 .

[33]  H. Damme,et al.  Microscopic physical basis of the poromechanical behavior of cement-based materials , 2004 .

[34]  F. Adenot,et al.  Modelling of the corrosion of the cement paste by deionized water , 1992 .

[35]  K. Scrivener,et al.  Mechanisms of chemical degradation of cement-based systems: proceedings of the Materials Research Society's Symposium on Mechanisms of Chemical Degradation of Cement-based Systems, Boston, USA, 27-30 November 1995 , 1997 .

[36]  F. Ulm,et al.  The effect of two types of C-S-H on the elasticity of cement-based materials: Results from nanoindentation and micromechanical modeling , 2004 .

[37]  F. Matsushita,et al.  CALCIUM SILICATE STRUCTURE AND CARBONATION SHRINKAGE OF A TOBERMORITE-BASED MATERIAL , 2004 .

[38]  W. Müller-Warmuth,et al.  MAS NMR Studies of Partially Carbonated Portland Cement and Tricalcium Silicate Pastes , 1993 .

[39]  R. Pellenq,et al.  Electrostatic Attraction between Two Charged Surfaces: A (N,V,T) Monte Carlo Simulation , 1997 .

[40]  George W. Scherer,et al.  Theory of Drying , 1990 .

[41]  Christopher M. Dobson,et al.  Progressive Changes in the Structure of Hardened C3S Cement Pastes due to Carbonation , 1991 .

[42]  I. Richardson,et al.  The carbonation of hardened cement pastes , 1990 .

[43]  G. Scherer Mechanics of syneresis II. Experimental study , 1989 .

[44]  C. Dobson,et al.  The carbonation of OPC and OPC/silica fume hardened cement pastes in air under conditions of fixed humidity , 1993 .

[45]  E. Garboczi,et al.  Modelling the leaching of calcium hydroxide from cement paste: effects on pore space percolation and diffusivity , 1992 .

[46]  D. Neumann,et al.  Ca-OH Bonding in the C-S-H Gel Phase of Tricalcium Silicate and White Portland Cement Pastes Measured by Inelastic Neutron Scattering , 2003 .

[47]  Pk Mehta,et al.  Materials Science of Concrete II , 1992 .

[48]  G. Verbeck Carbonation of Hydrated Portland Cement , 1958 .