Use of calorimetry to monitor cement hydration kinetics

- temperature effects, materials selection, performance prediction

Paul Sandberg
Cement hydration kinetics summit

July 27-29, 2009

 Why calorimetry for cement hydration kinetics?

• Cementitious mixtures release heat at a Workability

5

Heat flow (mW/g dry binder)

rate that resembles the rate of cement D Sulfate
hydration 4 Balance
• Heat evolution can be measured in equipment of a wide 3
range of cost and accuracy. C
2A
• Fits the practitioner as well as the researcher
1
Set
• Modern concrete uses very complex 0B 4 8 12 16 20
Time [hrs]
mixtures of different materials Strength

• Natural variability in cement that has to sell for few

cents on the kilogram
• Inherent variability in other industries “waste” becoming
“supplementary materials” for concrete
• Fundamental modeling of portland cement hydration
with water is promising – but industry needs practical
tools for easy testing while the science is developing for
an increasingly complex material

July 27-29, 2009 Cement hydration kinetics summit 2

 Isothermal calorimetry
• Isothermal calorimetry thanks to
temperature control gives very repeatable
“hydration patterns”
• Ideal for studies of the effect of temperature on
hydration rate Novel non-portland binders
• Mechanistic work in model paste – materials selection
in mortar or concrete

• Examples….

Detect “significant events”

Effect of temperature (normal) that need more research
6
1

cement
5 2

Thermal Power / mW/g

6
4 5
3
3
4
2
Effect of admix type, dose and time
1
of addition– test before you use
0
Lead to ASTM C1679 standard 0 500 1000
Time / min
1500

practice Effect of temperature (abnormal) Effect of mixing energy

July 27-29, 2009 Cement hydration kinetics summit 3
 Semi-adiabatic calorimetry
• Significantly less expensive
equipment base on simple
“temperature rise”
measurements
• Ideal for low-cost field testing
• Also used to capture impact of Effect of admix type, dose Ultra-low cost “coffee cup”
coarse aggregates on thermal and time of addition calorimeter
properties of concrete – for New standard in
maturity modeling and prediction development
of property development over time

•100% T-I

• T-I 25% C ash

•100% T-II
Compare admixture type and dose

• T-II 25% C ash

Compare cements or SCM (data from G. Knight)

July 27-29, 2009 Cement hydration kinetics summit 4
 Maturity predictions

ØA combination of isothermal and semi-adiabatic calorimetry for maturity-based

prediction of degree of hydration, set, strength development and risk of cracking
ØLab as well as in-place concrete with known dimensions and weather forecast

Arrhenius’ law works? YES

Effect of temperature by
isothermal calorimetry
• Effect of temperature on reaction
rate – activation energy YES Calculate apparent activation
• Arrhenius law works in most energy – slope of Arrhenius plot
cases – Use isothermal
Issues with maturity
calorimetry to determine
applicability and to calculate • Current Maturity meters do not work
well for concrete with high levels of
apparent activation energy NO SCM and admixture, especially
accelerators because reliable
literature data on temperature
Evaluate reaction rate at
effects is often not available.
3+ different temperatures
Maturity predictions
• Assumes the overall reaction
proceeds along the same path at
different temperatures according to
the Arrhenius law
• Assumes the activation energy is Isothermal
only dependent on the produced
energy (the degree of hydration)
• Thermal properties of given
concrete mix design with actual
aggregates measured by semi-
adiabatic calorimetry with known
heat loss
• Software for effects of dimensions, Software
climate conditions (ConcreteWorks)
July 27-29, 2009 Semi-adiabatic Cement hydration kinetics summit 5
 Calorimetry – do’s and don’t’s
• Calorimetry like most other tools can be misused
• Ideal for studies of model systems and trouble shooting, but results are RELATIVE and not
necessarily representative for the end product - CONCRETE
• Can easily simulate almost any temperature condition, but of limited value unless the real concrete
conditions are assessed
14:00
23 C20%CashC109 40 C
Initial set concrete Thermal methods mortar2oz/cwtretarding
vs C403
Thermal Initial Setting Time Indicator,

12:00 water reducer

Setting Setting
indicator indicator
10:00
hours

8:00
N-0 N-5 N-1 PLAM
N-2 N-3 N-4 N-3 N-4 N-0
6:00
N-2 N-5 N-1 PLAM

•Grace
2nd “fractions”
derivative max = initial method A “linear” admixture at room temp may become non-
4:00
4:00 6:00 8:00 10:00 12:00 14:00
linear at elevated temperatures!
ASTM C 403 initial set time, hours

Maximum
temperature

Baseline
Retardation in paste may be different or even
Calorimetry does not measure set but may indicate opposite the effect in concrete – mixing energy!
set at good accuracy for a given mix design
July 27-29, 2009 Cement hydration kinetics summit 6
Conclusions
§ Calorimetry moving from lab to field
§ Cost and convenience driven
§ Care in testing and interpretation necessary
§ Extensive field use likely to uncover more instances needing
investigation
§ Perhaps this will lead to more samples to challenge our models
ability to predict what really occurs

July 27-29, 2009 Cement hydration kinetics summit 7