The physic-chemical properties and chemical composition of petroleum and its products can be

controlled by various analytical methods. Studies carried out in many years ago shown that thermal
analysis can be used as one of these methods because thermal methods of analysis such as differential
thermal analysis (DTA), differential scanning calorimetry (DSC), thermogravimetry (TG), derivative TG
(DTG), dilatometry (DT) and penetrometry (TMA) supply much information concerning petroleum
products (fuel and lubricating oils, greases, paraffin waxes, petrolatums and asphaslts) [1].

Knowledge of the chemical composition of various crude oils and petroleum heavy residues is
indispensable for correct product quality assessment and choice of optimal petroleum processing
technologies. To obtain such knowledge one needs methods, preferably rapid, sufficiently accurate, easy
to use and capable of performing on-line in industrial conditions [2].

Determination of the composition and properties of crude oils is of great importance for the petroleum
industry. When characterizing oil, it is very important to determine some thermal properties such as
specific heat, enthalpy, and thermal conductivity, among others. These properties can be measured by
Differential Scanning Calorimetry (DSC) with great sensitivity and precision [3].

The present review is indicative of the potentiality of the DSC technique as an assay tool for rapid
screening of oil. By use of this technique, a sample can be assayed in about 1 h. More importantly, this
technique offers the advantage of being relatively simple and also does not involve sophisticated
measurement procedures. [4]

DSC is a thermal analysis technique which measures heat flow into or out of a material as a function of
temperature or time. Measurement of glass transition temperature, melting point, percentage
crystallinity, decomposition temperature, and oxidative stability are specific examples of some of the
more common DSC measurements. [5]

In spite of the fact that thermodynamic equilibrium is not usually achieved, DSC provides much valuable
information characterizing phase transitions of samples and making possible a relatively accurate
determination of a series of thermodynamic constants [1].

DSC gives information which, even if in certain cases cannot be considered completely accurate, is
generally more reliable than the result of normal technological tests. Moreover, a great amount of data
is collected simultaneously, which means that only one test is needed to acquire information usually
obtained with many conventional tests [6]

In Shishkin, et. al. [7] High-resolution differential scanning calorimetry was used to accurately establish
the temperature intervals of oxidation/distillation of the major components of crude oils. Some
theoretical aspects of the method of dynamic microdistillation, enabling consecutive distillation
(oxidation) of the main components of hydrocarbon mixtures, are discussed. The experimental TG-DSC
curves show that the temperature scan of the run can be divided into six regions, of which the first
belongs to simple distillation of the sample’s liquid constituent (the distillate) and the others to oxidative
cracking distillation of the solid (heavy) residue. The latter occur in the order paraffins + light oils, middle
base oils, heavy base oils, condensed aromatics (resins) and asphaltenes. The probable oxidation
mechanisms of different classes of petroleum hydrocarbons operating in different temperature regions
are discussed. Full quantitative fractional and group component analysis of a number of crude oils of
different chemical classes and geological age was carried out by the combined TG-DSC techniques under
specially chosen experimental conditions (those of dynamic microdistillaion).

The technique of Differential Scanning Calorimetry (DSC) records, on a continuous basis, the apparent
heat capacity or specific heat of any macromolecule according to temperature, through thermograms.
This is characterized by a peak of heat absorption corresponding to a transition process or thermally
induced, which, according to the second principle of thermodynamics (considering the case in
equilibrium), is an endothermic process. [8]. At a constant scanning speed, the excess power dissipated
in the crucible of measurement is directly proportional to the difference in heat capacity between the
crucibles, the latter being one of the fundamental magnitudes obtained in this instrument. The DSC
sensor measures both the temperature of one side of the specimen and the heat flow into it. A heat sink
of known temperature is constructed to contact the opposite side of the test specimen. From the
recorded heat flow and the temperature difference between the DSC cell and the heak sink (along with
the test specimen dimensions), thermal conductivity can be calculated using the equation (1):

dQ /dt=−KAdθ/dx (1)

Where Q is heat in J, t is time in s, K is thermal conductivity in W/°C.m, θ is temperature in °c, x is

height of test specimen in m, and A is cross sectional area of the test specimen in m 2 [3]. The effect of
purge gas may be reduced by the sue of vacuum or low conductivity gases such as argon, krypton and
xenon.

A diagram of DSC cell is shown in Figure 1.

Fig. 1. Diagram of DSC cell

DSC of heat flow is an efficient technique used for thermal characterization of such materials. The DSC
calorimetry by dynamic or isothermal means is one of the most frequently outlined in the literature.
Modulated Differential Scanning Calorimetry

In modulated DSC the same heat flux DSC cell arrangement is used as in conventional DSC, but a
different heating profile is applied by the furnace to the sample and reference. Specifically, a sinusoidal
temperature modulation (oscillation) is overlaid on the traditional linear heating ramp to yield a cyclic
heating profile. The temperature increases at a rate which is sometimes faster, sometimes slower, than
the underlying heating rate. The actual variations in heating rate obtained depend on three experimental
variables: the underlying heating rate, the amplitude of modulation, and the frequency of modulation.
The combination of the underlying heating rate with the more rapid instantaneous heating rate results in
improved sensitivity without loss of resolution, (Figure 2) [9].

Fig. 2. MDSC heating profile (cyclic heating only)

In MDSC, the heat flow values during a scan are converted directly to heat capacity values at the
indicated temperature by dividing the modulated heat flow amplitude by the modulated heating rate
amplitude. Fig. 3 gives the results expressed in this fashion for an experiment on n-dodecane. It is
apparent that if no physical transformations occur in the sample the real heat capacities can be easily
determined by calibrating this cyclic heat capacity signal [9].
 Fig. 3. Heat capacity from MDSC raw signals (experiment on n-dodecane)

The heat capacities of petroleum hydrocarbons and their mixtures are of practical importance in
engineering work associated with petroleum refinery operations and related process. Not only does the
design of plant equipment require a knowledge of heat capacity data over wide ranges in temperature,
but these date are also helpful when prolonged storage or low temperature operability are considered.
Heat capacity can then be used in the evaluation of other basic thermodynamic properties of the fuel [9].

In Zanier et. al. [9], the usefulness of modulated DSC (MDSC) for measuring the heat capacity of
commercial hydrocarbon fuels is illustrated. Specifically, the reliability of the method is outlined by
testing five liquid fuels of diverse composition and origin over a temperature range between -70°C and
70°C. The experiments were carried out using a DSC 2910 module from TA instruments Inc., upgraded
with the MDSC option. The samples were exposed a cyclic heating profile which was generated by a
linear heating rate of 2°C/min while simultaneously superimposing a sinusoidally varying time-
temperature wave with an amplitude of ± 0.5°C and a period of 100 s. Sample masses were
approximately 20mg. The measurements were carried out using liquid nitrogen coolant and helium
purge gas with a flow rate of 40 ml/min. Helium was chosen because of its comparatively high thermal
conductivity so as to obtain maximum temperature uniformity across the test specimen, thereby
enhancing the accuracy of the measurement. On the basic of these measurements, MDSC proved to be a
valuable technique with which to measure directly the heat capacity of hydrocarbon fuels. Moreover,
the ability of MDSC to measure heat capacity with great accuracy and precision offers a powerful
approach for studying the effects of compositional differences on heat capacity.
In Jiang, et. al. [10] temperature modulated differential scanning calorimetry (TMDSC) is used for the first
time to measure the wax appearance temperature (WAT) of crude oil samples. The commercial
implementation of TMDSC is alternating differential scanning calorimetry (ADSC) marketed by Mettler-
Toledo. They show that changes in the ADSC signals exhibit excellent correlations with WATs measured
using conventional differential scanning calorimetry, DSC. For oil samples having low wax contents, ADSC
is a more sensitive technique for identifying the onset of wax crystallization and, specifically, the phase
angle between the heating rate and heat flow modulations is extremely sensitive to this process. All DSC
experiments were performed using a Mettler-Toledo DSC 821 equipped. The purge gas for all
experiments was nitrogen at a flow rate of 80 ml/min.

In Masson, et. al. [2] Naphthenic and paraffinic oils were analyzed by modulated differential scanning
calorimetry (MDSC). The heating and cooling experiment were performed between -110 and 50°C , at a
linear heating or cooling rate of 3°C /min, a modulation period of 60s and a modulation amplitude of
±0.47°C . The results showed several improvements in the analysis of thermal properties when compared
with standard DSC. The glass transition temperature (Tg), the enthalpy relaxation at Tg, and the melting
endotherms could be deconvoluted, and reversible melting could be identified. This allowed for an easier
interpretation of the thermal properties of the oils. With MDSC, the Tgs is mineral oils were found to
coincide with endothermic enthalpy relaxation, which is generally regarded as a melting endotherm with
standard DSC. A decrease in heat capacity after Tg was attributed to the existence of rigid amorphous
material. From Δc p at Tg and the oil molecular weight, the number of repeat units in the oil chains was
estimated at less than 20. The Tg of a hypothetical pure aromatic oil was found to be similar to that for
petroleum asphaltenes, and that for a naphthenic oil of infinite molecular weight to be similar to that of
petroleum resins.

WAX

Crude oils produced from the formations are transported and processed at low temperatures where
solid wax particles may precipitate. These solid particles cause additional pressure drop in production
tubing, pipeline, and processing equipment and eventually cause plugging. Great saving in the cost of
operating such equipment can be achieved from accurate modeling of wax appearance temperature
(WAT) and the amount of wax formed at given conditions. Crude and the amount of wax formed at given
conditions [11]. The preventions of wax formation, the production of diesels more resistant at low
temperature and the design of new and better additions requires a good understanding of the
crystallization behaviour of the paraffin molecules [12]. Crude oils contain mixtures of light and heavy
hydrocarbons that can be classified as paraffins, naphthenes and aromatics as heavy as C 60 or C70 in
addition to polar and asphaltenes. The lighter parts of the crude oils keep the heavier parts, wax and
asphaltenes, in solution. This solubility depends on pressure, temperature and composition of crude oils.
The presence of light ends increase, the solubility of wax in crude oil [11]. Better experimental
techniques to study the wax formation and reliable thermodynamical models, able to predict the solid-
liquid equilibrium of petroleum fluids, would help to prevent and overcome many of the problems
associated with wax deposition [12].

Two classes of wax are generally recognized, the distillate waxes which are crystallized to a high degree
are known as paraffin waxes and the residual waxes, in which the crystals are microscopic in size, are
known as microcrystalline waxes [6]. Microcrystalline waxes begin to melt at lower temperature and
over a wide temperature range with a single broad DSC peak. This is a result of their higher molecular
weight. They consist of branched and cyclic hydrocarbons as opposed to n-paraffin hydrocarbons which
have higher melting points. However, in the case of paraffin waxes two characteristic DSC peaks are
observed, one sharper due to melting and another due to the solid-solid phase transition (orthorhombic
to hexagonal) [1, 6]. While the melting curve of paraffin waxes shows relatively sharp endotherms,
microcrystalline waxes show only broad endotherms and no transitions other than melting. This reflects
the difference in the molecular structure between paraffin waxes which are composed mainly of
saturated normal paraffins in the approximate range C 18-C40 and microcrystalline waxes which are
composed of branched paraffins with a greater number of C atoms (C 25-C65) and a greater molecular
weight [6].

For a typical diesel, without additives, at temperatures below 10°C the paraffins start to crystallize
forming plates and needles that plug pipes and filters. A few degrees below the wax appearance point
(WAP) the solutions gels completely preventing the flow of the fuel. In Coutinho, et. al. [12] an
equilibrium cell previously used with synthetic mixtures is applied to study the influence of the
desulphuration on the low temperature behaviour of a Petrogal diesel. The compositions of the solid and
liquid phases in equilibrium and the fractions of solids in partly crystallized solutions were measured
between -5 and -20°C. The latter was also measured by DSC. Extensive measurements of composition
and phase equilibrium are done to the diesel before and after desulphuration and the results compared.
The experimental date was modeled using the Predictive UNIQUAC model. It is show that the model
provides an excellent description of the measured phase behaviour for these diesels. The desulphuration
of the diesel seems to make it slightly heavier and to increase its wax appearance temperature (WAT).
The calorimetric measurements were performed in a Setaram DSC 141. The sample was cooled to -140
°C kept at that temperature for 15 min to stabilize, and then heated up to 50°C at 3°C/min. After a glass
transitions at around -80°C, follow an exothermic peak due to the crystallization of species that did not
crystallize on cooling. Then a broad endothermic effect resulting from the dissolution of the paraffinic
crystals in the liquid matrix appears. The wax appearance temperature (WAT) was measured by DSC.
Runs at different heating rates were done and the value extrapolated to zero heating rate. The
composition and wax appearance temperature measurements indicate that after the desulphuration the
diesel becomes slightly heavier and thus somewhat less performing at low temperatures.

In Giavarini, et. al. [6] were reviewed the possibility of using the DSC method in studying processes of
thermal stability of oils under oxidative conditions and the effect of antioxidants [1]. In this paper some
petroleum products, as paraffin waxes, microcrystalline waxes, lube oils, fuel oils, bitumens, were
studied using DSC. DSC makes it possible to determine the wax content of various petroleum fractions,
to study the effects of additives, to determine the glass transitions of bitumen; it is a useful technique
both for research and for product analysis [6]. The test were carried out using a Perkin-Elmer Differential
Scanning Calorimeter model DSC-1A, working in a dynamic nitrogen atmosphere. Runs were performed a
temperature range of -80 and 80°C, using liquid nitrogen as coolant.

One of major problem for both refiners and users of diesel fuel or home heating oils is the behavior of
such fuels in cold weather. These products always contain varying amounts of n-alkanes (generally 10-
30%). As ambient temperature decreases, the solubility of n-alkanes also decreases. Precipitation occurs
over a temperature range of 10-15°C for standard commercial products, until solidification occurs. This
limits the use of petroleum products [13]
In the last 30 year, differential scanning calorimetry (DSC) has been widely used to study the thermal
behavior of oils. In Bosselet, et. al. [14] has been studied the thermal behavior of n-alkanes in complexes
hydrocarbon by differential scanning calorimetry, in the first part has been made a study the thermal
behavior of alkanes in linear temperature programming. The low temperature properties of many
petroleum products depend on the amount of n-alkanes that they contain. The thermal behavior of 14
alkanes ranging from n-C12H26 to C25H52 has been studied by means of a Mettler TA 2000 B heat flow DSC.
Different hydrocarbon matrices such as gas oil (diesel) where n-alkanes have been used. A comparative
study of the values of the enthalpy of dissolution obtained for each n-alkane in a gas oil with or without a
distribution of n-alkanes has been carried out. In the second part the study [15] the thermal behavior of
alkanes in a hydrocarbon matrix has been carried out by means of a Mettler TA 2000 B heat flow
differential scanning calorimeter. A quantitative method to determine the composition in n-alkanes
contained in a gas oil is described. It is assumed that the determination of the cloud point by means of
DSC measurements can be obtained with a good precision. The cloud point indicates the tendency of the
oil to plug filters or small orifices at cold operating temperatures; it is synonymous with wax appearance
temperature (WAT) an wax precipitation temperature (WPT). In the third part the study [16] of the
thermal behavior of n-alkanes in the solid state or in a hydrocarbon matrix has been carried out using a
stepwise programming of temperature. In the case of pure n-alcanes the separation between the
transition peak and the melting peak can be easily increased and the enthalpy of each thermal effect can
be determined. The precipitated amount of n-alkanes contained in middle distillates has been obtained
vs. temperature. In the fourth part [17] a lowering of the cloud point of middle distillates has been
obtained by the use of additives. A study of the cloud point vs. concentration in the additive and the
nature of the middle distillate has been carried out. It is assumed that the efficacy of the additives is
directly dependent on the amount of n-alkanes which are precipitated at the cloud point. Using a
stepwise program of temperature the selectivity of additives has been established and a thermodynamic
explanation has been proposed.

In Queimada, et. al. [18] the low temperature behaviour of five distillation cuts (230-375°C) from crude
oil from different sources (North Sea, Africa and Middle East) was studies. Precipitation curves for these
cuts, showing the evolution of the fraction of solid n-alkanes with temperature, were measure by DSC
and the compositions of the cuts were analysed by gas chromatography (GC). The measured
precipitation curves have been compared with the predictions form a thermodynamical model using the
compositional analysis. The model results agree well with the experimental data indicating that the
model used can be an adequate tool to predict the low temperature behaviour of refined oil products.
The calorimetric measurement were performed on a Setaram DSC 141. The sample was initially cooled to
130 K, kept at that temperature for 15 min to stabilize, and then heated up to 320K at 3 K/min.

Paraffin Waxes

Paraffins, or more generally waxes, can cause a lot of trouble or the productions, transportation and
storage of crude oils and also in the storage and operability of derived products such as diesel fuels,
home heating fuels, heavy fuels, asphalt cement or lubricating oils [19].
A hydrocarbon product does not change from the homogeneous liquid to the solid state at exactly one
temperature but in a more or less wide temperature range. As the temperature decreases, the solubility
of paraffins or waxes also decrease and precipitation of crystals of the heaviest paraffin or wax appears.
This precipitation can occur over a temperature range of 5 – 15°C until solidification occurs. This limits
the use of petroleum products [19].

Application of DSC to the study of petroleum products was elaborated in several articles since many
years ago, the heat of melting and the latent heat of the phase transition of paraffin wax were used to
calculate the paraffinicity of lubricating and spindle oils [20, 21]. Information obtained from de DSC
peaks was also used in evaluation of the quality of motor oils [22], which allow the evaluation of the
aging tendency of transmission and hydraulic fluids and enable the determination of the maximum
temperature for their use.

Paraffin oils are characterized by a shallow but broad DSC peak, while naphthenic-aromatic oils show
only variations in the slope from the baseline of the curve due to change in the heat capacity of the oil
[6]. Examination of fractions obtained by vacuum distillation of paraffin oil showed that the extent of the
crystallization and melting range decreases with increase in the average molecular weight of melting and
the heat of melting decrease, thus indicating the suppressed paraffinic character and enhanced iso-
paraffinic and naphthenic character for the subsequent fractions [6, 23]. These studies showed that the
information obtained by analysis of the temperature range and the shape of endothermic and
exothermic DSC peaks as well as the characteristic heats of transitions calculated from them, can be
successfully utilized in quality evaluation of the different types of commercial oils [1].

Based on the DSC curves, it is possible to determine the heat of solid-solid phase transitions and the heat
of melting of paraffin waxes. The determination of the latter value is particularly important for carrying
out engineering calculations because it can be used together with the heat capacity to calculate the total
amount of energy required to melt a given quantity of wax [1]. Moreover, a knowledge of the values of
the heat of melting, those experimentally determined and theoretically calculated, makes possible the
evaluation of the crystallinity of wax (content of amorphous fraction comprising frequently cyclic and iso-
paraffin hydrocarbons) [1].

In Hipeaux et al. [19] a conventional base stock, solvent refined (SR) and a hydroisomerized base stock
(HI) in which differences in behavior of Pour Point Depressant Additive are observed, have been
dewaxed and these oils and their fractions have been characterized by analytical methods and thermal
analysis. Differences between these base stocks, more particularly in the amount of crystals which
precipitate versus temperature can explain selective effectiveness of pour point Depressant (PPD)
additives. Tg of the hydrocarbon matrix is determined by DSC by heating from the solid state of the
previously cooled hydrocarbon. The homogeneous liquid can be cooled using DSC to obtain Tc and the
amount of waxes which precipitates versus temperature. The base stock were dewaxed and fractionated
into 8 cuts. DSC measurement were carried out using a Mettler TA 2000 B apparatus. Studies done on
warning to determine DSC profile and wax content were carried out from -130°C up to 25°C at 5°C /min.
the cooling rate from 25°C to -130°C was 10°C/min. Additional cooling studies were performed at a rate
of 0.5°C/min from -10°C to -40°C to determine Tc and PP. Several thermal effects occur similarly to those
observed with diesel fuels or crude oils. An increase of the heat capacity (ΔCp) causes an endothermic
shift and corresponds to the transition glass T g (1 in Fig. 4) The Tg value depends on the molecular weight
of the matrix and takes place in the temperature range -100 to -80°C. After T g a small exothermal effect
(2 in Fig. 4) due to the crystallization of species that does not crystallize on cooling. A broad endothermal
effect (3 in Fig. 4) corresponding to the dissolution of the wax into the liquid matrix.

Fig. 4 DSC curves on heating of SR (mineral oil), HI (hydroiosomerized oil) and PAO6 (Polyalphaolefin).

Claudy et al. [24] used the differential scanning calorimetry (DSC) to determine the amount of
crystallized paraffins and the temperature at which appear in a diesel fuel containing no additive. DSC.
measurements were carried out by means of a Mettler TA 2000 B apparatus controlled by an HP 85
computer. Diesel fuels (20-25 mg) were transferred into an aluminum crucible, which was sealed and
weighed. The calorimeter was set at constant temperature and computerized cooling began at a rate of
0.5°C/min. The DSC cell cross section is shown in Figure 5. The sampling period was 5s. In the
temperature range -30°C to 20°C the percentage of crystallized paraffins was responsible for pour and
filter plugging point which corresponded to 1% and 0.4% respectively. It has been shown that ASTM pour
and cloud points and European filter plugging points could be obtained in a single DSC experiment with
better reproducibility than standard test.

Fig. 5. D.s.c. cell cross section.

Crude oils contain various amounts of wax, that tends to separate from oil during cold weather. The
precipitation of this fraction gives rise to a variety of problems well known in the petroleum industry.
Any petroleum product can be considered as:

1. A hydrocarbon matrix which becomes a glass at low temperature (from -30°C for an asphalt
cement to -140°C for kerosene); and
2. Fractions which can crystallize into the matrix. Their amount varies from 0 to 20 wt%. These
fractions are often complex mixtures that can contain essentially n-alkanes (fuel oil, kerosene),
but also various amounts of iso-alkanes and cyclo-alkanes (asphalt cement and crude oils).

Létoffé, et. al. [25] using differential scanning calorimetry (DSC) apparatus developed an experimental
procedure in order to determine the wax content of 29 crude oils from several sources. The amount of
wax, which is obtained with good reproducibility (5%), is higher than the values obtained by gas
chromatography (GC). In fact, GC evaluates n-alkanes and DSC evaluates the total amount of crystallized
species (n-alkanes isoalkanes, cycloalkanes, …,). All analyses were performed using a Mettler TA 2000 B
DSC apparatus and was flushed with argon. Each sample was heated at 80°C for 1h in closed containers
and shaken thoroughly to enable complete dissolution of the wax. The container was then left to cool to
50°C. A 20-25 mg portion was then transferred into an aluminium crucible, which was sealed and
weighed. Studies, on warming, were carried out between -150 and 80°C at 5°C/min, employing a cooling
rate of 10°C/min from 50 to -150°C.

A typical DSC curve of a crude oil is shown in Figure 6. [25]

1. An increase of the heat capacity, ∆ C p, by 0.4 J/g.K, corresponding to the glass transition, T g,
occurs. Its value depends on the molecular weight of the matrix, and takes place in the
temperature range of -130 to -80°C. T g is assumed to be the temperature when half of the heat
capacity increase is reached.
2. After T g, a small exothermal effect is experienced due to the crystallization of species that
cannot crystallize on cooling, ∆ H =−0.3 J / g.
3. A broad endothermal effect, corresponding to the dissolution of wax, ∆ H diss , into the liquid
matrix, is noticed.
 Fig. 6. Example of the computation of the wax content.

Evolution of the calorimetric signal after T g is always a straight line, corresponding to a linear variation of
the thermal capacity of the hydrocarbon matrix. T e, the end temperature, is taken 20K above the end of
dissolution and after different determinations, and for all further experiments, the value of T s is taken to
be 30K above T g in the crude oil.

Hansen, et. al. [26] used differential scanning calorimetry to study wax precipitation from 17 North Sea
crude oils in the temperature range from 70 to -140°C whit a rate of -10°C/min. For all oils, both the glass
transition temperature (T g) and was precipitation (appearance) and dissolution (disappearance)
temperatures (WPT and WDT) have been studied together with the transition enthalpies involved in the
precipitation and dissolution of wax (ideally, heats of crystallization and fusion), ∆ H ℘ and ∆ H wd,
respectively. All analyses were performed using a Perkin-Elmer System 4 thermal analyzer and the
sample compartment was flushed with helium. With respect to physical characteristics, the oils ranged
from very light paraffinic condensates to heavy waxy crudes including biodegraded and asphaltenic oils.
On the basis of glass transition temperatures, the oils could be sorted into groups that corresponded to
their physical descriptions, whereas a similar grouping according to the precipitation temperatures
ranged from -128.5 to -81.5°C, while wax precipitation and dissolution temperatures ranged from 39.5 to
-26.0°C and -16.0 to 53.5°C, respectively. Dissolution temperatures were generally higher than
corresponding precipitation temperatures, 13°C on the average, and nonequilibrium conditions caused
by undercooling and overheating during temperature scanning were probably responsible for these
temperature differences. Measured precipitation and dissolution enthalpies based on total sample
amounts ranges from 0.55 to 9.79 cal/g and 0.32 to 10.63 cal/g, respectively. On the average, dissolution
enthalpies were ca. 14% greater than the corresponding precipitation enthalpies; this excess of enthalpy
required for dissolution of wax cannot be accounted for thermodynamically and is supposed to be
related to exothermal effects taking place during heating scans and hence the way data are processed.
By combining the amount of wax precipitated by cooling from 45 to -40°C, as determined by pulsed
NMR, with the accumulated enthalpy of the same temperature interval, it was possible to express the
average precipitation and dissolution enthalpies based on the actual amount of wax; values ranged from
23.7 to 70.6 cal/g and from 32.3 to 71.7 cal/g for the precipitation and dissolution enthalpies,
respectively. Furthermore, by combining the incremental amount of wax precipitated as function of
temperature in 5°C intervals from 45 to -40°C, as determined by pulsed NMR, with the incremental wax
enthalpies accumulated in the same temperature intervals, an almost reversed parabolic dependency of
wax precipitation and dissolution enthalpies on temperature was revealed; the maxima were about
-20°C.

Some important definitions that can be remembered are:

Wax (high molecular weight) precipitation, which basically is a result of a decreased carrying capacity of
the fluid solvent (low molecular weight), commences when the crude oil is cooled below its cloud point.
The crystals formed may develop an interlocking 3D structure that can effectively entrap the solvating
oil; this will lead to higher viscosity and ultimately gelling and congealing. The temperature at which this
this happens is known as the pour point [26]. In this work has been defined some properties:

Wax Precipitation Temperature (WPT). WPT is the temperature at which the first wax crystals appear
upon cooling of an oil as an effect of the decreased solvating capacity of the oil matrix; this temperature
may be compared with the cloud point. In DSC analyses WPT is defined as the onset temperature of the
exothermal peak [26].

Wax Dissolution Temperature (WDT). WDT is the temperature at which all precipitated wax has been
dissolved upon heating the oil [26].

Glass Transitions Temperature (T g). Upon continued cooling, that part of the oil matrix which cannot
crystallize transforms into a frozen solid (a glass) with drastically reduced molecular mobility. This
transition, accompanied by rapid increase in viscosity and decrease in heat capacity, is called the glass
transition, and its midpoint is defined as T g. Below T g a glassy and a crystalline phase can exist, while
above T g a crystalline and a liquid phase is possible. The glass transition is lowered with decreasing
boiling range of the oil. Cooling rapidly below the glass transition could partly prevent crystallization due
to the drastically reduced molecular mobility of the frozen matrix. On reheating to a temperature above
the glass transition, the mobility would increase and additional exothermal crystallization could take
place. The content of very low molecular weight compounds (<C 10) plays a major role In determining the
glass transition and onset of wax dissolution. T g was not influenced by wax content [26].

Wax Precipitation Enthalpy (∆ H wpo). The total energy released during cooling is proportional to the area
enclosed by the exotherm and the processing baseline as shown in Figure 7. For most oils are as
enthalpies increased with increasing C 20+ or C30+ content. In general, a linear relationship between
transition enthalpies and n-paraffin content has been observed. It must be emphasized that crude oils
are very complex systems and that wax precipitation depends not only on temperature, bus also on
composition, wax content, and natural wax inhibitors, which may inhibit either nucleation or
crystallization or both.
 Fig. 7. Typical DSC thermograms of a crude oil showing the processing baseline, T g, WDT, WPT, and a
spike; lower curve, exotherm; upper curve, endotherm.

Wax Dissolution Enthalpy (∆ H wdo). On heating the oil samples from below the glass transition up to
70°C, broad endotherms were obtained as a result of wax dissolution. The measure ∆ H wpos are
supposed to be directly proportional to the amount of wax precipitated during a cooling scan and hence
should be comparable to the corresponding ∆ H wpos [26].

Elsharkawy, et. al. [11] reports measurements of wax content by acetone precipitation techniques as
well as appearance temperature (WAT) by viscosity measurement and differential scanning calorimetry
(DSC) of eight different stock-tank crude oils from the Middle East. WAT during cooling and wax
dissolution temperature (WDT) during heating were measured using the scanning calorimeter (Mettler
Toledo TA 4000 system). The sample was cooled at a rate of 10°C/min from 70 to -140°C using liquid
nitrogen. A cooling rate of 10°C/min might produce an undercooling effect. Under heating condition, the
sample was heated from -140 to 80°C at a rate of 10°C /min. Comparison of WAT measured by DSC and
viscosity indicates that the viscosity method overestimates the WAT. Crude oil gravity measured, by
digital density meter, and molecular weight, by vapor pressure osmometer, were used to characterize
the plus fraction and predict WAT and amount of wax formed at a given condition by the thermodynamic
model. Comparison between predicted and measured results shows that measured WAT by DSC
compares very well with that predicted from the model for most crudes. Figure 8, is a typicical
thermogram showing the exothermal peak during cooling, the glass transition temperature, T g, and the
processing baseline. The exothermal peak corresponds to the crystallization and hence precipitation of
solid particles of wax during the cooling process. The endothermal peak corresponds to dissolution or
melting of all wax crystals during the heating process. WAT is taken as the temperature at which the first
crystal of wax appears. On the DSC curve, it is taken as the onset temperature of exothermal peak.
 Fig. 8. Effect of wax precipitation on viscosity of crude oil.

The difference between WAT and WDT might be caused by undercooling and overheating that result in
non-equilibrium conditions during fast temperature scanning (10°C /min). WDT is taken as the
temperature at which all the precipitated wax has been dissolved into the oil matrix during the heating
process, as shown in Figure 9. It is the temperature corresponding to the endothermal peak on the DSC
curve during heating temperature scanning. The total energy released during cooling or heating process
is proportional to the area between the base line and the exothermal peak or endothermal peak,
respectively. Differences between enthalpy of precipitation and dissolution may reflect the differences in
oil composition (i.e. molecular weight and molecular weight and molecular structure) and their waxy
content [11].

Fig. 9. DSC thermogram of oil F during cooling.

Fingerprint of the crude

Crude oils are highly complex mixtures due to their formation processes. They contain families of
compounds which can usually be divided in six classes:

1. Normal paraffins
2. Branched paraffins
3. Cycloparaffins
4. Aromatic
5. Metals
6. Polycyclics and heteroatomic compounds with a high molecular weight such as resins and
asphaltenes.

The determination of any one of these families has potential for providing a fingerprint of the crude oil
[27]. Claudy et al. [27] used again the differential scanning calorimetry (DSC) to characterize crude
petroleum. It has been shown a thermal fingerprint can be obtained in a short time with a single
experiment and several parameters such as the glass transition temperature Tg of the hydrocarbon
matrix, temperature of crystallization and paraffins content can be measured with good reproducibility.
DSC measurements have been carried out using a Mettler TA 2000 B. The apparatus was flushed with
argon, chosen because of its density and low thermal conductivity. Each sample was heated at 70°C for
1h and vigorously shaken to homogenize the crude oil. 20-25 mg was then transferred into an aluminium
crucible, which was sealed and weighed. For cooling studies, the calorimeter was set at a temperature
above the thermal effect, and the cooling rate was 2°C/min for crudes or 0.5°C/min for distillates (Figure
10).

Fig. 10. D.s.c. curves of crude oils (cooling rate 2°C/min). Arrows show the crystallization temperature Tc. 1. Crude’s
Angola, 8. Crude’s Colombia, 11. Crude’s Nigeria, 12. Crude’s Gabon.

Studies done on warming were carried out from -150°C up to 80°C with a heating rate of 5°C/min (Figure
11). Several thermal effects occur, similar to those observed for diesel fuels:

1. An increase of the heat capacity: the glass transition (Tg) of the hydrocarbon matrix is
responsible for this phenomenon;
2. After Tg , a small exothermal effect: annealing near Tg shows that it is due to the crystallization of
species which cannot crystallize on cooling;
 3. A broad endothermal effect: the dissolution of n-paraffins in the hydrocarbon matrix occurs;
4. A slow evolution of the calorimetric signal is seen up to the end of the experiment. [27]

Fig. 11. DSC curves of crude oils (heating rate 5°C/min). A weak exothermal effect after Tg is shown. 1. Crude’s
Angola, 8. Crude’s Colombia, 9. Crude’s Gabon 11. Crude’s Nigeria.

The freeze-resistance properties of middle distillates are defined according to the following three
parameters [13]:

1. Cloud point (CP) and crystallization temperature (Tc) are the temperature at which crystals first
appear. The cloud point depends on the concentration, the molecular weight of the n-alkanes
and on the chemical nature of the hydrocarbon matrix (the non-waxy part of the oil). It is well
known that heavy n-alkanes are responsible for a cloud point that corresponds to an equilibrium
controlled by thermodynamic relationships [13, 19]. Is the temperature at which the incipient
crystallization of wax in the oil results in an opacity or cloud, without complete solidification. At
this temperature the oil does not fail to pour.
2. Pour point (PP). As the temperature gets colder, crystal growth continues and simultaneously,
the amount of precipitated paraffins or waxes increases. A lattice is obtained leading to
solidification at the pour point [13, 19]. The pour point method indicates the lowest temperature
at which an oil can be stored or handled without congealing in the tanks or pipe line. This test
gave the lowest temperature at which the oil flows under prescribed conditions [28].
3. Cold filter plugging point (CFPP). CP and PP cannot be directly correlated to the phenomenon
leading to the plugging of filters by n-alkanes crystals, so a third parameter is used, the cold filter
plugging point, which corresponds to the plugging of 45µm filter under standardized conditions.

The freeze-resistance properties of crude oils are defined by the following parameters [29]:
 1. Wax appearance temperature (WAT): the temperature at which visible crystallization occurs. It
depends on the concentration and molecular weight of the waxes and the chemical nature of the
non-waxy part of the crude oil, termed the hydrocarbon matrix.
2. Pour point (PP). As the temperature falls, crystal growth continues and simultaneously the
amount of precipitated waxes increases. A lattice is obtained leading to the solidifications of the
crude at the pour point.

Lubricating and fuel oils can be characterized for their low-temperature specifications with better
repeatability and reproducibility than the standard pour point and cloud point methods. These low-
temperature tests are non-destructive and can be followed by using the same sample for measuring the
high-temperature thermal stability of the oil (DSC destructive test). The oil sample can be as small as 10
mg. the presence of pour point depressant additives separated the wax crystallization DSC effect
(exotherm) from the wax melting effect (endotherm), and also produced heat-flow effect in the higher
temperature region [28].

Kok et. at. [29] presents the results of an experimental study of the determination of wax appearance
temperature (WAT) of 15 crude oils by differential scanning calorimetry (DSC), thermomicroscopy and
viscometry. Good agreement is obtained among the three techniques for crude oils having a significant
precipitation rate. Considering the great diversity of crude oils, it is concluded that DSC and
thermomicroscopy should be used together for a better understanding of the determination of WAT of
crude oils.

In Coto, et. al. [30] A new procedure has been developed including the effect of the fluid composition on
the precipitation temperature and the melting heat. Solid-liquid equilibrium equations were introduced
through a simplified thermodynamic model in the integration procedure resulting in an iterative method
combining experimental and calculated values. The final method yields the wax appearance temperature
(WAT), the full wax precipitation curve (WPC) and the estimated wax composition. In order to validate
the procedure, several crude oil fractions were used as standards due to the advantage of a narrow n-
alkane distribution. Experimental characterization for the cloud point temperature, the n-alkane
distribution and DSC was carried out. The experimental apparatus used is a DSC Mettler-Toledo DSC822e
in the temperature range between 80 and -120°C.

In Chen, et. al. [31] a new method to measure the wax content of crude oil has been developed by the
use of differential s canning calorimetry (DSC). In this paper, the wax content of a crude oil is proposed
and proved to be the Q (total thermal effect of wax precipitation in sample) ratio of the crude oil and its
corresponding wax obtained by using standard acetone method, i.e. Qoil/Qwax. For the 14 studied crude
oils with the wax content ranging from 1 to 27 wt%, the wax contents determined by the presented
method are in good agreement with those determined by standard acetone method, with an absolute
average deviation of only 0.82 wt%. This method has an advantage over reported DSC methods in which
the exact dissolution or precipitation enthalpy of wax is a must. It is also found that the wax contents
determined by either of the two methods show good linear relationship with the total thermal effect Qoil,
with the correlation coefficients over 0.96 According to the empirical correlations, the wax content of a
crude oil can be easily determined by using the DSC total thermal effect Qoil. In addition and more
significantly, the new method can be applied to improve the accuracy in determining the amount of
precipitated wax in a waxy crude oil at different temperatures. Before experiment, all the crude oils are
thermally pretreated, are heated to 80°C for 2 h and shaken thoroughly to ensure complete dissolution
of wax. Then the closed containers are left to cool to environmental temperature. TA2000/MDSC2910
apparatus was used. Experiments are carried out by heating the crucible to 80°C and keeping the
temperature for 1 min, and then cooling it at a cooling-rate of 5°C/min from 80 to -30°C. The total
thermal effect Q of the wax precipitation in specimen can be computed by integrating the area between
DSC calorimetric signal curve and the line connecting the two signals at temperature of -20°C and WAT
(see Fig. 12).

Fig. 12 A sample of DSC curve of crude oil

The linear relation between the Qoil and the corresponding wax contents determined by Qoil/Qwax method
can be expressed as Eq. (2) with a correlation coefficient of R2=0.9837.

c wax =0.75Q oil +0.20 (2)

Where c wax ( wt %) is wax content of crude oil, Q oil ¿ is the total thermal effect Q of crude oil between
WAT and -20°C.

In Létoffé et. al. [32] mixtures of 2% and 4 wt% of pure paraffins in a crude oil matrix and 14 crude oils
were characterized by differential scanning calorimetry (DSC) and thermomicroscopy at cooling rate of 2
K/min (this cooling rate allows a better approach to the solid-liquid equilibrium temperature) in the
temperature range from 80 to -20°C. Pour points were also determined. The crystallization temperature
T c is defined as the temperature at which the thermal power developed by the heat of crystallization of
paraffins is 15µW. It was concluded that pure paraffins in a crude oil matrix have a non-ideal behavior
and that interactions occur and the enthalpy of precipitation is lower than the enthalpy of melting. In the
temperature range used, a constant value of 200 J/Kg for the enthalpy of precipitation was determined.
For crude oils which contain >10 wt% of n-paraffins, the pour point is reached when ~2% of waxes have
precipitated. By thermomicroscopy, it was observed for mixtures of pure paraffins and crude oil matrix
that the size of the crystals is small and depends on the length of paraffinic chains at the pour point. For
crude oils, at the pour point the same final state is obtained (unlike diesel fuels). Even if the rates of
precipitation are very different, the crystal size is always small (1-3µm). This fact suggest that each crude
contains nuclei which are responsible for heterogeneous germination.
Aboul-Gheit, et. al [28] was characterized fabricating and fuel oil in low-temperatures. Samples of 10 mg
were placed in uncovered standard Al crucibles in the sample cell of a DSC 30 unit of the Mettler thermo-
analytical system TA-3000. Cooling the system to -50°C was achieved using liquid nitrogen. The nitrogen
flow rate was adjusted at 60 cm3/min as purge gas while a programmed heating at a rate of 5 K/min was
used until a final temperature of 125°C. The purge gas was then shifted to oxygen using the same heating
rate up to 250°C. Full scale heat flow was 20 mW and a plot of 10 can was used. In the low-temperature
region, the thermogram exhibits two distinct DSC effect. At the start, the sample was cooled to -50°C. On
programmed heating, a relatively low intensity exothermic peak appeared between -8 an -3°C with a
maximum at -6°C. This represents the wax crystallization effect, during which the oil exists in the solid
phase. Between -4 and 7°C, a second DSC peak with larger intensity, flowing in the endothermic
direction, appears with a maximum at around 3°C. On shifting from nitrogen to oxygen purging at 125°C,
the thermogram continues with no change in the heat-flow directions up to 157°C, where an exothermic
inflection take place (onset oxidation temperature), Figure 13. The wax melting peak becomes even
broader as the additive in the oil increases. The additive slightly increases the thermal stability of the oil.

Fig. 13. DSC Thermogram of the base oil showing the wax crystallization exotherm, wax melting endotherm and the
thermo-oxidation onset.

In Létoffé, et. al. [33] differential scanning calorimetry (DSC) and thermomicroscopy were used to
provide a better understanding of the antagonistic effect on cold filter plugging point (CFPP) when cloud
point depressants (CPD) and CFPP additives are mixed into a diesel fuel. Sixteen European diesel fuels
were used. It is show that the CFPP achieved by using only CFPP additive can be attained in the presence
of CPD if a small, homogeneous size of crystals of paraffins is again obtained. Two ways are proposed to
obtain this result: modification of the chemical structure of the CPD, and optimization of the
concentration of each component of the blend. In either case a decrease in efficiency of the CPD is
observed, but the antagonism disappears. It is possible to predict the efficiency of CFPP additives in a
diesel fuel containing CPD by evaluation of T g of the hydrocarbon matrix and determination of the
percentage of light n-alkanes by DSC:

 If T g is below -125°C and C<13 is > 1 wt%, a neutral or synergistic effect is observed;
 If T g is above -120°C and C<13 is <0.6 wt%, a very antagonistic behavior occurs.
Heino, E. [34] developed a method for determining the cloud point of petroleum middle distillates by
differential scanning calorimeter (DSC). None of the 95 samples failed to crystallize at a rapid cooling rate
on the DSC, and the degree of supercooling was quite low. The onset temperature of the crystallization
peak tended to be a few degrees lower than the cloud point measured by the standard method, ASTM D-
2500, but a very good correlation between the onset temperature of the crystallization peak and cloud
point was found. On the basis of this correlation the cloud point can be determined satisfactorily by DSC.
This method is over three times more accurate and two to eight times less time consuming than the
standard ASTM method. DSC measurements were carried out with a sample of weight 5 to 15 mg were
cooled from 35°C to 100°C using a cooling rate of 10, 5 or 2 °C/min.

Claudy, et. at. [13] studied the interactions between n-alkanes and cloud point (CP) and cold filter
plugging pont (CFPP) depressants using several experimental techniques such as differential scanning
calorimetry (DSC), thermomicroscopy and isoperibolic calorimetry. DSC measurements were carried out
using a Mettler TA 2000 B. The apparatus was flushed with argon. Diesel fuels (20-30 mg) were cooled
whit a cooling rate of 0.5 °C/min. It has been used thermomicroscopy investigations for correlating
morphological or structural changes to the thermal effects observed in DSC. The mode of action of CP
additive has been explained by a change in the thermodynamic functions of the solubility equilibrium.
Lowering of CP depends on the interactions between long chains of n-alkanes and additives in the fuel,
leading to solute complexes. CFPP depressant also cause weak interactions in the fuel but it cannot
strongly modify the solubility of n-alkanes. In this case, the mode of action can be characterized by
decrease of the size of n-alkanes crystals, this additives controls the rate of precipitation of the n-
alkanes. It has been shown that the efficiency of CP and CFPP depressants can be evaluated using DSC
and thermomicroscopy results.

In other studies [35, 36], thermogravimetry (TG) and differential scanning calorimetry (DSC) were used to
investigate the kinetics of non-isothermal pyrolysis of Aleksinac oil shale from Yugoslavia and Jordanian
shale oils, respectively. In Skala, et. al. [35], the sample used included oil shale, demineralized oil shale
and bitumen extracted from the original, as well as from the thermally treated oil shale. The DSC derived
kinetic parameters were determined by using the maximum-rate method. The method is based on
equation (3), with holds for a first-order reaction at Tm, the temperature at which the maximum rate of
heat absorption during DSC analysis is observed.

E /R T 2m=( A /q ) exp (−E/ R T m ) (3)

By plotting Ln(1/q) versus 1/Tm at at different heating rates, the activation energy can be determined
from the slope, and the frequency factor from the intercept of the resulting straight line.

The experiments were made with a Du Pont 990 Thermal Analyser with DSC cell, using approximately 10
mg of powdered sample and with the standard procedure for determining kinetic parameters of ASTM E-
698. Heating rate of 5, 10 and 20°C/min were used, in a stationary atmosphere of argon at 1 bar, and an
empty pan as the reference. DSC derived kinetics seem to be more appropriate for describing those
stages of the pyrolysis process where decomposition of organic material mainly results in the formations
of non-volatile products, i.e. solids and heavy liquids.
In Khraisha, et. al. [36] the analyses were performed in an inert atmosphere. The weight loss data show
that the pyrolysis of shale oils takes place in one regime, and the major weight loss occurs in the range of
175-450°C. The DSC data reveals the endothermic behavior of the decomposed samples. The kinetics of
the non-isothermal pyrolysis of shale oils have been derived using the TGA data. DSC technique is used
to enable one to follow the changes in heat flow during the history of reactions.

Kok, M. V. [37] used a Du Pont 9900 differential scanning calorimeter (DSC) and thermogravimetric
analyzer (TGA) to characterize the pyrolysis and combustion properties of two heavy crude oils, with API
gravities of 18.7 and 12.9°. The experimental procedure involves placing 10 mg of sample in a pan,
setting the heating rate and flow rate of the purge gas (nitrogen or air), then commencing the
experiment. All experiments were performed at a linear heating rate of 10°C/min over the range 25-
600°C with a gas flow of 53 ml/min. In pyrolysis runs, temperature ranges where distillation (between
ambient temperature, and 400°C) and visbreaking and thermal cracking (between 400 and 600°C) occur
were identified. In combustion with air three different reaction regions were identified, know as low
temperature oxidation (a reaction up to 390°C), fuel deposition (between 390-490°C), and high
temperature oxidation (between 490-600°C). DSC-TGA curves have also been used to determine the heat
values and reaction parameters of crude oils. Kinetic date were obtained from de high temperature
oxidation region of the DSC thermograms, assuming a first order combustion reaction for the fuel laid
down in this region, higher activation energies were found as the API gravity of the crude oil decreased.

In Shishkin, et. al. [38], a calorimetric-thermogravimetric method is described of determining mass

percent contents of distillate fractions, paraffins, base oils, resins, asphaltenes and carbines in various
crude oils. The method is based on recording DSC curves of a 10-15 mg sample heated in air in a
calorimetric cell at a rate of 40-50°C/min. additionally, weight loss of sample is found at temperatures
before and after the reaction. At temperatures from 220°C or higher distillation of the hydrocarbon
mixture starts to be accompanied by its exothermic oxidation, thereby making possible monitoring the
distillation (oxidation) of consecutive HC fractions by simple calorimetric-techniques. Differential
scanning calorimeter “Thermodat” of high-calorimetric-resolution and sensitivity equipped with
dedicated software was used for conducting the experiments and performing all the calculations.
Percent contents of the main constituents in a number of heavy and light crude oils were determined
and formulas for establishing paraffinic, base oil and coke-forming potentials of crude oils and oil
residues derived. One full analysis of a sample takes no longer than 1.0-1.5 h. the method can be used
for on-line quality control of various petroleum products, such as atmospheric and vacuum oil residues,
cracking residues, lubricants, ceresins and paraffins.

In Kok, et. al. [39], thermal characterization of lignite, crude oils and their 10 and 20% mixtures were
investigated by differential scanning calorimetry (DSC). Heat of combustion of the samples were
determined in a Parr 1241 oxygen bomb calorimeter, whereas specific heat and kinetic parameters were
determined with differential scanning calorimetry (DSC) connected to a Du Pont 9900 thermal analysis
system. The calorific value of the lignite increased in mixtures depending on the crude oil type. In
pyrolysis runs, temperature ranges where distillation and visbreaking occur were identified for the crude
oils studies. The thermal effects were endothermic and no exothermic reaction was observed. The effect
of heating rate was also studied, and higher reaction temperatures and higher heat flow rates were
observed at DSC peak thermograms with increasing heating rate (5, 10, 15, 20 and 25°C/min). Thermal
experiments were conducted with a sample size of 10 mg; the gas flow rate was kept at 53 ml/min. The
specific heat of samples was examined in the temperature range 20-600°C, increasing at 10°C/min, and
showed an increase with increasing temperature until the decomposition temperature was reached.
Kinetic parameters of the samples were investigated and an increase was observed in the activation
energy and Arrhenius constant of the mixtures, this increase was higher when the oil mixed was heavier.

Levin et. al. [40] used differential scanning calorimetry (DSC) from TA instrument (292MDSC) to analyze
the glass transition temperature of refined hydrogenated naphthenic mineral oils. The impact of the
aromatic content and the degree of hydrogenation have been studied. A change in aromatic content for
refined hydrogenated mineral oils was found to give only a limited impact on the glass transition
temperature of the oil. The aromatic content and the viscosity of mineral oils influence Tg. However, for
the oils in this stydy, the change in Tg was small for relatively large change in aromatic content.

In Aboul-Gheit, A. K. [41], the volatility characteristics of commercial petroleum fractions (gasoline

(petrol)), kerosene (paraffin) and gas oil) are studied by evaporation using open pans, closed pans with
very narrow orifices in their lids and a differential scanning calorimetry (DSC) unit. The effect of varying
the pan orifice size, the rate of DSC sensor heating and the flow rate of the purge gas (N 2) has been
investigated. Correlation of the temperature ranges of the curves shows to what extent evaporation can
be retarded by using closed pans with a narrow orifice. The DSC peak temperatures and evaporation
termination temperatures are significantly decreased by increasing the size of the orifice in the pan lid.
Lower heating rates are evidently giving thermograms with peak maxima and evaporation termination at
lower temperature. Integration of the DSC thermograms obtained for evaporation of the fractions, in
terms of percentage fraction evaporated vs. temperature, gives curves that can be correlated with
standard distillation curves. A DSC-30 unit of the thermo-analytical system TA-3000 (Mettler) was used.
Two sets of DSC runs were carried out using standard aluminium pans; one set with open (uncovered)
pans and the other with pans covered with lids containing a very narrow orifice in the centre. DSC
measurements were carried out from 35°C up to 350°C with a heating rate of 10°C/min; the purge gas
and its flow rate was N 2 ( nitrogen is used to prevent possible oxidation) at 50 cm 3/min and samples of
weight 20 mg were used. In an open system, the solid →liquid transition is sharp and independent of
pressure, whereas the liquid→vapour change is controlled by pressure which depends on mass transfer
from the liquid surface to the vapour phase. Consequently, the DSC peak shape depends on the rate of
evaporation which is a function of the temperature and of the rate at which vapour is removed.

Bitumens

Bitumens are mainly obtained as a residue of the petroleum refining process. These products are of
great importance to the chemical industry because of their great variety of special properties, which has
favored the development of a wide field of applications. The specifications that bitumens must meet
depend on the needs for each particular use (paving, roofing, coating, insulation, etc); however, these
requirements are generally concerned with rheological properties [42]. Bitumen is an oligomeric material
with a time-dependent microstructure that affects viscoelastic properties. After it is cooled from the melt
bitumen becomes harder over time, and the hardening process may last up to 2 weeks. Hardening is the
result of the slow crystallization of high molecular weight saturated compounds and the slow formation
of a mesophase due to resins and asphaltenes [43].

Petroleum bitumens can be considered as colloidal systems in which micelles of high-molecular-weight

organic molecules (asphaltenes) are dispersed in an oily phase (maltenes)[42].

In Jiménez-Mateos, et. al. [42] thermogravimetric analysis (TGA) and differential scanning calorimetry
(DSC) were applied to the characterization of petroleum bitumens and their chromatographic fractions.
The influence of the different constituents on the thermal stability of bitumens was studied by TGA.
Characteristics such as the glass transition temperature ( T g) and the percentage crystallized fraction of
these samples were determined by DSC. Three petroleum bitumens from different crude sources with
the same penetration grade (40/50) and three mixtures were used. The bitumens were fractionated by
solubility procedures and chromatographic techniques. The separation process was based on the
different polarity of the constituents of bitumen, and consisted of two steps: first, the extraction of
asphaltenes (AS); and second, the chromatographic separation of maltenes (MA) into saturates (F1),
aromatics (F2) and resins (F3). DSC experiments were carried out on 10-15 mg samples in 50 µL
aluminium crucibles with perforated covers. First, the samples were cooled from room temperature to
193 K at rate of 50 K/min. Then, heating and cooling cycles at a rate of 15 K/min were recorded from 193
to 393 K under a nitrogem gas flow of 30 mL/min.

A low temperature, an increase in the heat capacity, observed as an abrupt change in the slope of the
calorimetric signal and also reflected as a peak in the first-derivative curve, corresponds to the glass
transition of the hydrocarbon matrix. The glass transition temperature ( T g) is one of the most important
parameters of theses glassy materials: on the one hand, T g provides information about their
composition, since it is related to the average molecular weight of these products; on the other hand, it
characterizes their viscoelastic behaviour at low temperature. The rheological properties of bitumens
below and above T g differ significantly: below T g, they exhibit bitumens behave like a glass, while above
T g, they exhibit rubbery behaviour. At higher temperatures, a series of endothermic effects is observed.
These enthalpy changes have been associated with the dissolution of the so-called crystallized fractions
(CF). These crystallized fractions consist mainly of paraffins that dissolve or precipitate in the
hydrocarbon matrix on heating and on cooling. From the results, it seems clear that the glass transition
temperature of these samples is related to their percentage of crystallized fraction. T g is almost constant
for high crystallized fraction contents (F1), increases significantly as the CF content decreases within the
intermediate range (MA, F2) and finally increases strongly as the CF content tend to zero (F3). In the
region corresponding to samples with intermediate CF contents a linear relation between T g and CF is
found. The information obtained from thermal analysis is shown to be suitable for correlation with the
composition and the physical properties of these products. Hence the characterization of the thermal
behaviour of bitumens and related compounds may provide a useful initial step for further studies on
their chemical and physical features [42].

In Chambrion, et. al. [43] the behavior of bitumen during thermal treatment was investigated by
differential scanning calorimetry and a better understanding of the interactions between the paraffinic
and aromatic fractions was provided. All DSC experiments were carried out on ~20 mg of material under
a flow of dry nitrogen. Samples held at 278 or 373K in the DSC cell were cooled to 153K at a linear rate
ranging from 15 to 0.5 K/min. The DSC signal was subsequently recorded at a linear heating rate of 15
K/min. It is shown that two glass transitions take place after cooling at constant rate. The magnitude and
temperature of\ these transitions depend on the cooling rate. T g 1 decreases with increasing cooling
rate. Rapid cooling favours the lower-temperature transitions, and at cooling rates < 1k/min the higher-
temperature T g vanishes and an endothermic peak is obtained. From these observations, a segregation
mechanism is proposed to explain the behavior of bitumen during cooling as outlined in Figure 14.

Fig. 14. Representation of bitumen structure in the course of solidification. Shaded, Aromatics, aliphatics,

resins, asphaltenic.

At 370K, local fluctuation in paraffin concentration takes place. On quenching (cooling rate 50 K/min),
aliphatics and aromatics tend to separate, but viscosity increases to a point where further separation is
hindered. Hence two glass transitions are observed, one at high temperature ( T g 2) giving material
enriched in paraffinic fraction and one at low temperature ( T g 1) giving material depleted of paraffins.
The composition of each frozen glass fraction obviously depends on the extent of paraffin segregation,
i.e. on the cooling rate. Changes in T g and ∆ C p take place accordingly. In very slow cooling, enough time
is available for total separation of the paraffins, which are then able to crystallize, giving rise to an
endothermic peak in DSC. A similar situation can be obtained by annealing at a temperature close to the
melting point of the paraffin [43].
Asphaltenes and Asphalt Cements

Asphaltenes are the most complex fraction of crude oils. They consist of fused aromatic and naphtenic
rings core with short aliphatic side chains. Asphaltenes rings high amounts of sulfur oxygen, nitrogen and
traces of metals such as nickel, vanadium and iron. Asphaltenes are the most polar of fractions of crude
oil and defined as aromatic-soluble, and n-paraffinic-insoluble. Its, unlike common chemicals, do not
have any well-defined chemical or physical properties such as molecular weight, melting point, boiling
point, vapor pressure, solubility and chemical reactivity, by which they can be characterized [44].

In Yasar, et. al [44] six Turkish asphaltenes were characterized by elemental content, proton NMR,
carbon NMR, GPC, DSC. Differential scanning calorimetry (DSC) provides parameters for comparing the
glass transition temperatures, endothermic behavior of asphaltenes and a hypothetical melting
temperature of the asphaltenes which is within the range of the pyrolysis temperature of asphaltenes.
The glass transition temperature points (Tg) of asphaltenes were determined using DSC. Hypothtical
melting poin temperature (Tm) of the asphaltenes was also calculated. The DSC thermograms of the
asphaltenes were measured a Mettler-Toledo STAR system and DSC822. Three different heatin rates of
10, 30 and 50°C/min over the temperature range of 25-600°C with nitrogen flow rate of 50 mL/min.

Ekulu et. al. [45] used the differential scanning calorimetry (DSC) technique to detect changes of the oil
microstructure as a function of temperature. Differential scanning calorimetry (DSC) was used to study
the effect of temperature on the colloidal stability of crude oils and mixtures {crude oil + toluene} and
{crude oil + n-alkane +toluene}. The mains objective was to evaluate the capacity of DSC to determine
changes of the colloidal structure of the crude oils. A TA Instruments DSC 2010 CE differential scanning
calorimeter was used to examine the phase behaviour of the crude oils and mixtures of them. The
temperature rise rate was 5°C/min with all experiments performed. The thermal curves of crude oils
were determined in a temperature range between 20 and 200°C. It was shown that DSC analysis of crude
oils and mixtures {crude oil + n-heptane + toluene} might contribute to assessing changes of the crude oil
microstructure occurring under the influence of temperature or solvent. Endothermic effects imply
disintegration of asphaltene-containing aggregates. Calorimetric data indicate that aggregates form a
polydisperse system with low cohesion energy. The presence of toluene or n-heptane generates thermal
effects characteristic of a given solvent and both solvents play an active role in aggregation processes. In
the case of pure oils thermal effects depend on the history of the sample.

In Fulem et. al. [46] the phase behaviour of Maya crude oil and its nano-filtered sub fractions was
studied using differential scanning calorimetry and phase angle measurements in the temperature range
173-573 K at atmospheric pressure. The combination of these two techniques elucidated key phase
behaviours, i.e. temperatures and enthalpies of phase transitions and their nature. Based on this
information a preliminary pseudobinary temperature-composition phase diagram for Maya crude oil was
constructed.As nano-filtration partitions samples on the basis of asphaltene content, within
experimental error, the composition coordinates are maltenes and asphaltene. Broad solid to liquid
transitions are identified for both maltenes and asphaltenes individually and the phase diagram is
dominated by 2 three-phase zone: solid maltenes + liquid maltenes + solid asphaltenes at low
temperature and liquid maltenes + liquid asphaltene + solid asphaltene at higher temperature. The heat
capacity data for Maya crude oil samples are reported in the temperature range 210-560 K. A differential
scanning calorimeter TG-DSC (Setaram, France) wass used. The measurements were carried out with a
heating rate of 5 K/min with isothermal periods of 1200s at the beginning and the end of each trial. The
typical mass of sample was 50 mg.

Asphalt cements (AC) are highly complex mixtures of hydrocarbon molecules whose thermal behavior is
of prime importance for petroleum and road industry. From DSC, the determination of several thermal
properties of asphalts is given, e.g. glass-transition temperature and crystallized fraction content. In
Claudy, et. al. [47] a DSC apparatus Mettles TA 2000 B was used. The apparatus was flushed with argon
chosen on the ground of its density and its low thermal conductivity. The thermal properties of AC
depend much on their thermal past. Experiments have shown that the sample must have a known and
reproducible thermal past so as the DSC experiment can give reproducible results. For this purpose: a)
The AC is warmed at 100°C during a few hours. b) It is cooled at room temperature (25°C), and kept at
this temperature during 24h. c) It is put into the DSC and cooled at 10 K/min from room temperature to
-100°C and d) It is warmed at 5 K/min up to 100°C, on recording the experiment. The dissolution of a
pure n-paraffin CnH2n+2 in an asphalt, as seen by DSC, should be a single peak. For 20 < n < 32 two
peaks were observed. This means that their dissolution occurs in two liquids, and explains the usual
shape of the DSC traces of AC, which shows a minimum at 35° to 40°C.

At room temperature, an asphalt cement is a mixture of two liquids containing some crystallized
fractions. Above 80°C, it appears as a single liquid phase. At low temperature, the study of the glasses
formed was done, using either constant or variable heating rate DSC. This technique shows two glass
transitions, for an asphalt containing a high quantity of crystallized fractions. The T g of these glasses
change with time and temperature. The formation of the crystallized phases is superposed to the
enthalpic relaxation of the glasses, making a kinetic study very difficult [47].

The strategic Highway Research Program allowed to define some parameters that characterize the
rheological properties of asphalt cement(s) (ACs). Those parameters implied that ACs follow the time and
temperature superposition principle. However, highly asphaltic or waxy ACs deviates from this rule since
their structure changes as a function of time and temperature. Some of these transitions clearly appear
on differential scanning calorimetry curves. Planche, et. al. [48], was studied over 70 ACs of different
origins-straight run vacuum residues from various crude oils and with different penetration grades. DSC
measurements were carried out between -100 and 100°C at a heating rate of 5°C/min. AC rheological
properties were characterized by dynamic mechanical analysis (DMA) using a dynamic shear rheometer
Rheometrics RDA 700. This paper shows some analogies between thermo-analytical and rheological
properties of ACs. In particular, it emphasizes the roles of crystallized fractions(s) (CFs) and of the glass-
transition temperature (T g) on the whole temperature range of end use. Thus, at low temperature, CF
seems greatly responsible for the physical hardening (PH) occurring with time. PH magnitude also
depends on the position of T g relative to the given conditioning temperature. At higher temperatures,
CF also plays a role on the rheological behavior since their dissolution-precipitation mainly occurs at
temperature between 0° and 80°C.

Has been the subject of many works…

Application of DSC to the study of petroleum products was previously elaborated in several articles..

DSC

The DSC makes is possible to:

- Determine the waxes in a crude oil and in various fractions such as oils and bitumens, in a much more
practical and rapid way than with the conventional methods normally used;

- distinguish between the principal types of waxes and determine their purity;

- study the behavior of oils and gas oils during oxidation;

- study the effects of various additives (antioxidants, pour point depressants, etc.) added to lubricating
oils and fuel oils;

- check how much an oil has been used and check the quality of the regenerated oil;

- determine the glass transitions of the bitumens;

- control the oxidation process of bitumens (using Tg measurements) [2]

- the determination of several thermal properties of asphalts, e.g. glass-transition temperature and
crystallized fraction content.

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detector de quimioluminescência para análise de composto de enxofre

Thermal conductivity is a measure of the ease with which temperature is transmitted through a material
and is a basic material property. Materials with high thermal conductivity are called “conductors” and
those with low conductivity are called “insulators”. Solid conductors (such as metals) typically have
thermal conductivities in the range 10-400 W/°C.m, while insulators (such as polymers, glasses and
ceramics) have values in the range 0.1-2 W/°C.m [3]