DSC 214 Polyma – Differential Scanning Calorimeter (-170°C to 600°C)

8/12/2019 DSC 214 Polyma Differential Scanning Calorimeter (-170C to 600C)

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Analyzing & Testing

DSC 214 PolymaSurprisingly Easy The New All-Inclusive Product Package for DSC


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High PerformanceDSC 214 Polyma

Powerful sensor-furnace combi-nation for fast heating/cooling

Outstanding sensitivity andexcellent reproducibility

Easy SamplePreparation

Clever and unique SampleCutter ,especially for brittle materials Comprehensive samplepreparation set

UniqueConcavus Pans

High-performance pans forexcellent reproducibility 3in1 Box for organizedstorage

Polyma More Than a DSC

Working with DSC (DifferentialScanning Calorimetry) involves notonly the handling of a device, but alsosample preparation, evaluation andinterpretation of the resulting curves.The NETZSCH 360 view for polymer

characterization takes this intoaccount, streamlining operationalprocesses while simultaneouslysimplifying them.

The new DSC 214 Polyma is a key partof this concept. It provides everythinga user needs in polymer analysis.

A Smart System for Polymers

Thermal Characteristics Which CanTypically Be Detected by Using DSC

Melting temperatures andenthalpies (heats of fusion)

Crystallization temperatures andenthalpies

Glass transition temperatures Oxidative-induction time (OIT) and

oxidative onset temperature (OOT) Degree of crystallinity Reaction temperatures and

enthalpies Cross-linking reactions (curing) Degree of curing Specific heat capacity Distribution of molecular weight

(peak shape), etc.


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SmartMeasurement

Simplied user interface

Automated measurement

AutoCalibration

AutoEvaluation

Automatic analyses ofunknown DSC curves User-independent analysis

InnovativeIdentification

Data-based testinterpretation Open for users'own data


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Corona SensorThis fast-responding sensor isunmatched in both reproducibil-ity and robustness.

Concavus Pans The unique geometry of this

sample pan features a concavebottom. In combination with aat sensor, it provides a ring-shaped contact zone that isalways clearly dened.

DSC 214 Polyma The New Benchmark in Cell Design

1 Arena Furnace Its oval geometry drastically

reduces the furnace mass,resulting in faster heating andcooling rates. The double-

symmetric design also leads to aneven temperature distribution.

32


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The DSC 214 Polyma sets newstandards, incorporating the premium Arena furnace in combination with aperfectly matched sensor and pan. Thisunique solution achieves excellentsensitivity and resolution at the sametime, which is reected in the peakheight-to-width ratio. Only in this way

is it possible to detect weak effects andseparate overlapping ones.

The peak height-to-width ratio,called the Indium Response Ratio,is generally used to characterizethe separation capability of a DSC.The DSC 214 Polyma generates anIndium Response Ratio of more than100 mW/C, a unique number forheat-ux DSC systems.

The ideal combination of the lowthermal mass Arena furnace with thefast-responding Corona sensor allowsfor high heating and cooling rates ofup to 500 K/min values unachiev-able with common heat-ux DSCs onthe market. Its high reproducibility androbustness are the hallmarks of the

Corona sensor.

The Concavus pans in combinationwith a at sensor always yield auniform ring-shaped contact zone.These premium pans are speciallydesigned to align to the shape of theCorona sensor, resulting in unmatchedreproducibility. In addition, theConcavus pans are subjected to acareful cleaning process prior todelivery, which eliminates any

contamination.

New Furnace, Sensor and PanCombination Fast heating and cooling rates Excellent reproducibility Unmatched indiumresponse ratio

Technical key data for the instrument can be

found on page 23

First-Class Performance Via an Optimum Combination ofFurnace, Sensor and Pan

DSC/mW

exo35

30

25

20

15

10

5

0

154 159 160156152 162 164

Temperature/C

Peak Widthat 50% Height:0.33 K

Indium Response Ratio:106 mW/C

Peak Height:35.08 mW

DSC measurement on indium (7.3 mg)


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3in1 Box The Clever Solution forTransport, Sampling and Archiving

Even the transport and storage of theConcavus pans is consistent withtheir premium quality, thanks to the3in1 Box: 96 pans and lids arepackaged in an anti-static boxdivided into 96 separate compart-

ments. This elaborate packingprevents deformation of the panswhile allowing easy access to them

and providing a fully functionalarchiving system. The integratedsample register including nameand mass makes it easy to locateretained samples.

The Concavus pans are actuallyalso compatible with commonheat-ux DSCs.

Sample Preparation

Clever and unique SampleCutter New 3in1 Box for easywithdrawal, storage and

practical archiving

Tray supports a defined sample position


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DSC 214 Polyma Opens the Window for Flexibility

With a stand-alone footprint of only35 cm x 51 cm, the new DSC 214Polyma is extremely compact andleaves room for the set-up of yourchoice. The instrument can becombined with a variety of computerdevices to meet your needs: You canchoose to plug it directly into your

classical desktop PC or laptop, or youcan use it with an all-in-one touch PCor even a compact tablet PC for smallwork spaces. A touch interface ormouse and keyboard work equallywell. The system runs under WindowsXP, Windows 7 or Windows 8.1.It's up to you.

Epic Versatility


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-40CRT -70C -170C

Thanks to the automatic samplechanger (ASC), the measurement ofup to 20 samples either belongingto a single series or independent ofeach other can be carried outwithout operator intervention.

Different crucible types, different gasatmospheres and individualcalibration curves can be handledwithin the same carousel run.

High Sample Throughput

Liquid nitrogen cooling system(-170C to 600C)

Closed-loop intracooler IC40(-40C to 600C)

Compressed air cooling(RT to 600C)

Closed-loop intracooler IC70(-70C to 600C)

For fast cooling back to room temperature or for tests atsub-ambient temperatures, optimized cooling is required.NETZSCH offers several options for meeting these needs.

Broad Temperature Range and Economic Cooling


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The novel, greatly simplied user interface of the Proteus measurement softwarereects a true "intuitive design" concept. There's no need to be an expert inthermal analysis to start test runs with the DSC 214 Polyma .

The Proteus Software Ushers In a New Era

Unmatched Ease of Use The New SmartMode User Interface

SmartMode Right at YourFingertips

The user interface boasts a clearstructure, a consistent navigationconcept and easy-to-access buttons.Thus, even customers unfamiliar withthe software immediately know howto proceed. Several instruments can beoperated in parallel. Each activeinstrument is marked by a colored tab.Using Wizards (measurementtemplates), it is possible to start ameasurement with just a few inputs.Alternatively, customized methods orpredened methods can be selectedto set up an experiment. Thepredened methods already containall required parameters for thosematerials which are listed in theNETZSCH Thermal Properties ofPolymers poster.

New simplified user interface for measurement definition predefined methods are activated

During the course of a measurement,the curve evolution can be followed even on a tablet computer. Thisfeature affords the operator a greatlatitude of action and can signicantlyimprove work effi ciency.


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ExpertMode Not Just forProfessional Users

For those who wish to dive deeper

into the software for enhanced optionsetting or for method denition,switching from SmartMode over toExpertMode is the answer. Here, theuser has access to the establishedProteus software functionality,including dozens of features and alladjustment settings.

AutoCalibration Allows forFull Concentration on theMeasurement Tasks

DSC calibration is essential for ensuring

that the instrument is always in a denedstate. Calibration procedures, however,should be simple, fast and ideally done along the way.

The solution is AutoCalibration . Thisfeature provides automatic creationroutines for all relevant calibrationcurves, automatically loading thecurrent calibrations while taking theselected measurement conditionsinto account and checking theirvalidity periods.

SmartMode and ExpertMode

SmartMode for fast operation

ExpertMode for sophisticatedtest procedures AutoCalibration


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AutoEvaluation is somethingcompletely new. It is the rst and onlysoftware feature which automaticallyanalyzes unknown curves of

amorphous or semi-crystallinepolymer samples such as thermo-plastic materials, rubbers, thermo-plastic elastomers or cured resins.

Users thus obtain a self-actingsoftware package which evaluatesglass transition temperatures, meltingenthalpies or peak temperatures. Formelting effects, for example, boththe peak temperature and theenthalpy are determined; in the caseof a glass transition, the softwarecalculates T g (the glass transitiontemperature) and the step height,expressed as c p.

The plot on the right presents ameasurement on an unknownpolymer. Three effects are visible in

AutoEvaluation The First Truly Automatic Evaluation Routine

Autonomous Detection of DSC Effects

the curve: an endothermic step andtwo peaks an exothermic and anendothermic one. Users familiarwith the thermal behavior of such

semi-crystalline polymers know thatthe exothermic peak is related topost-crystallization of the material;the endothermic one belongs to themelting range and the step reectsthe glass transition of the polymer.For all those who haven't seen suchmeasurements yet, AutoEvaluation will handle the curve independently without any effort on the opera-tor's part.

This ground-breaking technologyallows, for the rst time in history,test analyses which are fully user-independent and thereforecompletely objective.

Of course, users can still run manualevaluation if required.


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Result without evaluation

Mid: 747.5CDelta Cp*: 0.33 J/(g*K)

Area: 401.0 J/gPeak: 251.2C

Area: -33.93 J/gPeak: 137.4C

DSC/(mW/mg)

1.0

0.8

0.6

0.4

0.2

0.0

-0,2

500 100 200150 250

Temperature/C

exo

DSC curve evaluated by means of AutoEvaluation

DSC/(mW/mg)

1.0

0.8

0.6

0.4

0.2

0.0

-0,2

500 100 200150 250

Temperature/C

exo


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DSC/(mW7mg)

0,5

0,3

0,4

0,2

0,1

-0,5

-1,0

100 150 200 2500 50

As far as software-controlled automaticdata handling is concerned, AutoEvalu-ation is not even the summit. NETZSCHgoes yet a step further and additionally

offers software which searches forsimilar results stored in polymerlibraries, providing instantaneousinterpretation of the measurementat hand.

With the Identify software package, itis possible to carry out one-on-onecomparisons with individual curves or

literature data from selected libraries,or to check whether a particular curvebelongs to a certain class. These classesmay contain sets of data for various

types of the same polymer e.g.,several types of PE but also curves,such as ones which are classied asPASS or FAIL in terms of quality control.

Both the libraries and the classes areboundless and editable; i.e., users canextend them with experiments andknowledge of their own. As standard

libraries, all data and exemplarymeasurements from the NETZSCHThermal Properties of Polymersposter are provided. The Identify results

are portrayed as hits sorted by degreeof similarity as a percent.

The plot below depicts the results of asearch for an unknown sample curve.The DSC curve for the best hit is shownfor direct comparison with theunknown sample. The similarities areobvious: The unknown sample is PET.

Identify : Unprecedented Database System for Identificationand Verification of Polymer Measurements

View of Identify results after only one click. The unknown curve is marked in green; the most similar

database curve in black.

Glass Transition:Mid: 80.8CDelta Cp*: 0.208 J/(g*K)

Complex Peak:Area: 41.7 J/gPeak: 248.2C

Temperature/C

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Identify Makes Every User an Expert


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PET 2

76.67%

PVAL

64.48%

PET 1

95.93%

15

Identify...

is a unique DSC curve recognitionand interpretation system providing

results with a single click!is useful for material identificationand quality control.

is both easy to use andsophisticated.

includes a database withNETZSCH libraries for polymersand libraries that can be createdby the user.

manages measurements, literaturedata and classes in consideration ofthe user's knowledge.


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Temperature/C

DSC/(mW/mg)

exo0.50

0.45

0.40

0.35

0.30

0.25

0.15

0.20

-50 0 50 100 150 200

2nd heating1st heating

Glass Transition:Mid: -47.2 CDelta Cp*: 0.455 J/(g*K)


Partial Area: 4.88 J/g1.9 C ... 32.5 C 36.71 %

Area: 0.05 J/gPeak: 108.7 C

Area: -6.44 J/gPeak: 168.7 C


Area: 4.85 J/gPeak: 32.7 C 58.4 C

18.0 C

Temperature/C

DSC/(mW/mg)

exo

0.50

0.45

0.40

0.35

0.30

0.25

0.20

-50 0 50 100 150 200

2nd heating1st heating



Area: 10.19 J/g


182.3 C206.9 C

Low-Temperature Performanceof Rubber

DSC measurements are important forrubbers used in tires because theirservice temperature range is limitedby the glass transition temperature.In this example, an SBR sample wasmeasured twice between -100C and

220C. The endothermic step detectedat -47C (mid-point) in both heatingsequences is associated with theglass transition of SBR. Between 0Cand 70C, endothermic effects aredetected. They are most probablycaused by the melting of additives.The exothermic peak at 169C (peaktemperature), exhibited only in theheating, is due to post-curing ofthe elastomer. Thermal behavior of SBR rubber.

Sample mass: 15.41 mg; heating from -100C to 220C at 10 K/min, twice; dynamic N 2 atmosphere.

Thermal Behavior ofThermoplastic Polyurethane

This plot shows a measurement onTPU. During the 1 st heating, theendothermic step at -42C (mid-point)reects the glass transition of the softsegments of the sample.

Additionally, the curve exhibits an

endothermic double peak between100C and 210C. The reversible partof it, which can be detected again inthe 2 nd heating (7.40 J/g), is caused bythe melting of the hard (thermo-plastic) segments. The irreversible partis probably due to evaporation ofvolatiles or distribution of additives inthe polymer matrix. This processexplains the fact that the glasstransition was detected at a highertemperature (mid-point at -28C) in

the 2nd

heating.

Thermal properties of the soft and hard segments in a thermoplastic polyurethane (TPU).Sample mass: 10.47 mg; heating from -100C to 250C at 10 K/min, twice; dynamic N 2 atmosphere.


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Temperature/C

DSC/(mW/mg)

exo-0.5

-1.0

-1.5

-2.0

40 60 80 100 120 140 160

Material AMaterial B

Area: -84.37 J/gPeak: 117.6 CEnd: 121.6 C

Area: -90.84 J/gPeak: 120.9 CEnd: 125.9 C

106.8 C97.0 C

125.9 C123.5 C

Area: 87.11 J/gPeak: 163.3 C

Area: 94.58 J/gPeak: 165.0 C

Temperature/C

DSC/(mW/mg)

exo

1.2

1.0

0.8

0.6

0.4

60 80 100 120 140 160 180

Material AMaterial B

110.1 C

DSC 214 Polyma An Essential Aid for Process Optimization

Failure Analysis Influence of Recycled Material

In this example, two recycled polypropylenes were being used for injectionmolding. Material A was completely crystallized after the molding processwhereas material B was still molten. To discover the reason for the differingbehavior, DSC measurements were performed.

Different solidification of two recycled PP samples.Sample mass: approx. 13 mg; cooling at 10 K/min after heating to 200C;dynamic N 2 atmosphere.

Melting of recycled PP with different PE contamination.Sample mass: approx. 13 mg; heating to 200C at 10 K/min after cooling at

10 K/min; dynamic N 2 atmosphere.

The 2 nd heating reveals furtherinformation. Besides the peaks at

165C and 163C, which are typical forthe melting of polypropylene, the bluecurve exhibits two additional peaks at110C and 124C, indicating theexistence of additional LDPE, LLDPE orHDPE: The melting temperatureincreases with increasing density. Incontrast with this, material B has onlyone further peak at 126C.

The exothermic peaks appearing

during cooling can be attributed tocrystallization of the polymer.Recycled material A starts tocrystallize at a higher temperature(endset temperature at 126C, bluecurve) than the second material(endset temperature at only 122C,red curve). Furthermore, in additionto the peaks at 121C (blue curve)and 118C (red curve), a peak at97C (blue curve) and a shoulder at107C (red curve) occur clearindications for the presence of asecond component. The additionalcomponents in material A causeearlier nucleation.


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exo

DSC/(mW/mg)

-2

-4

-6

-8

-10

-12

100 120 140 160 180 200Temperature/C

[1.20]20 K/min

187.7 C

180.0 C

188.2 C

181.4 C

170.4 C

193.5 C

50 K/min

100 K/min

200 K/min170.8 C

156.0 C

exo

DSC/(mW/mg)

Previous cooling rates:

-0.5

0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

100 120 140 160 180 200 220 240 260Temperature/C

[1.6]

20 K/min50 K/min

100 K/min200 K/min

Development of Process Parameters for Injection Molding

Semi-crystalline polymers such as polybutylene terephthalate (PBT) exhibit arelationship between completion of crystallization and the cooling speed. Thisfactor is important for estimating the temperature at which the mold canbe opened in practice to remove a nished solid part.

In the example, PBT with 30 wt% glass bers was subjected to a temperatureprogram consisting of various cooling segments at cooling rates between 20 K/min

and 200 K/min.

Different cooling curves of PBT resulting from different cooling speeds.Sample mass: 10.1 mg; cooling at 20 K/min, 50 K/min, 100 K/min and

200 K/min; dynamic N 2 atmosphere.

Heating curves of PBT GF30 following different cooling rates.Sample mass: 10.1 mg; heating at 50 K/min.

As to the subsequent heating steps (allperformed at 50 K/min), the shoulderof the -phase, as is typical for PBT, isclearly visible for the sample which hadbeen cooled at 20 K/min (red curve).This effect is shifted to lower tempera-tures and therefore better separatedfrom the main peak for the samplewhich had been cooled at 50 K/min(blue). Finally, for the curves with acooling rate of 100 K/min (green) and200 K/min (black), the endothermiceffect completely disappears and givesway to exothermic post-crystallization.

During cooling at 20 K/min (red),solidication starts at about 194C and

exhibits its maximum at 188C (peaktemperature), whereas during coolingat 200 K/min (black curve), thetemperatures are shifted to 171C and156C, respectively. Here, theexothermic crystallization does not endbefore approx. 120C, where a smallbend is visible in the curve.


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20 40 60 80 100 120 140 160Temperature/C

-1.0

-0.8

-0.6

-0.4

-0.2

0

Heat ow rate/(mW/mg)

A B1

10.0 K/min

5.0 K/min 2.0 K/min

exo

110.1 C

91.2 C

76.7 C

0 2 4 6 8Time/min

0

20

40

60

80

100

Partial Area/%

50 C

60 C

70 C

80 C

90 C

100 C110 C120 C

95 %

Kinetic Analysis of an EpoxyAdhesive

The NETZSCHThermokinetics software module is used forcreating kinetic models of chemicalprocesses. It can also be used topredict the behavior of chemicalsystems for user-dened temperature

conditions and for processoptimization.

In this example, the curing of a2-component epoxy adhesive wasinvestigated. Three samples wereprepared and heated to 200C atdifferent heating rates (2 K/min,5 K/min, 10 K/min). As expected, thepeak temperature of the curing effectshifts to higher temperatures as theheating rates increase.

The kinetic model of a one-stepreaction is in good agreement withthe experimental data, with a corre-lation coefficient higher than 0.999.Therefore, this model can be used forpredictions on isothermal conditionsor for a temperature program denedby the user.

The plot shows the degree of curingfor different isothermal temperatures.A degree of curing of 95% is reached

after nearly 3 minutes at 120C. Twomore minutes are necessary to reachthe same degree of curing at atemperature of 110C.

DSC 214 Polyma Sophisticated Measurement and Analysis

Comparison of measured curves (dotted lines) and theoretical curves (solid lines)with a one-step reaction.

Prediction of the curing reaction for different isothermal temperatures.


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exo

DSC/(mW/mg) Temp./C

Approx. 21 s

296 C

237 CTemperature

-29.8 J/g DSC

6

-6

-8

4

-4

2

-2

0

15 16 17 18 19 20

120

140

160

180

200

220

240

260

280

300

Time/min

Isothermal Crystallization of aSemi-Crystalline Thermoplastic

Isothermal crystallization testsare often used to simulate therapid cooling of nished polymerparts during production(e.g., injection molding).

The graph on the right depicts anisothermal crystallization experimenton PA66 GF30 (containing 30 wt%glass ber) using the DSC 214 Polyma in combination with the IC70 intra-cooler. The low thermal mass of the Arena furnace allows for a temper-ature interval of almost 60 K to bebridged within seconds (programmedcooling rate: 300 K/min). Based onthis, it is possible to separate solidi-cation of PA66 from the startingphase of the segment. This clearlydemonstrates the superior coolingperformance of the heat-uxDSC 214 Polyma .

Isothermal crystallization of a semi-crystalline thermoplastic.11.4 mg PA66 GF30 in a dynamic nitrogen atmosphere, intracooler for the temperature range -70C to

600C, programmed cooling rate: 300 K/min. The temperature curve is marked in red; the DSC curve inblue. The total crystallization enthalpy at 237C amounts to approx. 30 J/g.


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There are several relevant standards existing for application, evaluation andinterpretation of DSC data in the polymer eld. The DSC 214 Polyma operatesbased on all of them. A selection of standards can be found in the following table.

Appendix

Important Standards for Polymer Testing

Category Standard Description

General

ISO 11357, Part 1 to 7 Plastics Differential Scanning Calorimetry (DSC)

ASTM D3417 Heats of Fusion and Crystallization of Polymers by Thermal Analysis

ASTM D3418 Transition Temperatures and Enthalpy of Fusion and Crystallization by DSC

ASTM D4591 Temperatures and Heats of Transitions of Fluoropolymers by DSC

ASTM E793 Heats of Fusion and Crystallization by DSC

ASTM E794 Melting and Crystallization Temperatures by Thermal Analysis

ASTM E1356 Glass Transition Temperatures by DSC

ASTM F2625Enthalpy of Fusion, Percent Crystallinity, and Melting Point of Ultra-HighMolecular Weight Polyethylene by DSC

DIN 50007 Differential Thermal Analysis (DTA): Basics (in German)

DIN 53545 Low-Temperature Performance of Rubbers (in German)

EN 61074 (IEC 1074)Heats and Temperatures of Melting and Crystallization by DSC of ElectricalInsulation Materials

IEC 1006 Glass Transition Temperature of Electrical Insulation Materials

OIT

ASTM D3350Polyethylene Plastics Pipe and Fittings Materials Oxidative-Induction

TimeASTM D3895 Polyolefins by DSC Oxidative-Induction Time

DS 2131.2Pipes, Fittings and Joints of Polyethylene-Type PEM and PEH for BuriedGas Pipelines

DIN EN 728 Polyolefins Pipes and Fittings Oxidative-Induction Time

ISO TR 10837 Thermal Stability of Polyethylene for Use in Gas Pipes and Fittings

Resins/Curing

ISO 11409 Phenolic Resins Heats and Temperatures of Reaction by DSC

DIN 65467Aircraft/Spacecraft: Testing of Thermosetting Resins with and withoutReinforcement, DSC Method (in German)


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NETZSCH-Gertebau GmbHWittelsbacherstrae 4295100 SelbGermanyTel.: +49 9287 881-0Fax: +49 9287 881 505

When it comes to Thermal Analysis, Adiabatic Reaction Calorimetry andthe determination of Thermophysical Properties, NETZSCH has it covered.Our 50 years of applications experience, broad state-of-the-art product lineand comprehensive service offerings ensure that our solutions will not onlymeet your every requirement but also exceed your every expectation.

The NETZSCH Group is a mid-sized, family-owned German company engaging inthe manufacture of machinery and instrumentation with worldwide production,sales, and service branches.

The three Business Units Analyzing & Testing, Grinding & Dispersing andPumps & Systems provide tailored solutions for highest-level needs. Over3,000 employees at 163 sales and production centers in 28 countries acrossthe globe guarantee that expert service is never far from our customers.

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DSC 214 Polyma – Differential Scanning Calorimeter (-170°C to 600°C)