recent advances in sulfoaluminate-belite cement...
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Recent Advances in
Sulfoaluminate-Belite Cement
Research
Maria Juenger & Irvin Chen
University of Texas at Austin
SAB/CSA Cements
Also called calcium sulfoaluminate cements
Primary phases are:
C4A3$ (Ye’elemite or Klein’s compound)
C2S
Anhydrite/Gypsum
Early strength from ettringite
Late strength from C-S-H
Renewed Interest
Less lime = less CO2
Lower clinkering temperature (1250 C)
More friable = less grinding energy
High sulfate content makes it ideal for use of
waste as kiln feed
Cement Phase Lime Content (%)
C3S 73.7
C2S
C3A
C4AF
65.1
62.2
46.2
C4A3$ 36.7
History
Made in China since 1970s
Properties
Rapid setting
High early-age strength
Self stressing and shrinkage compensating
Uses
Pre-cast concrete applications and cold
environments
Challenges - Clinkering
No accurate “Bogue” equations
No defined or specified phase assemblage(s)
Unreliable analysis of phases present (in literature)
Lose sulfur during firing
Impurities in the raw materials have unknown effects on later cement properties
Difficult to create a consistent product on the large scale
Challenges - Hydration
C4A3$ + 2C$H2 + 34H → C6A$3H32 + 2AH3
C4A3$ + 8C$H2 + 6CH + 74H → 3C6A$3H32
AH3 + 3CH + 3C$H2 + 20H → C6A$3H32
Ettringite easy to quantify
AH3 is difficult to observe, even in microscopy – best way is with TGA/DTA
Ettringite may not react to form AFm in low gypsum conditions
Hydration is very dependent on w/c
Our research
Refinement of “Bogue” type equation for
phase prediction in clinkers
Dependence of hydration and properties on
phase composition
Optimum gypsum content and optimum SAB
cement composition
Impurities
Admixtures
Phase assemblages and Bogue
Target Compositions “Bogue” Equations
%C4AF = 3.043(%Fe2O3)
%C4A3$ = 1.995(%Al2O3) –
1.273(%Fe2O3)
%C2S = 2.867(%SiO2)
%C$ = 1.700(%SO3) –
0.445(%Al2O3) +
0.284(%Fe2O3)
#1 #2 #3 #4 #5 #6 #7
C2S 20 40 60 20 30 40 50
C4A3$ 60 40 20 50 40 30 20
C4AF 10 10 10 20 20 20 20
C$ 10 10 10 10 10 10 10
Made in a laboratory muffle furnace
with reagent grade materials
Higher C2S
Higher C4A3$
Phase Composition
Phase
TG (Target) R (Actual - Rietveld)
(weight %)
#2 #C #F
TG R TG R TG R
C2S 40 44.94 41.91 43.06 40.64 40.47
C4A3$ 40 41.96 40.16 43.87 39.43 42.40
C4AF 10 6.11 7.90 8.34 7.06 8.30
C$ 10 6.83 4.36 1.60 6.47 3.90
Periclase 0 0 2.34 1.97 0.90 2.20
C5S2$ 0 0 0 1.16 0 2.73
Lime 0 0.16 0.46 0 2.23 0
Others 0 0 2.87 0 3.28 0
Hydration – Proportioning Gypsum
Sample #2: 41.96% C4A3$
Sample C4A3$ Optimum Gypsum
#1 65.34% 25%
#2 41.96% 15%
#3 15.38% 8%
Gypsum Addition = 0.4461(%C4A3$) + 0.8403(%C4AF) – 1.000(%C$)] × 1.2645
Hydration –
Effect of Composition
Sample C4A3$ Optimum Gypsum
#1 65.34% 25%
#2 41.96% 15%
#3 15.38% 8%
Compressive Strength
Sample C4A3$ C2S Gypsum Addition
#1 65.34% 22.32% 25%
#2 41.96% 44.94% 15%
#3 15.38% 70.82% 8%
55 MPa
48 MPa
41 MPa
34 MPa
14 MPa
7 MPa
21 MPa
Dimensional Stability – In Water
Sample C4A3$ Gypsum Addition
#1 65.34% 25%
#2 41.96% 15%
#3 15.38% 8%
Hydration –
Waste Clinkers
Sample C4A3$ C$ Optimum Gypsum
#2 41.06% 6.83% 15%
#C 43.06% 1.60% 20%
#F 42.40% 3.90% 20%
Materials #C #F
Gray Limestone 56% 45%
Bauxite 14% 14%
Flue Gas Desulfurication Sludge 10% 6%
Class C Fly Ash 20% 0%
Fluidized Bed Ash 0% 35%
Hydration – effects of alkalis
Sample C4A3$ C$ Gypsum Addition
#2 41.06% 6.83% 15%
#C 43.06% 1.60% 20%
#F 42.40% 3.90% 20%
Sample C4A3$ C$ Gypsum Addition
#2 41.06% 6.83% 15%
#C 43.06% 1.60% 20%
#F 42.40% 3.90% 20%
Hydration - Retarders
Conclusions
Proportioning SAB clinkers can be done through a Bogue-type process, but must account for sulfur emissions
The optimum gypsum content can be defined as the minimum needed to have a consistent shape of the heat evolution curves and low expansion in water
High C4A3$ clinkers lack dimensional stability in water and do not have the highest long-term compressive strength
Intermediate (~40%) C4A3$ clinkers have hydration rates, compressive strength, and dimensional stability in water similar to OPC
Conclusions
Impurities from natural and waste materials
tested did not have a large effect on phase
formation during clinkering
Impurities, particularly alkalis, do have a large
effect on hydration
Admixtures can be used to control reaction
kinetics