Nuclear Magnetic Resonance Spectroscopy of Cement-Based Materials

Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Santa Clara Singapore Tokyo

P. Colombet, A.-R. Grimmer, H. Zanni, P. Sozzani (Eds.)

Nuclear Magnetic Resonance Spectroscopy of Cement-Based Materials

With 235 Figures and 55 Tables

Springer

Editors:

Dr. Pierre Colombet CTG Italcementi-Ciments Fran~ais rue des Technodes 78931 Guerville, France

Dr. Amd-Rtidiger Grimmer Institut fUr Chemie Humboldt-Universitat Rudower Chaussee, Haus 4.1 12484 Berlin, Germany

ISBN-13:978-3-642-80434-2

Die Deutsche Bibliothek - CIP-Einheitsaufnahme

Professor Helene Zanni ESPCI 10 rue Vauquelin 75231 Paris Cedex 5, France

Professor Piero Sozzani Universita degli Studi di Milano Dipartimento di Scienza dei Materiali Chimica e Technologia dei Materiali Via Emanueli 15 20126 Milano, Italy

Nuclear magnetic resonance spectroscopy of cement based materials / P. Colombet ... (ed.). -Berlin; Heidelberg; New York; Barcelona; Budapest; Hong Kong; London; Milan; Paris; Santa Clara; Singapore; Tokyo; Springer, 1998

ISBN-13:978-3-642-80434-2 e-ISBN-13:978-3-642-80432-8 DOl: 10.1007/978-3-642-80432-8

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law.

© Springer-Verlag Berlin Heidelberg 1998 Softcover reprint of the hardcover 1 st edition 1998

The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

Product liability: The publisher cannot guarantee the accuracy of any information about dosage and application contained in this book. In every individual case the user must check such information by consulting the relevant literature.

Typesetting: Camera-ready by authors Cover: de'blik, Berlin SPIN:I0558403 66/3020-543210-Printedonacid-freepaper

Contributors

Y.Adachi G.W.Groves T.Nunes F.Adenot D. Heidemann P. V.Nuss J. P. Amoureux V.N. Izmailova Y.Okada F.Bergaya J.F. Jacquinot A. N. Ovchinnikov C. Bessada HJ. Jakobsen A. Papageorgiou P. Bodart O. Jarh G. Papavassiliou L. Bonafous P. Jevnikar L. Pel B. Bresson S. Jiang D. Petit H. Brocken H. Justnes S. Philippot A.R.Brough RJ. Kirkpatrick B. Pollet L. Cassar K. Kopinga E. W. Randall E. Chaniotakis J.-P. Korb N. Richard M. Cheyrezy I. Klur I. G. Richardson M. Chloup-Bondant R. Kovacevic J. C. Rifflet P. Colombet X. Lecoq V.V.Rodin A. Comotti A. Leventis A. Sepe X. Cong N. Lequeux E. D. Shchukin J-.P. Coutures B. LeRolland R. Simonutti M. Crespin I. Lognot J. Skibsted M. Dakkouri C. Magnenet P. Sozanni L. Delevoye V.Manic M. Stefanovic P. Dion V.Maret M.Takada C.M. Dobson T.Masuda R. Toffanin R. Dron S. Masse B. Touzo Y.Dumazy D. Massiot D. Trumeau A.Douy Y.Matsuda Z. D. Tulovskaya O.Evrard P.F. McMillan H.VanDamme M. Fardis F. Milia J. Virlet I. Farnan L. Miljkovic V. Waller P. Faucon T. Mitsuda W. Wieker M.-P. Faugere V.Mlynarik L.Xu C. Fernandez V. Montouillout H.Yamada A. Feylessoufi N. Nestle G. P. Yampolskaya P. Florian T. Nishino J. L. Yarger N.Funduk C. Noik T. Yokoyama N. Gautier H.Noma H.Zanni A.-R. Grimmer A. Nonat

Participants at the 2nd International Conference on NMR-Spectroscopy of Cement-Based Materials, Bergamo, June 1996

Foreword

The 2nd International Conference on NMR Spectroscopy of Cement Based Materials was held in Bergamo in June 1996, four years after the 1st Conference organised by Ciments Fran~ais [1]. The Italcementi Group strongly wished to reinforce the widespread interest in this modern technique of investigation as applied to cementitious materials by organising the 1996 conference.

There had been a surge of interest in the application of the NMR technique to cement as shown by the number of papers presented at the Bergamo Conference -more than twice as many as presented in 1992 in Guerville. Many internationally renowned research teams are currenty directing their work towards cement thus making this material into a topic of high academic interest.

Among the most prominent teams attending the Conference were those headed by J.P. Coutures (CNRS-Orleans), J.P. Korb (Ecole Polytechnique-Palaiseau), J.Virlet (CEA-Saclay), P. Sozzani (University of Milano), L. Pel (University of Eindhoven), T. Nunes (University of Lisboa) and H. Noma (University of Kyushu). These prominent researchers have thus joined the teams that have always been working in the cement field, in particular A-R Grimmer (the Humboldt University of Berlin), H. Zanni (ESPCI, Paris), J. Kirkpatrick (University of Illinois), J. Skibsted and H. Jakobsen (University of Aarhus), A Nonat (CNRS-Dijon), AR. Brough (University of Oxford), H. Justnes (SINTEF, Trondheim) and H. Van Damme (CNRS-Orleans).

An even deeper impression of these investigation efforts was the active participation of a number of major industrial Groups, among which we would like to mention the Italcementi Group, Chichibu-Onoda, Titan, Bouygues, EDF, Novi Popovac. This means that, apart from the outstanding scientific interest, these studies have started yielding "concrete" returns on the initial equipment investment costs.

Three especially outstanding case studies can be quoted here. The first one involved the study of mortar adhesion to bricks undertaken by Brocken, Pel and Kopinga from the University of Eindhoven. Two types of brick (fired-clay and sand-lime) previously subjected to drying were investigated, researchers found that the moisture profile of the mortar remains constant throughout the entire water extraction process and this is irrespective of the type of brick being tested. This indicates that water diffusiveness is definitely greater in mortars than in bricks. All the available water has been extracted from the mortar during the first minute after placing. Moreover, the authors found that equilibrium is attained more rapidly in the fired-clay brick (3 minutes) than in the sand-lime type (10 minutes). At a later stage, the experimental results were used to investigate the

VIII

influence of the brick pre-wetting rate on the final water content of the relevant mortar.

A second case study with an immediate application concerns the effect of the silica fume on the kinetics of hydration in Portland cements. The study was carried out by H. Justnes and collaborators. The practical interest of this study is most evident in terms of both the formulation of cement binders containing silica and the selection of the most adequate curing temperature. A host of most helpful data have been obtained so far. For example, it was shown that the presence of silica fume delays the hydration of I-day old Portland cement, while, before that stage, hydration is accelerated. Such a trend is more and more marked at later ages especially with a decreasing waterlbinder ratio. It was also shown that the curing temperature affects the composition of the paste considerably more than the setting temperature does. Therefore, at 28 days, the rate of hydration of the cement is notably increased for curing temperatures exceeding 70 DC in comparison to a curing temperature of 20 DC. By contrast, hydration is slightly lower for more moderate temperatures (50-60 DC). Moreover, effects are more pronounced with weak waterlbinder ratios.

Another case study concerns clinkering reactions. This work, resulting from the collaboration between the Italcementi Group and the Orleans-based CNRS CRPHT (High Temperature Physics Laboratory) headed by J.P. Coutures, is something of a novelty in that the high temperature equipment developed for the purpose is unique. Static NMR spectra can be obtained from ambient temperatures to temperature as high as 1500 DC! This technique has been specifically used to investigate the effect of the addition of fluorine to an industrial raw mix.

There are many other case studies which should be mentioned in more detail, e.g. those concerning the quantitative analysis of the clinker phases with an accuracy of one per cent, the proportions of aluminates incorporated into silicates, ettringite and calcium monosulfate (Skibsted and Jacobsen), the determination of the crystallographic structure of silicates and calcium hydrates (Heidemann et aI., Zanni et aI., Kirkpatrick et aI., Nonat et aI.), the determination of the interphase domain range in cement-polymer composites (Sozzani et aI.), and so on.

In conclusion, the NMR technique is proving to be one of the most significant tools for obtaining industrially applicable scientific information in the field of cementitious materials.

Bergamo, September 1997 Luigi Cassar

Reference 1. Colombet P, Grimmer A-R (1994) Application of NMR spectroscopy to cement

science. Gordon and Breach, Amsterdam

Preface

The main topics of research on cement based materials can be addressed by Nuclear Magnetic Resonance. After the first monograph edited by some of the authors three years ago, which was mainly devoted to the introduction of basic principles of cement chemistry as well as of NMR, this book enlarges the field of applications and updates the results with the contribution of the most active groups worldwide. It appears as a unique blend of basic science and applied science in the field of building technology.

Its 36 papers written by leading experts illustrate how fast this field of interest has grown in just a very few years. They are collected into thematic areas. These include both ambient- and high-temperature investigations of the various mineral phases which constitute Portland and special cements (Chapter I), structural aspects of hydrated pure phases (Chapter IT), the effect of mineral or organic admixtures on the structure of hydrates and on hydration kinetics (Chapter ill), and the dynamic characterisation of cement matrices, giving e.g. the pore size distribution and its contribution to the properties of real construction materials (Chapter IV). Through those particular aspects, the book reveals the broad range of applicability of NMR spectroscopy as well as its ability to promote new methodologies and interpretations for the study of a wide range of physical and chemical features of cement-based materials.

The collection of these papers would not have taken place without the meeting held last year in the medieval town of Bergamo, which rises where the Po valley turns into the Bergamask Alps. More than 80 scientists from 14 countries gathered in the Conference Centre Giovanni xxm for a few hot summer days in June 1996 for the 2nd International Conference on NMR Spectroscopy of Cement-Based Materials.

The preparation and realization of such a meeting was based on the help of many colleagues and friends. We are happy to express our gratitude to the other members of the Steering Committee (James Kirkpatrick, Paul McMillan, Henri Van Damme and Jean-Pierre Coutures) for having efficiently contributed to the original selection of papers and ensuring the international character of the Conference. We also warmly thank the Session chairmen: James Kirkpatrick, Franco Massazza, Adrian Brough and Harald Justnes who stimulated fruitful discussions during the meeting, and the authors who rapidly complied with the revisions we suggested. Finally we are grateful to Anne­Marie Lebrun and Luisa Baggi for their crucial help in organizing the Conference and preparing the manuscript.

September 1997 Pierre Colombet Arnd-Rudiger Grimmer Helene Zanni Piero Sozzani

Contents

Part I Clinkerization Reactions and Anhydrous Phase Characterization

1. Charaterization of the Calcium Silicate and Aluminate Phases in Anhydrous and Hydrated Portland Cements by 27 Al and 29Si MAS NMR Spectroscopy J Skibsted and H. J Jakobsen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2. In Situ High Temperature Multinuclear NMR Study of Clinker Formation L. Bona/ous, C. Bessada, D. Massiot, J-P. Coutures, B. LeRolland and P. Colombet ..................................... 47

3. 29Si NMR Study of Chemical Shift Tensor Anisotropy ofTricalcium Silicate A.-R. Grimmer and H. Zanni. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

4. Relationship Between NMR 29Si Chemical Shifts and FT-IR Wave Numbers in Calcium Silicates Y Okada, T. Masuda, M Takada, L. Xu and T. Mitsuda . . . . . . . . . . . . . . . . . 69

5. Multiquantum (3Q and 5Q) MAS NMR Spectroscopy of Aluminium-27 in Solids C. Fernandez, J P. Amoureux, Y Dumazy and L. Delevoye . . . . . . . . . . . . . 79

6. New Progress in High Resolution 27 Al and 170 Solid State NMR (MAS and MQ-MAS) of Aluminium Bearing Phases D. Massiot, B. Touzo, D. Trumeau, C. Magnenet, V. Montouillout, P. Florian, C. Bessada, A. Douy, J-P. Coutures and J Virlet ........... 89

XII

7. Time Resolved Very High Temperature NMR Study of the Cooling Process of CaO-AI20 3 Liquids D. Massiot, B. Touzo, D. Trumeau, I. Farnan, J C. RifJlet, C. Bessada, A. Douy and J-P. Coutures . . . . . . . . . . . . . . . . . . . . . . . . . . . .. to7

Part II The Nanostructure of C-S-H

8. C-S-H Structure Evolution with Calcium Content by Multinuclear NMR I. Klur, B. Pollet, J Virlet and A. Nonat . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 119

9. The Structure of Calcium Silicate Hydrate: NMR and Raman Spectroscopic Results X Cong, R. J Kirkpatrick, J L. Yarger and P.F. McMillan. . . . . . . . . . . . .. 143

to. 29Si MAS NMR Spectroscopy of Poorly-Crystalline Calcium Silicate Hydrates (C-S-H) H. Noma, Y. Adachi, H. Yamada, T. Nishino, Y. Matsuda and T. Yokoyama. 159

II. Characterization of Protons in C-S-H Phases by Means of High-Speed 1 H MAS NMR Investigations D. Heidemann and W. Wieker ..................................... 169

12. Structural Investigation of Calcium Silicate Hydrates by X-Ray Absorption Spectroscopy N. Lequeux and N. Richard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 181

13. NMR and Infrared Spectroscopies ofC-S-H and AI-Substituted C-S-H Synthesised in Alkaline Solutions I. Lognot, I. Klur and A. Nonat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 189

14. The Structure, Stoichiometry and Properties ofC-S-H Prepared by C3S Hydration Under Controlled Condition A. NonatandX Lecoq ............................................ 197

15. Tricalcium Silicate Hydration at High Temperature. A 29Si and 1 H NMR Investigation

XIII

B. Bresson, S. Masse, H. Zanni and C. Noik . . . . . . . . . . . . . . . . . . . . . . . . .. 209

16. Influence of Heat Treatment Kinetics on Calcium Silicate Hydrates Phase Evolution M-P. Faugere, M Crespin, P. Dion, F. Bergaya, A. Feylessoufi and H. Van Damme .............................................. 217

17. Thermochemical and Macromolecular Approach ofthe C-S-H Structure R. Dron and V Waller. ..... ..... ........ ........... ........ ... ... 227

Part III Effect of Admixtures on Hydration

18. Hydration ofTricalcium Silicate by D20: 29Si and 2H Solid State NMR Spectra A. Comotti, R. Simonutti and P. Sozzani ............................. 237

19. Kinetics of Reaction in Cementitious Pastes Containing Silica Fume as Studied by 29Si MAS NMR H. Justnes ...................................................... 245

20. 29Si Enrichment and Selective Enrichment for Study of the Hydration of Model Cements and Blended Cements A. R. Brough, 1. G. Richardson, G. W Groves and C. M Dobson . . . . . . . .. 269

21. Alkali Activation of Reactive Silicas in Cements: In Situ 29Si MAS NMR Studies of the Kinetics of Silicate Polymerization A. R. Brough, 1. G. Richardson, G. W Groves and C. M Dobson . . . . . . . .. 277

22. Effect of Post Set Heat Treatment on Hydrate Formation"in Reactive Powder Concrete Studied by 29Si NMR S. Philippot, V Maret and H. Zanni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 287

XIV

23. Tricalcium Aluminate and Silicate Hydration. Effect of Limestone and Calcium Sulfate AI. Chloup-Bondant and O. Evrard .................................. 295

24. The Interaction ofPolyvinylalcohoVAcetate with CA, C3A and C3S in MDF Materials, as Described by Spin-Propagation Across Heterogeneous Interfaces L. Cassar, A. Comotti, R. Simonutti and P. Sozzani . ..................... 309

25. Changes in Structure ofCaAI2014H20 During Heat Treatments: X-Ray Absorption Spectroscopy and 27 Al NMR Studies N. Richard, N. Lequeux and P. Florian ............................... 321

Part IV Porosity, Texture and Transport Properties

26. Nuclear Relaxation of Water Confined in Reactive Powder Concrete J.-P. Korb, D. Petit, S. Philippot, H. Zanni, V Maret and AI. Cheyrezy . .... 333

27. NMR Study of Growth Dynamics in Hardening Cement Gels G. Papavassiliou, AI. Fardis, A. Leventis, F. Milia, E. Chaniotakis and A. Papageorgiou .............................................. 345

28. NMR-Approach in the Study of the Influence a Nonionic Surfactant on Water State During Cement Hardening V N. Izmailova, V V Rodin, E. D. Shchukin, G. P. Yampolskaya, P. V. Nuss, A. N. Ovchinnikov and Z. D. Tulovskaya . ..................... 355

29. A Study of Na-Montmorillonite Additions Influence on Portland Cement Hydration by I H T I Relaxation V. Manic, L. Miljkovic, AI. Stefanovic and R. Kovacevic . ................ 363

30. NMR Microscopy of Glass-Ionomer Cements 0. Jarh, A. Sepe, P. Jevnikar, N. Funduk, R. Toffanin and V. Mlynarik ..... 369

xv

31. Influence of Fillers on Textural and Mechanical Properties of C3S Pastes S. Jiang and H. Van Damme ........................................ 379

32. Water Extraction Out of Mortar During Brick Laying: A NMR Study H. Brocken, L. Pel and K. Kopina .................................... 387

33. Moisture Transport Over the BrickIMortar Interface H. Brocken, L. Pel and K. Kopinga ................................... 397

34. 27 Al MAS NMR Study on Cement Paste Degradation by Water P. Faucon, J. F. Jacquinot, F. Adenot, N. Gautier, D. Massiot and J. Virlet . . 403

35. The Hardening of Portland Cement Studied by IH Stray-Field Imaging: Influence of Concentration and Evaporation Rate of Water T Nunes, P. Bodard and E. W Randall ............................... 411

36. Bringing Applied Research Into the Student's Lab: Pulse NMR of Cement Based Materials N. Nestle and M Dakkouri ......................................... 417

Subject Index ..................................................... 425