temperature modulated differential scanning calorimetry (tm dsc) at high temperatures by netzsch

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Temperature-Modulated Differential ScanningCalorimetry (TM-DSC) at High-Temperatures byNetzsch

Topics Covered

Introduction

Theoretical Background of TM-DSC

Dynamic Measuring Modes

What Kind of Signals Can Be Separated?

Examples

Steel

Isothermal cp Determination

Conclusion

Introduction

Temperature modulated DSC, abbreviated TM-DSC, is an extension of the conventional DSC technique. It was introduced by

Reading et al. in the early 1990s when they went public with a software modification allowing the superimposition of a sinusoidal

temperature fluctuation onto an underlying heating or cooling rate. Since then, use of the method has become widespread, especially

in the low-temperature field in the areas of polymers and pharmaceuticals.

With the launch of the new 400 series instruments in 2008, NETZSCHhas expanded the application range of this technique to higher

temperatures for the first time. This allows TM-DSCto now also be applied to inorganic materials like metals, alloys, minerals or

glasses.

Theoretical Background of TM-DSC

The benefit of the method is the separation of complex overlapped effects. In order to realize this, the heating rate used is not

constant but superimposed by a sinusoidal wave.

T(t) = T0 + HR.t + A.sin(? t) --> dT/dt=HR+A ? cos(? t)

where:

T0: starting temperature

HR: underlying heating rate

? : angular frequency

t: period

A: amplitude

Temperature-Modulated Differential Scanning Calorimetry (TM-DSC) at High-Temperatures by Netzsch

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Therefore, it should be possible to easily separate glass transitions from relaxation or re-crystallization effects (as can be seen in Fig.

2 and 3). Melting processes, however, as well as fast chemical reactions, are visible in both the reversing and non-reversing DSC

signals. In this context, the experimental parameters have a decisive impact on the test result. For specific parameter sets, it may be

feasible to achieve a good separation between, for example, melting and the decomposition process; for other sets it may not.

Figure 3.Measurement curve of fig. 2 split into the reversing and the non-reversing signal. The glass transition is clearly visible in the

reversing signal (green curve); the non-reversing signal (red curve) shows the relaxation as well as two crystallization effects. The

blue curve is the total heat flow curve, equivalent with the curve of a conventional DSC instrument.

The reversing (or alternating) heat flow is heat capacity-dependent and represents the thermodynamic component. The non-

reversing (or non-alternating) heat flow represents the kinetic component.

Examples

The following test runs (1) and (2) were carried out with an STA 449 F1Jupitersystem equipped with a steel furnace, a type S

sample carrier and Pt/Rh crucibles with lids. The corresponding modulation was performed by using liquid nitrogen cooling in the

manual mode (35% basic power).

SteelAccording to the iron-carbon phase diagram, the alpha-beta transition of iron will take place at around 700C to 800C, mainly

depending on the carbon content of the sample. In the same temperature range, the Curie transition from the ferromagnetic to the

paramagnetic state of iron occurs, sometimes leading to an overlapping of the two effects (see Fig. 4).



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Figure 4.STA measurement on steel (heating rate: 5 K/min)

The result of the corresponding TM-DSCexperiment can be seen in Fig. 5. The magnetic change as a second-order transition

appears in the reversing part (black dashed curve), whereas the structural change becomes evident in the non-reversing part (red

dashed curve), with an extrapolated onset temperature of 756C.

Figure 5.TM-DSC measurement on steel (heating rate: 5 K/min, period: 60 s, amplitude: 0.5 K) blue: total heat flow, red: non-

reversing curve, black: reversing curve

Isothermal cp Determination

At the moment, the ASTM International Technical Committee is working on a new standard (ASTM E 37; 3rd draft was published in

August 2008) for determining specific heat capacity by sinusoidal modulated temperature differential scanning calorimetry. The

operating range of tests is defined to be between -100C and 600C.

In order to find out if this method can also be applied to higher temperatures, a measurement on sapphire was performed with

isothermal steps (30 minutes each) at 600C, 700C, 800C and 900C (see Fig. 6).



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Figure 6.TM-DSC measurement on sapphire (heating rate: 5 K/min, period: 60 s, amplitude: 0.5 K) blue: sapphire as sample, red:

sapphire as standard

The evaluation procedure for such tests is already included in the NETZSCH Proteus software. The calculated results are depicted in

Fig. 7 together with the theoretical cp curve for sapphire, already stored in the software.

Figure 7.Specific heat determination on sapphire - comparison between experimental (colored symbols) and theoretical data (violet

curve)

The difference between the experimental and the nominal values is within the given temperature range less than 2% and therefore in

the same range of accuracy what can be achieved with the DSC 404or STA 449 systemsby using the dynamic ratio method or the

method according to ASTM E 1269.

Conclusion

TM-DSCas a method does indeed meet its requirement of being able to separate superimposed effects in various cases. Glass

transitions can be separated well from decomposition, relaxation, evaporation, or cold-crystallization processes. Additionally, it is a

suitable tool for determining cp in the quasi-isothermal mode within tight tolerances. But if melting is involved, the choice of the

modulation parameters has to be taken into consideration. Under certain circumstances, these can have a decisive influence on the

measurement results for the reversing and non-reversing part.

Source: Temperature-Modulated Differential Scanning Calorimetry (TM-DSC) in the High-Temperature Range

Author: Gabriele Kaiser

For more information on this source visit NETZSCH-Gertebau GmbH.

Date Added: Nov 3, 2009 | Updated: Jun 11, 2013



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NETZSCH-Gertebau GmbH

Wittelsbacherstrasse 42Selb95100GermanyPH: 49 (9287) 881-0Fax: 49 (9287) 881-505Email: [email protected] NETZSCH-Gertebau GmbHWebsite

Primary Activity

Analyzing and testing equipment

Company Background

The NETZSCH Group is a mid-sized, family-owned German company engaging in the manufacture of machinery and instrumentation

with worldwide production, sales, and service branches.

The three Business Units Analyzing & Testing, Grinding & Dispersing and Pumps & Systems provide tailored solutions for

highest-level needs. Over 3,000 employees at 163 sales and production centers in 28 countries across the globe guarantee that

expert service is never far from our customers.

When it comes to Thermal Analysis, Calorimetry (adiabatic & reaction) and the determination of Thermophysical Properties,

NETZSCH has it covered. Our 50 years of applications experience, broad state-of-the-art product line and comprehensive service

offerings ensure that our solutions will not only meet your every requirement but also exceed your every expectation.

Make your choice from among our diverse variety of instruments for Thermal Analysis, Calorimetry (adiabatic & reaction) and the

determination of Thermophysical Properties. NETZSCH Analyzing & Testing has consistently invested its long-time experience into

innovative new developments and advanced technologies conceived for state-of-the-art application tasks in materials research and

development, quality assurance and process optimization.

Our products and services embody technological leadership, expertise, and reliable quality for the users benefit.

Differential Scanning Calorimetry / Differential Thermal Analysis (DSC /

DTA)

DSC and DTA quantitatively determine conversion temperatures and

enthalpies for solids and liquids by measuring the heat flows to both the sample

and to a reference as a function of temperature and time.

more information

Thermogravimetric Analysis / Thermogravimetry (TGA, TG)

Thermogravimetric Analysis/Thermogravimetry (TGA, TG) determines the

temperature- and time-dependent changes in the mass of a sample that occur

during a specific temperature program and in a defined atmosphere. The

respective instrument is called a thermobalance.

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Simultaneous Thermogravimetry - Differential Scanning Calorimetry STA

(TG-DSC)

STA denotes the concurrent application of two or more measuring methods to

the same sample. The classic simultaneous method is the combination of

thermogravimetry with DSC or DTA.

more information

Dilatometry / Thermomechanical Analysis (DIL / TMA / GST)

For precise measurements of dimensional changes on solids, dilatometry (DIL)

is the method of choice. With thermomechanical analysis (TMA), the loading

can additionally be adjusted.

more information

Dynamic-Mechanical Analysis / Dynamic Mechanical Thermal Analysis

(DMA / DMTA)

Dynamic-Mechanical Analysis (DMA) / Dynamic Mechanical Thermal Analysis

(DMTA) measures visco-elastic properties by applying an oscillating force to

the sample.

more information

Adiabatic Reaction Calorimetry

Adiabatic calorimeters that help industry operate safely and profitably. As

highly versatile, miniature chemical reactors, they measure thermal and

pressure properties of exothermic chemical reactions. The resulting information

helps engineers and scientists identify potential hazards and address key

elements of process safety design including emergency relief systems, effluent

handling, process optimization, and thermal stability.

more information

Dielectric Analysis (DEA)

Dielectric Analysis (DEA) measures changes in dipole orientation and ion

mobility in polymers and cross-linked systems by stimulation with an alternating

voltage via sensor electrodes. The DEA method can also be used for online-

processes (e.g. cure monitoring) with a suitable sensor technique.

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Thermal Diffusivity / Thermal Conductivity (LFA / GHP / HFM / TCT)

The Laser Flash Method (LFA) is a well established technique for the

determination of thermal diffusivity, in which the increase in the samples

temperature resulting from the absorption from a laser flash is measured. With

HFM (Heat Flow Meter), GHPand TCT (Thermal Conductivity Tester), thethermal conductivity of insulating materials and refractories can be determined.

more information

Refractory Testing (RUL/CIC, HMOR, PCE, TCT)

Refractoriness under load (RUL) and creep in compression (CIC) describe thedeformation resistance of a sample body under loading as a function of

temperature and time. The bending strength (HMOR Hot Modulus of

Rupture) is determined with a hot bending strength tester. The melting behavior

is described by the pyrometric cone equivalent (PCE).

more information

Gas Analysis / Couplings (QMS, FTIR, SKIMMER)

Mass- and Infrared spectrometry serve to detect and identify volatile emissions

from a sample during a temperature treatment. We offer perfect solutions for

coupling of QMS and FTIR with our thermal analyzers.

more information

Software

The Proteus software package integrates all functionalities for carrying out

measurements on any NETZSCH instrument with comprehensive routines for

the evaluation of measuring data and import of external data.

Additionally, we deliver unique Advanced Software solutions, such as

Thermokinetics.

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Thermomechanical Analysis (TMA)

For highly precise measurement of dimension changes to solids, melts,

powders and pastes at a programmed temperature change and with negligible

sample strain, Thermo-Mechanical Analysis (TMA) is the method of choice.

The measurement of the dimensional changes can additionally be carried out

with adjustable sample strain.

more information

Multiple Mode Calorimetry (MMC)

Like a DSC, the Multi Modul Calorimeter (MMC) measures chemical reactions,

phase changes, and specific heat but on gram-size samples. The NETZSCH

development team has created a totally new calorimeter system which can be

used in commercial R&D, universities and research centers and QC/QA of

various industries.

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temperature modulated differential scanning calorimetry (tm dsc) at high temperatures by netzsch

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