The use of isothermal calorimetry in cement productionPaul Sandberg
Calmetrix products are used where cement is: around the world
What is calorimetry?What is calorimetry?Almost all chemical reactions & physical transformation involve heat release or uptake – oftenproportional to the amount of reaction. The measurement and interpretation of this heatexchange is the science of “calorimetry”Heat flow (mW/g dry binder)A Calorimetry curve indicates a number of concrete quality parameters54WorkabilityInterpretation of a calorimetry curvegives information about:Sulfate BalanceSet time Workability3 Setting time Strength gain2 Material incompatibility104812Time [hrs]1620Cement CalorimetryCompressiveStrength
Principles of an isothermal calorimeterSchematics of an isothermal calorimeter1.1. Heat is produced inthe sample.2. and a smalltemperaturedifference developsacross the heat flowsensor which resultsin a voltage output.3.2.3. while heat flowsto the heat sink. The isothermal calorimeter operates at nearconstant temperature Most instruments allow a wide range ofoperating temperatures You need to select test temperature well inadvance of your test!4
Uses of calorimetry: R&D and Quality ControlCalorimetry is like taking the Blood Pressure of Cement Simple Low cost method for measuring the rate of cement hydration,with no laboratory required. Level of Hydration will determine rate of set and strength development. Used to measure effects of materials and mix design on reactivitySome basic uses of isothermal calorimetry Heat of Hydration ASTM C1702 Sulfate optimization Temperature effects – winter vs summer formulations Early stiffening – co additives, raw materials selection, formulation Special procedure to capture very early hydration effects Accelerator formulations – concrete, cement, shotcrete Cement – SCM – admixture incompatibility Customer Service – troubleshooting ASTM C 1679
How to read calorimetry power and energy graphsThermal power graph Shows the RATE of cement hydration, as affected bytemperature, sulfate, other active materials such asadmixture, SCM, etc Very easy to detect by calorimetry, typically notseen by compressive strength testingFig-1: Isothermal calorimetry thermal power graph of a typical cement insulfate balanceHeat (energy) graphFig-2: Isothermal calorimetry heat (energy) graph of a typical cement insulfate balance Shows the degree of reaction, e.g. degree ofcement hydration, which correlates with mechanicalproperty development Hydration before set is not considered to contributeto mechanical properties, hence excluded exceptwhen investigating early stiffening issues
Isothermal calorimetry – Basic interpretationBy integrating the thermal power curve – measuring the area under the power curve – we get“Energy”, or “Heat of Hydration” in cement terms.Power, main peak excluding 1st hSet1st peak 0-2 hWorkability lossStrengthEnergy – Heat of Hydration excluding 1st hEnergy or “Heat of Hydration” correlates withcompressive strength7
Correlation between HoH and compressive strengthExample: Relationship between HoH and 1 to 7 -day mortar strength for two differentcements based on two distinctly different clinkers – study conducted by Aalborg Cement(Cementir)Graphics & data courtesy of AalborgCement8
ASTM C 1702 – Heat of hydration using isothermal calorimetry Heat of Hydration is the single largest use of isothermal calorimetry in the North AmericanCement industryOther major applications include Sulfate optimization and admixture compatibilitySeveral Round Robins in North America and Europe on Heat of Hydration using Isothermalcalorimetry, based on early Nordtest document developed by Lars WadsoASTM 2012 RR the largest with 28 labs, 4 makes of isothermal calorimeters, and 6 differentcements using ASTM C1702– 3 portland and 3 blended cements– Cement paste at 23 C, w/c 0.50– Method A – Internal mixing 120 tests completed for 6 cements– Method B – external mixing 440 tests completed for 6 cements9
C1702 Coefficient of variation by age and cement As in the past – excellent repeatability within each labInternal mixing was NOT more repeatable- but difference was insignificantCompare with 3% CoV for a good compressive strength testing lab ASTM C1702 requires water to be pre-conditioned to the same temperature as thecalorimeter within 0.2 C Further improvements through better calibration routines are possible!
Sulfate optimization – why is it important? Calcium sulfate is added to the mill to control the aluminates, which wouldotherwise cause premature stiffening and poor strength development Traditionally, the cement producer only tests cement and water, bymeasuring the compressive strength at different sulfate addition levels inorder to find an optimum sulfate addition at a target curing age. The effects of admixture, SCMs and temperature is known to be veryimportant – but are largely ignored by the cement standards. No air conditioned laboratory required – the isothermal calorimeter isthe lab Anyone can do sulfate optimization using calorimetry with basictraining11
Traditional sulfate optimization using compressive strength Traditionally, the cement is optimized by measuring the compressivestrength at different sulfate addition levels in order to find an optimumsulfate addition at a target curing age Traditional strength testing gives no informationabout the sulfate balance at early age Cement could be unbalanced beforeset, experiencing poor workability,and still be optimized for compressivestrength developmentAir conditioned lab withcontrolled moist curing andand compressive strengthtesting at precise ages –many cement plants are notequipped to do this.12
“Sulfate Depletion Peak” methodHeat flow (mW/g dry binder)5432Sulfate depletionMax. MainHydration Peak104812Time [hrs]1620 Visually simple, provided that the depletion peak does not completelyoverlap with the alite hydration peak For a given cement and test condition define the target time elapsed fromthe maximum of the main peak and the beginning of the sulfate depletionpeak Most isothermal calorimeters will work very well for the “sulfate depletionpeak” method13
Step 1 – Define sulfate optimum Traditional compressive strength – lab neededOR New: Isothermal calorimetry Heat of Hydration Correlates very well with compressive strengthCEM II/A-WASTM T-IPCEM II/A-LASTM T-IL Define time between maximum of mainpeak to sulfate depletion At maximum Heat of Hydration or compressivestrength at desired age(s)14
Step 2 – Continuous QC calorimetry on finished cement Time from main peak max to sulfate depletion Heat of Hydration Excellent strength predictionOptimum SO3 at optimum time between main peak max and sulfate depletionBest correlation between HoH and strengthMaximum strength Optionally analyze initial peak forabnormal aluminate hydration Alkali-sulfate balance in kiln, ortho C3A etc15
Defining and QC optimum SO3 using isothermal calorimetrySummary sulfate optimization Heat of Hydration by isothermal calorimetry is an excellent alternativeto compressive strength testing when testing for optimum SO3. No lab or AC is required since the calorimeter itself is the “lab” Can easily test for the effect of temperature, admixtures, SCM, etc. If the 1st hour gives noisy data, depending on sample preparationmethod and calorimeter used, then accuracy is improved by eliminatingthe heat from the 1st hour16
Temperature effects on cement hydration20% FA 20 C30% FA 20 C20% FA 12 C30% FA 12 C17
Admixture – Non-Linearity with Temperature20% C Ash, 130 mL/100 kg Type Awater reducer18
Early stiffening - An example of uncontrolled aluminate Industrial clinker was produced using fixed raw materials and raw meal composition except for the type offuelTypes and amounts of secondary fuels were used to reduce dependency on traditional fossil fuelsClinkers were ground to a constant fineness in conjunction with different sulfate forms added to thelaboratory millExample shows calorimetry of clinker with increase use of pet coke – a common case in the industryAll clinkers were ground with calcium sulfate to a “base” 3.0% SO3 level Over a certain threshold, the petcoke introducedthe formation of orthorhombic C3A, causing highearly reactivity and slump loss (left), andpremature sulfate depletion (right)19
Isothermal Calorimetry to Examine Additive Effect Detection of somethingsignificant Red cement additivepromotescarboaluminate But does not indicatewhat exactly ishappening Very little effect on initialsilicate peak Fact that third peakmoved out in time withadded SO3 indicates it isaluminateGreen – No additiveYellow 20% limestoneRed - 20% limestone plus 200 ppm TIPABlue - 20% limestone plus 200 ppm TIPA 0.5% SO3
A typical dosage ramp of a water reducer in mortar or concreteGreen is blank (noadmixture)Yellow, red, dark blueare mixes in balance Red is target.Overdose, light bluetested to see howclose mix is toabnormal retardationof AliteConcrete or mortar – careful with paste, unless formechanistic research
Contact Information:www.calmetrix.comResearch and Quality Control for Cement and Concrete . Made Easy
ASTM C 1702 – Heat of hydration using isothermal calorimetry Heat of Hydration. is the single largest use of isothermal calorimetry in the North American Cement industry Other major applications include . Sulfate optimization . and . admixture compatibility Several Round Robins in North America and Europe on Heat of Hydration .
Overview of Isothermal Titration Calorimetry ITC experimental design Data analysis Troubleshooting . What is isothermal titration calorimetry (ITC) A direct measurement of the heat generated or . calorimetry is a direct readout . 19 GE Title or job number 11/2/2012 Stoichiometry
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Applications of Calorimetry in a Wide Context - 76 Differential Scanning Calorimetry, Isothermal Titration Calorimetry and Microcalorimetry 2.2. The Adair's equation This equation defines the type of equilibrium that can be established between a macromolecule and its ligand upon binding. 2.2.1. Binding to one site
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