brant walkley
TRANSCRIPT
![Page 1: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/1.jpg)
Brant WalkleyMaterials for a Sustainable Future
Composition-’local-structure’-property relationships in sustainable cements
The University of Sheffield
![Page 2: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/2.jpg)
The University of Sheffield, UK
Brant Walkley
The University of Melbourne, Australia
![Page 3: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/3.jpg)
Improve the well-being of society and environment by driving new advances insustainable materials for• Infrastructure• Environmental remediation• Energy and electronics
Research Vision
CO2
![Page 4: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/4.jpg)
Optimise material synthesis, processing and properties by exploiting cutting-edge characterisation techniques to probe• composition-‘local-structure’-property relationships• reaction mechanisms• kinetics
Research Vision
![Page 5: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/5.jpg)
Improve the well-being of society and environment by driving new advances insustainable materials for• Infrastructure• Environmental remediation• Energy and electronics
Research Vision
CO2
![Page 6: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/6.jpg)
Environmental impact of cement
2012
2050
cement
cement
cement8%
16%
24%2050
Low cement production
High cement production
Global CO2 emissions from Portland cement
All other human activity
All other human activity
All other human activityCO2
Time
![Page 7: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/7.jpg)
Innovative, sustainable cements are crucial for• Sustainable infrastructure• Immobilisation of nuclear waste• Advanced performance• Contribute over £110 bn pa (7% GDP)
Innovative, sustainable cements
![Page 8: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/8.jpg)
Innovative, sustainable cements are crucial for• Sustainable infrastructure• Immobilisation of nuclear waste• Advanced performance• Contribute over £110 bn pa (7% GDP)
Innovative, sustainable cements
There are many types of sustainable cements• Supplementary cementitious materials (limestone, slag, fly ash, calcined clays)• Calcium aluminate cements• Calcium sulfoaluminate cements• Alkali-activated cements
![Page 9: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/9.jpg)
Innovative, sustainable cements are crucial for• Sustainable infrastructure• Immobilisation of nuclear waste• Advanced performance• Contribute over £110 bn pa (7% GDP)
Innovative, sustainable cements
There are many types of sustainable cements• Supplementary cementitious materials (limestone, slag, fly ash, calcined clays)• Calcium aluminate cements• Calcium sulfoaluminate cements• Alkali-activated cements
![Page 10: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/10.jpg)
Alkali-activated cements• Low-CO2 emissions• Excellent mechanical properties and
durability• Waste valorisation• Waste immobilisation• Industrial use still low
Source of precursor materials Alkali-activated cements in use
Uni of QLD, Australia
![Page 11: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/11.jpg)
Alkali-activated cements• Low-CO2 emissions• Excellent mechanical properties and
durability• Waste valorisation• Waste immobilisation• Industrial use still low• Limited understanding of composition-
structure-property relationships
Source of precursor materials Alkali-activated cements in use
Uni of QLD, Australia
![Page 12: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/12.jpg)
Key challenge is to understand composition-’local-structure’-property relationshipsof sustainable cements, and to use this knowledge to design tailored materials fordemanding applications
Key challenge
Many techniques available• Spectroscopic (solid state nuclear magnetic resonance, infrared, Raman etc.)• Diffraction (X-ray, neutron, electron)• Microscopic (transmission/scanning electron microscopy)
![Page 13: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/13.jpg)
Key challenge is to understand composition-’local-structure’-property relationshipsof sustainable cements, and to use this knowledge to design tailored materials fordemanding applications
Key challenge
Many techniques available• Spectroscopic (solid state nuclear magnetic resonance, infrared, Raman etc.)• Diffraction (X-ray, neutron, electron)• Microscopic (transmission/scanning electron microscopy)
![Page 14: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/14.jpg)
Solid state NMR spectroscopy
Provides information about• Local (nano- or atomic-scale) structure• Coordination spheres• Electric field gradient (symmetry)Probes specific nucleiVery useful for disordered materials
![Page 15: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/15.jpg)
Alkali-activated cementsCase study
Understanding the nanostructure of synthetic alkali-activated cements
![Page 16: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/16.jpg)
Why isn’t use widespread?silica fume
SiO2
CaO Al2O3
slag
fly ashnatural pozzolans
metakaolin
portland cement
fine limestone
Alkali-activated cements
![Page 17: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/17.jpg)
Aqueous precursors& polymer carrier
Reactive powder Synthetic AAC
Organic steric entrapment method
Synthetic alkali-activated cements
![Page 18: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/18.jpg)
Precursor synthesis
![Page 19: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/19.jpg)
TEM-EDX
Characteristics similar to commercial precursors, but with controlled composition, high purity and no minor constituents (e.g. Fe, Mg, K)
SSNMRTG-MS
Precursor characterisation
![Page 20: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/20.jpg)
Sodium silicate solution Alkali-activated cementPrecursor
SiO2/Na2O = 1 pH >13
Sealed in tubes and cured at ambient temperature (~23°C)
Alkali-activation
![Page 21: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/21.jpg)
Sodium silicate solution Alkali-activated cementPrecursor
SiO2/Na2O = 1 pH >13
Sealed in tubes and cured at ambient temperature (~23°C)
Alkali-activation
![Page 22: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/22.jpg)
X-ray diffraction SEM-EDX
Al/Si = 1
Al/Si = 0.5
Microstructural analysis
![Page 23: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/23.jpg)
27Al solid state MAS NMR
• Al in binder is predominantly tetrahedral
• Nanostructural development occurs in first 7 days
Al/Si = 1 Al/Si = 0.5
Solid state NMR analysis
![Page 24: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/24.jpg)
29Si solid state MAS NMR w/ Gaussian peak deconvolution
180 days
28 days
7 days
• Predominantly Q4(4Al) sites (Si-(O-Al)4) atearly ages
• Increase in Q4(3Al), Q4(2Al) and Q4(1Al) sitesat later ages
• Nanostructural development continues atlater ages
Al/Si = 1 Al/Si = 0.5
Solid state NMR analysis
Q4(4Al)Q4
![Page 25: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/25.jpg)
Multiple-quantum SS MAS NMR27Al, 23Na and 17O are quadrupolar nuclei
MAS NMR spectra of quadrupolar nuclei are difficult to deconvolute due toquadrupolar interactions
Quadrupolar interaction is between the quadrupole moment and electric fieldgradient of the nucleus – related to symmetry
This means quadrupolar parameters must be determined first to enable accuratedeconvolution and identification of chemical environment
Can do this with multiple-quantum SS MAS NMR
Multiple-quantum SS MAS NMR
![Page 26: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/26.jpg)
27Al solid state 3QMAS NMR
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMR
![Page 27: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/27.jpg)
27Al solid state 3QMAS NMR
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMR
Chemical connectivity
![Page 28: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/28.jpg)
27Al solid state 3QMAS NMR
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMR
Symmetry
![Page 29: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/29.jpg)
Fit the anisotropic slice to determine initial estimates for NMR parameters of each site
27Al solid state 3QMAS NMR Fit w/ Czjezek Gaussian Isotropic Model
Al/Si = 1
Precursor
Multiple-quantum SS MAS NMR
![Page 30: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/30.jpg)
Multiple-quantum SS MAS NMRUse initial estimates to guide deconvolution of single pulse MAS NMR spectra
27Al solid state 3QMAS NMR w/ Czjezek Gaussian Isotropic
Model deconvolution
Precursors Alkali-activated cement
![Page 31: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/31.jpg)
Multiple-quantum SS MAS NMRUse initial estimates to guide deconvolution of single pulse MAS NMR spectra
27Al solid state 3QMAS NMR w/ Czjezek Gaussian Isotropic
Model deconvolution
Precursors Alkali-activated cement
![Page 32: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/32.jpg)
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMR
Can use biaxial Q-shearing to orthogonally separate the chemical shift and quadrupolar parameters
![Page 33: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/33.jpg)
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMR
Can use biaxial Q-shearing to orthogonally separate the chemical shift and quadrupolar parameters
![Page 34: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/34.jpg)
Al/Si = 1
Al/Si = 0.5
Precursor AAC
Multiple-quantum SS MAS NMRBiaxial Q-shearing
![Page 35: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/35.jpg)
27Al solid state 3QMAS NMR w/ Czjezek Gaussian Isotropic
Model deconvolution
Precursors Alkali-activated cement
Multiple-quantum SS MAS NMRCan use biaxial Q-shearing to prove existence of two Al distributions (i.e. two Al sites)
![Page 36: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/36.jpg)
23Na solid state 3QMAS NMR w/ Czjezek Gaussian Isotropic
Model deconvolution
Al/Si = 1 Al/Si = 0.5
Multiple-quantum SS MAS NMRAl/Si = 1 Al/Si = 0.5
AAC AAC
AAC AAC
![Page 37: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/37.jpg)
17O solid state 3QMAS NMR w/ Czjezek Gaussian Isotropic
Model deconvolution
Al/Si = 1 Al/Si = 0.5
Multiple-quantum SS MAS NMRAl/Si = 1 Al/Si = 0.5
AAC AAC
AAC AAC
17O natural abundance = 0.037%
![Page 38: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/38.jpg)
New structural models for AACAlkali aluminosilicate hydrate gels
Calcium (alkali) aluminosilicate hydrate gels
![Page 39: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/39.jpg)
• Synthesised a novel class of stoichiometrically controlled reactive precursor powders via the organic stericentrapment method
• Produced a novel class of stoichiometrically controlled alkali-activated materials to study nanostructuraldevelopment
• Applied advanced characterisation techniques, particularly solid state MAS and 3QMAS NMR spectroscopy
• Revealed new insight into composition-’local-structure’-property relationships in alkali activated cements
• Developed new structural models for alkali aluminosilicate hydrate and calcium (alkali) aluminosilicatehydrate gels – the key binding phases in alkali activated cements
Conclusions
![Page 40: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/40.jpg)
Further information
• Walkley, B. et al. (2018), Journal of Physical Chemistry C, 122 (10) 5673-5685
• Walkley, B. et al. (2016), Dalton Transactions, 45(13) 5521-5535.
• Walkley, B. et al. (2016), Cement and Concrete Research, 89 120-135.
![Page 41: Brant Walkley](https://reader033.vdocuments.mx/reader033/viewer/2022041912/6254f6c39d423b5b0a45945c/html5/thumbnails/41.jpg)
Dr Gregory Rees and Dr John Hanna, Department of Physics, The University of Warwick, UKDr Marc-Antoine Sani and Dr John Gehman, School of Chemistry, The University of Melbourne, AustraliaGeopolymer & Minerals Processing Group, Department of Chemical & Biomolecular Engineering, The University ofMelbourne, AustraliaCements@Sheffield Research Group, Department of Materials Science and Engineering, The University ofSheffield, UKCements@Sheffield, Particulate Fluids Processing Centre and Melbourne Scholarships Office and AustralianResearch Council for fundingThis research was performed in part at the MIDAS Facility, University of Sheffield, which was established withsupport from the Department of Energy and Climate Change.
Acknowledgements