Calibration of calorimeters and thermal

analyzers.
S3 Project
Raffort Théo, Bouvier Téo, Starosta Yvann, MCPC A

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 Introduction 
Calorimetry and thermal analysis are universally recognized technics in chemistry,
physics and biology for the characterization of fluids and materials. They allow access to the
evolution of the material according to time, temperature or pressure. This is a science that
deals with the measurement of heat quantities. Thermal analysis can be simple or
differential depending on whether the measurement of the physical quantity under
consideration is carried out directly or by comparison with the behavior of a reference
sample. After the acquisition of a thermal analyzer 10 CHIP DSC, we have the mission to take
it in hand and fulfil different measurements that we will analyze and criticize. This will lead
us to a calibration of the device. We have at our disposal four standards on which to base
our measurements. How can we best use this calorimeter and how can we draw relevant
conclusions about the measurements it performs?
To carry out this project, we are going to follow a systematic plan to achieve our objectives.
First we are going to establish the state of the art which will allow us to better understand
this field. In addition, we will look at our thermal analyzer and thus deal with experimental
details. Finally, we are going to discuss about the exploitation of our measures that will be
carried out in the next semester. 

1. State of the art

1.1 Calorimetry and Thermal Analysis

Calorimetry is the part of thermodynamics whose purpose is the calculation and

measurement of heat. An adiabatic calorimeter is an isolated thermodynamic system (no
exchange of energy with the outdoor environment). The heat flow is a physical quantity, that
should not be confused with the notion of temperature. The heat flow is an energy
(expressed in Joules or Watts) transferred during a raise of temperature. The first
calorimeter was created in 1780 by Lavoisier and Laplace, it was based on the weighing of
the melted ice. Albert Tian invented the first microcalorimeter in 1922, able to measure
microcalories. Thermal analysis is a series of technics measuring the evolution of a physical
or chemical quantity of a material, in function of temperature, time and atmosphere.
Calorimetry is an integral part of the thermal analysis.

1.2. Thermal analysis: Different types of measurements and DSC

There are two types of Thermal Analysis: 

Simple Thermal Analysis (STA) which consists in taking directly the results of and
experimentation, or Differential Thermal Analysis (DTA), where you make a comparison with
a calibrated sample. The DSC Chip 10 is using DTA, it’s a Differential Scanning Calorimeter
(DSC). It means that the measurements are done under the scanning of an inert gas (argon,
nitrogen…) in order to avoid a reaction between the sample and the oven atmosphere. In
our case, the sample is isolated from the outside environment with a glass dome fixed with
screws.

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 1.3. The Chip 10 DSC : an innovating technology

The analyzer was created by the Linseis Company, and the University of Annecy bought it
in July 2019.It’s an innovating technology because of its small size (around 30 cm long) and
its high rate of performance. Indeed, every component is miniaturized (oven, sensors,
electronics…). Despite its small size, the Chip 10 can reach 600°C, with a heating rate up to
300°C/min which allows to repeat many manipulations in a row.

2. Experimental details

2.1. Clarification on the analyzer

This miniature oven of approximately 4 centimeters long is compound with an oven,

and many sensors. Indeed, under the circular part (where we put the crucible), there are
many resistors, surrounded by a lot of sensors. When the resistors (1) are supplied by a
voltage (line voltage), it heats up until 600°C. All the sensors (heat, temperature, time, ...) (2)
are saving and transferring these data to Rhodium, which can draw curves in real time in
front of our eyes. But this blue oven is extremely brittle, and its cost is extremely high. That’s
why we have to manipulate it carefully and use tweezers to put the sample in the crucible.

2.2. The software “Rhodium”

The software allows a significant improvement of our workflow so as to realise a

measure that only requires arbitrary parameter input (example: mass, heating rate, choice of
the sample…).
Positive points: a guide for the user when evaluating standard processes such as the melting
points. Asset with the identification of polymers in our sample. The thermal library gives us a

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lot of data including 600 polymers allowing an automatic identification of our tested
polymers.
Negative points: the software is not easy to understand at the first time, there are a lot of
parameters to take in account, and it’s not always intuitive. (Appendice D).

Description of a typical curve obtained with Rhodium for the Tin: 

First, we can see this curve represents the Heat flow (mW) in function of the Temperature
(°C). Careful! Heat flow is energy, not a temperature!
The curve is composed of four important parts:
 at 79.8°C, this little step is a regulation of the analyser at the beginning of the
manipulation. 
 between 79.8 and 148.0°C, it’s the glass transition
 at 148.0°C, the Tin starts to crystallize 
 at 230.6°C (melting temperature of Tin), it melts

2.3. Tricks and tools

During our first meeting with Mr. Lomello, we saw that the curve delivered by the
software was truncated with respect to a raw curve.
Where does this come from and is it possible to disable this feature?
According to the manual, the curve obtained is the result of a comparison between the
sample and a database available in the data folder (USB key). Apparently, it would not be
possible to acquire the raw curve. The database is made to be used with a calibration
defined in the manual and for the crucibles provided. Without these conditions, the curve
obtained by comparison would be erroneous. However, the tool command allows to find
and point the actual position of the characteristic peak of the sample’s melting, and not the

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value relative to the database (cf package leaflet, samples). Moreover, Rhodium can also
integrate the peak of the melting curve (area under the curve), which is equal to the melting
enthalpy during the transformation. (Appendice C).

3. Realization in S4

3.1. Influence of parameters

To perform our measurements with this device, we will use four different standards:
Indium, zinc, lead and tin and their theoretical melting temperatures. These values will be
helpful to calibrate our analyzer. Moreover, it’s interesting to vary several parameters in our
heat measurements to draw potential features on the machine. In other words, we will see
the influence of many parameters. Instinctively, we think of varying the value of the mass of
the sample, the rate of warming and the position of the sample in the crucible. Given the
small size of our samples, we must measure their mass accurately. To be sure of these
masses in the crucible, we must weigh them with a very precise device: a precision balance,
enclosed in a housing, in order to have a mass value, accurate at 10 -4 grams. Thus, in the
crucible these modifications can be used to observe a potential thermal gradient. The
crucibles we are going to use are made of Alumina of about 5 millimeters of diameter. Their
melting temperature is about 2070°C and therefore we are sure the crucibles won’t melt.
They must be chemically inert not to disturb the process. In addition, the mass and the
material that compose these crucibles have an influence on the quality of the acquisition.
However, we’ll use the ones provided by Linseis. They allow us to work in the optimal
conditions. It is therefore a question of making several measurements of melting of a
sample, and observe the value of the melting temperature according to the placement of the
sample, either on the edge or in the center of the crucible. Thus, our task will be to deduce
the optimal placement of the sample where the melting temperature is the closest of the
theoretical value.

3.2. Metrological aspects of the measurements

Once we have obtained our measurements, we will use metrology in order to express
the uncertainties on our measurements. It seems relevant to recall that the assessment of
uncertainties is associated with two main methods: Type A and Type B. We will use the Type
A method in repeatability conditions. Type B uncertainties are not appropriate because
there are too many parameters to take in account, and the result would not be suitable. In
practice, we will realize several measurements (N) to study the fusion of a sample during the
calibration, in conditions of repeatability.

σ n−1
We will use the relation of Type A uncertainty: u=σ=
√N
(σn-1 = standard deviation on the N measurements)

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In addition, to be able to express the results of our measurements we will need the Student
coefficient (appendice B). It will allow us to express our results with a certain confidence
interval. Thus, we must estimate an associated risk in order to be able to give reliable
results. In most general cases, the confidence interval is associated with a 5% risk, because
it’s a good compromise between accuracy and certainty. After getting N measurements of
the melting temperature of our standard (knowing his theoretical temperature of fusion:
Tfusion), obtaining the value of “σ” and “k”, we can create the confidence interval:

[Tfusion- k σ; Tfusion+ k σ]

1.1. Technical conclusion

The aim of this project was to understand the thermal analyzer “DSC Chip 10”.
Thanks to our tutor Marc Lomello, we have acquired many notions in thermal analysis, such
as comprehension of the curves, use of the software, and also an apprehension of the Chip
10 thanks to manipulations. This project allows us to use notions previously learned in
metrology, statistics, thermodynamics and English courses. Indeed, using English in a
scientific topic is interesting because we know that it could be a major part of our future job.

1.2. Personal conclusions 

Yvann : For my part, this project was an opportunity to work in a group as part of a
concrete project to put our theoretical knowledge into practice. The subject was quite
interesting because it allowed me to learn more about thermal analysis and materials.
Finally, the fact that we had to use English only was beneficial. This has allowed me to enrich
my vocabulary in this language that is very useful in the scientific field.

Théo : The project proved to be very enriching in that it consisted of a concrete approach
to a field of physics. Indeed, meeting deadlines and teamwork will be essential aspects of
our future professional development. It is all the more interesting to make this report in
English. In short, it is always a pleasure to work under conditions of autonomy and to be able
to develop your technical and linguistic knowledge.

Téo : The S3 project has been very useful so as to apply our knowledges in a concrete
project, especially the metrology part for me. I think that the English part is a good thing so
as to make us practice. There is no way around the fact that working on an innovative topic
is a real source of motivation for the group. To conclude, I think it’s undeniably in a good
way for the S4 project, and it will be enriching to work in collaboration with the lab SYMME.

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 Bibliography and netography

1.) First researches, définitions.

Wikipédia, Calorimétrie, 07/27/2010 https://fr.wikipedia.org/wiki/Calorimètre

2.) First researches, définitions.

Wikipédia, Analyse Thermique, 07/27/2010

https://fr.wikipedia.org/wiki/Analyse_thermique 

3.) Principle of measurements with the DSC.

Malvern Panalytical, Méthodes de mesure de la calorimétrie (DSC), 2019,

https://www.malvernpanalytical.com/fr/products/technology/microcalorimetry/differential-
scanning-calorimetry?
msclkid=aeb70cb0cb791f023d71516fb0cd2c7f&utm_source=bing&utm_medium=cpc&utm_
campaign=FR%20-%20Malvern%20-%20Technology%20Type&utm_term=%2BCalorim
%C3%A9trie%20%2Bdiff%C3%A9rentielle%20%2B
%C3%A0%20%2Bbalayage&utm_content=Calorim%C3%A9trie%20diff%C3%A9rentielle
%20%C3%A0%20balayage

4.) History of the firsts calorimeters.

Universalis, Calorimétrie et microcalorimétrie,

https://www.universalis.fr/encyclopedie/calorimetrie-et-microcalorimetrie/

5.) Documentatin of the Chip DSC 10.

Linseis, Chip DSC 10 : https://www.linseis.com/fr/produits/calorimetre-differentiel-a-

balayage/chip-dsc-10/ 

6.) Metrology, sources of uncertainties.

“Métrologie : vocabulaire et définition dans le laboratoire au quotidien, 1ère partie :

justesse, fidélité et exactitude” In Mettler Toledo (2009). Suisse, MarCom Analytical.

7.) Description of curves.

 “Thermogravimétrie et analyse de gaz, Partie 5 : ATG-Micro GC/MS” In Mettler Toledo

(2019). Suisse, MarCom Analytical.

8.) Informations about the DSC and the way to use it in optimal conditions.

ROUQUEROL J. ; ROUQUEROL F. ; LLEWELLYN P. ; DENOYEL R. . Calorimétrie : principes,

appareils et utilisation. Techniques de l’ingénieur, 2012, P1202v1.

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9.) Informations about the DSC and the way to use it in optimal conditions.

GRENET Jean ; LEGENDRE Bernard. Analyse calorimétrique différentielle à balayage (DSC).

Techniques de l’ingénieur, 2010, P1205v1.