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Thermochimica Acta 560 (2013) 8994

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Design, construction and calibration of a portable multi sample DTA setup


Luz Mara Martnez , Marcelo Videa, Julio Mesquita
Department of Chemistry, Tecnolgico de Monterrey, Campus Monterrey Ave. Eugenio Garza Sada 2501 Sur. Monterrey N.L., Mxico c.p. 64849, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Calorimetric techniques have become essential tools for the characterization of materials such as ceram-
Received 4 January 2013 ics, polymers, metals, drugs, foodstuffs as a function of their thermal properties. The knowledge of these
Received in revised form 4 March 2013 thermal properties (melting temperature, crystallization, glass transition, denaturation or decomposition
Accepted 12 March 2013
temperature) plays a role of great importance in the selection of the material and its manufacturing condi-
Available online 21 March 2013
tions. Despite the importance of thermal characterization there are no simple and accessible alternatives
to commercial instruments, whose main limitations are their high costs and the fragility of their consti-
Keywords:
tutive parts during operation. In this work we present the design and construction of a portable, robust
DTA
Thermal-characterization
and low cost differential thermal analysis instrument which allows for the simultaneous analysis of three
Thermal-analysis samples and it is suitable when corrosive substances are intended to be thermally characterized. This
Phase diagrams device represents an alternative to commercial devices, with applications in research and development
Instrumentation of materials in various types of industries and apt for academic training.
2013 Elsevier B.V. All rights reserved.

1. Introduction The principle of thermal analysis techniques is based on the


comparison of temperature or heat ow between a sample and an
Calorimetric techniques like differential thermal analysis (DTA) inert reference when they are subjected to a controlled heating pro-
and differential scanning calorimetry (DSC) are widely used gram; this difference between the sample and reference allows the
in research and in industry for the thermal characterization detection of processes that involve absorption or liberation of heat.
of materials of a wide variety of properties and applications DSC is a technique in which the difference in heat ow (or power) to
such as pharmaceuticals, foodstuffs, ceramics, alloys, polymers, the sample and reference is monitored against time while the sam-
biomolecules, etc. [15]. These calorimetric methods enable the ples are exposed to the same temperature program; DTA technique
measurement of various phase transition as a function of tempera- monitors the difference in temperature between the sample and a
ture but must rely on highly sensitive instrumentation to be able to reference [8]. Since registering temperature changes is easier than
measure transitions that sometimes produce very small signals like measuring heat ow, DTA is the best option for the construction
glass transitions. There are many companies that sell these devices, of a custom designed device. The measurements of temperature
but commercial DTA and DSC instruments available are expensive on a DTA must be sensitive enough for the thermal process to be
(between 30,000100,000 US dollars) and the associated mainte- observed since some of these processes may involve very small
nance costs are also high. As an additional drawback of commercial temperature differences, such as glass transition, even when using
devices, these are not always suitable for use with all purposes a sample size of a few tens of milligrams.
because of their fragility, which limits their use in education or The present work describes the improved version of a DTA appa-
with corrosive samples. Although there are reports of some custom ratus previously reported [9] that has the following advantages
designed thermal analysis devices published on literature, these with respect to that previous prototype and to commercial devices:
are not instruments suitable for high precision measurements. it is low-cost, portable, suitable for a wide range of sample sizes to
Furthermore, data acquisition or computer-assisted hardware and be used (15150 mg), allows the visual inspection of the sample
software in these previous works are not described in enough detail since the holders used are made of Pyrex glass, it is robust, and
or are not accessible for educators or researchers with no previous therefore it can be used by inexperienced users without the risk of
experience in thermal analysis or computer programming [6,7]. damage to the equipment. This DTA instrument is able to measure
three samples simultaneously and allows a wide range of temper-
atures, from 150 to 300 C, with the combination of a cryogenic
substance like liquid nitrogen and the heating element. The selec-
Corresponding author. Tel.: +52 81 83284489; fax: +52 81 81582024.
tion of the analogic acquisition card makes this instrument very
E-mail addresses: luzvidea@itesm.mx, luzmavidea@gmail.com (L.M. Martnez),
sensitive and is suitable for measurements that have a very small
mvidea@itesm.mx (M. Videa), j.mesquita@itesm.mx (J. Mesquita). signal such as vitreous transitions (Tg ) and thermal denaturation of

0040-6031/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tca.2013.03.016
90 L.M. Martnez et al. / Thermochimica Acta 560 (2013) 8994

Table 1
Description of the building elements of the multi-sample DTA.

Material Supplier Price (dollars)

Aluminum heating block Custom made (see Fig. 1 for $60


details)
Teon insulated Omega $21
thermocouple wire type
TT-K-30 (spool 25 feet)
One 60 W cylindrical Firerod Watlow $46
resistance cartridge
Variable voltage regulator Superior Electric (USA) $250
(Variac)
USB measurement card NI National Instruments (USA) $793
9211 specic for
thermovoltage readings
Plus a Compact DAQ
Chassis9171
Computer controlling Executable le of the
program written in program is available for any
LabVIEW interested user in the
Fig. 2. Schematics diagram of the wiring of thermocouples for temperature mea-
supplementary material.
surement on the reference and differential thermovoltage measurements on three
LabVIEW software from
samples.
National Instruments is
necessary only to modify the
current program and sample holders and one small orice aside for a handle to be
inserted. The resistance cartridge has to t tightly into the central
orice to optimize heat transference. The heating rate is controlled
proteins. Examples of measurements of thermal characterization
by adjusting the output voltage of the voltage regulator. In our
of different materials are presented that illustrate the accuracy and
experience, a single setting gives a reasonably constant heating
versatility of this instrument.
rate. Generally, the heating rate is set to 10 C/min. For experiments
which require sub ambient temperatures the block is inserted in a
2. Materials and methods Dewar ask and cooled using either dry ice, dry ice with acetone or
liquid nitrogen, depending on the range of temperature required
2.1. DTA construction for each measurement.

The DTA instrument was constructed in a modular fashion


2.1.2. Data acquisition hardware
which includes the following modules: a heating system compris-
Data acquisition system consists of a data acquisition card (USB
ing the sample and reference holders, the data acquisition hardware
NI921 from National Instruments) with four differential channels
and the data recording software. Table 1 presents the detailed
in which four 70 cm long K type thermocouple wires are connected
description of the parts used in the assembly of the multi-sample
for the sensing of the temperature of the reference and the three
DTA. The providers and prices of each part are also included. In
differential temperatures of the three samples, as shown in Fig. 2.
order to record the experimental data, a personal computer is also
A photograph of the USB NI9211A card with a compact DAQ
needed.
chassis 9171 from National Instrument selected to record the
The assembling of all the parts of the multi sample DTA instru-
experimental data is shown in Fig. 3 with the rest of the parts of
ment (heating system, data acquisition hardware, software and
the DTA instrument.
sample cells) is following described.

2.1.3. Data acquisition and recording program


2.1.1. Heating system
A computer program that allows the recording of the temper-
The heating system consists of a custom made aluminum cylin-
ature and the three differential temperature signals was written
der (see Fig. 1), a heating resistance cartridge and a commercial
using LabVIEW software. For every input, the data acquisition card
voltage regulator. The aluminum cylinder has several orices: one
makes three thermocouple readings per second for each of the three
in the center for the resistance cartridge, four smaller concen-
samples and one for the reference. The program displays two plots
tric orices evenly spaced around the center to host the reference
in real time: one corresponding to the temperature reading from
the reference versus time, and a second plot which displays the dif-
ferential thermovoltage readings of the three samples versus time.
After the experiment is nished a graph that shows thermovoltage
difference versus temperature is displayed, as shown in Fig. 4. The
slope of the temperature vs. time plot gives the heating rate which is
numerically displayed in order to keep control of the desired heat-
ing rate. When the experiment is nished, the program records the
data in a text le in ASCII format. The le contains data of time,
temperature and three differences of thermovoltage. Front panel
of the program is shown in Fig. 4.

2.1.4. Sample and reference cells


The sample and reference cells are made from Pyrex glass tubes
with 5 mm outside diameter. The thermocouple wires, which are
Fig. 1. Technical drawing of the aluminum heating block used for the heating system inserted in the sample and reference, are introduced in capillary
of the multi-sample-DTA. tubes in order to avoid direct contact and contamination with
L.M. Martnez et al. / Thermochimica Acta 560 (2013) 8994 91

Fig. 3. Elements of the portable multi-sample-DTA: (a)USB-NI-CARD-9211with a compact DAQ chassis 9171, (b) voltage regulator, (c) aluminum-heating-block, (d) top-view
of the aluminum-heating-block with the glass sample and reference cell holders.

Fig. 4. Front panel of data acquisition and recording computer program written for the multi- simple DTA.

samples (see Fig. 5). The procedure to prepare the samples and noise of the baseline from an inert alumina sample is 0.003 a.u.
reference was described on a supplementary material of an earlier with a 95% condence interval. Therefore, the signal to noise ratio
work [9]. Glass sample cells have the advantage of allowing visual between the signals for a 10.5 mg sample of Indium, which has a
inspection of the sample before and after thermal treatment. The peak height of 0.012 a.u., and the alumina baseline is 4, which is
size of sample cell allows measuring a wide range of sample sizes an acceptable value. For a specic enthalpy of fusion of 28.66 J g1
(15150 mg). [10], this corresponds to a heat absorption of 0.3 J for this process.

2.2. Testing and calibration of the device 2.2.2. Calibration of the device with metallic indium
The portable multi-sample DTA was calibrated measuring the
To test the constructed multi sample-DTA instrument several melting point of metallic Indium. This metal is normally used as
measurements were carried out. First, a calibration was performed
with determination of melting temperature of metallic indium;
then, evaluation of base line was done to determine noise signal
ratio. The results of the melting temperature of indium were also
compared with the results obtained with a commercial device (Dia-
mond Perkin Elmer-DSC). The substance used for calibration of the
DTA was: Indium (99.99%) obtained from Sigma Aldrich. For all
measurements Aluminum Oxide, Al2 O3 (99.7%) also from Sigma
Aldrich was used as reference inert material.

2.2.1. Evaluation of the sensitivity of the instrument


The evaluation of the baseline was carried out measuring an
inert sample of aluminum oxide in order to determine the accept-
ability of the noise/signal ratio. One of these aluminum oxides
measurements was compared with two samples of metallic indium
of different mass. Results are shown in Fig. 6.
The USB NI9211A card has an accuracy of 24-bit of analog to Fig. 5. Schematic representation of a glass tube sample cell. A magnication of a
digital conversion and therefore a digital resolution of 10 nV. The capillary tube that protects thermocouple tip is also shown.
92 L.M. Martnez et al. / Thermochimica Acta 560 (2013) 8994

Fig. 9. Comparison of the result of melting temperature of 56.3 mg of indium on the


Fig. 6. DTA thermogram showing a comparison of aluminum oxide (Al2 O3 ) sample non-commercial DTA presented in this work with the result of melting temperature
signal with the melting of two samples of metallic Indium of different masses. of indium (5.74 mg) of a commercial DSC (Diamond-Perkin Elmer).

established with the corresponding mass of the sample (see Fig. 8b).
A coefcient of determination, r2 , of 0.9721 was obtained, suggest-
ing a good correlation between the DTA signal and the amount of
the sample.

2.2.3. Comparison of the non-commercial DTA with a commercial


DSC
A measurement of melting temperature of metallic indium
taken with the non-commercial multi sample DTA presented in
this work was compared with a measurement taken with a Dia-
mond Perkin-Elmer DSC. As it can be seen in Fig. 9, they both yield
the same result for the melting temperature of indium. The differ-
ence between the areas of the endothermic peaks is due to the size
of the sample.
Finally, to show the application of the instrument on the ther-
Fig. 7. DTA thermogram showing melting temperature of three samples of indium mal characterization of materials of different nature, several phase
99.99% measured simultaneously. Heating rate was 10 C/min. transitions were measured. For this purpose several substances
(cyclohexane, lysozyme, urea, antipyrine, sucrose, trehalose, para-
cetamol) were obtained from Sigma Aldrich with a purity of
calibration material because it shows a high endothermic peak at 99.9%.
156 C. It was found that all of the three sample holders gave consis-
tent results that matched with the reported melting point of indium
[11]. Fig. 7 shows the DTA curves of the melting process of three 3. Results and discussion
samples measured simultaneously.
As part of the calibration of the device several samples of dif- In this section the thermal characterization of several materials
ferent mass of metallic Indium were measured. Fig. 8 shows the presenting different phase transition like melting, crystallization,
DTA curves of these measurements. The area of each of these denaturation and glass transition temperature measured with the
endothermic processes was calculated and a linear regression was multi-sample DTA are presented.

Fig. 8. DTA thermograms showing the endothermic melting process of indium samples of different masses. On the right side, the area of each melting peak was calculated
and plotted against the corresponding mass of the sample to nd a linear correlation.
L.M. Martnez et al. / Thermochimica Acta 560 (2013) 8994 93

Fig. 10. DTA thermogram, of three samples of cyclohexane measured simulta-


Fig. 12. DTA thermogram showing glass transition temperature (Tg ), crystalliza-
neously showing two endothermic phase transitions. Heating rate was 10 C/min.
tion temperature (Tc ) and melting temperature (Tm ) of amorphous paracetamol.
Inset gure shows magnication of the glass transition process. Heating rate was
10 C/min.
3.1. Determination of a solidsolid phase transition
denaturation temperature of this enzyme was reported to be at
The multi-DTA is capable of measuring different phase tran- 73 C (the measurements in their work were done in a commercial
sitions of a solid substance: Cyclohexane was used to show an instrument: MDSC 2920 microcalorimeter of TA instruments).
example of this kind of measurement; as it is shown in Fig. 10, cyclo- The small difference is ascribed to heating rate which in [13] was
hexane presents two endothermic peaks: it undergoes a rst order 2 C/min and 10 C/min in the present work. Even when the peak
phase transition at 87 C, when the crystal structure transforms is small, concentrations as low as 20% by weight are observable.
from a low temperature monoclinic phase to a high temperature
fcc plastic crystal phase and then nally melts to its liquid phase 3.3. Glass transition temperature (Tg )
at 7 C; these values are in good agreement with results reported
by Renaud et al. [12]. In order to detect these transitions, liquid Glass transitions is an important measurement for the food,
nitrogen was used to cool down the heating system. polymer and pharmaceutical industries because it indicates at
which temperature a substance stops being an amorphous solid,
3.2. Enzyme thermal denaturation representing the temperature at which the material loses its ther-
momechanical stability. Glass transition temperature (Tg ) is an
When a thermolabile biomolecule like a protein or an enzyme is endothermic pseudo second order transition, therefore magnitude
heated a small endothermic signal will appear that correspond to of this transition is very small and it can only be observed with
its thermal denaturation. The temperature of this peak represents high sensitive devices. Glass transition is observed not as peak but
the point where the biomolecule loses its active or native congu- as a small shift of the baseline. Fig. 12 shows the endothermic
ration. Lysozyme was chosen to show how our multi-sample DTA signal corresponding to the Tg of paracetamol (acetaminophen)
can measure the thermal stability of an enzyme. Fig. 11 shows together with the crystallization and melting of this substance.
the denaturation process of Lysozyme in aqueous solution where Notice the difference in magnitude of Tg signal compared with that
denaturation temperature occurred around 75 C, this result is in of rst order transitions (crystallization and melting). Comparing
agreement with results published by Hdoux et al. [13], in which the results of phase transitions shown on Fig. 12 with the results
previously reported by Qi et al. [14] who reported glass transition
(Tg ) at 25 C, a strong exothermic transition due to crystallization
observed at 65 C which is followed by the melting of the sam-
ple at 167.7 C, all of these transitions show coincidence with our
results. Furthermore, in Qis work an exothermic transition circa
120130 C was observed, which corresponds to the existence of
polymorphic phases for paracetamol; a weak exotermic process
can also be observed close to 120 C in Fig. 12.

3.4. Construction of phase diagrams and determination of


eutectic temperature and composition

The multi-sample-DTA is useful for experiments which require


of many measurements, like the construction of a binary phase
diagram. In Fig. 13 the thermograms are shown for different com-
positions of antipyrine-urea mixture. Since the multi-DTA can
measure three samples at once it only takes three runs to mea-
sure the two pure substances plus seven compositions of a two
Fig. 11. DTA thermogram showing thermal denaturation (Td ) of the enzyme component system which allows the construction of a phase dia-
lysozyme in aqueous solution. Heating rate was 10 C/min. The smooth line was gram. Since each run takes about 30 minutes, it is possible to get
obtained by a quadratic Savitsky-Golay smoothing on the data. this experiment done in an hour and a half. This is an advantage
94 L.M. Martnez et al. / Thermochimica Acta 560 (2013) 8994

and Characterization of Nanomaterials and Advanced Materi-


als (CAT120) and Novus Fund for the initiative in educational
innovation. Funding for this project was also provided by the SEP-
CONACyT program (# 106847).

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We thank the nancial support provided for this project to Tec-
nolgico de Monterrey through the research chair for Synthesis