Recent Progress in Low Carbon High

Performance Cement-Based Materials

Caijun Shi , Ph.D., P. Eng., FACI, FRILEM

COLLEGE OF CIVIL ENGINEERING, HUNAN UNIVERSITY
President, Asian Concrete Federation

Viet Nam Concrete Association

Hanoi，2023 11.11

Contents

 Introduction

 High Performance Concrete with Multi Performance Targets

 Design and Application of UHPC

 Design and Properties of Ultra Performance ECC

 CO2 Mineralized Concrete Materials and Products

 Summary

1
Introduction Introduction

Hydropower Construction High-Speed west-east gas

Engineering engineering Railway transmission

Due to improper material

Rapidselection, design,
development andConstruction
of the construction, some infrastructure
industry
structures have failed prematurely.

nuclear power Highways Marine engineering Large scale bridges

engineering

Introduction
CO2 emission in China 2022 is 11.48 billion tons, Proportion of construction materials
with 28.3% in global world produce in carbon emission

Production Construction Operation

Unprecedented scale of infrastructure construction and harsh environments cause increasingly

demands for civil engineering materials and structural performance

Construction engineering Sichuan-tibet railway Ocean bridge

Low carbon and high performance of civil engineering materials

is an important method to achieve the dual carbon strategy! 4

2
 Contents

 Introduction

 High Performance Concrete with Multi Performance Targets

 Design and Application of UHPC

 Design and Properties of Ultra Performance ECC

 CO2 Mineralized Concrete Materials and Products

 Summary

Background
Time Inventors Name Specificities
Cement pastes with a flexural strength of 60-70 MPa and a compressive str
1981 Birchall et al. Macro-defect free (MDF) pastes
ength of more than 200 MPa.
Dense packing is achieved through the use of large amounts of superplastic
1981 Bache Densified with small particles (DSP) concrete
izers.
High-Strength Concrete (HSC),
1980’s Shah , Zia Water reducing agent added, normal curing, good durability
High-Performance Concrete (HPC)

1984 Lankard Slurry Infiltrated Fiber Concrete (SIFCON) High content of steel fibers (8vol%-15vol%)

1987 Bache Compact Reinforced Composite (CRC) Concrete with extensive use of steel rebars and steel fibers

1992 Li, Wu Engineered Cementitious Composites (ECC) Contains polypropylene fibers with strain-hardening properties

Richard, Elimination of coarse aggregates, optimization of particle gradation, appli

1993 Cheyrezy Reactive Powder Concrete (RPC) cation of pressure during setting, curing by heat treatment, concrete comp
ressive strength up to 200-800 MPa.

UHPC is designed based on packing model theory with good flow properti
1993 De Larrard Ultra-High Performance Concrete (UHPC)
es and high compressive strength (236 MPa).
Ulm, Graybeal, Rossi Ultra-High Performance Fiber-Reinforced Concrete
2000 High strength, excellent toughness and durability
等 (UHPFRC)

High-Strength High-Ductility Cementitious Composites

2011 Ranade, Stults, Li等 Compressive strength over 100 MPa and tensile strain capacity over 3%
(HSHDCC）
6

3
 Background
Definition of UHPC
A cementitious composite with ultra-high strength, high toughness and excellent durability.
 Compressive Strength：＞120MPa（ACF - 120001 – 2020、ASTM C1856/C1586-17）
150MPa（NFP 18-470）或 180MPa（KCI-M-12-003）
 Tensile Strength：＞5MPa（ACF - 120001 – 2020）
＞ 8MPa（ NFP 18-470 、KCI-M-12-003）
 Chloride migration coefficient：＜ 10-14 m/s （ACF - 120001 – 2020）

NC matrix UHPC matrix 7

Background
 Comparison of UHPC and NC

Property NC UHPC UHPC/NC

Compressive Strength (MPa) 30~60 120~240 ≈3

Elastic Modulus (GPa) 30~40 40~60 ≈1.2

Density (kg/m3) ~2500 2500~2800 ≈1.2

Ultra-high strength and excellent toughness High durability in extreme environments Reduce carbon emissions
8

4
 UHPC Design Concepts
 Reducing Porosity  Adequate rheological properties
WFT on the surface of the particles;
Close-packed particles,
Improved fiber distribution and orientation
lowest w/c ratio

 Control of autogenous shrinkage  Enhancement of toughness

IRH：Internal curing
Incorporation of fibers
Reduce the surface tension of water in
capillaries（γ）: SRA

Fiber
WFT

UHPC Design Concepts – Strength and porosity

Balshin’s Equation:
 =  o .(1 - P ) A
Ryshkevitch’s Equation:

 =  o .exp(-B.P)
Schiller’s Equation:

 = D.ln( Po ) Low w/c Dense structure

P
Hasselmann's Equation:
 =  o .(1- AP)
Reduced w/c ratio by superplasticizers
10

5
UHPC Design Concepts– Enhanced toughness
Ductile damage

FRC Fiber

CC Brittle damage
CC and FRC damage modes

Strain hardening

ASTM C1018 Toughness indexes

Tensile stress

UHPC
Toughness Deflection Area Calculation
indexes criterion basis
FRC I0 δ OAB SOAB/SOAB
CVC I5 3δ OACD SOACD/SOAB
I10 3.5 δ OAEF SOAEF/SOAB
0 Strain I20 10.5 δ OADH SOADH/SOAB
11

Dry close packing theory

q
Di  Dmin
q
P ( Di )  q
Dmax  Dmin
q

RSS  in1Pmix(Di )  Ptar(Di )  min

2

Packing density diagram of particles P(Di) is a fraction of the total particles smaller than Di;
Di is the particle size (μm)；
Dmax is the maximum particle size (μm) ；
Dmin is the minimum particle size (μm)，respectively；
q is the distribution modulus=0.23；
Pmix is the composed mixture；
Ptar is the target grading calculated from Eq. (1).
12

6
Packing Effects

Without With
superplasticizer superplasticizer
Particle loosening and wall effects cement particle suspension with and without
superplasticizer

Particle wedging effect 13

dispersion of particles with and without superplasticizer

Dispersion of silica fume in wet mixture

100
(a)
80
Volume (%)

60

40
U-SF
D50=0.64μm
20 U-Cement
D50=13.8μm

0
0.1 1 10 100 1000
Particle size (μm)

Structure of silica fume agglomerates14

7
 UHPC Design Methodology – Typical Mixture

Water
Water Paste
18%
15%
710 kg/m3 Silica fume Phase
Cement Paste 10%
Glass
Cement 24%
Phase powder 9%
Silica fume 66%
8%

230 kg/m3 Cement

28%
Sand
22%
Cement
210 kg/m3 Quartz Powder SP 1% 28% Particle
Phase
Fibers 3%
Particle Aggregate 76%
Sand 2 54%
Phase 9%
34%
Sand Sand 1
22%
1020 kg/m3

Fiber
UHPC NC
40-160 kg/m3 SP 13 kg/m3 w/c=0.19 w/c=0.45
140 kg/m3 Water 190 MPa 30 MPa

15

UHPC Design Methodology-Statistical mixture design method

Cement Cement
56d compressive strength (MPa)

Dry Close Packing Wet Close Packing

Fly ash Slag Fly ash Slag

Fly ash
Cement Silica fume Slag
矿粉
水泥
(1.0) (0.5)

Slag Cement (0.5)

Silica fume Silica fume
Silica fume
Dry Close Packing Wet Close Packing

Y  1 x1   2 x2   3 x3   4 x4  12 x1 x2  13 x1 x3  14 x1 x4   23 x2 x3   24 x2 x4   34 x3 x4

 123 x1 x2 x3  124 x1 x2 x4  134 x1 x3 x4   234 x2 x3 x4  1234 x1 x2 x3 x4

Y is the property or microstructure (flowability, strength, porosity, etc.) ;

βi is coefficient; xi is a component, i=1-4.
16

8
 Composition and the heat of hydration
Cement
No. t0(h) P72(KJ/Kg) No. t0(h) P72(KJ/Kg)
N-1 8.31 151 N-9 6.98 153
N-2 7.05 137 N-10 8.43 141
N-3 10.75 138
N-11 8.43 141
N-4 7.07 144
N-12 8.18 141 Fly ash Slag
N-5 8.2 152
N-6 7.89 146 N-13 9.42 154

N-7 7.1 144 N-14 7.72 136

N-8 7.78 143 N-15 7.95 141 Silica fume

Yt 0 =8x1  12x 2 +67x 3 +23x 4 +23x1x 2  73x1 x 3  26x 1 x 4  555x 2 x 3  543x 2 x 4 -1361x 3 x 4
+722x1x 2 x 3 +770x1 x 2 x 4 +1914x1x 3 x 4 +22504x 2 x 3 x 4  31896x1 x 2 x 3 x 4

YP72 =151x1  145x 2 +61x 3 +237x 4 +356x1x 2 +67x1x 3  156x1x 4 +5611x 2 x3 +7944x 2 x 4  7389x3 x 4
7667x1x 2 x 3  10556x1x 2 x 4 +10556x1x3 x 4  26185x 2 x 3 x 4 +20741x1x 2 x3 x 4
17

Cement-silica fume-slag binder

Y3  0.79x1  0.51x2  0.66x3  0.0062x1 x2  0.062x2 x3  0.0009x1 x3  0.0008x1 x2 x3
 Compressive
strength Y56  1.09x1  2.14 x2  0.54 x3  0.049 x1 x2  0.098 x2 x3  0.0099x1 x3  0.0022 x1 x2 x3

Y3  0.15x1  0.36x2  0.2x3  0.0039 x1 x2  0.0096 x2 x3  0.0013 x1 x3  0.0001x1 x2 x3

 Porosity
Y56  0.091x1  0.014 x2  0.15x3  0.0007 x1 x2  0.0013x2 x3 -0.0005x1 x3

 Ca(OH)2 Y3  0.075x1  0.13x2  0.079x3  0.0014 x1 x2  0.0041x2 x3  0.0005 x1 x3  0.0001x1 x2 x3

Y56  0.15x1  1.12 x2  0.3x3  0.019 x1 x2  0.027 x2 x3 -0.0068x1 x3  0.0004 x1 x2 x3

 Heat of Yp0  2.2778x1  4.4444x2  2.2778x3  0.0556 x1 x2  0.2222 x2 x3  0.0278 x1 x3

hydration Yt0  0.072x1  0.68x2  0.0089x3  0.009 x1 x2  0.025 x2 x3  0.0023x1 x3  0.0003x1 x2 x3

Yt  0.17x1  2.3x2  0.84x3  0.028x1 x2  0.043x2 x3  0.01x1x3  0.0012x1x2 x3

50

18
(Shi et al. CCC, 2015)

9
 Cement-silica fume-slag binder

Compressive strength：
a) 3d；b) 56d

Ca(OH)2：
a) 3d；b) 56d

(Shi et al. CCC, 2015) 19

Rheology Control

Normal Superplastic
 Extra-long side chains to increase
the thickness of the adsorbent layer
 Introduction of phosphonate
adsorption substrate to enhance
adsorption capacity

Rheological parameters of low w/c ratio cement-silica fume pastes

Yield stress Consistency Equivalent plastic

Samples n
Superplastic Viscosity Reducing (Pa) coefficient (Pa·sn) viscosity (Pa·s)
 Strong adsorption and good adaptability C-PCEs 1.51 6.38 0.988 6.10

 Low residue, low viscosity S-PCEs 1.39 1.68 1.090 2.36

20

10
Rheology Control VS fiber orientation
The rheological properties of UHPC have a great influence on fiber distribution and orientation,
and we propose a method for fiber distribution based on UHPC viscosity control.

100 1.0
Viscosity hq

80 0.8

Viscosity (Pa.s)
60 0.6
UHPC slurry flow and fiber distribution hq
40 0.4

20 0.2

0 0.0
0 5 10 15 20 25
Silica fume content (%)

SF0-Poor fiber dispersion SF15-good fiber dispersion

UHPC粘度与纤维分散特性关系

Flow curves measured over stepwise rotation speed for UHPC

21

Autogenous shrinkage control – SAP+SRA

1600
REF L10-D
Autogenous shrinkage (μm/m)

1400 L10-S L10-E

L10-V
1200

SRA 1000

800

600
Where:
400
△P is the pore tension
𝜸 is the surface tension 200
of the pore solution 0
5 15 25 35 45 55 65 75
Blank Blank + SRA 100 Time (h)
SAP or SRA
96
RH (%)

92

88 REF
L-10-D
L-10-S
SAP SAP r 1＜ r 2 ＜ r 3 ＜ r 4 84 L-10-E
L-10-V

0 8 16 24 32 40 48 56 64 72
Time (h)
SAP + SRA Blank + SAP Blank + SAP + SRA
LWA on autogenous shrinkage
Synergistic mechanism of relative humidity-surface tension-autogenous and internal RH of UHSC
shrinkage with the addition of SAP and SRA. (Liu et al. 2019 CCC) 22

11
Uniaxial tensile properties – Testing and Simulation
Based on the numerical simulation results, the design of the loading surface was optimized, and a
measurement method applicable to uniaxial tensile of UHPC was developed.
2.1
2.0
1.9
No CFRP
1.8 2.08 CFRP
1.7

Stress/M Pa
2.06
stress concentration

Stress/M Pa
1.6 2.04
1.5 2.02
1.4 2.00
1.3 1.98
1.2 1.96
1.1 2 3 4 5 6 7 8 9 10 11 12 13
1.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13
Point
Stress at different locations
 Applying CFRP can reduce the

No CFRP CFRP stress concentration during the

tensile test. 23

Bond behavior between UHPC matrix and steel fibers

Straight steel fiber (Zhang et al. CCR 2019) 24

12
Bond behavior between UHPC matrix and steel fibers

Hooked steel fiber 25

Bond behavior between UHPC matrix and steel fibers

Corrugated steel fiber 26

13
A numerical model in Finite Element Method
1. 研究背景

 Stress transfer from fiber to UHPC matrix

 Fiber stresses greatly exceed those in the matrix, ranging 6 to 13 times higher.
 During the partially debonded stage, the stresses of the fiber and matrix
increased obviously.
 the hooked and corrugated steel fibers were gradually straightened during
the fiber pullout.
 Hooked steel fiber＞Corrugated steel fiber＞Straight steel fiber

Straight steel fiber Hooked steel fiber Corrugated steel fiber

27

Analysis of fiber-matrix bonding properties

Where：
；
Le=L-Ld. ；
Straight steel fiber： Ld is the fiber debonding length

Le is the length of the fiber in the matrix

Where：
； ；
Hooked steel fiber：
P1， P2， P3 are the pull-out forces at different stages.

Where：
； ；
Corrugated steel fiber：

P1， P2， P3 , P4 are the pull-out forces at different stages.

28

14
 Constitutive relation of UHPC
Uniaxial tensile Uniaxial compression Multiaxial force
0.0 0 .2 0 .4 0 .6 0 .8 1 .0 300
1 .0 1 .0

250
0 .8 0 .8

新 200

(MPa)
0 .6 0 .6

发
U0-0-1 纵向应变
150 U0-0-1 横向应变

偏应力
U0-10-1 纵向应变
0 .4 0 .4

现
U0-10-1 横向应变
100 U0-20-1 纵向应变
U0-20-1 横向应变
0 .2 0 .2 U0-30-1 纵向应变
50 U0-30-1 横向应变
U0-40-1 纵向应变
0 .0 0 .0 U0-40-1 横向应变
0.0 0 .2 0 .4 0 .6 0 .8 1 .0 0
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
x
应变 (%)
300
1 .0 1 .5 2 .0 2 .5
1 .0 1 .0
250
0 .9 0 .9
200
0 .8 0 .8

(MPa)
U3-0-1 纵向 应 变
150 U3-0-1 横向 应 变

偏应力
0 .7 0 .7 U3-10-1 纵 向应 变
U3-10-1 横 向应 变
y

100 U3-20-1 纵 向应 变
0 .6 0 .6 U3-20-1 横 向应 变
U3-30-1 纵 向应 变
50 U3-30-1 横 向应 变
0 .5 0 .5 U3-40-1 纵 向应 变
U3-40-1 横 向应 变
0
0 .4 0 .4 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
1 .0 1 .5 2 .0 2 .5 应 变 (%)
x
 x
 0 x 1  y  1 . 2 x  0 .2 x 6 0  x 1
 0.92 x 1.09
 0.08  σ 1μ / f c'  1  2 .4 5 σ 3 / f c '
y 
y


x
1 x
 x
x 1 ε 1μ / ε c'  1  5 .7 3 σ 3 / f c'
10( x  1)  x
2
29
 0.1( x  1)  x
2.4

UHPC uniaxial compression - Different length steel fiber

s

(a) L0S0 (b) L2S0 (c) L1.5S0.5

(d) L1S1 (e) L0.5S1.5 (f) L2S0

Relationship between hybrid
fibers and peak stress, strain in
peak stress and elastic modulus：
 Peak stress = 99.014 + 12.713Vl + 2.273Vs -2.629Vl2 R2 = 0.90
 Strain in peak stress = 3.591 + 0.564 Vl + 0.084 Vs -0.343 Vl2 R2 = 0.99
 Elastic modulus = 37.897 + 2.431 Vl + 0.151 Vs -1.714 Vl 2 R = 0.75
2 30

15
 Mechanical behavior and damage analysis of UHPC
Dynamic failure pattern of UHPC
210
L1.5S0.5
180 L1S1 L0.5S1.5

150

Stress (MPa)
120
L0S2
90
L2S0
60 L0S0
30

0.00 0.02 0.04 0.06 0.08 0.10

Strain
Dynamic flexural properties Dynamic compressive properties of UHPC with hybrid steel fiber reinforcements

Crack control mechanism for UHPC with hybrid steel fiber reinforcements. 31

UHPC—Modulus of elasticity

75
GB/T 50010-2010 Norwegian Standard NS 3473
160 70 ACI 318-14 CSA A23.3-04
UHPC with High elastic modulus ACI 363-10 CEB-FIP
140 65
M odulus of elasticity/G Pa

UHPC Eurocode 2 AFGC

Compressive strength (MPa)

Plain Concrete 60
120
55
100
High deformability 50
80
45
60
40
40 35 Ec =6.059 fc0.42

20 30
Ec =12.26 fc0.27
0 25
0.000 0.002 0.004 0.006 0.008 0.010 0.012 0.014
Strain 20
0 20 40 60 80 100 120 140 160 180 200 220 240
Compressive strength/MPa
Crack resistance

 The deformation of UHPC is controlled by the modulus of elasticity.

 UHPC with high modulus of elasticity has excellent crack resistance. 32

16
 Modulus of elasticity- Microstructure
 Micro-scale: C-S-H, cement clinker, etc.
LD C-S-H HD C-S-H
w/b Curing condition Cement
(GPa) (GPa)
0.15 20°C CEM I - 27.7±5.7
0.20 20°C CEM I 19.4±4.8 31.8±6.1
0.30 20°C CEM I 21.9±4.9 31.3±4.5
0.15 90°C for 48h CEM I - -
0.20 90°C for 48h CEM I 15.4±3.4 23.9±2.5
0.25 90°C for 48h CEM I 23.1±2.0 32.4±3.4
0.17 20°C±2°C, RH>90% CEM I
0.19 20°C±2°C, RH>90% CEM I with fly ash
19±5 29.5±5.5
CEM I with silica
0.26 20°C±2°C, RH>90%
fume
20°C±2°C, RH>95% P.I 52.5 with silica
0.23
for 28 d fume

Curing Elastic modulus 20°C±2°C, RH>95%

P.I 52.5 with silica 19±5 29.5±5.5
0.23 fume and lithium
for 28 d
slag
condition LD C-S-H (GPa) HD C-S-H (GPa) 0.18 20°C±2°C, RH>95% CEM I 20±2 31±4
0.19 20-25°C, 35 to 55%
CEM I with water
w/b<0.2 ~ RH for 6 d, heated for
reducer, silica fume, 18.6 32.2
20 30 0.21
48 h at 90°C and 90%
quartz powder
(no-heat and heat) RH
19.03±4.7 30.75±6.9
0.3 20°C for 28 d CEM I
5 7
w/b>0. No heat 20 30 0.3 20°C for 28 d
CEM I with 25%
23.7±5.9 36.1±3.4
calcareous filler
2 Heat 23 32 (Ouyang et al. CCR 2020) 33

High elastic modulus UHPC design and preparation

 A formula for calculating the modulus of elasticity of UHPC based on material composition
was proposed, and UHPC with a modulus of elasticity of 62 GPa was prepared.
Level I C-S-H
10-6~10-4 m Pore w/b Maximum
f LD  1.773 w c  0.057 s f c  0.207  R 2 =0.91 60 Minimum
55
1
 Coarse aggregate Cement
 
1 1 50
Clinker  K   K
Level II Sand
est
K hom   f i K i  1    i  1      f i 1    i  1    45
10-4~10-2m
  K0   i   K0   
ITZ-sand i
 40
1
 G 
1
  G  
1
35
est
Ghom   f i Gi  1    i  1      f i  1    i  1   
Fiber
  G0   i   G0   
Level III Coarse aggregate
i

体积分数 剪切/体积模量
10-2~10-1m
ITZ-coarse
Sand Silica fume
est
9 K hom est
G hom est
3 K hom  2G hom
est
est
E hom  ; hom
est

est
3 K hom  G hom
est est
6 K hom  2G hom
est

Fiber
Multiscale theory Calculation of the percentage Influence of different components
of micro-constituents
70
静弹性模量 55 60
动弹性模量
60

50 55
Elastic modulus(GPa)
Elastic modulus(GPa)

50
弹性模量 (GPa)

40 45 50

30 40 45

20
35 Mixture 1 40 Mixture 1
10 Mixture 2 Mixture 2
Mixture 3 Mixture 3
30 35
0
0 400 600 800 1000 1200 0.14 0.16 0.18 0.20 0.22 0.24 600 700 800 900 1000 1100 1200
粗骨料掺量 (kg/m 3) w/b Cement (kg/m3)

Modulus of elasticity formula: E=35.10 141.28w b  0.025Mc  0.004Ms f  0.013Msand  0.015Magg  0.011Vfiber 34

17
UHPC multiscale model validation
Cement paste

Mortar

65
Predicted results
UHPC 60
Test results

Elastic modulus(GPa)
55

50

45

40

0
00

0
C0

00
4

00
6

00

20
0.1

0.1
0.1

C8
C4

C6

C1
C1
H-

H-
H-
Error ≤ 2%
35

Seawater Sea Sand UHPC – Compressive Strength and Porosity

Sample Cement (%) SF(%) GGBS (%) SP (%) W/C C/A Water Aggregate
U-f 70 2 0.16 1:1 Freshwater River sand
U-sw 70 2 0.16 1:1 Seawater River sand
U-ss 70 2 0.16 1:1 Freshwater Sea sand
10 20
U-swss 70 2 0.16 1:1 Seawater Sea sand

P-sw 70 0 0.45 1:3.6 Freshwater River sand + Crushed stone

P-ss 70 0 0.45 1:3.6 Seawater Sea sand + Crushed stone
140 18
U-f U-swss U-sw U-ss
15
Compressive strength (MPa)

130
Porosity (%)

12

9
120

110 3
0 200 400 600 800 1000 U-f U-swss U-sw U-ss P-ss P-sw
Age （d） NO.

 Incorporation of seawater and sea sand: Promoting UHPC

early strength growth 36

18
Seawater Sea sand UHPC – Half-cell potential and current density

-700 100
U-f U-sw U-ss U-f U-sw U-ss
U-swss P-sw P-ss
-600 U-swss P-sw P-ss
10
-500
高速率锈蚀
1

Icorr (uA/cm2)
-400
Ecorr(mv)

-350mv 中/低速率锈蚀
-300 0.1

-200
-200mv
0.01
-100
钝化状态
0 0.001
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Age(d)
Age(d)

Half-cell Potential Current Density

 Normal concrete: With the addition of seawater sea sand, corrosion of reinforcing bars occurs
very quickly.

 UHPC: with the addition of seawater sea sand, the corrosion rate of reinforcing bars remains
very low within 1080 days. 37

Seawater Sea sand UHPC – corrosion of reinforcement

 After 120 days, the internal

reinforcement of NC has
shown serious corrosion,
120d
and no corrosion occurred
on the surface of the internal
reinforcement of UHPC.

 After 1080 days, there was

no surface corrosion of the
reinforcement inside the
1080d UHPC, and the reinforcement
was well bonded to the
cement paste.

38

19
 Contents

 Introduction

 High Performance Concrete with Multi Performance Targets

 Design and Application of UHPC

 Design and Properties of Ultra Performance ECC

 CO2 Mineralized Concrete Materials and Products

 Summary

39

Design methods of conventional and modern concrete

Conventional concrete Modern concrete
 Selection of materials and composition  Closing packing of particles
based on experience
 Use of superplasticizer / low water-to-
 Water-to-binder ratio calculated by binder ratio
Belomey’s formula
 Use of supplementary cementitious
 Selection of mix proportion based on materials
experience
 Consideration of Service life
 Consideration of only workability and
strength of concrete

40
40

20
 Design Principle of green low-carbon HPC

Scientific basis for the design of green low-carbon HPC:

 The deformation and some durability problems of concrete are basically caused by
cement paste
 Application of multiple supplementary cementitious materials and chemical admixture
 Cement and cementitious materials are the composition of high cost and high carbon
content in concrete

Close packing of aggregate and the smallest thickness of excess paste

Aggregate Aggregate

Paste for Voids Excess paste

Add paste

Void
Thickness of excess paste
Vpaste  Vvoid
Vpaste =Vvoid +VExcess t paste 
( M S AS,C  M G AG,C ) 41
41

Design of cementitious material compositions

Belomey W  a  fb 28d Strength
(1) Water-to-binder 
B f cu ,0   a   b  f b
ratio Designed strength Regression coefficient

According to 《Code for design of concrete structural durability》(GB 50476-2008), the biggest water-to-binder ratio is
obtained, and chooses the smaller one
N Composition w/%
u
m. Cement Fly ash Slag
(2) Design of material
1 100 0 0
compositions based on
2 85 15 0
the centroid factoral
3 75 0 25
design theory
4 72.2 11.1 16.7
5 70 30 0
6 58.3 16.7 25
7 50 0 50

Y  1 x1   2 x2   3 x3  12 x1 x2   23 x2 x3  13 x1 x3  123 x1 x2 x3

Where: Y is structural or performance characteristic of cement-based material, βi is coefficient,
42
Xi is composition constitute of three cementitious materials 42

21
 Relationship between composition and properties of concrete
composition and alkali aggregate reaction

Relationship between experimental value

Isoline between cementitious materials Fly ash

and predicted value of alkali aggregate

reaction expansion value
expansion value

Slag Cement
Isoline between cementitious materials

Isoline between cementitious materials

compositions and strength of concrete

compositions and cracking time

43
43

Regulating the rheological properties and thickness of excess paste

by chemical admixture
w/b= 0.5,sand ratio = 0.38,superplasticizer= 0.5% w/b= 0.5,sand ratio = 0.38,without superplasticizer
700 60 240 700 35 240
屈服应力
Yield stress 塑性粘度
Plastic viscosity Slump
坍落度 Yield stress Plastic viscosity Slump
600 I II III 220 600 I II III 30 220
50
塑性粘度 (Pa.s)

500 200 500 25 200

坍落度 (mm)
stress (Pa)

40 40
400 180 400 20 20 180
Plastic viscosity
Plastic viscosity
屈服应力

Yield stress

170
Slump

170
Slump

300 160 300 15 160

280 30 280
Yield

200 140 200 10 140

20
100 120 100 5 120

0 10 100 0 0 100
10 15 20 25 30 35 35 40 45 50 55 60 65 70

excess paste(μm)
富余浆体厚度
Thickness of Thickness of excess paste

300 360 400 420 460 500

Cement (kg/m3) Cement (kg/m3)
The amount of cementitious materials decreases from 440~460 kg/m3 to 340~360 kg/m3 with superplasticizer
If superplasticizer is added during the preparation of 60% concrete, the amount of cement decreases by 20%,
and then the decreased amount of CO2 emission achieves:14*0.6*0.2 = 0.168 billion tons CO2 44
44

22
 Regulating the usage of the cementitious materials by chemical admixture

Fresh properties of concrete Harden properties of concrete

50
Ref T1 T2

Compressive Strength (MPa)

40
35 MPa
30
24 MPa
20
15 MPa
10

470 380 250

0
3d 7d 28 d

• High cementitious • Low cementitious

materials amount materials amount
• High water demand • Low cement amount
amount Conventiona The • Suitable slump
• High slump
l Method method • Good stability
• Excessive high • Satisfy the grade of
compressive strength strength
45
45

Design of HPC with multiple performance targets

2. Design and determination of
1. Close packing of aggregate and excess paste
paste composition
Cement
Aggregate Paste for Aggregate 1
The minimum value
voids
calculated by
5 7 Belomey formula
Add 1
Fly ash 11 6 15
3 1 and obtained design
paste 2
102 value of the
Voids 14
4
8 durability of
Excess paste 9 Slag
Dry close Wet close thickness concrete
Silica fume 3
packing packing
4. Composition of cementitious 5. Composition of HPC with
3. Determination of the smallest
materials and properties of multiple performance
thickness of excess paste
concrete targets
0.0 0.5

0.1 0.4
F ly

0.2 26 0.3
g
S la

As
h

0.3 0.2

Flowability
24
2
0 0.4 Cracking 22
0.1
20 18
0.5 0.0
0.5 0.6 0.7 0.8 0.9 1.0
Cement
0.0 0.5
0.0 0.5

0.1 0.1 0.4

0.4
Fly

0.2
Fly

0.2 0.3 0.3

g
g

Sla
S la

A
As

sh

Chloride carbonatio
h

0.3 0.3

Strength 70 0.2 0.2

2.8

migration n depth
0.4 0.1 0.4
3.6 0.1
68 64
66 3.2
64 60 4.0
0.5 4.6
0.0 0.5 0.0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
Cement Cement
46
Cement Superplasticizer =0.5%
46

23
Triangular cone orthogonal design of four compositions
Design proportion of cement-slag-fly ash-
limestone Cement
Composition of cementitious materials（%）
Num.
Cement Limestone Fly ash Slag
1 100 0 0 0
2 50 50 0 0
3 50 0 50 0
4 50 0 0 50
5 75 25 0 0
6 75 0 25 0
7 75 0 0 25
8 50 25 25 0
9 50 25 0 25 Slag
10 50 0 25 25 Limestone
11 67 17 17 0
12 67 17 0 17
Fly ash
13 67 0 17 17
14 50 17 17 17
15 62.5 12.5 12.5 12.5

47
47

Application of design method of green low-carbon HPC

Yueyang Dongting Lake

Changsha Subway
The total length of Changsha
subway line is about 450 km, and
design life of concrete is 100
years
Chenzhou Chishi Bridge
The largest span (380 m) and the
first high pier (182 m) multi-
tower concrete cable-stayed
bridge in the world
Second Bridge
The second longest span, and the
first Steel-UHPC lightweight
composite deck self-anchored
suspension bridge in the world

Yuanshui Bridge, Gai Huai China Resources Cement Beijing Xinao Concrete Group
Highway, Dajiang Estuary Concrete Group Co., Ltd Co., Ltd
48
48

24
 Contents

 Introduction

 High Performance Concrete with Multi Performance Targets

 Design and Application of UHPC

 Design and Properties of Ultra Performance ECC

 CO2 Mineralized Concrete Materials and Products

 Summary

49

Introduction
Background
Definition and characteristics of ECC
 ECC（Engineered Cementitious Composite）also known as “Strain Hardening Cementitious
Composites (SHCC)” or “Ultra-High-Toughness Cementitious Composites (UHTCC)” or
“Ultra-high Ductility Cementitious Composites (UHDCC)”.

 ECC represents a family of materials with the common feature of being ductile, with tensile
strain capacity typically beyond 2%.

Mechanical performance of OC, UHPC, and ECC Crack width

(Huang B, et al., CCC, 2020 ; Şahmaran et al., CCR
50

2009)

25
 Introduction
Design theory of ECC
Background

Criteria for Composite Strain-Hardening

(1) Strength criterion: the first cracking strength σfc not

exceed the fiber-bridging capacity σ0 crossing
σfc ≤ σ0
(2) Energy criterion: the crack tip toughness Jtip must
be less than the complementary energy Jb’
Jtip ≤ Jb’
51
拉应力-拉应变5

Introduction
Tensile strength
Types of fiber
PVA-ECC PE-ECC PVA-ECC

PE-ECC

 The PVA fiber has high strength. However, excessive chemical bond and frictional bond reduces its Jb’,
leading to a composite with relatively low strain capacity.

 Alarge number of stress fluctuations of small magnitude in PVA-ECC, compared to PE-ECC.

(Lu C et al., JBE 2023)

52

26
 Introduction
Background
Introduction
Tensile strength
Tailor matrix flaws

Light-weight Plastic beads

shale aggregates

Reference 7% shale aggregates 7% plastic beads

53
拉应力-拉应变5
（Wang et al. PFMCA
拉应力-拉应变 5 2004）

Design theory of HSHDCC

Micromechanics-based design procedure for HSHDCC.

(1) Strength criterion: the first cracking strength σfc not
exceed the fiber-bridging capacity σ0 crossing
σfc ≤ σ0
(2) Energy criterion: the crack tip toughness
Jtip must be less than the complementary
energy Jb’
Jtip ≤ Jb’
The typical single-crack stress opening (δ-σ) relation （ Ranade R. et al. 2016； Li V. et al. 1993） 54

27
 Dynamic compressive strength

Failure patterns
Compressive stress–strain relationship of HSHDCC at high strain rates.

 Compared with the quasi-static compressive strength, the dynamic compressive strength increased by
about 6%-55% and the energy absorption after peak stress increased by 2.86-3.28 times, but the peak
compressive strain gradually decreased with increasing strain rate.
 The failure pattern gradually changed from maintaining good integrity and fewer cracks to several large
pieces along the through cracks with increasing strain rate. 55
（ Zhao et al. JBE 2023）

Quasi-static tensile strength–hybrid fiber

 Due to high steel fiber-matrix bond, the

first cracking stress and tensile strength
were increased and residual crack width
was reduced with the increase of steel fiber
content.

56
（ Liu T. et al., CCC 2020）

28
 Quasi-static flexural strength –Hybrid fibers
2% PE

1.5% PE+0.5% steel

1% PE+1% steel

Stress versus displacement of HSHDCC with Multiple cracking

hybrid PE and steel fibers

0.5% PE+1.5% steel

 Increasing PE fiber content from 0 to 2%, flexural strength

2% steel
and deflection increased by 88% and by 203%, respectively.

 The crack number increased gradually with the increasing

amount of PE fiber and the distribution was more uniform.
（ Zhou Y. et al. 2018） 57
HSHDCC 破坏状态

Mechanical properties
12 Ranade et al. 2011
 Ranade et al. (2011) first developed with 14-d Ranade et al. 2013
10 Lei et al. 2016
Tensile strain capacity (% )

compressive strength of 160 MPa and a Coruse et al. 2017

8 Yu et al. 2017
tensile strain capacity f 3.5%. He et al. 2017
6 Zhou et al. 2018
Zhou et al. 2018
 Yu et al. developed HSHDCC with tensile Chen et al. 2018
4
Yu et al. 2018
strength of 20 MPa and a tensile strain Lei et al. 2019
2
Li et al. 2020
capacity of 8% through increasing fiber Huang et al. 2020
0
80 100 120 140 160 180 200 220
aspect ratio to 900.
Compressive strength (MPa)

 By prolonged the heat curing time to 9 d, Note: The colors in symbols up represent the tensile strength as indicated below.

Huang et al. developed HSHDCC with a

compressive strength of over 210.

58
(Zhang H et al., CPB，2022）

29
 Repairing & strengthening application
 The accumulated
energy absorption of
HS-ECC jacket RC
column under cyclic
loading increased by
394.5%.

Failure mode at axial compression ratios of 0.2, 0.3, and 0.4

ECC replaced OC and transverse rebar
 The use of ECC in OC
the connection plastic
zone can significantly
enhance the joint
shear resistance,
enhancing the joint
seismic resistance.

59
Failure mode （ Zhang C. ES 2023; Wei et al. 2020）

Contents

 Introduction

 High Performance Concrete with Multi Performance Targets

 Design and Application of UHPC

 Design and Properties of Ultra Performance ECC

 CO2 Mineralized Concrete Materials and Products

 Summary

60

30
Cement and concrete roadmap to net zero

61

Carbon capture, utilization and storage

62

31
 Carbonate binders at ICCC
15th  1 keynote presentation
ICCC  15 regular presentations

16th  4 keynote presentations

ICCC
 95 regular presentations

 Alkali-activated Materials
 Carbonate binders
 Belite-ye’elimite-based binders

63

Historical developments of CO2 curing

US Letters Patent No.109669 US Letters Patent No.128980
Nov 29, 1870 July 16, 1872

CO2 curing of dry mix compacted concrete CO2 curing of concrete wall, floor and roof
to accelerate the hardening process with high properties and performance
64

32
 Development milestones of carbonate binders
Year Authors Contributions
1870 J. L. Rowland CO2 curing technique was first patented for making concrete blocks.

1972 Klemm and Berger CO2 curing of calcium silicates, including C3S, β-C2S, γ-C2S and CS.

1992 M. R. Souza et al CO2 curing for rapid production of cement particleboard

1998 D. Hermawan et al Supercritical CO2 curing for production of cement particle board

2007 C. Shi and Y. Wu Pre-conditioning for CO2 curing of whole concrete product

2011 Solidia Solidia cement (CS and C3S2) and its CO2 curing

2014 Shi & Poon Carbonation of recycled concrete aggregates

2018 C. Shi et al Use of CO2 to convert waste hardened cement paste to reactive SCM

2021 Carbstone Conversion of steel slag to building productss by carbonation

65

Pre-conditioning of moulded concrete products

CO2 curing of concrete without pre-conditioning CO2 curing of concrete with pre-conditioning

66

33
 Importance of pre-conditioning
100 30

25
80

CO -curing degree (%)

20
Moisture loss (%)

60 35% R H 45% RH 35% R H 45% RH

60% R H 70% RH 60% R H 70% R H
15
80% R H 80% R H
40
10

20 5

2
0 0
0 300 600 900 1200 1500 0 300 600 900 1200 1500
P re -c u rin g tim e (m in ) P r e - c o n d it i o n in g t im e ( m in )
18
16 2h CO2 Curing after Pre-conditioning period
Immediately after Pre-conditioning

Compressive Strength (MPa)

14
12
10
8
6
4
2
0
2 4 68 12
8 18
10 Steam12
Curing
Pre-conditioning Time(h)

Pre-conditioning is critical for carbonation of whole products! 67

Carbonation product- calcium carbonates

△G0
Chemical Reaction
(KJ/mol) Illustration of Thermo-
Crystal
-
Polymorphs crystal dynamical
3CaO·SiO2 + 3HCO3 + 2H2O = 3CaCO3 + structure
-147.75 structure stability
H4SiO4 + 3OH-

2CaO·SiO2 + 2HCO3- + 2H2O = 2CaCO3 +

-35.14
H4SiO4 + 2OH- Calcite Hexagonal High stable

3CaO·2SiO2 +3HCO3-+4H2O = 3CaCO3 +

-8.81
2H4SiO4 + 3OH-

CaO·SiO2 +HCO3-+2H2O = CaCO3 + H4SiO4 + OH- -39.50

Aragonite Orthorhombic Sub-stable
C3A + 3CO2 + 3H2O = 2Al(OH)3 + 3CaCO3 -21.45

C4AF + CO2 + 3H2O = C3AH6 + CaCO3 + 2Fe(OH)3 -29.34

Ca(OH)₂ + HCO₃- = CaCO3 + OH- + H2O -38.19

Vaterite Hexagonal Unstable
xCaO·ySiO2 ·zH2O + xHCO₃- + (4y-2z)H2O =
-58.88
xCaCO3 + yH4SiO4 + xOH-

68
B. Lu et al., Cem. Concr. Res., 157 (2022); T. Holland et al., J. Metamorph. Geol, 8 (1990) P. Bots et al., Cryst. Growth Des., 12(7) (2012) .

34
 Polymorph control of calcium carbonate
 Inorganic additives, such as metal divalent ions, control the formation of calcium carbonate, by
changing the solubility or crystallization habit of calcium carbonate
 Organic additives, such as MEA, EDTA, PAA, control the formation of calcium carbonate by selective
adsorption to change the surface energy then get different polymorphes
Mg/Ca=1.5

Mg/Ca=2.0

Formation of carbonates ~ MgCl2 concentrations Thermodynamic modelling for polymorphy control of calcium carbonate
69
W.K. Park et al., J. Cryst. Growth., 310(10) (2008); X. You and C Shi, J. Cleaner Prod., 410 (2023), X. You and C. Shi , Unpublished results.

Strength of different calcium carbonates

Carbonation products
of Portland cement:
(a) control
(b) with 10% Mg(OH)2

70 16
M0 M0

60
M1
M5
M1
M5
Compressive and
Compressive strength (MPa)

Flexural strength (MPa)

M10
M0- Water curing 12
M10
M0- Water curing flexural strengths of
50
carbonated Portland
40
8 cement:
30
(c) control
20 4
(d) with different
10
Mg(OH)2 replacements
0
0 1d 3d 7d 28d 28d
1d 3d 7d 28d 28d Age (d)
Age (d)
70
F. Wu，… C. Shi et al., Cem. Concr. Compos., 141 (2023).

35
Carbonation of recycled concrete aggregates

T=20±2oC，

RH= 60 ± 5%，

CO2 = 20±2%

CO2

71

Properties of concrete with carbonated recycled aggregate

Compressive Strength
52
60 50 Carbonated RCA

Carbonated recycled
Compressive strength (MPa)

48
Compressive strength (MPa)

50 46

40
44
42
24.1% aggregates significantly
40 Uncarboanted RCA

30 NAC
38 32.9% increase compressive
36
RAC-50

20
RAC-100
CRAC-50
CRAC-100
34
32
strength
30
0 20 40 60 80 0 20 40 60 80 100
Age (d) RCA replacement ratio (%)

ITZ Microhardness Chloride Migration

Carbonated recycled
Chloride
Sand/
cement Sand Type
migration aggregates increase ITZ
coefficient
ratio
（10-12m/s2） microhardness and
Natural sand 1.1 decrease chloride
2.0 Uncarbonated 19.7 migration coefficient by
Carbonated 1.8 one order
72

36
 Recycled concrete fine (RCF)
 C-S-H and CH in RCF can be carbonated to calcium carbonate and silica gel.
 Carbonated RCF is a very reactive supplementary cementitious material.
 RCF can be directly carbonated to produce products.

Effects of carbonated RCF on compressive strength of cement paste Production of calcium carbonate concrete
Y. Mao, and C. Shi, to be published; 73
I. Maruyama, J. Ame. Con. Tec. 19 (2021)

Carbonated Recycled Concrete Fines

Uncarbonated powder Carbonated powder

 100
3
 Ca(OH)2  Arragonite
90
 C3S  AFt  Calcite 3.6%
3.4% 2
80
24.3%
CCPP UCPP 1
DTG (%/min)

70
TG (%)

   
  
     CCPP
60 0


 50
-1

 40 UCPP
       UCPP -2
CCPP
30

10 20 30 40 50 60 70 100 200 300 400 500 600 700 800 900

2θ(degree) Temperature (℃) 74

37
 Various use of CO₂ for crabonated products
Carbonation of recycled concrete Carbonation of steel slag

reuse reuse
Precast Products

Recycled Concrete Bricks Blocks Steel Slag

1.2BTonnes 900MPiece 18BPiece 120MTonnes

Use of CO2 @ 200Mtonnes/Year！ 75

CJS Technology (China)

 First production line of concrete bricks cured with CO2 from cement kiln exhaust gas.

 One line produces 100 million concrete bricks per year, consumes about 26,000 tonnes of
CO2 and saves 3.8 million Kw.h electricity annually.

Concrete bricks prepared by compression

Press conference on “The world’s first production line

Compressive strength of CO2 cured concrete bricks of concrete bricks cured with CO2 from cement kiln
exhaust gas” on Dec 28, 2021 76
CO2 curing tank for concrete bricks

38
 Certified Testing Reports of CO2 Cured Bricks

77

Applications of CJS Technology Products (China)

Building Wall Granary Building Underground Wall

Pavement Masonry Fence

Slope protection Storey block
78

39
 CO2-SUICOM Technology (Japan)

Paving blocks

Foundation blocks

CO2-SUICOM Concept CO2-SUICOM concrete products

(Courtesy of Japan Cement Association) 79

Self-pulverizing Low-calcium Clinker (China）

Raw materials φ40cm × 6m rotary kiln 1200°Calcination Clinker cooling

CO₂ Emission of SPLC Production

and Curing (kg/ton)
OPC SPLC CO2
clinker clinker Reduction

Limestone + 560 + 430

decomposition

Fuel + 270 + 190

combustion

Grinding +35 0

CO2 curing - - 230

Self-pulverized clinker
Total + 865 + 390
-53.0% Particle size distribution powder

80
S. Liu, G. Li and C. Shi, to be published

40
 Thank you！
Prof. Caijun Shi
COLLEGE OF CIVIL ENGINEERING,
HUNAN UNIVERSITY
cshi@hnu.edu.cn

41