TA Instruments

TAM AIR
New Castle, DE USA
Lindon, UT USA
Elstree, United Kingdom
Shanghai, China
Beijing, China
Taipei, Taiwan
Tokyo, Japan
Seoul, Korea
Bangalore, India
Paris, France
Eschborn, Germany
Brussels, Belgium
Etten-Leur, Netherlands
Sollentuna, Sweden
Milano, Italy
Barcelona, Spain
Melbourne, Australia
Mexico City, Mexico
TAM AIR
Technical Specifications 7
TAM Technology 8
TAM Ampoules 10
Applications 12
 TAM AIR Isothermal microcalorimetry

The ideal tool for large scale calorimetric experiments,

capable of measuring 8 samples simultaneously
 A POWERFUL TOOL FOR THE STUDY OF
CEMENT HYDRATION PROCESSES

Instrument of choice for standardized testing on cement

Determining the heat of hydration of cement is important and traditionally, the heat of
5
hydration has been determined by measuring the heat of solution (ASTM C186). More recently,
isothermal calorimetry tests using TAM Air are increasing because it accurately and reliably Phase 1: Rapid initial process - Dissolution of ions and initial hydration 4 1
measures the heat of hydration (ASTM C1702). The samples tested in the TAM Air are usually

Heat Evolution / mW/g

paste samples, where the cement hydration process can continuously be followed over time. The Phase 2: Dormant period - Associated with a low heat evolution and
shape of the heat flow curve will reflect the cement hydration process and the different phases of slow dissolution of silicates 3
the complex process can be determined. The addition of admixtures will change the shape of the 3
Phase 3: Acceleration period - Silicate hydration 2
heat flow curve, and the admixture effect can be quantified. The integrated heat flow over time will
give the extent of hydration. Using isothermal calorimetry, the heat of hydration is measured with Phase 4: Retardation period - Sulphate depletion and slowing down of
1 4
TAM Air by monitoring the heat flow from the specimen while both the specimen and the surrounding the silicate hydration process
environment are maintained at the same temperature. The TAM Air is widely used for 2
studying the reaction kinetics of pure cement pastes as well as the temperature dependence 0
0 10 20 30 40 50 60
of the reaction. TAM Air is an excellent tool for quality control in cement plants, for optimization
Time (h)
of additives to give a cement a certain property as well as a general research tool for the
cement laboratory.

4 5
 TAM AIR
SPECIFICATIONS

Thermostat Specifications
Calorimeter Positions 8
Operating Temperature Range 5 - 90 °C
Thermostat Type Air
Thermostat Stability ± 0.02 °C
Limit of Detection 4 µW
Precision ±20 µW

Calorimeter Specifications
Short Term Noise < ± 2.5 µW
Precision ± 20 µW

Baseline over 24 hours

Drift <40 µW
Deviation <±10 µW
Error <±23 µW

6 7
 TAM AIR Technology

Monitoring the thermal activity or heat flow of chemical, physical and biological processes provides information which cannot be generated with other techniques.
Isothermal microcalorimetry is a powerful technique for studying heat production or consumption and is non-destructive and non-invasive to the sample. The TAM Air
offers unmatched sensitivity and long term temperature stability with flexible sample requirements.

When using microcalorimetry there is little or no sample pretreatment required; solids, liquids and gasses can all be analyzed. Unlike other techniques that may only
give time interval snapshots of data, microcalorimetry presents continuous real-time data that reflects the process or processes taking place in the sample.

High Performance Temperature Control and Stability Isothermal Microcalorimetry TAM Air 8-Channel Calorimeter
The TAM Air is an air based thermostat, utilizing a heat sink to conduct the heat When heat is produced in a sample, isothermal microcalorimetry measures The TAM AIR 8 Channel calorimeter consists of an
away from the sample and effectively minimize outside temperature disturbances. the heat flow. The sample is placed in an ampoule that is in contact with eight (8) channel calorimeter block and data
The calorimeter channels are held together in a single removable block. This block a heat flow sensor that is in also in contact with a heat sink. When heat logging system required for use with the TAM AIR
is contained in a thermostat that uses circulating air and an advanced temperature is produced or consumed by any process, a temperature gradient across thermostat. The calorimeters are twin-type (sample and
regulating system to keep the temperature very stable within ±0.02°K. The high the sensor is developed. This will generate a voltage, which is measured. reference), and designed for use with 20 ml glass or plastic
accuracy and stability of the thermostat makes the calorimeter well suited for heat The voltage is proportional to the heat flow across the sensor and to the ampoules or the 20 ml Admix ampoules.
flow measurements over extended periods of time, e.g. weeks. The baseline drift rate of the process taking place in the sample ampoule. This signal is
is less than 40 µw/24 hours with very low short term noise. TAM Air Assistant™, recorded continuously and in real-time.
a powerful, flexible and easy-to-use software package is used for instrument control,
experimental setup, data analysis and reporting of results. For each sample there is a reference that is on a parallel heat flow sensor.
During the time that the heat flow is monitored, any temperature fluctuations
entering the instrument will influence both the sample and the reference
sensors equally. This architecture allows a very accurate determination
of heat that is produced or consumed by the sample alone while other
non-sample heat disturbances are efficiently factored out.

8 9
 TAM Air Ampoules

Admix Ampoule
The Admix Ampoule is a 20 ml accessory available for initiating
The ampoules used in the TAM Air are designed to handle up to 20 ml volumes. Either glass, stainless steel or plastic (HDPE) closed ampoules are available,
reactions inside the calorimeter, and can be used for monitoring
which enables maximum flexibility for sample management and maximum sensitivity.
a reaction from the initial injection. The Admix ampoule can be
configured with or without a motor for stirring. For suspensions such
as mixtures of cement and water, manual stirring is recommended.
For liquid systems, a motor may be used for stirring. The admix am-
poule can only be used with 20 ml disposable glass ampoules.

10 11
 Applications
Isothermal Calorimetry of Paste at 20 ˚C
4
0.15% CA

Rate of Hydration Heat (mW/g Cement)

3.5 0.15% CA/1.5% CN
3 Reference
1.5% CN
2.5
2
Cement Paste Setting Time 1.5
6.00
The synergy of citric acid (CA) and calcium nitrate (CN) is 1
clearly seen from the rate of hydration heat. CA is essentially a
Hydration of Calcium Sulfate Hemihydrate 5.00

Normalized Heat Flow (W/g)

0.5
setting retarder relative to the reference, although the heat of
hydration is slightly reduced and CN is clearly a setting accelerator. 0.00 Identical samples of 2g of Calcium Sulfate Hemihydrate powder were
0 6 12 18 24 30 36 42 48 4.00
Together they behave as a hardening retarder lowering the rate of mixed with a hydrating agent at a liquid to solid ratio of 0.50 using
hydration heat and distributing it over a longer time. Time (h) an admix ampoule in the TAM Air. The blue curve shows a sample
2.00
hydrated with deionized water. The red curve is a sample hydrated
The rate of hydration heat for the same mixtures at 40 °C shows Isothermal Calorimetry of Paste at 40 ˚C with a 5% Sodium Chloride solution. It is demonstrated that sodium
4 1.00
that the function as hardening retarder is reduced at higher chloride accelerates the calcium sulfate hydration reaction.

Rate of Hydration Heat (mW/g Cement)

temperature. This data along with the cumulative heat data indicate that 3.5
0.15% CA (AN) 0.00
the admixture combination may not function in the practical semi- 3 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.15% CA+1.5% CN (AN)
adiabatic case of massive concrete.1 Time (hr)
2.5 Reference (AN)
1.5% CN (AN)
2
1.5
1
0.5
0.00
0 6 12 18 24 30 36 42 48
Time (h)

12 13
 Applications

2
Cement Thermal Profiles with Contaminants
No Contamination
­­
Cement setting thermal profiles can be influenced by
1.5 Low Contamination
contaminants. The graph shows the steady decrease in

Thermal Power / mW/g

thermal power as the contamination of the cement mortar Medium Contamination
by a mixture of soil and sawdust increases (0; 0.9; 2.5 and High Contamination
Cement Sulfate Depletion 5.9% of w/c=0.6 cement mortar). Influence on hydration 1
This figure shows how Lerch’s criteria - sulfate rate of a mixture of soil and sawdust. 3
depletion peak to occur after the main silicate 6.00
0.5
peak – can be used for a rapid indication of the optimum
sulfate content of a laboratory ground clinker. The results 5.00 Second Peak
of the laboratory screening shown indicates
0

Heat Flow (mW/g)

that 2.5% added SO 3 might be sufficient to 4.00
0 20 40 60 80 100
bring the resulting Portland cement to optimum
SO3 level. Several factors may cause cement manufactured
3.00 Setting Time of Cement Time (h)
in the field to perform different as compared to the laboratory The TAM Air calorimeter has been shown to be excellent
2.00
ground cement. for diagnosis of problems related to setting time and
Sulfate Depletion premature stiffening of cement. The blue curve in the figure to
1.00
Calorimetry serves as an excellent indication as to the the right represents an industrial cement produced with too little
approximate values to aim for to avoid setting time and soluble calcium sulfate. This cement suffers from early 2.5
0.00
admixture incompatibility issues. Furthermore, the calorimetry 0 2 4 6 8 10 12 14 16 18 20 22 24 stiffening because of the aluminate reactions at 1–1.5 hours
can be used to assess the efficiency of any changes made Time (h) hydration. It also suffers from low early strength, because the
1.5

Heat Flow (µW/g)

to the cement production, such as changes in gypsum type aluminate hydrates formed retard the strength-giving silicate
or changes in raw material or fuel that may influence the hydration indicated by the unusually small silicate peak at
reactivity of the aluminate phase and thereby the demand 5-10 hours. When 0.5% (purple curve) and 1.0% (red 1.0
for soluble SO3. 2 curve) of calcium sulfate hemi-hydrate was added to the
cement the undesired early peak disappeared, and
the strength-giving silicate peak regained its normal shape. 0.5
The results indicate that premature stiffening is caused by a
lack of soluble calcium sulfate. 0
0 5 10 15 20
Time (h)

14 15
 Applications

0.007 0.005
Type l/la
0.006 75:25 Blend
Type l/lb 0.004

Heat Flow (W/g cement)

Heat Flow (W/g cement)

75:25 Blend
0.005 Type ll/Va
75:25 Estimated
0.004 Type ll/Vb 0.003
Cement Blending Type llla
0.003 0.002
Type llla
This figure provides plots of the heat release rate (heat flow) for the first 24 h of hydration for six cement pastes examined by Isothermal 0.002
calorimetry (3 pure and 3 blends). In general, results for the two replicate specimens for each cement paste fall directly on top of one another. For 0.001
the three initial cements, the heat release during the first 24 h increases with increasing cement fineness, as would be expected due to the increased 0.001
(in contact with water) surface area. Interestingly, for these six cements based on a single clinker, the peak in heat release rate always occurs at 0.000 0.000
about 6 h, while by 24 h, the heat release rate has diminished to a value close to 0.001 W/g cement. 0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (hr) Time (hr)
The heat flows measured during the first 24 h for the three blended cements are predicted quite well by applying the simple law of mixtures. The 0.007 0.007
results imply that for the w/c = 0.4 cement pastes examined in this study, the particles are likely hydrating independently of one another during 0.006 0.006
the first 24 h, such that the degree of hydration of blends of the fine and coarse cements can be quite accurately computed simply as a weighted 50:50 Blend 25:75 Blend

Heat Flow (W/g cement)

Heat Flow (W/g cement)

average of their (measured) individual hydration rates. 4 0.005 50:50 Estimated 0.005 25:75 Blend
0.004 Type ll/V 0.004 25:75 Estimated
0.003 0.003
0.002 0.002
0.001 0.001
0.000 0.000
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (hr) Time (hr)

16 17
 Applications
700
Food Testing Fungal Growth
600 25˚C 20˚C
This figure shows the Thermal treatment of carrot juice resulting in fresh At each temperature multiple inoculated specimens were
4 30˚C
increased shelf life only at the highest treatment temperature. 50˚C measured. This figure shows the results at the five temperatures. It 500 15˚C

Thermal power / µW
60˚C is seen that the results for each temperature agrees rather well with
The measured thermal power is the heat from the micro- 70˚C each other. Calorimetric measurements can be a valuable addition 400

Thermal power / mW
3
biological activity in the sample. It is seen that the lower treatment to the measurement techniques for predictive microbiology.7
temperatures gave only slightly lower thermal powers, but that the 300
70 °C treatment gave a substantially delayed signal. At 20 °C 2 10˚C
the shelf life was thus increased by more than 50% by the 70 °C 200
treatment. 5
1 100

TAM Air Battery Testing 0

0 0 50 100 150 200
0 20 40 60 80 100 120 The properties of batteries during discharge with three differ- Time (h)
ent resistance loads are shown. Single channels in TAM Air
Time (h)
were charged with 1.5 V alkaline batteries, size AAA. Three
6 resistors of different values were placed in an adjacent channel 500 1.35 R/Ω
for connection to the batteries. The solid line represents the

log (Heat Production rate, mW/g)

Epoxy Curing useful energy in the battery which is the heat production
5 measured in the resistor, while the dotted line is the heat production
Here we see the heat production and the heat production rate as a 0
function of time. It can be seen that the spread of results is low and that from the battery itself, i.e. the internal losses. 0 0.5 1 1.5

after an initial reaction period of five hours the heat production rate 4 300

Heat Production Rate, mW

decrease is similar to an exponential decay. After 45 h the thermal The batteries were fully discharged during the course of the 200 11.2 R/Ω
power is approx. 0.06 mW/g, i.e. 600 μW for a l0g sample. 3 evaluation in the TAM Air. The lowest resistances cause a
100
As the detection limit for TAM Air is better than 3 μW it would still rapid drain of the battery (e.g. as in a flashlight) whereas the
be possible to follow the reaction for an even longer time than was highest resistances cause a very low rate of discharge (e.g. as in an 0
2 0 5 10 15
done here.6 alarm clock).8

1 50
33.4 R/Ω

0
0 20 40 0
0 10 20 30 40 50 60
(Time, h)
Time, h

18 19
 NOTES

1
Justness, H., Wuyts, F. and D. Van Gemert. Hardening Retarders for Massive Concrete. Thesis. Catholic University of Leuven. 2007
2s2
2
Paul Sandberg, Grace Construction Products, W. R. Grace & Co. 2004.
3
Dr. L. Wadsö, University of Lund, Sweden 2002
4
Bentz, D.P. Blending Different Fineness Cements to Engineer the Properties of Cement-Based Materials. Mag. Concrete Res.
5
F. Gomez and L. Wadsö. Isothermal Calorimetry for Biological Applications in Food Science and Technology. 2000.
6
Wadso, L. Curing of Epoxy Adhesive Studied by TAM Air. TA Instruments Application Note 2007
7
Lars Wadsö and Yujing Li. A test of models for fungal growth based on metabolic heat rate measurements. 2000
8
Lars Wadso. Investigations into Dry Cell Battery Discharge Rates using TAM Air. 2000. TA Instruments, AN 314-03.
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