Geo-Inspired Clinker for a Low Carbon Future

Content
Introduction

Ordinary portland cement (OPC) is the second most widely consumed material in the world. It is responsible for ~8% of global CO 2
emissions.

OPC emissions are primarily generated by the calcination process. Where calcium carbonate (CaCO 3) is converted into reactive calcium
oxide via calcination.

CaCO3

Kiln

Clay

1300-1500C
Introduction

Paste Mortar Concrete

Introduction

Paste Mortar Concrete

How do we test ordinary portland cement (OPC)?

ASTM Standards!
Introduction

Paste Mortar Concrete

These values are for a single “mix” for a single ASTM

0.1-1kg 1-10kg >30kg

Introduction

Fresh state properties

Mi
ns.
Viscosity, setting
Shrinkage
Ho
urs
Hydration
Hardened State properties
Da
ys
 Compressive strength, durability

Mo …
nth
s
Introduction

In summary:
 Cementitious materials are produced at varying length scales.
 Each length scale has widely accepted standardized ways to measure performance.
 Performance goes beyond compressive strength and must account to everything from workability to durability.
 Cement takes time! Testing can occur from the second water hits the mixture, to years!

So how does it work? Why does it take so long?

A Note on Cement Chemistry

 Cement chemists developed their own short-hand naming convention for compounds in this field:

Compound Cement Chemistry Notation

Calcium Oxide (CaO) C

Silicon Dioxide (SiO2) S

Aluminum Oxide (Al2O3) A

Potassium Oxide (K2O) K

Sodium Oxide (Na2O) N

Water (H2O) H
Ordinary Portland Cement Hydration

What happens during cement hydration? – First, we need to look at the minerals!

 Tricalcium silicate (Alite), C3S

 Dicalcium silicate (Belite), C2S
 Tricalcium aluminate, C3A
 Tetracalcium aluminoferrite, C4AF
 Gypsum, CSH
Ordinary Portland Cement Hydration

I II III IV V

I – Dissolution, formation of
ettringite and C-S-H gel.
II – Induction period, increase in
Ca2+ and OH- concentration.
III – Rapid C-S-H and C-H
formation.
Heat Released

IV – Deceleration and Afm

formation.
V – Diffusion controlled
reaction.

Time
Ordinary Portland Cement Hydration

Rahimi-Aghdam et. al, 2017

Ordinary Portland Cement Hydration

Silicon

Silica Fume

Pozzolanic

Fly Ash

Metakaolin

? Novel Cement
Cementitious
Slag

OPC

Calcium Aluminum
Ordinary Portland Cement Hydration

Calcium Silicates Water C-S-H CH

SCM Water S C-S-H

Ordinary Portland Cement Hydration

This is the fundamental processes behind OPC chemistry.

 This does not account for the addition of supplementary cementitious materials (SCMs, formerly known as pozzolans).
 These processes can be accelerated/decelerated by various processing techniques (e.g., heating) and addition of admixtures (e.g. set
retardants).
 These reactions change for alternative cements.

How does this fit into our project?

Geo-Inspired Clinker for A Low Carbon Future

We want to produce a cementitious binder that emulates natures cementation processes and possesses a lower carbon footprint.
 This binder will have traits found in cements found in nature and in durable ancient cementitious binders.
 These binders show hybrid traits between OPC and other types of cements.
 Additionally, they are reinforced by naturally occurring mineral fibers (e.g, tobermorite).

Macfarlane, 2021
Geo-Inspired Clinker for A Low Carbon Future

These binders can be utilized to tackle a variety of problems related to OPC durability, especially in underground
applications
Geo-Inspired Clinker for A Low Carbon Future

15% for Wellbores

• Among the different sectors in which cement is used,

wellbore & underground applications represent 15%

• Although not the highest percentage, the serviceability

of cement in subsurface conditions presents the
Other greatest challenges

Cement use by sector

Geo-Inspired Clinker for A Low Carbon Future

Cement must withstand a variety of environmental and anthropogenic stresses and must last to maintain the integrity of the well for
many decades, even after abandonment. Most wells, however, lose their integrity after the first 15 years of life.
 The failure of OPC in oilwells is responsible for ~3-6% of global methane emissions.
 Additionally, failure of OPC in oilwells is responsible for damage to aquifers, and the environment.
 Lives have been lost due to the failure of OPC in these wells.

Casing Harsh Conditions Underground

Cement
Rock Formation • Pressure (steady or variable)
• Temperature (steady or variable)
• Sour Fluids (H2SO4, HCl)

• Alkaline Fluids (Na2CO3, NaOH)

• Radioactive Fluids
• Carbonation (CO2)
• Fluid reinjection

Modified after Yousuf et al. (2021)

 Raw volcanic blend
The use of an alternative rock precursor for a geo-inspired cement
(SEM, EDS, XRD)

The raw volcanic blend represents the first and main precursor we use to grow our fibers and create a network
of interconnected fibers, similar to what we observe in Roman Marine Concrete.
Raw Volcanic Blend - SEM
Raw Volcanic Blend – EDS, Chemical Composition

Raw volcanic blend in 3 different stubs

Normalised
A total of 12 measurements on each stubs Wt% Oxide

CaO 4.22
SiO2 57.95
Al2O3 20.86
K2O 11.28
SO3 0.26
Na2O 3.51
MgO 0.52
For each stub, each measurement Fe2O3 1.40
consists of an area scan at 1000x Tot 100.00
magnification
Raw Volcanic Blend – XRD, Mineralogical Composition
Raw Volcanic Blend – XRF, Chemical Composition

Oxid Na O
2 MgO Al2O3 SiO2 P2O5 S Cl K2O CaO TiO2 V2O5 Cr2O3 MnO Fe2O3
e
Wt. % % % % % % % % % % % % % %

RVB 0.000
5.5 0.65 24.9 56.7 0.13 0.13 0.03 7.7 2.6 0.3 0.01 0.09 3.3
4
 Calcination of Raw Volcanic Blend
(SEM, EDS)

After a series of experiments to understand what is the impact of calcination temperature on the raw volcanic
blend, we kept fixed the temperature to 1100 °C.
Starting from 1100 °C we form volcanic glass, indicative of rock amorphization.
The glass composition recalls k-feldspar and/or leucite (remember: k-feldspar melt at the lowest temperatures
compared to other minerals)
Raw Volcanic Blend @1100 - SEM
The rough surface recalls some conchoidal fracture happening generally on amorphous glass. We form amorphous volcanic
glass.
Raw Volcanic Blend @1100 - SEM

Pt. 1

1
 Calcined Volcanic Blend + Limestone “low-Calcium Series”
(SEM, EDS, XRD)

We supplemented the volcanic blend with limestone to achieve the following limestone/volcanic
blend ratios:

1. 0.1
2. 0.33
3. 0.54 (SEM, EDS)
4. 0.595 (SEM, EDS, XRD)

After calcination this composition yields a lime wt% of 25% (calculation based on lime and
volcanic blend only)

We only have SEM for 0.54 and 0.595

CaCO3/Volcanic Blend = 0.595 - EDS

C-A-S Compounds

Pt. 1
50
45
Weight %
40 Atom %
35
30
25

%
1 20
15
10
5
0
KK Fe L Mg K Na K Al K C K Ca K Si K OK

Lascio in sospeso perche mi serve il software

CaCO3/Volcanic Blend = 0.595 - EDS

C-A-S Compounds

Area 1
50
45
Weight %
40 Atom %
1 35
30
25

%
20
15
10
5
0
KK Na K Al K CK Ca K Si K OK
CaCO3/Volcanic Blend = 0.595 – EDS, Chemical Composition

Volcanic blend and limestone in 3 different stubs

Normalised
A total of 12 measurements on each stubs Wt% Oxide

CaO 35.80
SiO2 33.38
Al2O3 11.73
K2O 5.09
SO3 8.71
Na2O 1.99
MgO 0.73
For each stub, each measurement Fe2O3 2.57
consists of an area scan at 1000x
Tot 100
magnification
CaCO3/Volcanic Blend = 0.595 - XRD
Calcined Volcanic Blend + Limestone “Low-Calcium Series” – Summary

• At CaCO3/VB = 0.54, calcium appears to be embedded within the glassy volcanic grains

• At CaCO3/VB = 0.595, new compounds (e.g. cubic minerals) are formed containing high

amounts of Ca, Si, Al and Na and K.

Hydrothermal Treatment of calcined blend of the “low-calcium series”
(SEM, EDS, XRD)

• Ratio Limestone/Volcanic Blend:

1. 0
2. 0.1
3. 0.33
4. 0.54 (SEM)
5. 0.595 (SEM, XRD)

After calcination the limestone supplements a lime wt% from 5% to 25% (calculation based on
lime and volcanic blend only)
Autoclave “Large Reactor”

Hydrothermal Vessel (or Reactor, or Autoclave)

Modified after Unterlass (2017) Range in the red dashed lines is generally
1800
Viscosity used for hydrothermal synthesis and
mineral growth (e.g. fibers growth)

h (10-6 Pa*s)
1400

1000

600

200

0 50 100 150 200 250 300 350

Temperature (ºC)
Ionic Product
11
-log Kw (mol2*kg-2)
≈ 10”
12

13

14
Yanagisawa et al. (1997)

15
0 50 100 150 200 250 300 350
Temperature (ºC)
Autoclave “Large Reactor” – Conditions and Compositions

CONDITIONS COMPOSITION

1. Temperature (T) 1. % of different components

2. Pressure (P) 2. Molar Ratio Ca/Si
3. Curing Time

• T = 150 to 250 °C
• P = 0.5 to 4 MPa (5 to 40 Bar)
• Curing Time = 24hr
• CaO added = 0 to 25%
• Ca/Si = 0.05 to 0.7
(Based on XRF, Considering calcium
only from lime and VB source)
Autoclave “Large Reactor” – Simple Setup

Simple Setup
T (°C)

P (MPa)

Steam
Heater
Heater

20 cm

LIQUID 7 cm
Water
Calcined Blend
Autoclave “Large Reactor” – Simple vs Complex Setup

Simple Setup Complex Setup / Steam-assisted crystallization

T (°C) T (°C)
Valve Open
P (MPa)
P (MPa)

Cement
Quick P Steam Out (W/S = 0.4)
Steam Down
Steam Steam In

Heater
Heater
Heater
Heater

20 cm
T, P
LIQUID 7 cm Water
Water
Cement
(W/S = 5)
Hydrothermal Synthesis – No Calcium Supplemented, Simple Setup

225 °C 250°C

Sample 4 Sample 5
We form small plates (< 1 um)
The higher the temperature the higher the amount of plates
Hydrothermal Synthesis – Variable Calcium Content, Simple Setup

0 wt% CaO Supplemented 5 wt% CaO Supplemented

(CaCO3/VB = 0) (Ca/Si = 0.05) (CaCO3/VB = 0.1) (Ca/Si = 0.16)

Sample 4 Sample 11
Hydrothermal Synthesis – Variable Calcium Content, Simple Setup

16 wt% CaO Supplemented 23 wt% CaO Supplemented

(CaCO3/VB = 0.33) (Ca/Si = 0.41) (CaCO3/VB = 0.54) (Ca/Si = 0.63)

Sample 15 Sample 13
Hydrothermal Synthesis – Variable Calcium Content, Simple Setup

25 wt% CaO Supplemented

(CaCO3/VB = 0.595) (Ca/Si = 0.69)

Sample 17
Hydrothermal Synthesis – 25 wt% CaO, Steam-assisted crystallization (Complex Setup)

25 wt% CaO Supplemented (CaCO3/VB = 0.595) (Ca/Si = 0.69)

Simple Setup Sample 17 Sample 14 Complex Setup
Hydrothermal Synthesis – 25 wt% CaO, Steam-assisted crystallization (Complex Setup) - XRD
Hydrothermal Synthesis – 25 wt% CaO, Seeding, Steam-assisted crystallization (Complex Setup)

• We supplemented the new calcined material

with some hydrothermally treated material
containing fibers

• 18% Hydrothermally treated material (picture

above)

• 82% New calcined material with same

composition as above
Hydrothermal Synthesis – 25 wt% CaO, Seeding, Steam-assisted crystallization (Complex Setup) - XRD

Sample 19

XRD
Hydrothermal Synthesis – 25 wt% CaO, Testing Water to Solid Ratio with the Simple Setup

W/S = 5 Sample 35

W/S = 1 Sample 34
Hydrothermal Synthesis – Summary

• With no calcium supplemented and the simple setup, we only observe small plates growing onto the grain
surface

• For this kind of blend (no calcium), temperature only affects the plates yield

• The higher the calcium content the higher the fibers yield

• The steam-assisted crystallization improves fiber production and entanglement, but has a low reproducibility

• Seeding improves the yield in terms of quantity, although it produces shorter fibers

• The higher amount of water (W/S = 5) did not lead to fiber formation

• A large quantity of fibers was only obtained when the material cemented during hydrothermal treatment

• The hydrothermal products lack of reproducibility

 Simplified Hydrothermal Treatment: Bomb Reactor
(SEM, EDS, XRD)

Because of the high complexity arising from the large reactor, we used a simpler Teflon-lined
vessel, the “bomb reactor”.

• Ratio Limestone/Volcanic Blend:

1. 0.595 – We explored the water to solid ratio

After calcination, the limestone supplements a lime wt% of 25% (calculation based on lime and
volcanic blend only)
Hydrothermal Synthesis – Switch to a Simplified Hydrothermal Synthesis (Bomb Reactor)

Large Reactor

T (°C) Bomb Reactor Water remains in contact

with the material throughout
P (MPa)
the experiment improving
reproducibility
Poor reproducibility likely
due to continuous
exchange of water from Section
the inner to the outer
container
Heater
Heater

Inner container
Outer container
Water
LIQUID
Calcined blend
Calcined blend

Ø = 2 cm Capacity = 45 ml
Ø = 6 cm Capacity = 450 ml
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 0.595, variable water to solid ratio

• We explored the influence of water to solid ratio in the bomb reactor

• Experiments at W/S = 1, 2 and 4 for 24hrs of curing time

• Experiments with limewater and distilled water

For all water concentrations

the post treatment sample
resulted lighter at top and
darker at bottom

We observed the same in the larger reactor but for the bomb is more consistent
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 0.595, W/S = 1

Small fibers Larger bundled fibers

Sample 36 Distilled water Limewater Sample 38
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 0.595, W/S = 2

There are fibers in both samples, but they are concentrated in a few areas of the samples

Sample 37 Distilled water Limewater Sample 39

Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 0.595, W/S = 4

There are fibers in both samples, but they are concentrated in a few areas of the samples

Sample 40 Distilled water Limewater Sample 41

Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 0.595, W/S = 1 - XRD

Limewater Sample 38

T T T T Hydrothermally Treated

Calcined Blend
Hydrothermal Synthesis in Bomb Reactor – Summary

• The bomb reactor yields more consistent results

• Fibers can be found in all the samples and all the water to solid ratios, but in greater quantities for W/S = 1

• A lighter material is consistently produced at the top of the sample, indicative of an ongoing reaction during
hydrothermal synthesis.

• Despite the results, we did not produce a significant amount of fibers to be able to move on to the testing
phase
 Higher Calcium Concentration in Hydrothermal Treatment
(SEM, EDS, XRD)

I decided to increase the limestone content to reach a molar ratio Ca/Si = 1.15 (calculation based on
lime and volcanic blend only)
This ratio represents the upper limit for tobermorite formation

• Ratio Limestone/Volcanic Blend:

1. 1.017 – Explored the treatment time (8, 16 and 24hrs) and granulometry

After calcination, the limestone supplements a lime wt% of 36% (calculation based on lime and
volcanic blend only)
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs

90 µm
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs Rounded grains Elongated parallel fibers Long entangled fibers

Is very common to find the large pores coated with a layer of rounded pores and elongated parallel fibers
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs Rounded grains Elongated parallel fibers Long entangled fibers

The long entangled fibers seem to “sprout” from the rounded grains
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

24 hrs Chalcedony
(Microcrystalline Quartz) A geode-like structure

Elongated quartz pointing toward the center

https://carnegiemnh.org/how-do-geodes-get-their-colors/
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

16 hrs
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

16 hrs
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

8 hrs
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

8 hrs Evolution from small to long entangled fibers

Increasing fiber length

Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time

8 hrs These pores are only coated with the first layer of rounded grain
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time - XRD

We performed XRD and we found Tobermorite in repeated experiments, but we wanted to do this quantitatively.

Treated @ 24 hrs, 41% Tobermorite

Treated @ 24 hrs, 38% Tobermorite

Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, The effect of time - XRD

 We quantified the amount of tobermorite in a time series of 8, 16, 24 hours

Treated @ 24 hrs, 41% Tobermorite

Treated @ 16 hrs, 26% Tobermorite

Treated @ 8 hrs, 29% Tobermorite

Hydrothermal Synthesis in Bomb Reactor CaCO3/VB = 1.017 – Summary

• The higher calcium content resulted in more fibers than the composition with less calcium

• From XRD, tobermorite yield is higher for a treatment time of 24 hours

• The fiber length and entanglement in the large pores appear to increases with treatment time
Evolution of Fibers from Calcined Blend to Hydrothermal Treatment
(SEM, EDS, XRD)

• Ratio Limestone/Volcanic Blend:

1. 1.017 – Explored the treatment time (8, 16 and 24hrs) and granulometry

After calcination, the limestone supplements a lime wt% of 36% (calculation based on lime and
volcanic blend only)
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, Calcined Blend

C012 C014

Tiny grains can be tobermorite precursors C-A-S Compounds

Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, Calcined Blend - EDS

Very High Calcium content from EDS

C012
Pt. 1
60

50
Weight %
Atom %
1 40

30

%
20

10

0
Na K KK Al K Fe K CK Si K OK Ca K
(S)
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, Calcined Blend

C012 (Exposed to humidity at 60C for 3 days)

Tiny fibers
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, 8 hours of Hydrothermal Treatment

Large fibrous structures

Tiny fibers sprouting from larger grains
They seem to arise from the dissolution of larger grains
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, 16 hours of Hydrothermal Treatment
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017, 16 hours of Hydrothermal Treatment
Hydrothermal Synthesis in Bomb Reactor – CaCO3/VB = 1.017 – XRD

XRD Comparison in between the calcined blend and the hydrothermal product at 24 hours

Treated @ 24 hrs (43-

Lime Water)

Treated @ 24 hrs (40-

Distilled Water)
No Tobermorite
primary peak

Calcined Material (C012)

Hydrothermal Synthesis in Bomb Reactor CaCO3/VB = 1.017 – Summary

• Fibers might start forming right after calcination due to humidity exposure

• The presence of coarser grains yield to large C-A-S compounds who dissolve leaving behind hydrated fibers

• The fibers reorient along turbulent high-temperature flows to the interior of the pores
 Effect of Granulometry on Hydrothermal Synthesis
(SEM, XRD)

• Ratio Limestone/Volcanic Blend:

1. 1.017 – Explored the effect of granulometry

After calcination, the limestone supplements a lime wt% of 36% (calculation based on lime and
volcanic blend only)
Effect of Granulometry

Hand-Grinded Shatterbox

14

12 Coarse For cement production, we need a larger

Fine amount of material.
10

8 Grinding with shatterbox would improve

Mass (g)

6 the time efficiency and repeatability.

4 I tested the effect of shatterbox grinded

2 material in hydrothermal synthesis.

0
3 5 0 6 5 0 0 0
< 6 x < 7 x < 9 < 10 < 12 < 15 < 18 > 18
63
<
75
<
0 <x 6<x 5<x 0<x
9 10 12 15

Diameter (µm)
Effect of Granulometry – Fine Grained Material, Curing Time 24hrs
Effect of Granulometry – Fine Grained Material, Curing Time 24hrs
Effect of Granulometry – Fine Grained Material, Curing Time 24hrs

We observe a large amount of fibers (as in the case of hand-grinded material), but not as long and entangled as in the case of
hand-grinded.
Effect of Granulometry – Fine Grained Material, Curing Time 24hrs
Effect of Granulometry - Summary

• Fiber yield is likely dependent on the grain size of the calcined precursor

• For fine grained material, we do not observe the characteristic layers coating the large pores

• Despite the large number of fibers, we didn’t observe the long entangled fibers
Mass Change Post Treatment

8 4.6

7 Coarse 4.5 Coarse

Water Mass Post HT (g)

Fine Fine
6 4.4
Mass Gain (%)

5 4.3

4 4.2

3 4.1

2 4

1 3.9

0 3.8
6 8 10 12 14 16 18 20 22 24 26 6 8 10 12 14 16 18 20 22 24 26

Treatment Time (hrs) Treatment Time (hrs)

• 16 Hours is likely yielding more hydrothermal product

• Finer calcined blend means higher yield of hydrothermal product which are likely smaller fibers
Cement production: What we know from experiments
Curing of Volcanic Blend and Pozzolanic Ash alone

• We tested if the volcanic blend and the pozzolanic ash are able to cement by themselves,
without the addition of lime

• We calcined the volcanic blend at 1100 °C for 1.5 hrs, while we used the raw pozzolanic ash
(geological processes made it already amorphous and highly reactive)

• We mixed them with distilled water and limewater

• We cured in environmental chamber (100% RH) both at 55 °C and ambient T (~25 °C)

Results:
After 7 weeks of curing both the volcanic blend and the pozzolanic ash did not cement
Cementation Test for “low-Calcium” Formulation, Calcining Limestone and Volcanic Blend together

• We tested at which % of supplemented lime we achieve cementation

• We supplemented limestone to the volcanic blend from 0 to 23% (calculated considering lime
and volcanic blend only), corresponding to a Limestone/Volcanic Blend ratio:

1. 0 - (0 wt% CaO)
2. 0.1 - (5.5 wt% CaO)
3. 0.2 - (10.2 wt% CaO)
4. 0.3 - (14.6 wt% CaO)
5. 0.4 - (18.7 wt% CaO)
6. 0.54 - (22.9 wt% CaO)

• The mixture limestone – volcanic blend is calcined together and subsequently mixed with water

• Is cured for 28 days at 55 °C and 100% RH

Results:
Cementation is achieved only with CaO wt% = 22.9; However we observed fibers at 18.7 and 22.9%.
Cementation Test for “low-Calcium” Formulation, Calcining Limestone and Volcanic Blend together

CaO = 18.7 wt% We observe some large but rough fiber

Not Cemented They could have formed from the nucleation of small fibres on the surface of larger ones
Cementation Test for “low-Calcium” Formulation, Calcining Limestone and Volcanic Blend together

CaO = 22.9 wt%

Cemented

Fibers
Cementation Test for “low-Calcium” Formulation, Calcined Together - XRD
Cementation Test for “low-Calcium” Formulation, Calcined Together - XRD
Cementation Test for “low-Calcium” Formulation, Calcined Together - Summary

• Regardless of the water type, we achieved cementation only when wt% CaO is 23, when
the limestone and volcanic blend are calcined together.

• XRD data showed the presence of tobermorite both for 18.7 and 23% wt% CaO.
Mortar Production – Volcanic Blend Calcined Alone

After calcination, the volcanic blend is supplemented with lime After 28 days in environmental chamber @ 55C and 100% RH
Cement Paste Mortar
L+ VB + G L + VB + G + P L + VB + G + P + A

P A

VB P
VB
VB
G
G
G
L L L

L = Lime; VB = Volcanic Blend; G = Gypsum;

% of added CaO with
P = Pozzolanic Material; A = Aggregates
respect to the cement

12.5 to 25% of CO2 emitting materials (CaO)

Compared to 63% in Portland Cement Calculation based on Average Porosity = 50%
volcanic blend, lime and
60 to 80% less CO2 in our material pozzolanic ash only Average Permeability = 0.7mD (6.9x10-16 m2)
Mortar Production – CO2 Savings Calculation with Respect to OPC

In 1 kg of material
Heat
nCaCO3(s) → nCaO(s) + nCO2 1kg of CaCO3 = 0.56kg CaO + 0.44kg CO2
n = number of moles

Assuming that all CaO comes from decarbonization reaction

CaO in Portland 0.44

𝐶𝑂 2 ( 𝑘𝑔 ) = × 0.63 𝑘𝑔=0.495 𝑘𝑔
0.56
63 wt%

0.44
𝐶𝑂 2 ( 𝑘𝑔 ) = × 0.25 𝑘𝑔=0.196 𝑘𝑔 60% less
0.56
CaO in our blend for mortar
in between 12 and 25 wt%
0.44
𝐶𝑂 2 ( 𝑘𝑔 ) = × 0.125 𝑘𝑔=0.098 𝑘𝑔 81% less
0.56

CaO in our blend for 0.44

𝐶𝑂 2 ( 𝑘𝑔 ) = × 0.25 𝑘𝑔=0.196 𝑘𝑔 40% less
hydrothermal synthesis = 36 wt% 0.56
Mortar Production – Testing Petrophysical Parameters

We measure porosity and permeability through a helium porosimeter and an automated permeameter

Porosity Permeability
Mortar Production – Testing Mechanical Properties

Acoustic wave acquisition systems to

Sample within a Tygon sleeve to Triaxial Pressure Vessel
'hear' acoustic emissions triggered by
isolate from the hydraulic oil
micro-earthquakes and measure P-wave
applying confining pressure (PC)
velocity Sample

PZT

Tygon
Sleeve

PZT

Confining Pressure Strain Rate

𝑃 𝐶 =5 𝑀𝑃𝑎 Sensors to measure P-wave velocity
Mortar Production – Results Calculated including volcanic blend, lime, pozzolanic ash and gypsum

𝑃 𝐶 =5 𝑀𝑃𝑎 Peak
ID % CaO Strength Porosity (%)
35 (MPa)
M2
30 M1 M1 17.6 31 49.4
M2 17.6 33 47.6
Diff. Sress (MPa)

25 M3 12 16? 50

20
15 M3 M2
10
5
0
0 1 2 3 4 5 6 7 8
Axial Strain (%)

Stress – Strain curve and P-wave velocity variation

indicative of Ductile behavior
Mortar Production – SEM

SEM performed on mortar sample No fibers observed from SEM

Mortar Production – XRD
Mortar Production – FTIR

0.25
C-A-S-H
Geopolymer
C-A-S-H + Geopolymer Gel Mix-
0.20 ture
RMC
Naturally cemented Caprock
C_SCM2
0.15
Absorbance

0.10

0.05

0.00
1850 1750 1650 1550 1450 1350 1250 1150 1050 950 850 750 650 550
Wavenumber cm-1
Cement & Mortar - Summary

• When calcined together, the mixture volcanic blend and limestone cements only when lime wt%
is at 23%

• When lime is added after volcanic blend calcination, cementation is achieved with a lime wt% as
low as 12.5%

• Results from mechanical tests on mortars show the lime content of 18.7 wt% to have the highest
strength

• For the mortars, all the samples presented some fracture at surface during drying. The sample
with a lime content = 25 wt% had the highest fracturation leading to failure prior testing
Cement production: What we propose
Planning Cement Production with the New Formulation

Volcanic blend and limestone Reducing CaO% by adding

Control Tests pozzolanic ash Adding Fibers
calcined together as for
hydrothermal synthesis P 0 to 50% P 0 to 50%
F 0 to 2%
Ca/Si = 1.15, CaO = 36 wt%
VB + L 95%
VB = Volcanic Blend VB + L 45 to 95%
L = Limestone (CaCO3) Ca/Si = 1.15 VB + L 43 to 93%
Ca/Si = 1.15
G = Gypsum Ca/Si = 1.15

P = Pozzolanas (Volcanic Ash)

Very fine, mostly amorphous, G ≈ 5% G ≈ 5% G ≈ 5%
aluminosilicate material 3.5 80
F = Fibers Portland

CO2 Saving with respect

3 Cement 70
Ca/Si Molar Ratio

60
2.5
We keep the VB + L

OPC (wt%)
50
2
composition fixed to 40
1.15 which will always 1.5
10% Ca/Si = 1.15 30
yield fibers and we 1 30% 0% 20
50%
reduce the overall lime 0.5 20%
10
content by adding 40% Volcanic Ash wt%
0 0
10 20 30 40 50 60 70 0 10 20 30 40 50 60
pozzolanic ash
CaO (wt%) Volcanic Ash (wt%)
Planning Cement Production with the New Formulation – What we have done so far (06/22/2023)

What we produced so far:

1. Control test: Volcanic blend and limestone calcined together and supplemented with CaSO 4

2. Control test: Volcanic blend and limestone calcined together with no CaSO4 supplemented

What’s next step:

1. Control test: Portland Cement Type G (for wellbore applications)
2. Mechanical tests on the control tests
3. Produce cement with fibers from hydrothermal synthesis
Cement Production with New Formulation – Limestone/Volcanic Blend = 1.017, wt% CaO = 36%

1. Raw volcanic blend grinded with shatterbox 5. 1 week curing @55C and 100% RH
2. Volcanic Blend and Limestone calcined together (1.5h @1100C) 6. Demolding
• Ca/Si = 1.15 7. 3 more weeks of curing @55C and 100% RH
3. 2nd grinding with shatterbox
4. Hand-mixed with water (W/C = 0.5) for 3 mins

With CaSO4 No CaSO4

6 cm 5.5 cm