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 WHO’S WHO BENEFICIARIES Surrey (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 PARTNERS MR 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 Boniface EPFL Marie-Alix Dalang-Secretan EC Project Officer Szymon Sroda WORKPACKAGES WP WHAT Lead

Research: Hydrate materials: growth, nanostructure characterisation and EPFL 1 modelling

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

6Project Management and Co‐ordination Surrey

7 Dissemination and Impact TU Wien

8Ethics requirements Surrey KEY DATES

PROJECT

Project Start / Earliest Recruit 1st November 2017

Latest date to comply with ethics / start research 1st November 2018

Latest possible ESR start 1st November 2018

Formal mid‐project review September 2019

Project end 31st October 2021 ERICA Recruitment

Recruited ESRs ESR Host Name Nationality Start date 1 EPFL Maya Harris US 01/09/2018 Growth and synthesis of hydrates

2 UNIBO Rémi Albert FR 01/02/2018 1H NMR relaxation characterisation of Kogon hydrates 3 EPFL Masood Valavi IR 01/02/2018 Molecular dynamic simulations of hydrate structure 4 UNIBO Anastasiia RU 29/10/2018 1H NMR characterisation of first Nagmutdinova sorption cycle 5 USurrey Örs Istok HU 03/01/2018 Localised NMR measurements of sorption to separate spatio‐temporal effects 6 HTC Monisha IN 03/01/2018 Characterisation of water sorption Rastogi cycle in hydrates of controlled oxide composition 7 USurrey Arifah Abdu MY 01/11/2018 Molecular dynamic and Monte Carlo Rahaman study of water in hydrates during desorption and re‐sorption

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 6 12th & 13th November 2018, Dublin ERICA Recruitment Update

Recruited ESRs

ESR Host Name Nationality Start date 8 TU Wien Nabor Jiménez ES 03/11/2017 Multiscale modelling of shrinking C‐S‐H Segura 9 USurrey Magdalena PL 05/02/2018 Upscaling towards applications: Water Janota transport in agglomerates 10 EPFL Khalil Ferjaoui TN 01/10/2018 Modelling of hydrate microstructure at the particle size/agglomerate level (microns) 11 USurrey Miryea Borg MT 22/10/2018 Lattice Boltzmann modelling of water transport in hydrates agglomerates 12 TU Wien Petr Dohnalik CZ 03/11/2017 Multiscale design of engineered C‐S‐H in dentistry 13 HTC Alexandru RO 03/01/2018 Up‐scaling production of controlled Pîrvan hydrates

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 7 12th & 13th November 2018, Dublin ERICA Training & Dissemination Events

Summary of Training Schools, Workshops and Consortium meetings which have been held so far

Date Project Location Title Date Activity Detail Month

3 August ‐1EPFLRecruitment Interviews for 2017 event shortlisted candidates

20‐23 4SurreyWorkshop 0 20/2 From TRANSCEND to February 21/2 ERICA: Getting up to 2018 speed: Consolidation of existing know‐how. Consortium 22/2 Kick off; Meeting 1 1st Supervisory Board Meeting School 0 23/2 Research skills training school

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 8 12th & 13th November 2018, Dublin ERICA Training & Dissemination Events

Summary of Training Schools, Workshops and Consortium meetings which have been held so far Date Project Location Title Date Activity Detail Month

3–6 April 6 EPFL School 1 Cementitious Materials 2018 and Characterization (repeat Methods (except NMR) 2019) training school 11–15 8 Surrey School 2 11/6 Numerical Modelling June 12/6 2018 Workshop 13/6 Cement Applications: 1 Opportunities, Problems and Sustainability School 2 14/6 NMR Theory and 15/6 Practice

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 9 12th & 13th November 2018, Dublin ERICA Training & Dissemination Events

Summary of Training Schools, Workshops and Consortium meetings which have been held so far

Date Project Location Title Date Activity Detail Month

12–13 9EPFLWorkshop 2 12/7 Numerical Modelling: July 2018 13/7 State of the Art and Best Practice for Cements 12–13 13 Dublin ‐ Consortium 12/11 First year review. Nov. hosted by meeting 2 2018 Nanocem 13/11 2nd Supervisory Board Meeting

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 10 12th & 13th November 2018, Dublin ERICA Training & Dissemination Events

Summary of Training Schools, Workshops and Consortium meetings which have been held so far

Date Project Location Title Date Activity Detail Month

14–17 15 EPFL School 3 14/1 Numerical Modelling: January 16/1 2019

Modelling 17/1 Workshop 2

11‐15 16 TUWien School 4 Leadership, February Teamwork, Outreach, 2019 Impact and Entrepreneurship

ERICA 1st Year Review & 2nd Supervisory Board Meeting | 11 12th & 13th November 2018, Dublin ERICA Final Conference (Jan 2021)

Preliminary Programme Sunday, January 24 18:00‐19:30 Registration at NH Hotel 19:30 Dinner at NH Hotel Monday, January 25 08:00‐18:00 Conference at PMA 18:30 Dinner at Level12 (PMA) Tuesday, January 26 08:00‐17:00 Conference at PMA 17:00 Visit of old town of Heidelberg & University afterwards Dinner at University or Headquarters of HeidelbergCement (tbd) Wednesday, January 27 08:00‐12:00 Conference at PMA 12:00 Farewell

ERICA Final Conference | January 24‐27, 2021 | Heidelberg, Germany RESEARCH PROJECTS AND THEMES NANO-SCALEMICRO-SCALE MACRO-SCALE

WP 1: WP 2: WP 3: MATERIALS GROWTH SORPTION AND TRANSPORT & AND STRUCTURES STRUCTURE ENGINEERED CHANGES AGGLOMERATES

ESR 1: Grow controlled hydratesEPFL ESR 4: Characterise first sorption UNIBO ESR 9: Measure water transport SURREY cycle by 1H NMR in agglomerates by MRI

ESR 2: Characterise nano- ESR 5: Separate space-temporal validate correlate structure by 1H NMR effects by 1H NMR SURREY UNIBO ESR 6: Validate with alternate EPFL analyses HTC ESR 10: Models of hydrates at agglomerate level validate validate ESR 11: LB model of transport in SURREY ESR 3: Create a molecular EPFL agglomerates dynamic model Parametrise and Refine with and Refine Parametrise

build 2 1 & WP WP from Outputs ESR 7: Molecular dynamics to SURREY Monte Carlo model of sorption build

ESR 8: Poro-mechanics ESR 12: Hydrates for dental TUWIEN applications TUWIEN

ERICA GOAL: ESR 13: Upscaling production: HTC ENGINEERED construction HYDRATES ESR 1: EPFL ‐ Grow controlled hydrates

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 2: UNIBO ‐ Characterise nano‐structure by 1H NMR

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 characterisation of hydrates with other oxide mixes made in Project 1. ESR 3: EPFL ‐ Create a molecular dynamic model

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 4: UNIBO ‐ Characterise first sorption cycle by 1H NMR 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 irreversible changes 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 5: SURREY ‐ Separate space‐temporal effects 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 6: HTC ‐ Validate with alternate analyses 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 7: SURREY ‐ Molecular dynamics to Monte Carlo model of sorption 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 8: TU WIEN ‐ Poro‐mechanics

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 9: SURREY ‐ Measure water transport in agglomerates by MRI

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 10: EPFL ‐ Models of hydrates at agglomerate level

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 11: SURREY ‐ LB model of transport in agglomerates

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 12: TU WIEN ‐ Hydrates for dental applications

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 13: HTC ‐ Upscaling production: construction

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. 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 adsorbed space study of the changing filled pore size distribution in response to changing mass water content: this data is taken from a

Total 50 micron slice 1 mm below surface of a Data being incorporated cement sample dried at 40 C. The into a new model of surface is re‐wet at time 0. Data from 0 anomalous transport Root time to 1 hour is still being evaluated. Interpreting NMR experiments

Improves upon the New model of Korb model as Surrey+Bologna developing cement NMR currently used but a general purpose MATlab relaxation data fiendishly difficult GUI to allow rapid analysis interpretation integrals prevent of FFC NMR data of cement 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 7000 XRD –of 5 different C‐S‐H powders molecular dynamics (MD) simulations – showing better 6000 correspondence with experimental values where the

5000 100 surface has lowest interfacial energy

4000 10 mL NaOH Trial 1 Also Sulphate, Aluminium have been incorporated into 8 mL NaOH Trial 1 the new force field for future atomistic simulations of 3000 8 mL NaOH Trial 2 adsorption and incorporation into C‐S‐H Intensity (a.u.) Intensity 7 mL NaOH Trial 1 2000 6 mL NaOH Trial 1 001 100 101 1000 Surface Surface Surface

0 Energy Energy Energy 0 1020304050607080 (eV) (eV) (eV) Angle: 2 Theta MD MD MD 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 Cement_FF 0.11 0.13 0.09 secondary phases e.g. Calcium hydroxide) (old FF) The scale up of synthesis using the Segmented Flow Tubular Reactor ERICA FF1 0.16 0.10 0.14 (SFTR) has been started –to produce >100g batches for partner ESRs (new FF) Multiscale modelling of chloride transport in cementitious materials –ESR 10@EPFL WP3: Upscaling and experimental validation

Monte Carlo Simulation

Poisson Boltzmann Modelling WP2: Transport at the pore network

WP1: Understanding atomistic mechanisms ERICA Project status at TU Wien

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 Nabor Petr • Studying/extending multiscale Segura Jimenez Dohnalík modeling techniques • Identification of pore size distributions from adsorption isotherms • Developing miniaturized testing techniques for dental biomaterials

24 HTC ESR 6: Characterization of sorption cycle of C‐S‐ H to quantify microstructural and dimensional changes introduced during first drying.

1H NMR relaxometry Length change isotherm

Moisture sorption isotherm

Using these probes to address

Drying Irreversible/Reversible microstructural C‐S‐H changes on first drying? Factors governing reversibility? How different morphology of C‐S‐H responds to moisture Rewetting changes ?

25 With the preliminary data, it has been demonstrated that short‐term moisture Representative C‐S‐H sample 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.

26 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 Raw > 80 % hydrated of reactive ‐C SH C S binder binder materials 2 2 after 24 hours (calorimetry and QXRD)

100 Reactivity of phases decreases as shown: portlandite portlandite scawtite 100 scawtite X‐ray amorpous > x‐C2S>‐C2S>‐C2S calcite calcite 80 -C2SH 80 -C2S

-C2S 6 C S (232 J/g) 60 x-C S 2 60 2 5 amorphous

4

40 91.95 40 3 P (mW/g) 2 Phase composition (%) composition Phase Phase composition (%) 20 20 1

0 0 12243648 0 Time (hours) 0 -C2SH_K1

Binder w/b= 0.35 2. Microstructure of fully hydrated binder Ca (BSE imaging) (w/b= 0.35 ….. 0.8) Elemental distribution of Si and Ca in C‐S‐H matrix is homogenous. Si

0.00

Thermal analysis results on fully hydrated samples show CH w/b=0.80 -0.05 w/b=0.35 presence of C‐S‐H and low amount of CH at 0.8 until almost no DTG (%/K) DTG Portlandite at low W/B ratio of 0.35

-0.10 0 200C‐S‐H 400 600 800 1000 Temperature (°C) 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

adding 10 % nano‐silica before hydration addition of sulfate leads Reactive belite binder changes the morphology to a formation of finer from needle‐like to foil‐like needle‐like hydrates

*Link, 2017 Proposed mixtures to have different C‐A‐S‐H composition

Reactive Micro‐silica Metakaolin Calcium sulphate dicalcium silicate hemihydrate binder 10 – 25 % Al/Si = 0.02 –0.10 5% ERICA Final Conference (Jan 2021)

SAVE THE DATE! ERICA Final Conference January 24‐27, 2021

Print Media Academy (PMA) Heidelberg, Germany