30
ERICA
ERICA
Engineered Calcium‐Silicate‐Hydrates for Applications
Key facts
• EC H2020 MSC Innovative Training Network• continues where Transcend left off.
• Circa £3.5 million euros• EC H2020 MSC Innovative Training Network• 13 ESRs• Formally led by University of Surrey
BENEFICIARIESSurrey (Coordinator) Peter McDonald & David Faux
EPFL Karen Scrivener & Paul Bowen
Bologna Villiam Bortolotti & Paola Fantazzini
TU Wien Bernhard Pichler & Christian Hellmich
HeidelbergCement Mohsen Ben Haha
PARTNERSMR Solutions David Taylor & Peter Doughty
Saint-Gobain Angelique Vichot
CHRYSO Vanessa Kocaba
Septodont Gilles Richard
LafargeHolcim Bruno Huet – joining STC
NTNU Alex Hansen – joining STC
Central Admin Support
Surrey Michele Dodd & Lynn BonifaceEPFL Marie-Alix Dalang-SecretanEC Project Officer Szymon Sroda
WHO’S WHO
WP WHAT Lead
1 Research: Hydrate materials: growth, nanostructure characterisation and modelling
EPFL
2 Research: Water sorption and nano‐structure rearrangements Surrey
3 Research: Water transport and upscaling to engineered agglomerates HTC
4 Training EPFL
5 Recruitment Bologna
6 Project Management and Co‐ordination Surrey
7 Dissemination and Impact TU Wien
8 Ethics requirements Surrey
WORKPACKAGES
KEY DATES
Project Start / Earliest Recruit 1st November 2017
Formal mid‐project reviewSeptember 2019
Latest possible ESR start 1st November 2018
Latest date to comply with ethics / start research 1st November 2018
PROJECT
Project end31st October 2021
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 6
ERICA Recruitment
ESR Host Name Nationality Start date1 EPFL Maya Harris US 01/09/2018 Growth and synthesis of hydrates
2 UNIBO Rémi Albert Kogon
FR 01/02/2018 1H NMR relaxation characterisation ofhydrates
3 EPFL Masood Valavi IR 01/02/2018 Molecular dynamic simulations ofhydrate structure
4 UNIBO Anastasiia Nagmutdinova
RU 29/10/2018 1H NMR characterisation of firstsorption cycle
5 USurrey Örs Istok HU 03/01/2018 Localised NMRmeasurements ofsorption to separate spatio‐temporaleffects
6 HTC Monisha Rastogi
IN 03/01/2018 Characterisation of water sorptioncycle in hydrates of controlled oxidecomposition
7 USurrey Arifah Abdu Rahaman
MY 01/11/2018 Molecular dynamic andMonte Carlostudy of water in hydrates duringdesorption and re‐sorption
Recruited ESRs
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 7
ERICA Recruitment Update
ESR Host Name Nationality Start date8 TU Wien Nabor Jiménez
SeguraES 03/11/2017 Multiscale modelling of shrinking C‐S‐H
9 USurrey Magdalena Janota
PL 05/02/2018 Upscaling towards applications: Watertransport in agglomerates
10 EPFL Khalil Ferjaoui TN 01/10/2018 Modelling of hydrate microstructure atthe particle size/agglomerate level(microns)
11 USurrey Miryea Borg MT 22/10/2018 Lattice Boltzmann modelling of watertransport in hydrates agglomerates
12 TU Wien Petr Dohnalik CZ 03/11/2017 Multiscale design of engineered C‐S‐Hin dentistry
13 HTC Alexandru Pîrvan
RO 03/01/2018 Up‐scaling production of controlledhydrates
Recruited ESRs
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 8
ERICA Training & Dissemination Events
Date Project Month
Location Title Date Activity Detail
3 August 2017
‐1 EPFL Recruitment event
Interviews for shortlisted candidates
20‐23 February 2018
4 Surrey Workshop 0 20/221/2
From TRANSCEND to ERICA: Getting up to speed: Consolidation of existing know‐how.
Consortium Meeting 1
22/2 Kick off;1st Supervisory Board Meeting
School 0 23/2 Research skills training school
Summary of Training Schools, Workshops and Consortium meetings which have been held so far
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 9
ERICA Training & Dissemination Events
Date Project Month
Location Title Date Activity Detail
3–6 April 2018(repeat 2019)
6 EPFL School 1 Cementitious Materials and Characterization Methods (except NMR) training school
11–15 June2018
8 Surrey School 2 11/612/6
Numerical Modelling
Workshop 1
13/6 Cement Applications: Opportunities, Problems and Sustainability
School 2 14/615/6
NMR Theory and Practice
Summary of Training Schools, Workshops and Consortium meetings which have been held so far
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 10
ERICA Training & Dissemination Events
Date Project Month
Location Title Date Activity Detail
12–13 July 2018
9 EPFL Workshop 2 12/713/7
Numerical Modelling: State of the Art and Best Practice for Cements
12–13 Nov. 2018
13 Dublin ‐hosted by Nanocem
Consortium meeting 2
12/11 First year review.
13/11 2nd Supervisory Board Meeting
Summary of Training Schools, Workshops and Consortium meetings which have been held so far
ERICA 1st Year Review & 2nd Supervisory Board Meeting | 12th & 13th November 2018, Dublin 11
ERICA Training & Dissemination Events
Date Project Month
Location Title Date Activity Detail
14–17 January 2019
15 EPFL School 3 14/116/1
Numerical Modelling:
Modelling Workshop 2
17/1
11‐15 February 2019
16 TUWien School 4 Leadership, Teamwork, Outreach,Impact and Entrepreneurship
Summary of Training Schools, Workshops and Consortium meetings which have been held so far
Preliminary ProgrammeSunday, January 24
18:00‐19:30 Registration at NH Hotel19:30 Dinner at NH Hotel
Monday, January 2508:00‐18:00 Conference at PMA18:30 Dinner at Level12 (PMA)
Tuesday, January 2608:00‐17:00 Conference at PMA17:00 Visit of old town of Heidelberg & Universityafterwards Dinner at University or Headquarters of HeidelbergCement (tbd)
Wednesday, January 2708:00‐12:00 Conference at PMA12:00 Farewell
ERICA Final Conference | January 24‐27, 2021 | Heidelberg, Germany
ERICA Final Conference (Jan 2021)
RESEARCH PROJECTS AND THEMESNANO-SCALE MACRO-SCALE
ERICA GOAL:ENGINEERED
HYDRATES
WP 1: MATERIALS GROWTH
AND STRUCTURES
WP 3: TRANSPORT & ENGINEERED
AGGLOMERATES
WP 2: SORPTION AND
STRUCTURE CHANGES
MICRO-SCALE
ESR 2: Characterise nano-structure by 1H NMR
ESR 10: Models of hydrates at agglomerate level
ESR 9: Measure water transport in agglomerates by MRI
ESR 1: Grow controlled hydrates
ESR 11: LB model of transport in agglomerates
ESR 5: Separate space-temporal effects by 1H NMR
ESR 7: Molecular dynamics to Monte Carlo model of sorption
ESR 4: Characterise first sorption cycle by 1H NMR
ESR 8: Poro-mechanics
ESR 6: Validate with alternate analyses
ESR 3: Create a molecular dynamic model
ESR 13: Upscaling production: construction
ESR 12: Hydrates for dental applications
validate
Para
met
rise
and
Ref
ine
with
O
utpu
ts fr
om W
P 1
&
WP
2
build
build
validate
validate
correlate
EPFL
EPFL
EPFL
UNIBO
UNIBO
SURREY
HTC
SURREY
TUWIEN
SURREY
SURREY
TUWIEN
HTC
This project has two objectives: (i) To optimise growth conditions (particularly minimising supersaturation require‐ment) of hydrates in order to produce a range of materials with different and carefully controlled oxide composition including water content; (ii) To provide characterisations of these materials by conventional methods including X‐ray diffraction, scanning electron microscopy, 29Si high resolution MAS NMR and differential scanning calorimetry.
ESR 1: EPFL ‐ Grow controlled hydrates
This project has two objectives: (i) to make measurements of 1H NMR relaxation at early hydration times (0.1 to 6 hours) in order to confirm or otherwise the Gartner model of early stage hydration and the emergence of gel pores from the stacking (“zipping‐up”) of Gartner sheets; (ii) to use, refine and set limits on the 1H NMR analysis used to characterise C‐S‐H for the characterisationof hydrates with other oxide mixes made in Project 1.
ESR 2: UNIBO ‐ Characterise nano‐structure by 1H NMR
The objectives are: (i) to test using atomistic modelling whether the Gartner model is representative of hydrates at very early stages of growth and whether bringing two or more “Gartner sheets” together yields the bi‐modal porosity seen by 1H NMR; (ii) to deliver a molecular dynamic model of hydrate structure as a function of oxide composition, e.g. CaO to SiO2 ratio, that is consistent with all current experimental evidence, especially that from Project 2.
ESR 3: EPFL ‐ Create a molecular dynamic model
The objectives are: (i) to understand the temporal dependence of the porosity in hydrates of different oxide composition as the relative humidity, (RH), is cycled quickly (hours) and slowly (months) around full and partial drying / wetting cycles; (ii) to understand the effects of absolute RH achieved, time at RH and temperature; (iii) to quantify the reversible and irreversiblechanges that occur and the severity of drying required for “structural relaxation” and (iv) to correlate results with NMR porosity and other analyses in Project 2.
ESR 4: UNIBO ‐ Characterise first sorption cycle by 1H NMR
The objective is to explain previously inexplicable and contradictory features of sorption in cement hydrates that show deviations from the t0.5 dependence expected from pure diffusion / capillary action control. The project starts from the premise that water sorption hysteresis arises from both “conventional” concepts of pore blocking (“ink‐bottle effect”) and also from “new effects” associated with the reversible and irreversible changes in nano porosity (Projects 2 and 4). These processes will be separated by careful measurement of porosity evolution around water drying and wetting fronts passing a fixed depth in a sample using GARField MRI (spatial resolution 10‐50 microns).
ESR 5: SURREY ‐ Separate space‐temporal effects by 1H NMR
The objective is to characterise the first two cycles of hydrate drying, rewetting and subsequent storage by Maruyama’s length change method, by gravimetric uptake and by environmental scanning electron microscopy to augment and cross check against the 1H analyses in Projects 4 and 5.
ESR 6: HTC ‐ Validate with alternate analyses
The project has two objectives: (i) starting with molecular dynamics (MD) hydrate structures from ESR Project 3, to explore structural changes seen in MD as water is systematically removed, and to see whether these MD structures go on to show the reversible and irreversible changes after re‐wetting seen in experiment (Projects 4, 5 & 6); (ii) to use the MD results to parametrise a Monte Carlo model of water sorption in hydrates built using the “Etzold continuous sheet model” and in particular to introduce structural relaxation into the “Etzold model” so as to create a platform for larger scale transport studies.
ESR 7: SURREY ‐Molecular dynamics to Monte Carlo model of sorption
This project has the objective to develop a predictive multi‐scale poromechanical model establishing a quantitative link between: (i) sorption‐induced nano‐structural processes, such as observed by 1H NMR and modelled by MD simulations; and (ii) experimentally measured shrinkage/swelling of engineered C‐S‐H.
ESR 8: TU WIEN ‐ Poro‐mechanics
The objective is to understand anomalous water transport in hydrate agglomerates in terms of changing microstructure by (i) pore‐size resolved magnetic resonance imaging (MRI) measurements of time dependent water concentration profiles during water egress / ingress; (ii) comparing MRI data with models of transport which do / do not include time and water content dependent microstructure emergent from WPs 2 and 3.
ESR 9: SURREY ‐Measure water transport in agglomerates by MRI
The objective is to enhance the state‐of‐the‐art micro‐scale model of hydrates, μIC, to enable modelling of drying shrinkage in the μIC platform using calculations of local stress. Introductions include: (i) information on hydrate properties at a resolution below particle size from from WP 1; (ii) the reversible and irreversible changes in sub‐particle size properties resultant from sorption cycles from WP 2.
ESR 10: EPFL ‐Models of hydrates at agglomerate level
The objectives are (i) to use combinations of multiphase (liquid / vapour) and multi‐scale (effective media) Lattice Boltzmann (LB) methods to model water transport in model hydrate structures derived from (i) μIC, (Project 10); (ii) the “Etzold model” (Project 7) and (iii) the Jenning’s colloidal model with a view to demonstrating which, if any, is consistent with experimental data from WPs 2 and 3 & (ii) to push the LB method to accommodate the microstructural changes as they become understood within ERICA.
ESR 11: SURREY ‐ LB model of transport in agglomerates
This project has the objective to engineer patient‐specific mineral trioxide aggregates (= low‐volume, high‐value C‐S‐H‐based products) for endodontic applications in dentistry. The targets of engineering are to provide the required in‐situ sealing and optimal mechanical biocompatibility in terms of stiffness and strength, as compared to the surrounding tooth material. Success will be demonstrated by in vitro experiments.
ESR 12: TU WIEN ‐ Hydrates for dental applications
To develop means by which laboratory scale production of carefully controlled hydrates can be up‐scaled to an industrial production environment & conditions. To engineer materials with optimised microstructure for transport properties as well as mechanical properties, these materials composed of C‐S‐H manufactured using industrial by‐products. To verify the findings from sub‐particle size microstructure as understood from ESR projects 1 to 8.
ESR 13: HTC ‐ Upscaling production: construction
Some early taster results
Exploring the role of dynamic porosity in water capillary sorption by MRI – ESRs 5 & 9 @ Surrey
3‐D multi‐parameter NMR image data sets from which location specific filled pore size distributions are obtained on cm or micron scale
Highly localised GARField time and space study of the changing filled pore
size distribution in response to changing water content: this data is taken from a 50 micron slice 1 mm below surface of a
cement sample dried at 40 C. The surface is re‐wet at time 0. Data from 0
to 1 hour is still being evaluated.
Data being incorporated into a new model of anomalous transport
Total m
ass a
dsorbe
d
Root time
Interpreting NMR experiments
New model of cement NMR relaxation data interpretation
Surrey+Bologna developing a general purpose MATlabGUI to allow rapid analysis of FFC NMR data of cement
Improves upon the Korb model as
currently used but fiendishly difficult integrals prevent widespread usage.
Control and Atomistic simulation of Calcium‐Silicate –Hydrates (C‐S‐H) – and interaction with secondary ions– ESRs 1 & 3 @ EPFL ESR 3 ‐ Interfacial energies for Calcium hydroxide –
(Portlandite) from new Force Field (ERICA FF1) for molecular dynamics (MD) simulations – showing better correspondence with experimental values where the 100 surface has lowest interfacial energy Also Sulphate, Aluminium have been incorporated into the new force field for future atomistic simulations of adsorption and incorporation into C‐S‐H
001Surface Energy(eV)
100 Surface Energy(eV)
101 Surface Energy (eV)
MD MD MD
Cement_FF(old FF)
0.11 0.13 0.09
ERICA FF1 (new FF)
0.16 0.10 0.14
ESR 1 ‐ C‐S‐H with Ca/Si ratios from 1‐2 have been produced and characterised (above XRD showing pure phase C‐S‐H without secondary phases e.g. Calcium hydroxide)The scale up of synthesis using the Segmented Flow Tubular Reactor (SFTR) has been started – to produce >100g batches for partner ESRs
0
1000
2000
3000
4000
5000
6000
7000
0 10 20 30 40 50 60 70 80
Inte
nsity
(a.u
.)
Angle: 2 Theta
10 mL NaOH Trial 1
8 mL NaOH Trial 1
8 mL NaOH Trial 2
7 mL NaOH Trial 1
6 mL NaOH Trial 1
XRD – of 5 different C‐S‐H powders
Multiscale modelling of chloride transport in cementitious materials – ESR 10@EPFL
Monte Carlo Simulation
Poisson Boltzmann Modelling
WP1: Understanding atomistic mechanisms
WP2: Transport at the pore network
WP3: Upscaling and experimental validation
ERICA Project status at TU Wien
24
Two ESR projects at TU Wien:• Multiscale poromechanics of
shrinking C‐S‐H (ESR 8)• Engineered C‐S‐H in dentistry
(ESR 12)
Progress to date• Studying/extending multiscale
modeling techniques• Identification of pore size distributions
from adsorption isotherms• Developing miniaturized testing
techniques for dental biomaterials
NaborSegura Jimenez
Petr Dohnalík
HTC ESR 6: Characterization of sorption cycle of C‐S‐H to quantify microstructural and dimensional changes introduced during first drying.
25
Drying
Rewetting
C‐S‐H Irreversible/Reversible microstructuralchanges on first drying?
Factors governing reversibility?
How different morphology ofC‐S‐H responds to moisturechanges ?
1H NMR relaxometry Length change isotherm
Moisture sorption isotherm
Using these probes to address
26
Representative C‐S‐H sample
With the preliminary data, it has been demonstrated that
short‐term moisture isotherm could serve as potential tool to evaluate pore size distribution in a
given sample and that above 40 nm all the pores are
empty.
Rawmaterials ‐C2SH C2S binder
HTC ESR 13: optimizing microstructure of C‐S‐H from hydrated reactive dicalcium silicate binder to study transport through C‐S‐H matrix with different Ca/Si composition incorporating other ions
1. Production of reactive binder
91.9
5
-C2SH_K10
20
40
60
80
100
Phas
e co
mpo
sitio
n (%
)
portlandite scawtite calcite -C2SH
Binder
0
20
40
60
80
100
Phas
e co
mpo
sitio
n (%
)
portlandite scawtite calcite -C2S -C2S x-C2S amorphous
> 80 % hydrated after 24 hours
(calorimetry and QXRD)
Reactivity of phases decreases as shown:X‐ray amorpous > x‐C2S > ‐C2S > ‐C2S
0 12 24 36 480
1
2
3
4
5
6 C2S (232 J/g)
P (m
W/g
)
Time (hours)
2. Microstructure of fully hydrated binder (BSE imaging)
(w/b= 0.35 ….. 0.8)
Elemental distribution of Si and Ca in C‐S‐H matrix is homogenous.
w/b= 0.35
Si
Ca
0 200 400 600 800 1000-0.10
-0.05
0.00
DTG
(%/K
)
Temperature (°C)
w/b=0.80 w/b=0.35
Thermal analysis results on fully hydrated samples show presence of C‐S‐H and low amount of CH at 0.8 until almost no
Portlandite at low W/B ratio of 0.35
C‐S‐H
CH
Optimizing microstructure of hydrated reactive dicalcium silicate binder for studying transport through C‐S‐H matrix
3. Changing the chemistry of C‐S‐H change of morphology studying influence on transport properties
*Link, 2017
Reactive belite binderaddition of sulfate leads to a formation of finer needle‐like hydrates
adding 10 % nano‐silica before hydration
changes the morphology from needle‐like to foil‐like
Proposed mixtures to have different C‐A‐S‐H composition
Reactive dicalcium silicate binder
Micro‐silica Metakaolin Calcium sulphatehemihydrate
10 – 25 % Al/Si = 0.02 – 0.10 5%
SAVE THE DATE!
January 24‐27, 2021
Print Media Academy (PMA)Heidelberg, Germany
ERICA Final Conference
ERICA Final Conference (Jan 2021)
