New Advanced Admixtures

for UHPC

Vietnam Concrete Association (VCA)

Hanoi, 13 March 2019

Prof. Dr. Johann Plank

Chair for Construction Chemicals
Technische Universität München, Germany
 Introduction of Munich and TUM

© Prof. Plank 2019

 1995 - Ultra-High Strength Concrete
w/c ratio < 0.25 !

Microsilica

Dense particle packing in UHPC

UHPC can reach 200 MPa compressive strength !

© Prof. Plank 2019

 Iconic Buildings

Singapore, Marina Bay Sands Casino

© Prof. Plank 2019
 Iconic Buildings Using Hi-Tech Concrete

Viewing platform at 800 m

Kingdom Tower, Jeddah, Saudi-Arabia, 1007 m,

built by Saudi Bin Ladin Group
© Prof. Plank 2019
Content …..
….. PCEs – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
 1981 – Invention of Polycarboxylates (PCEs)

CH3 CH3

CH2 C CH2 C

C O C O

ONa a O b
CH2

CH2

O
n Dr. Tsuyoshi Hirata
CH3 Nippon Shokubai, 1981

Methacrylic acid – MPEG Methacrylate ester copolymer

© Prof. Plank 2019

 Development of PCE Technology

MPEG PCE APEG PCE

PAAM PCE
Nippon Shokubai 1981 Nippon Oil & Fats 1989
Sika / Toho 2000

VPEG PCE
BASF 1995

© Prof. Plank 2019

 Development of PCE Technology

IPEG PCE
Nippon Shokubai 1998 HPEG PCE

China, 2000

X PCE
China, ~ 2004

© Prof. Plank 2019

 Different Molecular Conformations of PCEs

(1) MPEG

(2) APEG

(3) VPEG

(4) PAAM PCE

(5) HPEG

(6) IPEG

(7) X PCE

© Prof. Plank 2019

 Microstructure of PCEs

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Regular (statistical) copolymer gradient polymer

© Prof. Plank 2019

 PCE Structures For Precast and Ready-Mix Concrete

Precast concrete PCE: Ready-mix concrete PCE:

• High anionic character • Low anionic character

• Long side chain • Short side chain

© Prof. Plank 2019

 Examples of Commercial PCEs
Used in Precast Concrete

MPEG-PCE HPEG-PCE

© Prof. Plank 2019

 PCE Effectiveness and Time of Addition
➢ Generally, superplasticizers should be added to concrete
as late as possible
➢ Delayed addition can save up to 50 % in dosage

PCEs can introduce significant amounts of air into concrete

© Prof. Plank 2019
 PCEs Introduce Foam into Concrete

Foam of beer

American beer –
unstable foam
German beer –
stable foam
© Prof. Plank 2017
 Defoaming of PCE Concrete
PCEs always require a defoamer !

Jeffox WL5000 Jeffamine M2005

Mild defoamer, easy to disperse Strong defoamer, stable ion-pair with PCE

Problems associated with defoamers:

• Must not separate from PCE solution

• Shelf life over at least 1 year required
• Different PCEs need different defoamers Tributylphosphate
• Defoamers for short and long-term effect Moderate defoamer, requires emulsion
• PCE solutions typically contain mixture
of defoamers

A. Jeknavorian,
“Overview of Defoamer Technologies for Polycarboxylates”, in: J. Plank, L. Lei (eds.), workshop on PCE Technology,
27 September 2017, Munich, Germany.

© Prof. Plank 2019

 Working Mechanism of Defoamers

Spriting effect of defoamers on foam lamella

defoamer

a defoamer spreads on the surface of the foam lamella (= spriting)

and pushes the surfactant molecules away

the foam lamella becomes unstable and releases the air

© Prof. Plank 2019

Content …..
….. PCEs – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
 Importance of Flow Behavior of Concrete

concrete with
viscous concrete
superplasticizer

© Prof. Plank 2019

 PCEs Decrease the Size of Ettringite Crystals

PCEs can modulate the crystal size of ettringite

5 μm 200 nm

Ettringite, precipitated in Ettringite, precipitated in

absence of PCE presence of MPEG-PCE

© Prof. Plank 2019

 Cement Compatibility of PCEs

Size of ettringite crystals, formed in the presence of

different PCEs
PCE Size of ettringite crystals Compatibility with
HLB Value
Polymer [nm] “difficult” cements

MPEG-7 718 ± 14 16.4 incompatible

MPEG-45 981 ± 24 18.2 incompatible
APEG-23 1,238 ± 27 19.3 medium
IPEG 50 1,936 ± 86 18.6 compatible
APEG-34OH 2,050 ± 65 19.7 compatible
Referenz
~ 5,000 ± 300 - -
ohne PCE

MPEG-PCEs: very small crystals, incompatible with this cement

APEG-PCEs: medium crystal size, moderately compatible

IPEG-PCEs: large crystals, very compatible

© Prof. Plank 2019

 Effect of MPEG-PCE on Size of Ettringite
Preparation of synthetic ettringite from Ca(OH)2/Al2(SO4)3
solutions in presence of PCE

© Prof. Plank 2019

Content …..
….. PCE – the basis for UHPC
….. Admixtures for fast-flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
 The Process of Adsorption of PCE

Molecular simulation of the adsorption

of polyacrylic acid (10 monomer units)
on (104) surface of calcite

(water molecules not shown here)

ΔGads = ΔHads - TΔSads

Plank J., B. Sachsenhauser, J. de Reese

"Experimental determination of the thermodynamic parameters affecting the adsorption
behaviour and dispersion effectiveness of PCE superplasticizers",
Cement and Concrete Research 2010, 40, 699 – 709.

Courtesy of Paul Bowen,

EPFL Lausanne

© Prof. Plank 2019

 Fluidizing Effect of Non-Adsorbing Polymers

Highly important in low w/c concrete like UHPC

© Prof. Plank 2019

 Dependence of Effect on w/c Ratio

Effect much more pronounced at w/c = 0.22

Jeffamine® more effective than DEG

© Prof. Plank 2019

Content …..
….. PCEs – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
…... Early strength
enhancing admixtures
…… Conclusion
 Phos – PCE Via Free Radical Copolymerization

• Phos-PCEs perform better than pure phosphated comb polymers

• very robust in presence of other admixtures (no desorption)
• work well in blended cements
• Patents from Kao / Japan

© Prof. Plank 2019

 Phos – SP Via Polycondensation

phenol

• highly effective in cement and gypsum

• works very well also at low w/c ratios (< 0.30)
• provides high flow speed to concrete
• technology of BASF

© Prof. Plank 2019

 Polyphosphate Superplasticizer

Dispersing performance
in CaSO4 hemihydrate

Dispersing performance
in cement

© Prof. Plank 2019

Content …..
….. PCE – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
 Strength Development From Clinker Phases

C3S responsible for early strength of concrete:

© Prof. Plank 2019

 The Difference Between C3S and C2S

Ca3(SiO4)O (triclinic) Ca2(SiO4)

O2-

C3S is tricalcium oxy silicate

© Prof. Plank 2019

 Admixtures For High Early Strength

Conventional accelerators

Ca(NO3)2, Ca(HCOO)2

Alkaline accelerators

Na2SiO3, NaAl(OH)4

Alkali-free accelerators

Al(OH)SO4, Al(OH)2(HCOO),
Al(OH)3 amorphous

Disadvantage: they all reduce final strength !

© Prof. Plank 2019
 C-S-H Foils as Nuclei for C-S-H Needles

C-S-H foils C-S-H needles

1. I.G. Richardson, The calcium silicate hydrates, Cement and Concrete Research, 38 2008, 137-158.

2. E.T. Rodriguez, I.G. Richardson, L. Black, E. Boehm-Courjault, A. Nonat, J. Skibsted,

Composition, silicate anion structure and morphology of calcium silicate hydrates (C-S-H) synthesized by silica-lime
reaction and by controlled hydration of tricalcium silicate, Advances in Applied Ceramics, 114, 2015, 362-371.
© Prof. Plank 2019
 Seeding Effect of C-S-H-PCE Nanocomposites
Preparation of Nano C-S-H Seed Crystals using PCE :
PCE
Na2SiO3 + Ca(NO3)2 C-S-H - PCE
Thin foils, dispersed by PCE

• C-S-H seed crystals accelerate C-S-H formation

Source: BASF

© Prof. Plank 2019

 Early Strength Enhancement with C-S-H-PCE
• Nanofoils of C-S-H - PCE composite produce significantly
higher early strengths

500 nm

TEM image of C-S-H – PCE Mortar testing according to DIN EN 196-1

nanocomposite after 6 and 10 h; CEM I 52.5 R, w/c = 0.5

© Prof. Plank 2019

 Metamorphosis of C-S-H – PCE
2h 2h 4h
Foils

Foils

50 nm PCE shell 50 nm 50 nm

Nanofoils form inside the metastable C-S-H droplets

Recrystallisation of C-S-H
5h 4,5 h 4h

50 nm 50 nm 50 nm

© Prof. Plank 2019

 Acceleration of CEM II /B-V by C-S-H – PCE

OPC Clinker + 35 % fly ash + 2,0 % C-S-H – PCE:

Portlandite reflection

Earlier consumption of Portlandite (Ca(OH)2) signifies

that pozzolanic reaction starts earlier
Kanchanason V., Plank J.,
"Effectiveness of a calcium silicate hydrate – Polycarboxylate ether (C-S-H-PCE) nanocomposite on early strength
development of fly ash cement",
Construction and Building Materials 169 (2018) 20 – 27.
 Acceleration of CEM II /B-S by C-S-H – PCE

OPC Clinker + 35 % Slag + 2,0 % C-S-H – PCE:

Portlandite

Strength exceeding
that of OPC !

Hemicarbonate

© Prof. Plank 2019

 Acceleration of CEM II /B-V by C-S-H – PCE
OPC Clinker + 35 % Calcined clay + 2.0 % C-S-H – PCE:

Portlandite

Strength exceeding
that of OPC !

Hc
Hemicarbonate

© Prof. Plank 2019

 C-S-H-PCE Accelerator Improves Durability of Concrete

C-S-H - PCE initiates C-S-H crystallization also in the pore solution

between cement particles

normally, C-S-H crystallizes only on the surface of cement particles

decreased porosity and permeability increase durability

→ more ecological concrete !

Valentini L., Ferrari G., Russo V., Stefancic, M., Serjun V.Z., Artioli G.,
„Use of nanocomposites as permeability reducing admixtures“,
Journal of the American Ceramic Society 101(2018) 4276.- 4284.
© Prof. Plank 2019
C-S-H-PCE Produces More Dense Microstructure

© Prof. Plank 2019

Content …..
….. PCE – the basis for UHPC
….. Admixtures for fast flowing concrete
….. Non-adsorbing flow enhancers
….. Phosphate ester superplasticizers
….. Early strength
enhancing admixtures
….. Conclusion
 Low Ductility – The Main Problem of Modern Concrete !

C-S-H phases in concrete

The tensile strength of

concrete is too low !

Concrete has poor

fracture toughness and
no ductility

US warship from WW II made from LWAE concrete

© Prof. Plank 2019

 Improvement of Concrete Microstructure
Brittleness of concrete: very low tensile (bending) strength
Ratio between compressive & tensile strength is too high!

Natural
100
elastomers Bone
Bone
Skin Keratin
10 Natural Wood
polymers, (fibrous mode)
Toughness, Jc (kJ m -2 )

polymer
1 Cork composites
Mollusk shell
Dentine
Enamel Natural
Wood (splitting mode)
ceramics,
0.1
UHPC
ceramic
composites

0.01 Concrete
Concrete Hydroxyapatite

For comparison: Calcite

0.001
-3
Carbon fibre (stiffness 300 GPa, strength 4 GPa, toughness 25 MJ m )
High-tensile steel (stiffness 200 GPa, strength 1.5 GPa, toughness 6 MJ m -3)
(Meyers et al. 2008. Progress in Mat. Sci., 53, 1-206)
0.0001
0.001 0.01 0.1 1 10 100 1000
Modulus, E (G Pa)
Modified after Dunlop and Fratzl (2010). Annu. Rev. Mater. Res. , 40, 1 -24.

© Prof. Plank 2019

 Importance of Construction Acitivity

o Germany has highest growth rate in Europe

o Reason: larger construction activity

Expanding highways
Construction of homes and appartments

© Prof. Plank 2019

 Global Superplasticizer Market

Worldwide volume: ~ 4.5 mio tons 40 % liquid

Total PCE produced in China:

Germany Total Superplasticizer
~ 2.2 mio tons
PCE

Top 10 PCE producers in China:

BNS, MFS
~ 1.2 mio tons

Largest PCE producer in China:

~ 300.000 tons

In Germany PCE is used much more than BNS, MFS

© Prof. Plank 2019

Acknowledgement of Group Members .…

© Prof. Plank 2019

 PCE 2019 in Munich, 24 - 25 September 2019

© Prof. Plank 2019

Educational Courses in Building Materials
TUM Singapore