Thermal Analysis

Information for Users

User Com
Contents 2/2007
TA Tip - Optimum choice of method and evaluation in DMA measurements of composites New in our Sales Program - New STARe Excellence products - Liquid crystals as certified reference materials for the calibration and adjustment of DSC measuring cells in heating and cooling modes Applications - Thermogravimetric and calorimetric analyses of yeasts - Determination of the oil content in elastomers by TGA - Determination of calcium sulfate dihydrate and hemihydrate in cement - Determination of oxidation stability by pressure-dependent OIT measurements - Thermochromism of HgI2 Dates - Exhibitions - Courses and Seminars

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Dear Customer,
We are delighted to present two new thermal analysis Excellence instruments and a new software version in this issue of UserCom. Both the performance and the operating convenience of the instruments have been improved. For example, they can now be operated using the intuitive touchscreen display or by actuating the hands-free SmartSens infrared sensors. The new TGA and DSC models offer a choice of several different detectors. The TGA-DSC sensors simultaneously detect both weight and enthalpy changes with great accuracy. They differ in their maximum sample size and performance. The unique TGA-DSC sensor measures heat flow using six thermocouples and is very sensitive.

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Optimum choice of method and evaluation in DMA measurements of composites

Dr. Jrgen Schawe This article discusses the differences in mechanical behavior between isotropic and anisotropic materials. In particular, with laminates, it takes a look at the measurement results that can be expected through the use of different measurement modes, explains how optimum results can be obtained, and indicates which measurement curves should be displayed. The study shows that when systems consisting of several layers are measured it is often better to evaluate the compliance rather than the modulus.

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Introduction
Besides being used to measure mechanical quantities of materials, dynamic mechanical analysis (DMA) is also an excellent method for determining characteristic values such as the glass transition temperature. This often yields information that relates to the composition of materials. The evaluation and interpretation of data is relatively easy for isotropic materials because the properties and hence the measured values do not vary with the direction of measurement. Furthermore, with isotropic materials, the data obtained from different measuring modes such as shear, tension and bending can be directly compared. In the case of anisotropic composites, the mechanical properties and hence quantities depend on the spatial direction, the structure of the material and the measuring mode. The influence of these factors is discussed using laminates as an example.

TA Tip

served as a phase shift, . The complex modulus can be derived from the amplitude of the force, Fa, the deformation, xa, and the phase shift, taking into account the geometry factor. Depending on the type of applied stress, one obtains the shear modulus, G*, or the elastic modulus (Youngs modulus, tensile modulus), E*. Both G* and E* consist of a storage component (G or E ) and a loss component (G or E ). The components of the modulus are functions of temperature, T, and frequency, f ( = 2 f).

the complex modulus. One distinguishes between shear compliance, J*, and tensile compliance, D*:

The complex shear compliance is then

where the storage compliance

and the loss compliance

Representation of the mechanical data

The modulus In a DMA measurement, the sample is subjected to the action of a dynamic force, F, at a selected frequency. The sample responds to the applied stress with a dynamic deformation, x. The deformation has the same frequency as the force but is somewhat delayed. The delay is obFigure 1. Curves of G, J and tan at frequencies between 1 Hz and 1 kHz of vulcanized, unfilled SBR.

The storage modulus characterizes the elastic behavior of the material. It corresponds to that part of the deformation which occurs in phase with the applied periodic force. In the viscous component, force and deformation are phase-shifted by /2 relative to one another. This component corresponds to the loss modulus and is a measure of the mechanical energy that is dissipated (i.e. converted to heat). In eqs (1a) and (1b), the difference in the phase shift is expressed by the imaginary unit i = 1. The compliance While the modulus describes the stiffness of a material, the compliance characterizes its softness. In general, the compliance is the reciprocal value of

Similar relationships can be derived for the tensile compliance. The loss factor The determination of modulus and compliance depend on the sample geometry. In particular, when E* and D* are determined in bending, tension or compression measurements, the result is significantly influenced by changes in the geometry of the sample that occur during the measurement. A quantity that in theory is not influenced by this change is the loss factor, tan .

Similarly, tan can also be determined from the quantities of the shear measurement. In practice, the invariance of the loss factor with the geometry factor is only true within certain limits. With larger changes in geometry, for example changes in length in tension measurements, the operating point in the stress-strain diagram and hence tan change.

Isotropic materials
With isotropic materials, the mechanical properties are the same in all directions. Comparison of modulus, compliance and loss factor In an isotropic material, the storage modulus decreases stepwise in a relaxation region, for example in a glass transition. The modulus can change by several decades (with polymers, typically three
2
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decades). The loss modulus shows a peak in this region. The peak temperature is near the point of inflection of the storage modulus curve. The compliance curves show similar behavior. However, the storage compliance increases while the loss compliance exhibits a peak. The loss modulus has its maximum at lower temperatures than the loss compliance. The difference between the peaks depends on the change in the storage modulus in the relaxation region. The larger the change in modulus, the greater is the difference between the two loss peaks. The loss factor (tan ) peak is almost in the middle between the peak of the modulus and that of the compliance. This is illustrated in the example in Figure 1. With isotropic materials, the information provided by the modulus and the compliance are equivalent. Comparison of shear modulus and elastic modulus As shown in Figure 2, in principle, the shear and tension measurement curves differ only in their absolute modulus values and not in their shape and temperature location. In the example shown in Figure 2, the elastic modulus is three times greater than the shear modulus. At temperatures above 30 C, the sample is very soft. With samples of this thickness, the measurement is influenced by sample clamping. The influence of clamping can be reduced but not completely eliminated by using thinner samples. With shear measurements, such clamping effects do not occur. This allows a much wider temperature range to be measured with one sample geometry. Figure 3 illustrates why the elastic modulus is larger than the shear modulus. In a shear measurement, the sample undergoes deformation. In the linear region, the volume of the sample remains constant. In contrast, when the elastic modulus is measured, for example in tension, the length of the sample changes. This causes either a reduction of the cross-sectional area or an increase in the sample volume. In both process-

Figure 2. Elastic modulus, shear modulus and loss factor of a filled elastomer. For better comparison, the curves of the shear modulus have been multiplied by a factor of 3 (dashed curves).

es, work has to be done. This originates from the mechanical energy supplied in the measurement and therefore reduces the expected length change. The volume change, V, in tension for a length change, l, is described by the Poissons ratio, :

terials, not only the direction of measurement but also the mode of measurement plays a decisive role. An example of this is the measurement of a material consisting of a polymer layer deposited on a metallic substrate. In a tension measurement, the stiffer metal determines the total modulus, whereas in a shear measurement the total modulus is mainly determined by the softer polymer layer. To illustrate the relationship, let us consider a simple model, for example a composite such as a laminate or a fiber-reinforced thermoset. The components with the high modulus are present in one layer. The other layer is the softer component. In the case of a fiber-reinforced thermoset, the hard component is the fiber and the soft component the polymer. Figure 4 shows different measuring modes of a two-component laminate. In a tension experiment in the direction of the layers, the moduli normalized with respect to the thickness of the layers are additive. For example, if the modulus of the hard component is a decade greater
Figure 3. Illustration of the difference between the shear modulus and the elastic modulus.

With constant volume (V = 0), this gives a Poissons ratio of = 0.5. With constant cross-sectional area, A, (see Figure 3), it follows that = 0. These are the limiting values for Poissons ratio with isotropic materials. The relationship between the shear modulus and the elastic modulus is given by

It follows that 3G E 2G, whereby the larger value is true for constant volume. The curves in Figure 2 agree well with this estimate. It should however be noted that the estimate is only valid for isotropic materials. With anisotropic materials, the elastic modulus can be significantly larger than the shear modulus.

Anisotropic materials
Anisotropic materials have mechanical properties that vary with the spatial direction to which they refer. An important class of materials that is in principle anisotropic are oriented composites, for example laminates or thermoplastics filled with long fibers or fabric. With such maMETTLER TOLEDO

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than that of the soft component, the soft component contributes only 10% to the measured modulus for the same thickness of the layer. This contribution decreases as the thickness of the layer of the soft component decreases. If the system is measured in shear at right angles to the direction of the layers, a similar relationship exists. The shear modulus of the individual layers must of course be taken into account in this case. In such measurements, the total modulus is mainly determined by the stiffer component with the higher modulus. The situation changes if the measurements are performed in the opposite direction. In a shear measurement in the direction of the layer, the normalized compliances are additive, not the moduli. This measurement is dominated by the softer material with the higher compliance. A similar picture is obtained if the tensile compliance is measured in a tension experiment at right angles to the direction of the layers. In principle, compression measurements

similar to the tension measurements can be described. With measurements in bending or single (or dual) cantilever, the situation is much more complicated because the geometry factor changes depending on the structure of the sample and the thickness of the layer. If information is required about the properties of individual material components, the appropriate experiment should be performed. For example, to estimate the degree of cure of a filled epoxy system, a shear measurement in the direction of the fibers or a tension (or compression) measurement at right angles to the fiber direction is preferable to other measurement modes.

ure 5. If the measurement results are displayed as the modulus, only one relaxation transition can be seen. The change in modulus is mainly determined by the layer that first exhibits a glass transition. The loss factor curve also emphasizes the first glass transition. The glass transition of the second polymer layer is only visible as a weak shoulder at about 10 C that can easily be overlooked. The result is different if the compliance is evaluated. Due to the additivity of J in this measurement, both glass transitions can be clearly identified.

TA Tip

Conclusions
With isotropic materials, the modulus and compliance are equivalent to one another. In contrast, since the mechanical properties of anisotropic composites are direction dependent, the measurement results depend not only on the direction of measurement but also on the measuring mode used. This has to be taken into account when planning measurements in order to obtain the maximum amount of information. If possible, simple geometry factors should be used because they allow interrelationships to be more easily identified. This means that shear, tension and compression measurements are preferable to bending measurements such as three-point-bending or single cantilever. Due to the versatility of the METTLER TOLEDO DMA/SDTA861e , there are almost no restrictions regarding the measurement modes that can be used. The main factors that contribute to this are the high stiffness of the clamping assemblies, the large force range, the external preparation of samples, and the precise force and displacement measurement. Depending on the particular analytical problem, attention should also be given to the optimum presentation of measurement data. It is quite possible that compliance curves show the required information more clearly than the widely used modulus curves [1].

Measurement of a laminate
The relationships described above are illustrated using a laminate as an example. The sample consisted of 0.4-mm thick aluminum foil coated with two layers of different elastomers. The sample was measured in shear mode at 10 Hz in the direction of the layers. The resulting measurement curves are shown in Fig-

Figure 4. Schematic diagram of different measurement possibilities in shear and tension. A is the crosssectional area, d the thickness of the layer and l the length.

Figure 5. Measurement curves of an aluminum/elastomer/ elastomer laminate measured in shear in the direction of the layers at 10 Hz. Top: shear modulus; middle: loss factor; bottom: loss compliance.

Literature
[1]

J. Schawe, UserCom 16, 15.

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New STARe Excellence products

New in our Sales Program

STARe Excellence V9.10 software

The extremely powerful and easy-to-use S TA R e software has been further enhanced to take important new customer requirements into account. The S TA Re software is nowadays the standard for professional thermal analysis. The comprehensive S TA Re software offers: Unlimited evaluation possibilities enormous flexibility Automation high sample throughput with result assessment Modular concept tailor-made solutions for current and future needs. Measurements can be evaluated in the Evaluation Window as soon as they are completed. In contrast to previous software versions, you can now automatically combine one or more evaluations

into a report that can contain graphics and text. To do this you can use predefined report templates or your own templates created with the aid of the Report Generator. For larger laboratories, it is now possible to integrate the STARe System into a Laboratory Information Management System (LIMS). This can communicate with the STARe software via a gateway and thereby exchange data. Analytical tasks can be sent to the STARe System via the LIMS. A typical LIMS task consists in minimum of an identification through to a complete experiment description, including the expected results and their acceptability limits. LIMS task: Identification Method (optional) Sample name and sample size (optional) Result acceptability limits (optional) Comments (optional)

The results can then be sent back to the LIMS as soon as the analysis and evaluation have been completed. They are assigned to the particular task in the LIMS by means of the identification that had to be entered at the beginning. LIMS results include: a single evaluation graphic or a report or results checked with regard to their acceptability limits. The efficiency of the STARe software has been increased: it is now possible to evaluate several curves together in a single step. This is frequently the case in measurement series. The software also helps with the maintenance of the entire system. You can schedule reminders for maintenance (service), calibration and database backup.

send task STARe gateway send data LIMS

Figure 1. Data flow with integration of the STARe software into a LIMS system.

Experiment Window

Evaluation Window

results

method

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DSC 1
The DSC 1 is the most powerful DSC instrument currently available on the market. Highest sensitivity coupled with excellent resolution thats what you nowadays expect from a DSC. The heart of the DSC is the innovative, patented DSC sensor. This has 120 thermocouples and guarantees unmatched sensitivity. The DSC1 offers Amazing sensitivity for the measurement of weak effects Outstanding resolution allows measurement of rapid changes and close-lying effects Modular concept tailormade solutions for current and future needs.

New in our Sales Program

High priority was given to the optimization of ease of use and ergonomics. The new instrument features 1. a large and easily readable display or a clearly visible status display, 2. a place for you to label and identify the instrument according to your requirements, 3. the Please Do Not Touch warning plate indicating that the instrument is busy and must not be touched, 4. an ergonomically shaped support surface with integrated crucible tray and 5. hands-free operation of the instrument using the SmartSens Terminal. New is that instruments can be connected to a computer directly via TCP/IP, or via a network. This is an important advantage in a larger laboratory with several instruments, analysts, and computers.

Figure 2. The DSC 1, pictured here without the sample robot.

Specifications: Performance details Temperature range Sensors Options Values 150 C to 700 C FRS5 (fast full range sensor) HSS7 (high sensitivity sensor to 500 C) SmartSens Terminal and automatic furnace opening Cooling options air (standard), cryostat, IntraCooler or liquid nitrogen cooling Photocalorimetry Sample robot with 34 sample positions Gas switching (GC 10 and GC 20) Gas control (GC 100 and GC 200)

Figure 3. MultiSTARe FRS5 and HSS7 sensors.

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Gas controllers
Different gas controllers are available depending on your experimental requirements.
Name GC 10 Description 2 gas inlets and 1 gas outlet Gas flow is manually set. Deviations from the set value are measured and documented. Only one gas can flow at any one time. GC 20 2 gas inlets and 2 gas outlets Gas flow is manually set. Deviations from the set value are measured and documented. Two gases can flow simultaneously if required. GC 100 4 gas inlets and 1 gas outlet Gas flow is software controlled. Deviations from the set value are measured and documented. Only one gas can flow at any one time. GC 200 4 gas inlets and 2 gas outlets Gas flow is software controlled. Deviations from the set value are measured and documented. Two gases can flow simultaneously if required. Schematic diagram

TGA/DSC 1
The new TGA/DSC 1 re-establishes links with the very first METTLER TOLEDO TGA instrument introduced in 1964 with different sensors. It was a sweeping success and was used in many leading research laboratories throughout the world. The new TGA is much smaller and more efficient. It yields much more accurate information much more quickly. The heart of the TGA is the highly accurate UMX weighing cell that can resolve 5 g with 50 million points without range switching. This corresponds to a resolution of 100 ng. Thanks to the parallel-guided balance, the position of the sample does not influence the measurement. For example, if a sample melts and its position in the crucible changes, no change in weight occurs.
Figure 5. Cross-section of a parallel-guided balance (yellow: parallel guidance with bending bearings).

Figure 4. The TGA/DSC 1 with sample robot and gas controller.

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New in our Sales Program

New is that a DSC signal is also measured. Both weight and calorimetric data are simultaneously obtained from the same sample. This allows measurement results to be much more easily interpreted. All METTLER TOLEDO TGA instruments are equipped with micro- or ultra-micro balances with built-in ring adjustment weights. This guarantees unmatched accuracy. The TGA/DSC 1 offers High resolution ultra-microgram resolution over the whole measurement range METTLER TOLEDO ultramicro balance rely on the balance technology leader Modular concept tailor-made solutions for current and future needs. The internal adjustment weights ensure unsurpassed accuracy and reliability.

MultiSTAR TGA-DSC sensors For simultaneous measurement of heat flow (DSC) and weight change there are the following sensor choices:
Sensors Main feature SDTA Maximum sample volume (100 uL) (900 uL) (900 uL) 1 platinum 0.5 mW DTA Platinum surface, ideal with ceramic crucibles (150 uL) (150 uL) 2 platinum 0.2 mW DSC Maximum sensitivity (150 uL) 6 ceramic 0.1 mW

SF (1100 C) LF (1100 C) HT (1600 C) Number of thermocouples Surface material Sensitivity

Specifications
Performance details Temperature range MultiSTAR TGA-DSC sensors Balances Values Room temperature to 1600 C SDTA, DTA and DSC MX1 UMX1 MX5 UMX5 Options 1g 1g 5g 5g 1.0 g 0.1 g 1.0 g 0.1 g

Figure 6. The two internal ring adjustment weights. Figure 7. TGA-DSC sensor.

TGA-EGA (TGA-MS, TGA-FTIR or TGA-FTIR-MS) Sorption Sample robot with 34 sample positions Gas switching (GC 10 and GC 20) Gas control (GC 100 and GC 200)

Network connection New is that the TGA can be connected to a computer directly via TCP/IP, or via a network.

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Liquid crystals as certified reference materials for the calibration and adjustment of DSC measuring cells in heating and cooling modes
Dr. Steffen Neuenfeld, Merck KGaA Today nobody disputes the fact that a DSC measuring cell requires regular calibration if correct DSC measurement results are to be obtained. In recent years, temperature calibration in connection with DSC measurements has received more attention in the thermal analytical literature [1 to 4]. One important reason is surely the increased implementation of quality assurance systems such as DIN9001, GLP, or GMP in thermoanalytical laboratories. The honest intention of measuring as accurately as possible is no longer sufficient. There is an urgent need to apply appropriate calibration methods and to demonstrate their suitability. As far as temperature measurement is concerned, deviations result from the geometry of the measuring cell and the fact that the signal shifts to higher temperatures as the heating rate increases [1]. The latter literature reference describes a calibration method based on the measurement of the experimental transition temperature of a calibration substance as a function of the heating rate [1]. A linear plot of the measured temperatures versus heating rate extrapolated to heating rate zero yields the basic deviation. The slope of the straight line describes the influence of the heating rate (Figure1). Correction functions as a function of temperature can be obtained by performing the method at different temperatures using different calibration substances. A set of calibration functions is then obtained that allows the temperature to be corrected as a function of temperature and heating rate (Figure 1). Very pure metals such as indium, gallium and tin [2] are frequently used as calibration materials. In some cases, organic

T
T=0 Tf

Tcorr = T=0 + (T / )
T =0 T =0

Figure 1. Temperature calibration of DSC measuring cells.

Calibration function Tm = T=0 + m where m = (T / )

Different calibration temperatures Tm,1 = T=0,1 + m1 Tm,2 = T=0,2 + m2 Tm,3 = T=0,3 + m3 Tm,n = T=0,n + mn

T1

T2

T3

substances such as adamantane [3, 5, 6, 7], naphthalene or benzoic acid are also used. These calibration materials are however only suitable for heating measurements because the phase transitions used (usually first order melting processes) can exhibit a significant degree of supercooling in cooling measurements. In recent years, liquid crystals have often been used to perform calibration experiments in cooling modes or to check the linearity of the temperature deviation of the measuring cell at positive and negative heating rates [5, 6, 8, 12, 13, 14]. Unfortunately a number of the liquid crystals described in the literature are practically unavailable [10, 11] because they are not commercially produced in larger amounts.

erature as suitable substances for calibration in heating and cooling modes [5, 6, 8, 12, 13, 14]. Their phase behavior is shown in Figure2. The liquid crystals are secondary reference materials according to ISO9001 for guaranteeing the accuracy of DSC measurements in heating and cooling modes as well as for checking the symmetry of DSC measuring cells. The phase transitions suitable for temperature calibration are the SmA-N transition with HP-53, the SmA-N transition with M-24, and the N-I transition with BCH-52 [7, 8, 14]. The phase transition temperatures given for the materials are traceable to standard reference materials from NIST [16], (SRM 2222 - biphenyl) and the PTB [17] (ZRM 31402 - In, ZRM 31403 - Sn). The liquid crystal standards are supplied together with an analysis certificate. The three certified reference materials can be ordered from METTLER TOLEDO: ME-51191759 Certipur BCH-52 ME-51191760 Certipur HP-53 ME-51191761 Certipur M-24

Reference materials with certified transition temperatures

Merck [15] as a leading manufacturer of liquid crystals for display technology offers three liquid crystals commercially as certified secondary reference materials. The compounds, HP-53, M-24 and BCH-52, have been described in the lit-

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[8]

[9]

HP-53 K 73 SmB 93.6 SmA 120.5 N 181.2 I

ME-51191760 Certipur HP-53

[10]

[11]

[12]

M24

K 54.3 (45, 52) SmA 67.1 N 80.1 I

ME-51191761 Certipur M-24

[13]

[14]

BCH-52

K 39 SmB 146.9 N 164.8 I

ME-51191759 Certipur BCH-52

[15] Sabbath, R.; An, Xu-wu; Chickos, J.S.; Planas Leitao, M.L.; Roux, M.V.; Torres, L.A.: Reference materials for calorimetry and differential thermal analysis, Thermochim. Acta 331 (1999) 93204. Sarge, S.M.; Hhne, G.W.H.; Cammenga, H.K.; Eysel, W.; Gmelin, E.: Temperatur-, Wrme- und Wrmestromkalibrierung dynamischer Kalorimeter beim Khlen, PTB-Mitteilungen 109 (1999) 357375 Sarge, S.M.; Hhne, G.W.H.; Cammenga, H.K.; Eysel, W.; Gmelin, E.: Temperature, heat and heat flow rate calibration of scanning calorimeters in the cooling mode, Thermochim. Acta 361 (2000) 120. Neuenfeld, S.; Kunze, W.; Simon, E.; Wiese, M.: Temperaturkalibrierung von DSC-Mezellen mittels Adamantan im Heiz- und Khlmodus, Proceedings GEFTA-Jahrestagung, Braunschweig 2004

Figure 2. Phase behavior of the three liquid crystals.

For further information, please contact your local Merck or VWR organization [15]. Technical questions can be sent directly to the author [18].

[4]

[16] [17] [18]

Literature
[1]

[5]

[2]

[3]

Hhne, G.W.H.; Cammenga, H.K.; Eysel, W.; Gmelin, E.; Hemminger, W.: The temperature calibration of scanning calorimeters, Thermochim. Acta 160 (1990) 112. Cammenga, H.K.; Eysel, W.; Gmelin. E.; Hemminger, W.; Hhne, G.W.H.; Sarge, S.M.: The temperature calibration of scanning calorimeters. Part 2 Calibration substances, Thermochim. Acta 219 (1993) 333342. Schubnell, M.: Temperature and heat flow calibration of a DSC-instrument in the temperature range between 100 and 160C, J. Therm. Anal. Cal. 61 (2000) 9198.

[6]

Hhne, G.W.H.; Schawe, J.; Schick, C.: Temperature calibration on cooling using liquid crystal phase transitions, Thermochim. Acta 221 (1993) 129137. Menczel, J.D.: Temperature Calibration of Heat Flux DSCs on Cooling, J. Therm. Anal. 49 (1997) 193199. Martins, J.A.; Cruz-Pinto, J.J.C.: The temperature calibration on cooling of differential scanning calorimeters, Thermochim. Acta 332 (1999) 179188. Skoglund, P.; Fransson, A.: Accurate temperature calibration of differential scanning calorimeters, Thermochim. Acta 276 (1996) 2739. Hensel, A.; Schick, C.: Temperature Calibration of temperature-modulated differential scanning calorimeters, Thermochim. Acta 304/305 (1997) 229237 Vanden Poel, G.; Mathot, V.B.F.: Highspeed/high performance differential scanning calorimetry (HPer DSC): Temperature calibration in the heating and cooling mode and minimization of thermal lag, Thermochim. Acta 446 (2006) 4154. Neuenfeld, S.; Schick, C.: Verifying the symmetry of differential scanning calorimeters concerning heating and cooling using liquid crystal secondary temperature standards, Thermochim. Acta 446 (2006) 5565. VWR: www.vwr.com bzw. Merck KGaA: www.merck.de, M24 #1.00008.9005, HP-53 #1.00007.9005, BCH-52 #1.00006.9005 NIST: National Institute of Standards and Technology, Gaithersburg, USA PTB: Physikalisch-technische Bundesanstalt, Braunschweig, Deutschland Dr. Steffen Neuenfeld, Merck KgaA, Central Process Development, 64271 Darmstadt, Germany, Tel. +49 6151 727715, email: steffen neuenfeld@merck.de

New in our Sales Program

[7]

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Thermogravimetric and calorimetric analyses of yeasts

Applications

G. Dardelle, V. Normand, Firmenich S.A., Geneva, Switzerland

Introduction
Flavors in foodstuffs are often volatile and can be lost during production or when the consumer prepares food products. One possibility to reduce the loss of flavors during thermal processes (pasteurization, cooking) is to confine the volatile molecules in thermally stable particles such as empty yeast cells. This article describes how we investigated the release of flavors encapsulated in yeast cells as a function of temperature. The measurements were performed using thermogravimetric analysis and differential scanning calorimetry. Interpretation of the measurement results provides a better understanding of the release mechanisms of the flavor molecules from the yeast cells.

Experimental details
The yeast used for the experiments was Saccharomyces Cerevisiae (Firmenich SA, Item number 954794). The yeast was measured empty (unflavored) or loaded (flavored) with limonene (1-methyl-4isopropenyl-1-cyclohexene). Limonene is a flavoring that smells strongly like oranges and occurs naturally in the peel of citrus fruits. The thermogravimetric measurements were performed using a METTLER TOLEDO TGA/SDTA851e under inert conditions (nitrogen) with sample masses of about 10mg. The samples were heated in alumina crucibles from 25 to 400C at 20K/min. The calorimetric measurements were performed using a METTLER TOLEDO DSC822e. The samples were also heated in alumina crucibles in a static air atmosphere from 25 to 400C at 20K/min.

Results
Morphological characterization of the yeast The morphology of the yeast cells with and without limonene was studied using transmission electron microscopy (TEM). Typical images are shown in Figure1. The yeast cells are spherical with a diameter slightly greater than 2 m. The cell walls are clearly visible. The dark material in Figure1 (left) is the cytoplasm of the cell. In loaded yeast cells (Figure1, right), limonene has largely replaced the cytoplasm and occupies most of the internal volume of the yeast. Figure2 shows enlarged regions of the cell wall. This consists of glucans, mannoproteins and a small amount of chitin. The glucans form a rigid skeleton-like network that is filled with the mannoproteins. The mannoproteins maintain the porosity of the cell wall and shield it from external enzymatic attack (mannoprotein film on the external side of the cell wall). Figure2 shows detailed TEM images of a dead yeast cell. Replacement of the cytoplasm by limonene does not affect the structure of the cell wall to any extent. The cell membrane that separates the cytoplasm from the cell wall cannot be seen in the images. Thermal stability The thermal stability of the yeast (with and without limonene) was studied by TGA. The raw data is shown in Figure3 (blue curve: yeast loaded with limonene, red curve: empty yeast cells). The curves can be divided into five different regions that can be interpreted as follows:

Figure 1. TEM images of empty yeast cells (left) and yeast cells loaded with limonene (right).

Figure 2: TEM images of the cell wall of empty yeast cells (left) and yeast cells loaded with limonene (right). The scale bar is 200nm.

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Applications

Region I: 25 to 110 C. In this temperature region, both samples show a small mass loss. Karl Fischer titration showed that the loss of mass is due to the release of moisture (mainly from the cell walls). Region II: 110 to 245 C. The sample mass remains approximately constant. The cell walls are practically free of water, and only heating of the organic material occurs (yeast material with or without limonene). Region III: 245 to 263 C. The cells loaded with limonene show a large loss of mass due to the evaporation of limonene. The limonene is lost either

through forced diffusion of gaseous limonene through a porous cell wall, or through mechanical rupture of the cell wall due to increased internal pressure caused by the increasing temperature. Region IV: 263 to 293 C. Both samples show a relatively rapid mass loss in this region. This is interpreted as being due to cell wall rupture, which allows volatile compounds inherent to the yeast cells to escape. Range V: 293 to 400 C: The dry non-volatile constituents of the yeast cells undergo pyrolysis. The residue consists mainly of pure carbon.

Figure 4 shows the normalized TGA data. The data was normalized so that the weight of the dry material at 293 C was 100%. This presentation shows that both samples exhibit the same behavior from about 263 C onward and can therefore be assumed to be similar in nature from that point on. The difference between the two curves lies in the loss of limonene, which occurs between 246 and 263 C. Evaluation of the thermogravimetric measurements yields a limonene content of 26.7% w/w (see Figure 3), which is in good agreement with NMR results. DSC measurements DSC measurements were performed with pure limonene, empty yeast cells, and yeast cells loaded with limonene (limonene content: 26.7% w/w). The results are shown in Figure 5. Pure limonene boils at 202 C and is observed as the onset of the steep endothermic curve in the heat flow (green curve). The DSC curve of the empty yeast cells (red curve) shows an endothermic peak at 173 C. This peak is due to structural changes in the cell membrane. The cell membrane consists of phospholipids whose hydrophilic ends stick through the cell liquid or the cell wall in such a way that an ordered bilayer is formed (compare with Figure 6). This structure disintegrates at higher temperatures, leading to the peak at 173 C in the empty yeast cells. In the loaded yeast cells, the hydrophobic limonene lowers the stability of the bilayer. It therefore begins to disintegrate at a lower temperature, at about 131 C. Simultaneously with the mass loss from about 246 C onward, an endothermic peak is visible on the DSC curve for the yeast cells loaded with limonene (blue curve). This peak is missing in the measurement curve of the empty yeast cells. The exothermic process observed on the DSC curves of the empty or loaded yeast cells from about 263 C is due to the breakdown and combustion of the cell walls.

Figure 3: TGA curves of the yeast loaded with limonene (blue curve) and empty (red curve).

Figure 4. TGA curves normalized to the dry weight of yeast cells at 293 C. Red curve: empty yeast cells. Blue curve: yeast cells loaded with limonene.

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Conclusions
The thermal behavior of empty yeast cells and yeast cells loaded with limonene was studied by thermal analysis. The thermogravimetric data showed that the limonene did not vaporize and leave the yeast cells until temperatures above 246 C. This means that limonene would remain in the food products up until this temperature during cooking. With the aid of DSC measurements, structural changes in the yeast cells loaded with limonene were detected. The results are illustrated in Figure 6.

Figure 5. DSC curves of limonene (green), empty yeast cells (red) and yeast cells loaded with limonene (blue). The corresponding TGA curves are shown as dotted lines.

Literature

V. Normand, G. Dardelle, P-E. Bouquerand, L. Nicolas, D. Johnston; Flavour Encapsulation in Yeasts: Limonene Used as a Model System for Characterization of the Release Mechanism, J. Agric. Food Chem. 2005, 53, 75327543 Figure 6. Above: The hydrophobic limonene preferentially concentrates in the phospholipid bilayers of the cell membrane. Correspondingly, the disintegration of the bilayer in yeast cells loaded with limonene occurs at lower temperatures than with empty cells. Below: In loaded cells, disintegration of the cell membrane occurs at about 130 C, the limonene vaporizes and leaves the cell at about 246 C. Irrespective of whether the cells are loaded or empty, thermal decomposition begins from about 263 C onward.

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Determination of the oil content in elastomers by TGA

Applications

Ni Jing, Dr. Jrgen Schawe

The compositional analysis of elastomers is of major importance in quality control and product development. In this study, the oil content of an NR/SBR elastomer blend was determined using a TGA/SDTA851e system. The article investigates the extent to which the separation of the vaporization of the oil and the pyrolysis of the polymer can be improved by optimizing the heating rate and using vacuum. The results show that low heating rates improve the accuracy of the oil determination, but analysis times are of course longer. At reduced ambient pressure, however, the oil content can be determined both rapidly and with good accuracy.

overlap. Accurate determination of the oil content therefore requires measurement conditions which ensure that the oil vaporizes at lower temperatures. The vaporization of the oil from the elastomer involves both a phase transition and a time-dependent transport process. Preferential vaporization is promoted by increasing the surface/volume ratio of the sample by using a low sample mass, and by reducing the ambient pressure. Low heating rates can also prolong the time available for vaporization without the temperature rising to the level at which pyrolysis begins. In contrast, the decomposition temperature of a polymer is hardly influenced by the sample mass, heating rate, and pressure. It should therefore be possible to improve the separation of oil vaporization and polymer pyrolysis by optimizing these parameters and hence achieve a more accurate determination of the oil content. This is demonstrated below in the case of an an NR/SBR elastomer blend.

Introduction
An elastomer usually contains different polymer constituents as well as additives such as cross-linking agents, plasticizers, fillers, stabilizers, fire retardants, etc. The production process and physical properties of an elastomer depend mainly on the chemical composition of the elastomer.
Table 1. The composition of the NR/SBR elastomer blend in mass %.

The compositional analysis of elastomers is important both for manufacturers and purchasers of elastomers as well as for scientists engaged in research and development. The aim of such analyses is to assess the quality of the raw materials and the vulcanized products, to develop new formulations, and to optimize the different processing parameters during blending and vulcanization. The most important plasticizers used in elastomers are oils. They improve flow and processing behavior as well as the physical properties of the elastomers. The determination of the oil content in an elastomer is a difficult analytical task because the vaporization of the oil and the beginning of polymer pyrolysis often

NR SBR Vulcanization additives (e.g. sulfur) Oil Other plasticizers Carbon black Inorganic fillers

25.5% 7.2% 4.0% 9.1% 0.5% 4.3% 49.0%

Experimental details
The measurements were performed using a TGA/SDTA851e. The composition of the material investigated is given in Table 1. The samples were measured in 30-L aluminum oxide crucibles and the sample mass was approximately 20 mg. The change in mass of the sample was measured in the temperature range 50 C to 625 C at heating rates of 2, 10 and 30 K/min under nitrogen at normal pressure. A further sample was also measured at 10 K/min but at a pressure of 10 mbar (i.e. under partial vacuum). The measurements were performed under nitrogen because the determination of carbon black was not of interest in this study.

Figure 1. TGA and DTG curves of the NR/ SBR blend measured at 2, 10 and 30 K/min under nitrogen at normal pressure.

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Step 1a 1 2 3 Volatile compounds and water Oil NR pyrolysis SBR pyrolysis Residue in % Polymer + vulcanization additives

Step height in % 30 K/min 4.6 34.1 7.2 53.9 41.3 10 K/min 6.3 21.9 17.3 54.2 39.2 2 K/min 0.8 8.4 25.4 11.3 53.9 36.7

Formulation in % 0.5 9.1 25.5 7.2 53.3 36.7

Table 2. Results of the mass loss steps of the NR/SBR blend measured at 2, 10 and 30 K/min under nitrogen at normal pressure.

The influence of heating rate on the determination of oil content

The measurement curves of the sample recorded at heating rates of 2, 10 and 30 K/min at normal pressure are shown in Figure 1. Loss of mass occurs in three main steps. Step 1 corresponds to the loss of volatile components such as moisture and oil. At 2 K/min (the lowest rate), this step can be divided into two different regions of mass loss, namely loss of moisture up to about 170 C followed by vaporization of the oil up to 300 C. Steps 2 and 3 correspond to the pyrolysis of NR and SBR. The residue consists of inorganic additives and carbon black. The TGA curves were evaluated using the DTG curves. The results are summarized in Table 2. The measurement curves show that the effects involving loss of mass shift to lower temperatures at lower heating rates. This results in better separation of the individual processes. The improved separation of oil vaporization and pyrolysis leads to the value for the measured oil content changing from 4.6% (at 30 K/min) to 8.4% (at 2 K/min). The latter result is much closer to the true value of the formulation of 9.1%. The increased resolution at low heating rates also allows the individual polymer constituents to be more accurately determined.
Step 1a 1 2 3 Volatile compounds and water Oil NR pyrolysis SBR pyrolysis Residue in % Polymer + vulcanization additives

The total mass loss of the pyrolysis steps (2 and 3) agrees well with the sum of the polymer constituents (25.5% + 7.2%) and vulcanization additives (4%), that is, 36.7%.

The influence of pressure on the determination of oil content

The influence of pressure was investigated by measuring samples under nitrogen at 10 mbar and 1000 mbar at a heating rate of 10 K/min. The TGA and DTG curves are shown in Figure 2 and the results summarized in Table 3. The temperatures marked (M) are the midpoints of the step evaluation. The other temperatures are peak maximum temperatures of the DTG curves.

The DTG curves show that the oil vaporizes at lower temperatures in vacuum, but the pyrolysis temperature remains the same. The separation of the pyrolysis steps of the two polymer constituents is improved in vacuum because the gaseous decomposition products diffuse more rapidly out of the sample at reduced pressure. The oil content can also be accurately determined under vacuum at 10 K/min. The resolution of the measurement under vacuum at 10 K/min corresponds to that of the measurement at normal pressure at 2 K/min (see Table 2). The content of polymer constituents and vulcanization additives is 36.1%. The oil content
Figure 2. TGA and DTG curves of the NR/ SBR blend measured under nitrogen at 10 mbar and 1000 mbar at 10 K/min.

1000 mbar Temperature Step height (M) 264.2 C 371.6 C (M) 425.1 C 6.3% 21.9% 17.3% 54.2% 39.2%

10 mbar Temperature Step height (M) 130.8 C 246.1 C 370.4 C (M) 431.8 C 0.6% 9.2% 26.9% 9.2% 54.3% 36.1%

Formulation 0.5% 9.1% 25.5% 7.2% 53.3% 36.7%

Table 3. Results of the mass loss steps of the NR/SBR blend measured under nitrogen at 10 mbar and 1000 mbar at 10 K/min.

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measured under vacuum is much closer to the true value than the value obtained at normal pressure.

low heating rates and/or under reduced pressure (vacuum). Low heating rates improve the separation of different processes, in particular the separation of the vaporization of the oil and the pyrolysis of the polymer constituents. Measurement times are however significantly longer.

Applications

Conclusions
The oil content of elastomers can be determined by TGA. The best accuracy is achieved by performing measurements at

Measurements under reduced pressure shorten the measurement time and allow the content of plasticizer (oil) and polymer constituents in elastomers to be accurately determined. The separation of the residue into carbon black and ash requires measurements in an oxidizing atmosphere.

Determination of calcium sulfate dihydrate and hemihydrate in cement

Dr. Markus Schubnell

Introduction
Cement consists primarily of calcium silicates, calcium aluminates, and calcium aluminoferrites. Besides these main constituents, various additives are used in small quantities. One important additive is gypsum in the form of the dihydrate (CaSO42H20) or the hemihydrate (CaSO4H20). The gypsum is ground with the clinker and serves to retard the setting and hardening of the cement. Without gypsum, hydrated calcium aluminate crystallizes within about 10min; gypsum retards this process by several hours or even days depending on the gypsum content. In the quality control of cement, it is therefore important to know the exact content of the CaSO4 dihydrate or hemihydrate.

difficulty is that both reactions occur close together in the same temperature range and, depending on the conditions, overlap. This makes quantification of the two types of gypsum difficult or even impossible. To achieve a separation of the two types of gypsum, a sample must be heated in an almost completely sealed crucible. This shifts the dehydration of the hemihydrate to higher temperatures thereby improving the separation of the two processes. The gypsum content in cement is usually in the percent range. From stoichiometric considerations, dehydration of the dihydrate is expected to give a total mass loss of 20.9%, made up of steps of 15.7% (dihydrate hemihydrate) and 5.2% (hemihydrate anhydrous form, based on the mass of the dihydrate). The dehydration of the hemihydrate is expected to give a mass loss of 6.2%. Assuming, for example, a hemihydrate content of 1% in cement, dehydration of the hemihydrate in 1mg of cement gives rise to a mass loss of 0.61g. For this reason, the samples analyzed must be as large as possible. Since only aluminum

crucibles can be sealed, the experiments were performed using 100-L aluminum crucibles sealed with a lid with a 50-m hole. Samples of pure calcium sulfate dihydrate, calcium sulfate hemihydrate and a mixture of the two were first analyzed. This was followed by three cement samples with known dihydrate and hemihydrate contents.

Results
Figure 1 displays the measurement results of the pure samples and their mixtures. The results show that both the dihydrate and the hemihydrate samples already contained small amounts of the anhydrous form. Based on stoichiometry, the purities of the two hydrates were 93.1% (hemihydrate) and 94.5% (dihydrate). With these purities, a mass loss of 12.8% is expected for the mixture. This value agrees well with the measured value of 12.7%. Figure2 shows the measurements performed on the three cement samples containing different contents of the dihydrate and hemihydrate.

Experimental details
Thermogravimetry is good analytical method for determining the gypsum content. The dihydrate and the hemihydrate lose their water of crystallization on heating. In the case of the dihydrate, the elimination takes place in two steps (via the hemihydrate), and with the hemihydrate in just one step. The experimental

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The two mass loss steps that occur during the dehydration can be clearly seen. In contrast to the TGA curves of the pure calcium sulfate hydrates, a continuous loss of mass is observed in both cement samples over the whole temperature range measured. This is overlaid by the two mass loss steps of the dehydration. For this reason, the mass loss steps of the dehydration were determined using the tangential step evaluation program. Alternatively, the peaks from the first derivative of the mass loss curves could also be evaluated. The hydrate contents are calculated from the mass losses, 1 and 2, according to the equations:

Figure 1. Thermogravimetric analysis of calcium sulfate dihydrate (DH), calcium sulfate hemihydrate (HH) and a mixture of the two.

The coefficients in these two expressions come from the stoichiometry of the dehydration. The results obtained for the contents of the two hydrates in the three samples are summarized in Table 1 (dihydrate content) and Table 2 (hemihydrate content).

Figure 2. Thermogravimetric measurements of three cement samples containing different contents of calcium sulfate dihydrate and calcium sulfate hemihydrate.

Conclusions
The contents of calcium sulfate dihydrate and calcium sulfate hemihydrate can be determined in cement with good accuracy by thermogravimetry. A quantitative determination is only possible if the samples are measured in an almost hermetically sealed crucible. This is most easily done using aluminum crucibles sealed with a lid with a 50-m hole. If a pierced lid is not available, the same effect can be achieved by placing a grain of sand (about 20 m in diameter) on the rim of the crucible before sealing it.

Sample Sample 1 Sample 2 Sample 3 Sample Sample 1 Sample 2 Sample 3

Measured 0.48% 1.45% 2.03% Measured 2.42% 1.34% 0.99%

Formulation 0.5% 1.5% 2.0% Formulation 2.5% 1.5% 1.0%

Table 1. Dihydrate contents of the three samples.

Table 2. Hemihydrate contents of the three samples.

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Determination of oxidation stability by pressuredependent OIT measurements

Applications

Dr. Jrgen Schawe

The pressure dependence of the oxidation induction time (OIT) of different materials is measured. The results show that the OIT obeys a power law in pressure and that the exponent provides additional information on the stability, tendency to oxidize, and previous damage. The prediction assumes that the oxidation reaction develops from reaction nuclei and then spreads out across the entire sample. This process was confirmed by high-resolution chemiluminescence measurements.

Experimental details
The measurements described in this study on the pressure dependence of OIT were performed using the new high pressure DSC (HP DSC827e). The oxygen pressure and gas flow were set using a pressure and flow regulator. The gas flow was 40 mL/min and the oxygen pressure set to different values in the range 0.1 MPa to 10 MPa (1 to 100 bar). Since gas switching in pressure measurements is not always so easy, the oxygen pressure was set at room temperature and the sample heated rapidly at 50 K/min to the reaction temperature. The chemiluminescence measurements were performed in an HP DSC827e using a CCD camera and the relevant accessories (see UserCom 20).

Introduction
The determination of the oxidation induction time (OIT) is a method frequently used to estimate the oxidation stability of materials. This is done by first heating the sample to a sufficiently high temperature under inert conditions (purging the DSC cell with nitrogen). After a brief thermal equilibration time, the purge gas is switched from nitrogen to oxygen. If the temperature has been chosen correctly there is no immediate change in the DSC signal. However, after a certain induction time, the exothermic oxidation reaction begins. The OIT is the time at which the onset of the oxidation reaction occurs measured from the point when the gas is switched from nitrogen to oxygen.
Figure 1. OIT measurements performed in a conventional DSC at atmospheric pressure. The material originated from a piece of PE tubing. The reaction temperature is 210 C. The stressed (i.e. damaged) sample material originated from the inside of the tubing, the unstressed sample from the outside.

The OIT depends very much on the current chemical state of a material. For example, chemical aging causes a significant decrease in the measured OIT. An example of this is shown in Figure 1. This shows OIT measurements performed at 210 C on polyethylene (PE) tubing that had been used to transport aqueous solutions of chemicals. Two samples, one from the outside and the other from the inside were measured. The inside of the tubing had of course been in direct contact with the solutions. The OIT of the material from the outside of the tubing is significantly longer than that from the inside. The OIT therefore provides information on the extent of damage of materials.

Pressure dependence of OIT

Experimental results If the OIT is measured at constant reaction temperature but at different oxygen pressures, one sees that the OIT decreases with increasing pressure. This is illustrated in Figure 2 using mineral oil as an example. At an oxygen pressure of 0.5 MPa, the OIT is more than 120 min. In contrast, at 6.8 MPa the OIT is less than 40 min. Besides shorter measurement times, the measurement reproducibility also improves at higher pressure. Figure 3a shows the pressure dependence of the OIT of two different mineral oils, A and B at a reaction temperature of 195 C. The OIT of both oils decreases with increasing pressure, whereby the OIT values of oil B are always greater than those of oil A. In Figure 3b, the values have been plotted in a double logarithmic presentation in order to analyze the relationship between OIT and oxygen pressure more easily.

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In this presentation, the measured points lie on straight lines. It follows that the relationship between OIT (tOIT) and the oxygen pressure (p) can be described by a power law:

Figure 2. OIT measurements of samples of a mineral oil (A) at different oxygen pressures. The reaction temperature is 195 C.

Taking logarithms of both sides of the equation shows the linear relationship in the double logarithmic presentation:

The factor A is a measure of the rate of the oxidation reaction and the exponent q is the slope. The q values obtained for the two oils are 0.62 (oil B) and 0.45 (oil A). The general validity of the potential law and the meaning of the exponent q must first be considered before the results can be assessed in more depth. This was done by performing OIT measurements on a number of different polymers. Some of the results obtained are shown in Figure 4. Different reaction temperatures were chosen for each polymer so that the OIT values were all in a convenient time frame (between 20 and 300 min). This facilitated the analysis of the pressure dependence of OIT for the materials tested. The diagram shows that in double logarithmic presentation the relationship is linear for all the polymers investigated. The exponent q here lies between 0.6 (linear low-density polyethylene, LLDPE), and 0.3 (polypropylene, PP). Interpretation of the results In this section, possible reasons for the power law given in eq (1) will be considered without going into a detailed discussion about the reaction kinetics. First, we assume that the presence of oxygen is necessary for the oxidation reaction. The oxygen enters into the sample through diffusion from the atmosphere. This process depends on the difference in concentration, the size and the nature of the surface of the sample and the temperature-dependent diffusion constants. At the same time, the effective oxygen concentration is reduced through reaction of
Figures 3a (left) and 3b (right). Linear plot of the OIT of two synthetic motor oils as a function of oxygen pressure at 195 C (left). Double logarithmic plot (right); the slope of the straight lines is q.

the oxygen with stabilizers or the sample. Diffusion (production) and reactions (consumption) are competing processes that determine the oxygen concentration. A relationship can therefore be derived for the relative oxygen concentration in the sample as a function of time. Similar

to the situation in crystallization, it can be concluded that the oxidation reaction begins on nucleation points such as surface damage (e.g. microfissures) or inhomogeneities (internal stresses or concentration differences of inhibitors) and then spreads from these reaction nuclei
Figure 4. Dependence of the OIT on oxygen pressure for different polymers. The reaction temperature is given in the diagram. The slope q corresponds to the exponent in eq. (1).

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Applications

into all parts of the sample. If, in addition, the pressure dependence of the gas concentration in the sample is taken into account, the power law eq (1) for the OIT can be derived from kinetic considerations. The exponent, q, depends to a large extent on the mechanism for the formation of nuclei for the oxidation reaction. To confirm the assumption that the oxidation reaction spreads out from nuclei requires a method that can measure the reaction locally at high resolution. Chemiluminescence is an excellent technique for doing this. During the oxidation reaction, excited molecules are formed that emit light of low intensity when they return to the ground state. The

light emission can be measured using the DSC-Chemiluminescence System. This consists of the HP DSC827e equipped with the chemiluminescence accessory and a high-sensitivity CCD camera. In this case, the system enabled both intensity curves of the emitted light and sequences of emission images to be recorded. Figure 5 shows the intensity curve and emission images at different times for polypropylene (PP) at 130 C. Evaluation of the intensity curve yields an OIT value of 230 min. In the emission image at 205 min, a region can be seen at the lower edge of the sample where light emission begins. This is the initial oxidation reaction. In the image at 285 min,

three main regions of the reaction are apparent. The regions are highlighted by arrows in the box. With increasing reaction time, the regions spread until finally the entire sample emits light. This result proves that the reaction spreads from localized nuclei. The sample under investigation was a thin film. The orientation of the nuclei indicates that they originated as a result of the film production process. The chemiluminescence measurements therefore confirm the assumptions leading to the power law, eq (1). Assessment of experimental results In the previous section, it was shown that the pressure dependence of the OIT can be traced back to nucleation processes in the oxidation reaction, and that the nucleation is a result of local inhomogeneities in the sample and diffusion. These considerations lead to the power law tOIT = A p q, where q is the slope in a double logarithmic plot (log tOIT versus log p) is. Theoretically, the slope must lie between 0 and 1. If the slope, q, equals 1, the OIT is proportional to the oxygen pressure. This means that the variation of OIT with pressure depends only on the oxygen concentration in the sample. If the slope, q, equals 0, the oxygen concentration is of no importance. In this case, the sample is damaged to such an extent that hardly external oxygen is necessary for the oxidation. In a material like this, many radicals are present. From kinetic considerations at the beginning of the oxidative decomposition and taking into account the oxygen diffusion and nucleation of the reaction, q values between 0.75 and 0.2 are to be expected. This is shown schematically with the relevant slopes in Figure 6. A large value of the slope means a high degree of inherent oxidation stability, which can be reduced through mechanical or chemical stress. A material with a smaller q value thus contains a higher concentration of radicals. In the example in Figure 4, LLDPE was the most stable. The PP samples had been stored for several years and were more

Figure 5. Results of a chemiluminescence measurement of PP at 130 C.

Figure 6. Schematic diagram of the possible slopes in double logarithmic presentation (log t OIT versus log p) with the corresponding exponents from eq (1). The practically relevant region for q lies between 0.75 and 0.2.

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prone to oxidative stress. For comparison purposes, Figure4 also includes a sample of LLDPE stabilized with an antioxidant. The antioxidant hardly has any effect on the slope, q. The reaction rate is lowered, but the inherent tendency to oxidation remains almost unchanged.

Conclusions
The pressure dependence of OIT obeys a power law. The exponent q is mainly influenced through oxygen diffusion processes and radical formation in the material under test. Materials with small exponents tend to oxidize more read-

ily than those with large exponents. The power law dependence of OIT on pressure presupposes a nucleation process before the reaction. This means that the oxidation does not begin throughout the entire sample, but just in a few isolated regions in the sample where conditions are favorable for diffusion (e.g. microfissures) or where there is a greater concentration of radicals. This nucleation mechanism in the oxidation reaction can be measured by chemiluminescence. The pressure dependence of OIT provides additional information on the stability,

previous damage, and inherent tendency for oxidation of materials. It is important to remember when performing OIT measurements that the geometry of samples plays an important role because of its influence on diffusion processes. For this reason, it is best to use very thin samples with defined surface areas. The author would like to thank his colleagues Dr. R. Riesen, M. Zappa and DrM. Schubnell for valuable help and discussions.

Thermochromism of HgI2
Dr. Markus Schubnell

Introduction
Thermochromism is the term used to describe a reversible change in the color of a substance as its temperature is varied. It is a property often encountered in both inorganic and organic compounds. The phenomenon has to do with temperature-dependent structural phase transitions in the substance whereby the orbitals of electrons that absorb light in the visible wavelength region of the spectrum are deformed. This causes the absorption and reflection properties of a substance (and hence its color) to change. Most inorganic compounds of the light elements up to calcium are white. The reason for this is that atomic distances are short and the wavelength range in which absorption of light takes place (and hence colors occur) is in the ultraviolet region. This region is of course not accessible to the human eye. Colored compounds are therefore not encountered until they contain elements

in which the d-orbitals are increasingly occupied; for example ZnS is white, CdS yellow and HgS black. Thermochromic compounds are often used as optical temperature indicators where the colors distinguish between different temperature ranges.

Experimental details
DSC is an excellent method for detecting phase transitions resulting from structural changes in a substance. To observe color changes occurring at the same time, the sample is viewed and
Figure 1. Schematic diagram of the HP DSC827e with the accessory for reflected light microscopy. The sample has to be illuminated with an external light source so that it can be measured with the CCD camera.

Color CCD camera Zoom lenses

Quartz windows 40 l crucibles Sensor Furnace

(sample / reference)

Light guide and external lightsource

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Applications

recorded with a suitable camera and software. This is now very easy to do with the HP DSC827 e: a microscope objective is mounted on a special quartz glass cover and the sample monitored with a CCD camera. The setup is shown schematically in Figure 1. The experiments described in this article were performed with a JVC (KY-F55B) color CCD camera and the Soft Imaging Systems GmbH GrabIt frame capture card. AnalySIS software (also from Soft Imaging Systems GmbH) was used for image capture and analysis.

Results
It is well known that mercury(II) iodide can exist in two different crystalline forms. The change in structure that occurs when the substance is heated is accompanied by a color change from red to yellow. Figure 2 shows images of the sample taken at four different temperatures during a DSC heating run. The powdered sample (22.325 mg) was evenly distributed in a 40-L aluminum crucible. The images show behavior typical for solid-solid transitions of powders: each crystalline particle undergoes the phase transition individually on heating and on cooling. The structural change associated with the change in color gives rise to an endothermic peak in the DSC curve (Figure 3). The curve also shows that the transition is apparently accompanied by a change in specific heat capacity. The fact that

the baseline shows a marked downward tendency after the phase transition indicates that the sample sublimes. Residues of condensed material were in fact found on the furnace lid and on the quartz glass window after the experiment. Evaluation of the curve in Figure 3 gives an onset temperature of about 140 C for the phase transition. The color change can also be quantitatively evaluated from the mean image intensity, which corresponds to the mean value of the red, blue, and yellow color channels. The mean image intensity should be approximately proportional to the partial areas of the phase transition peak (i.e. proportional to the conversion of the phase transition peak). This comparison is made in Figure 4 and shows that the two curves are in excellent agreement.

Figure 2. Images of the HgI2 sample at 139 C, 142 C, 146 C and 148 C. The numerous bright spots are due to light reflected directly from individual crystals into the camera.

Conclusions
A simple microscope accessory allows the appearance of a sample to be observed and recorded while it is measured in an HP DSC827e . The technique measures the calorimetric behavior of the sample (DSC) and at the same time provides information on changes in color, shrinkage behavior, and flow or crystallization processes. This is extremely helpful for the reliable interpretation of a DSC curve. Measurements of HgI 2 as an example showed that a solid-solid transition occurs at about 140 C with an accompanying change in color from red to yellow. These and other measurements (not described here) showed that the individual crystals undergo this transition both on heating and on cooling.

Figure 3. DSC curve of the phase transition of mercury(II) iodide and the corresponding conversion curve.

Figure 4. Comparison of the light intensity (mean value of the image intensity of the red, blue and yellow color channels) with DSC conversion (the partial areas of the phase transition peak).

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Exhibitions, Conferences and Seminars Veranstaltungen, Konferenzen und Seminare Swissplastics January 1517, 2008 Lucerne, Switzerland LABORAMA Exhibition http://www.laborama.be/ March 1314, 2008 Brussels Kart Expo, Belgium 2008 Korean Society of Thermophysical Properties April 2425, 2008 Busan, Korea HET Instrument May 2024, 2008 Utrecht, Netherlands SLAP08 (Congreso Iberoamericano de Polmeros) July 1518, 2008 Lima, Peru

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TAKundenkurse und Seminare in Deutschland und der Schweiz Nhere Informationen unter www.mt.com/labtalk oder durch: Frau Petra Fehl, Mettler-Toledo GmbH, Giessen, Tel: ++49 641 507 404, e-mail: labtalk@mt.com Weiterbildungsseminar Thermische Analyse und Info at www.mt.com/labtalk Rheologie in Forschung u. QS (kostenfrei) Anwenderworkshop DSC (kostenpflichtig) 29./30.01.2008 Giessen 04./05.03.2008 Giessen Anwenderworkshop TGA (kostenpflichtig) Informationstag Thermische Analyse Excellence 05.02.2008 Hamburg (kostenfrei) 12.02.2008 Berlin 18.03.2008 Dsseldorf Weiterbildungsseminar Thermische Analyse und 11.03.2008 Potsdam Rheologie in Forschung u. QS (kostenfrei) 13.03.2008 Dsseldorf Greifensee und Lausanne

16./17.09.2008 Giessen 06./07.03.2008 Giessen 28.05.2008 Frankfurt 03.06.2008 Hannover 05.06.2008 Leipzig 17.06.2008 Ulm 16.09.2008 Karlsruhe

Corsi e Seminari di Analisi Termica in Italia

Per ulteriori informazioni Vi preghiamo di contattare: Simona Ferrari, Mettler-Toledo S.p.A., Novate Milanese, Tel: ++39 02 333 321, Fax: ++39 02 356 2973, e-mail: simona.ferrari@mt.com DSC base DSC avanzato TGA TMA 5 Febbraio 2008 6 Febbraio 2008 7 Febbraio 2008 8 Febbraio 2008 10 Giugno 2008 11 Giugno 2008 12 Giugno 2008 13 Giugno 2008 23 Settembre 2008 24 Settembre 2008 25 Settembre 2008 26 Settembre 2008 Novate Milanese Novate Milanese Novate Milanese Novate Milanese

Seminari: Analisi Termica applicazioni ed interpretazione dei tracciati Le tecniche termoanalitiche sono sempre pi utilizzate per il controllo qualit e la ricerca di nuovi materiali. Verranno presentate le principali applicazioni di tali tecniche e forniti dei validi consigli per una corretta interpretazione dei risultati. 5 Marzo 2008 Milano 12 Marzo 2008 Venezia 1 Aprile 2008 Roma 3 Aprile 2008 Pescara

METTLERTOLEDO

UserCom 2/2007

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Cours et sminaires dAnalyse Thermique en France

Renseignements et inscriptions par: Christine Fauvarque, Mettler-Toledo S.A., 18-20 Av. de la ppinire, 78222 Viroflay Cedex, Tl: ++33 1 3097 1439, Fax: ++33 1 3097 1660, e-mail: christine.fauvarque@mt.com Principe de la TMA/DMA DSC: notions de base DSC: perfectionnement Principe de la TGA Logiciel STARe: perfectionnement 6 octobre 2008 7 octobre 2008 8 octobre 2008 9 octobre 2008 10 octobre 2008 Viroflay (France) Viroflay (France) Viroflay (France) Viroflay (France) Viroflay (France)

TA School and Seminars in Korea

For details of training courses and seminars, please contact: KiHun Lee at Mettler-Toledo Korea, Tel: ++82 2 3498 3500, e-mail: kihun.lee@mt.com, Homepage: www.kr.mt.com Basic TA School in 1Q 2008 Basic TA School in 2Q 2008 Advance TA School in 3Q 2008 Basic TA School in 4Q 2008 TA Public Seminar March 2008 May 2008 August 2008 October 2008 November 2008 Seoul Kyung-Ki Seoul Dae-Jeon Seoul

TA Customer Courses and Seminars in China

For details of training courses and seminars, please contact: Lu LiMing at Mettler-Toledo Instruments (Shanghai) Co., Ltd., Tel: ++86 21 6485 0435, Fax: ++86 21 6485 3351, e-mail: liming.lu@mt.com TA User Training Course in 2008 TA User Training Course in 2008 TA User Training Course in 2008 TA User Training Course in 2008 TA Public Seminar in 1st half 2008 March 2008 June 2008 September 2008 December 2008 MarchJune 2008 Shanghai and Beijing Shanghai and Beijing Shanghai and Beijing Shanghai and Beijing Different cities

For further information regarding meetings, products or applications, please contact your local METTLER TOLEDO representative and visit our home page at http://www.mt.com

Editorial team

Dr. A. Hammer Chemist

Ni Jing Chemist

Dr. D. P. May Chemist

Dr. R. Riesen Chem. Engineer

Dr. J. Schawe Physicist

Dr. K. H. Hassdenteufel Material Scientist

Dr. M. Schubnell Dr. M. Wagner Physicist Chemist

J. Widmann Chemist

M. Zappa U. Jrimann Material Scientist Electr. Engineer

Mettler-Toledo AG, Analytical Postfach, CH-8603 Schwerzenbach Phone ++41 44 806 73 87 Fax ++41 44 806 72 60 Contact: urs.joerimann@mt.com

www.mt.com/ta
For more information

11/2007 Mettler-Toledo AG ME-51724613, Printed in Switzerland MarCom Analytical