Microstructure–toughness relationships in calcium aluminate cement–polymer composites using instrumented scratch testing


We investigate the influence of the microstructure on the fracture properties of calcium aluminate cement/polymer composites. We carry out microscopic scratch tests during which a Rockwell C diamond probe pushes across the surface of a polished specimen under a linearly increasing vertical force. We extend the scratch fracture method to heterogeneous materials. The scratch test induces a ductile-to-brittle transition as the penetration depth increases. Scanning electron microscopy imaging shows that the low porosity and the strong cement-binder interphase favor toughening mechanisms such as crack trapping and bridging. Nonlinear fracture mechanics theory yields the fracture toughness in the fracture-driven regime. The fracture toughness of macro-defect-free (MDF) cement is found to decrease as the polymer-to-cement ratio increases. This decrease in the fracture resistance can be explained by the decrease in anhydrous cement content and the increase in the inter-particle distance between cement grains. By evaluating the fracture toughness of the micro-constituents of MDF cement, we show that the high value of the fracture toughness at the composite level stems from tough calcium aluminate phases and a highly packed non-porous granular microstructure.

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  1. 1

    Taylor HFW (1997) Cement chemistry, 2nd edn. Thomas Telford Publishing, London

    Google Scholar 

  2. 2

    Scrivener KL, Cabiron JL, Letourneux R (1999) High-performance concretes from calcium aluminate cements. Cem Conc Res 29:1215–1223

    Article  Google Scholar 

  3. 3

    Robson TD (1962) High-alumina cements and concretes. Wiley, New York

    Google Scholar 

  4. 4

    Williams DF, McNamara A, Birchall JD, Howard AJ, Kendall K (1984) The interaction between MDF cement and tissues. J Mater Sci 19:637–644. doi:10.1007/BF00553589

    Article  Google Scholar 

  5. 5

    Alford NM, Birchall JD (1985) The properties and potential applications of macro-defect-free cement. In: MRS proceedings, vol 42. doi 10.1557/PROC-42-265

  6. 6

    Hasegawa M, Kobayashi T, Pushpalal GKD (1995) A new class of high strength, water and heat resistant polymer–cement composite solidified by an essentially anhydrous phenol resin precursor. Cem Concr Res 25:1191–1198

    Article  Google Scholar 

  7. 7

    McHugh AJ, Tan LS (1993) Mechano-chemical aspects of the processing/property/structure interactions in a macro-defect-free cement. Adv Cement Based Mater 1:2–11

    Article  Google Scholar 

  8. 8

    Qiao Y (2005) On the fracture toughness of calcium aluminate cement-phenol resin composites. Cem Concr Res 35:220–225

    Article  Google Scholar 

  9. 9

    Edmonds RN, Majumdar AJ (1989) The hydration of an aluminous cement with added polyvinyl alcohol–acetate. J Mater Sci 24:3813–3818. doi:10.1007/BF01168940

    Article  Google Scholar 

  10. 10

    Ekincioglu O, Ozkul MH, Struble LJ, Patachia S (2012) Optimization of material characteristics of macro-defect-free cement. Cem Concr Comp 34:556–565

    Article  Google Scholar 

  11. 11

    Popoola OO, Kriven WM, Young YF (1991) Microstructural and microchemical characterization of a calcium aluminate-polymer composite (MDF Cement). J Am Cer Soc 74:1928–1933

    Article  Google Scholar 

  12. 12

    Donatello S, Tyrer M, Cheeseman CR (2009) Recent developments in macro-defect-free cements. Constr Build Mater 23:1761–1767

    Article  Google Scholar 

  13. 13

    Pushpalal GKD, Kobayashi T, Kawano T, Maeda N (1999) The processing, properties and applications of calcium aluminate-phenol resin composite. Cem Concr Res 29:121–132

    Article  Google Scholar 

  14. 14

    Birchall JD, Howard AJ, Kendall K (1981) Flexural strength and porosity of cements. Nature 289

  15. 15

    Bonapasta AA, Buda F, Colombet P (2000) Cross-linking of Poly(vinyl alcohol) grains by Al ions in macro-defect-free cements: a theoretical study. Cehm Mater 12:738–743

    Article  Google Scholar 

  16. 16

    Rodger SA, Brooks SA, Sinclair W, Groves GW (1985) Double DD, high strength cement pastes Part 2 reactions during setting. J Mater Sci 20:2853–2860. doi:10.1007/BF00553048

    Article  Google Scholar 

  17. 17

    Rodger SA, Sinclair W, Groves GW, Brooks SA, Double D (1984) Reactions in the setting of high strength cement pastes. MRS Online Proc Libr Arch. doi:10.1557/PROC-42-45

    Google Scholar 

  18. 18

    Lewis JA, Kriven W (1983) Microstructure-property relationships in macro-defect-free cements. MRS Bull 18:72–77

    Article  Google Scholar 

  19. 19

    Zhang W (2014) Synthesis and fracture toughness of macro-defect-free-cement. M. Sc. Thesis, University of Illinois at Urbana-Champaign

  20. 20

    Mai Y-W, Barakat B, Cotterell B (1990) R-curve behaviour in macro-defect-free cement paste. Philos Mag A 62:347–361

    Article  Google Scholar 

  21. 21

    Chou YS, Mecholsky JJ Jr, Silsbee M (1990) Fracture toughness of macro-defect-free cement using small crack techniques. J Mat Res 5:1774–1780

    Article  Google Scholar 

  22. 22

    Pushpalal GKD (2000) Fracture behavior of calcium aluminate-phenol resin composite. J Mater Sci 35:981–987. doi:10.1023/A:1004771029440

    Article  Google Scholar 

  23. 23

    Akono AT, Ulm FJ, Bazant ZP (2014) Discussion: strength-to-fracture scaling in scratching. Eng Fract Mech 119:21–28

    Article  Google Scholar 

  24. 24

    Akono AT, Ulm FJ (2011) Scratch test model for the determination of fracture toughness. Eng Fract Mech 78:334–342

    Article  Google Scholar 

  25. 25

    Akono AT, Ulm FJ (2014) An improved technique for characterizing the fracture toughness via scratch test experiments. Wear 313:117–124

    Article  Google Scholar 

  26. 26

    Akono AT, Ulm FJ (2012) Fracture scaling relations of axisymmetric shape. J Mech Phys Solids 60:379–390

    Article  Google Scholar 

  27. 27

    Akono AT, Randall NX, Ulm FJ (2012) Experimental determination of the fracture toughness via micro scratch tests: application to polymers, ceramics and metals. J Mater Res 27:485–493

    Article  Google Scholar 

  28. 28

    Ange-Therese A (2016) Energetic size effect law at the microscopic scale: application to progressive-load scratch testing. J Nanomech Micromech. doi:10.1061/(ASCE)NM.2153-5477.0000105

    Google Scholar 

  29. 29

    Krakowiak KJ, Thomas JJ, Musso S, James S, Akono AT, Ulm FJ (2015) Nano-chemo-mechanical signature of conventional oil-well cement systems: effects of elevated temperature and curing time. Cem Concr Res 67:103–121

    Article  Google Scholar 

  30. 30

    Miller M, Bobko C, Vandamme M, Ulm FJ (2008) Surface roughness criteria for cement paste nanoindentation. Cem Concr Res 38:467–476

    Article  Google Scholar 

  31. 31

    Theophrastus, On Stones, c. 300 BC

  32. 32

    Broz ME, Cook RF, Whitney DL (2006) Microhardness, toughness and mohs scale minerals. aMER Mineralog 91:135–142

    Article  Google Scholar 

  33. 33

    Bard R, Ulm FJ (2012) Scratch hardness-strength solutions for cohesive frictional materials. Int J Numer Anal Methods Geomech 36:307–326

    Article  Google Scholar 

  34. 34

    Axén N, Kahlman L, Hutchings IM (1997) Correlation between tangential force and damage mechanisms in the scratch testing of ceramics. Tribol Int 30:467–474

    Article  Google Scholar 

  35. 35

    Bucaille J, Gauthier C, Felder E, Schirrer R (2006) The influence of strain hardening of polymers on the piling-up phenomenon in scratch tests: experiments and numerical modelling. Wear 260:803–814

    Article  Google Scholar 

  36. 36

    Bull SJ (1997) Failure mode maps in the thin film scratch adhesion test. Tribol Int 30:491–498

    Article  Google Scholar 

  37. 37

    Rice JR (1968) A path independent integral and the approximate analysis of strain concentration by notches and cracks. J Appl Mech 35:379–386

    Article  Google Scholar 

  38. 38

    Griffith AA (1921) The phenomena of rupture and flow in solids. Phil Trans Royal Soc A 221:582–593

    Article  Google Scholar 

  39. 39

    Irwin GR (1964) Structural aspects of brittle fracture. Appl Mat Res 3:65–81

    Google Scholar 

  40. 40

    Williams AJ (1996) Analytical models of scratch hardness. Tribol Int 29:675–694

    Article  Google Scholar 

  41. 41

    Desai PG, Lewis JA, Bentz DP (1994) Unreacted cement content in macro-defect-free composites-impact on processing structure-property relations. J Mater Sci 29:6445–6452. doi:10.1007/BF00354002

    Article  Google Scholar 

  42. 42

    Lewis JA, Boyer M (1994) Binder distribution in Macro-defect-free cements: relation between percolative properties and moisture absorption kinetics. J Am Cer Soc 77:711–716

    Article  Google Scholar 

  43. 43

    Bower AF, Ortiz M (1991) A three-dimensional analysis of crack trapping and bridging by tough particles. J Mech Phys Solids 39:815–858

    Article  Google Scholar 

  44. 44

    Mower TM, Argon AS (1995) Experimental investigations of crack trapping in brittle heterogeneous solids. Mech Mater 19:343–364

    Article  Google Scholar 

  45. 45

    Net S, Vandembroucq D, Roux S, Quantitative prediction of effective toughness at random heterogeneous interfaces(2013) Phys Re Lett, 110

  46. 46

    Rose LRF (1987) Toughening due to crack-front interaction with a second-phase dispersion. Mech Mater 6:11–15

    Article  Google Scholar 

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We acknowledge the support of the Department of Civil and Environmental Engineering and the UIUC CEE Structural Engineering group that provided a fellowship to Kevin Anderson during his Master studies. This investigation was funded by Prof. Akono’s start-up funds which were sponsored by the Department of Civil and Environmental Engineering and the College of Engineering at the University of Illinois at Urbana-Champaign. We are grateful to Prof. Leslie J. Struble for invaluable insights into the chemistry and microstructure of macro-defect-free cement. We acknowledge the generosity of industrial partners such as Kerneos and Kuraray that have provided free calcium aluminate cement and poly(vinyl alcohol-co-acetate) samples. Finally, part of this research was carried out at the Frederick Seitz Research Materials Laboratory.

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Correspondence to Ange-Therese Akono.

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Anderson, K., Akono, A. Microstructure–toughness relationships in calcium aluminate cement–polymer composites using instrumented scratch testing. J Mater Sci 52, 13120–13132 (2017). https://doi.org/10.1007/s10853-017-1416-8

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  • Scratch Test
  • Cement Grains
  • Crack Houses
  • Calcium Aluminate Cement (CAC)
  • Scratch Probe