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Flash DSC 1STARe System

Innovative Technology

Versatile Modularity

Swiss Quality

Flash Differential Scanning Calorimetry for Research and Development

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e A Quantum Leap in InnovationOpens up New Frontiers

Differential Scanning Calorimetry, DSC, is the most important method in thermal analysis. It measures the heat flow to or from a sample as a function of temperature or time and thereby allows physical transitions and chemical reactions to be quantitatively measured.

Features and benefits of the Flash DSC 1:

n Ultra-high cooling rates – allow materials with defined structural properties to be prepared

n Ultra-high heating rates – reduce measurement times and suppress reorganization processes

n Fast response sensor – enables the kinetics of extremely fast reactions or crystallization processes to be studied

n High sensitivity – low heating rates can also be used; scan rates overlap with those of conventional DSC

n Wide temperature range – measurements can be performed in the range -95 to 450 °C

n User-friendly ergonomics and functionality – sample preparation is quick and easy

The Flash DSC 1 allows you to prepare samples with defined structures such as occur during rapid cooling in injection molding processes. The application of dif-ferent cooling rates influences the crystallization be-havior and structure of the sample.

The use of high heating rates enables materials to be analyzed without interference from reorganization pro-cesses – there is no time for such processes to occur. The Flash DSC 1 is also the ideal tool for studying crystallization kinetics.

The heart of the Flash DSC 1 is the chip sensor based on MEMS tech nology.

MEMS: Micro-Electro-Mechanical Systems

The Flash DSC 1 revolutionizes rapid-scanning DSC. The instrument can analyze reorganization processes that were previously impossible to measure. The Flash DSC 1 is the ideal complement to conventional DSC. Heating rates now cover a range of more than 7 decades.

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MEMS-Based DSC Sensor Technology Unsurpassed Heating and Cooling Rates

Reusable chip sensorsSamples are positioned directly on the sensor. Used sensors can be stored in the chip sensor box sup-plied so that further measurements can be performed later on if needed.

It takes less than a minute to change a sensor.

In conventional DSC instruments, the sample is measured in a crucible in order to pro-tect the sensor. The heat capacity and thermal conductivity of the crucible however have a significant influence on the measurement. In the Flash DSC 1, the sample is placed di-rectly onto the MultiSTAR chip sensor. The patented dynamic power compensation control circuit allows measurements to be performed with minimum noise level at high heating and cooling rates.

MultiSTAR UFS 1 SensorThe Full Range UFS 1 sensor has 16 thermocouples and exhibits high sensitivity and excellent temperature resolution. The MEMS chip sensor is mounted on a stable ceramic substrate with electrical connections.

Sensitivity The high sensitivity results from the use of 16 thermocouples, 8 each on the sample and ref-erence sides. The thermocouples are arranged symmetrically around the sample measure-ment area in the form of a star so that temperatures are measured with great accuracy. The outstanding sensiti vity means that measurements can also be performed at low heating and cooling rates.

Temperature resolution The temperature resolution is determined by the time constant of the sensor. The smaller the time constant, the better close-lying thermal effects can be separated. The time constant of the Flash DSC 1 is about 1 millisecond or about 1 000 times less than that of a conventional DSC instrument.

BaselineThe revolutionary multiple temperature measurement around the sample guarantees excellent accuracy. The high degree of symmetry of the differential sensor results in flat and extremely reproducible baselines.

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TGADSC Flash DSC TMA DMA

Flash DSC 1 from METTLER TOLEDOthe Fastest Commercial DSC

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Complete thermal analysis systemA complete thermal analysis system comprises four different measurement techniques. Each characterizes the sample in a different way. The combination of all the results simplifies interpretation. Besides heat flow measure-ments using DSC or Flash DSC, the other instruments measure weight loss (TGA), change in length (TMA) or the mechanical modulus (DMA). All these quantities change as a function of temperature.

TerminalThe large easy-to-read color touchscreen terminal at the front of the Flash DSC 1 indicates the status of the instrument. If the instrument is not next to your PC, you can enter individual sequences and queries direct-ly via the terminal.

Sensor environmentThe sensor support is heatable. In the low-temperature operation, the sensor support can be brought to room temperature before the sensor is inserted. This prevents the gold contact pins from icing over.

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Thermal Analysis in Practice Collected Applications

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Application Handbook

Perfect ergonomicsThe preparation and insertion of a sample is performed sitting com-fortably in front of the instrument. The sample is first cut to size on a small glass microscope slide placed over the sensor. A suitable sample specimen is then trans-ferred directly to the sensor and po-sitioned using a hair.

Important support servicesMETTLER TOLEDO prides itself in supplying outstanding instruments together with the support needed for you to be successful in your field of work. Our well-trained engineers are ready to help you in any way possible:• Service and maintenance• Calibration and adjustment• Training and application advice• Equipment qualification

METTLER TOLEDO also provides comprehensive literature on thermal analysis applications.

Ergonomic Perfection Is What Customers Value

Sample preparationSample preparation is carried out using a microscope. The micro-scope is also used to accurately position the very small sample specimen on the sensor.

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Inno

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nUnbelievable Performance Leads to New Results

Measurement principleHigh heating or cooling rates are only possible when the sample is sufficiently small and is in good thermal contact with the sensor.In the first heating run, the sample melts. Thermal contact with the sensor is thereby greatly improved. Defined sample structures can then be produced by varying the cooling rate over a wide range.

In the second heating run, the sample has no time to reorganize because of the very high heating rates. The enormous range of cool-ing and heating rates allow many different sample structures to be measured in one experiment.

Chip sensor principleThe sample and reference sides of the sensor each have two thermal resistance heaters which together generate the desired temperature program. The smaller heater is for compensation control (dynamic compensation control). The heat flow is measured using the two sets of 8 thermocouples arranged symmetrically around the measure-ment area on the sample and refer-ence sides of the sensor.

Homogeneous temperature distributionThe sample measurement area of the chip sensor is made of silicon nitride and silicon dioxide coated with a thin layer of aluminum. This provides in an extremely homogeneous temperature distribution across the sensor. The small active measurement area is approximately 2.1 µm thick so that the time constant is mainly determined by the sample.

Melting of the sample opti-mizes thermal contact.

Different cooling rates al-low defined sample struc-tures to be formed.

High heating rates suppress the reorgani-zation of the sample. It can therefore be mea-sured “as received”.

Temperature

Sample preparation

Formation of sample structure

Analysis

Time

1. Ceramic plate2. Silicon frame3. Connecting wire

4 Resistance heater5. Aluminum plate (sample area)6. Thermocouple

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n Selection of curve segments – On opening the measurement, you choose only the curve segments of interest.

n Multicurve evaluation – Select the curves, click the evaluation and the individual results are immediately available.

n Rapid set up of function table with fit functions – Activate the re sult line: One click copies all the selected results into a table. Now choose the fit function and the evaluation is completed.

Optimized Evaluation SoftwareBrings Efficiency into the Laboratory

Software supportIn a typical Flash DSC experiment, the measurement results are ana-lyzed as a function of the heating or cooling rate or the isothermal time. The experiment is usually performed very quickly. Sample preparation needs somewhat more time. Evaluation and interpretation takes longest but is at the same time the most interesting part of the work.

The STARe software has been ex-panded to include new require-ments. For example, complex mea-surement programs are set up within a few minutes and large numbers of curves can be efficient-ly evaluated.

Reorganization of polyethylene terephthalate (PET)Many polymers exhibit reorganization effects in the DSC measurement curve when they are heated. The curve does not therefore show the melting of the crystallites originally present in the sample. This is demonstrated us-ing a sample of PET that had been allowed to crystallize at 170 °C for 5 min before cooling to room temperature. The measurement curves at heating rates between 0.2 K/s and 1 000 K/s show two peaks. The peak at lower temperatures shifts to higher temperatures with increasing heating rate (blue arrow). This peak occurs when the original crystallites melt. The high-temperature peak shifts to lower temperatures (red arrow). This peak is due to the melting of crystallites produced through reorganization during the measurement. Only one peak is observed at 1 000 K/s. Practically no reorganization occurs from this heating rate onward.

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M80 (Zoom)M50 (Step) M60 (Zoom)

Camera kitCamera kit Video/photo tube

ErgoTube ® 45°Binocular tube 45° Binocular ErgoTube ®

ErgoModule® ErgoWedge® ErgoWedge® Filter slide housing Video/photo tube

Video module Light housing

Modularity and ExpansionMany Options

Microscope optionsYou can adapt the microscope attachment according to your needs. There are two options:1. Not modular, but excellent value2. Modular, with adjustable viewing angle, different il-

lumination possibilities, and cameras.

Temperature range and cooling optionsThe IntraCooler is an electrical cooling device with a closed-loop cooling system. The vaporized coolant is liquefied by means of compressors and heat exchangers.

Three temperature ranges are available:

Air cooling: RT … 450 °C

IntraCooler (1 stage) -35 … 450 °C

IntraCooler (2 stage) -95 … 420 °C

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EfficiencyThanks to Practical Accessories

Chip sensor boxSince the chip sensors can only be used for one sample, it is a good idea to store them safely just in case you want to make more mea-surements afterward with the same sample. This avoids having to use a new sensor. Up to ten chip sen-sors with adhering sample material can be stored in the sensor box for experiments later on.

Microtome (optional accessory)The microtome can be used to cut 10 to 30 μm thick layers of a material, for example from small pieces of a polymer granule. The layers are then cut to small sample specimens for analysis using the knife supplied.

Standard accessoriesThe following tools needed to prepare thin layers are supplied with the instrument as standard equipment:• knife with spare blades• lancet-shaped needle• tweezers• leather cloth• grinding stone• brush• hair holder• glass support and• indium for calibration

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Appl

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Pow

er New Materials for the FutureFlash DSC Has the Answers

The Flash DSC 1 is the ideal addition for characterizing modern materials and optimizing production processes by thermal analysis.

Polymers, polymorphic substanc-es, and many composites and blends have metastable structures that depend on the cooling condi-tions used in their production. On heating, reorganization processes such as the melting and recrystalli-zation of unstable crystallites or the separation of phases may occur. The influence of reorganization on the heating curve can be analyzed by varying the heating rate.

Flash DSC can simulate technical processes in which rapid cooling occurs. This yields information about the effect of additives (e.g. nu-cleating agents) under near-process conditions. Isothermal measure-ments provide information on the ki-netics of transitions and reactions that take place in a few seconds.

Fast measurements save time in the analysis and development of materials. The quality of products can be improved through knowl-edge of structure formation at actu-al process cooling rates.

The data can be used for simula-tion calculations and to optimize production conditions.

Application Possibilities of Flash DSC

• Detailed analysis of processes involving the formation of structure in materials

• Direct measurement of rapid crystallization processes

• Determination of the reaction kinetics of fast reactions

• Investigation of the mechanism of action of additives under near-production conditions

• Comprehensive thermal analysis of materials in very short time

• Analysis of very small sample amounts

• Determination of data for simulation calculations

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Melting of indium at different heating ratesThe melting of indium (1 μg) was mea-

sured at different heating rates between

0.05 K/s and 10 000 K/s. As in convention-

al DSC, the conduction of heat between the

sensor and the sample (thermal lag) influ-

ences the measured onset temperature, Ton.

Without correction, Ton increases linearly

with the heating rate. The same is true for

the Flash DSC 1.

To accommodate the large heating rate

range, the abscissa is displayed logarithmi-

cally in the diagram. For this reason, the

linear function appears as a curve (blue).

Crystallization of isotactic polypropylene (iPP) on coolingIn technical processes such as injection

molding, the molding materials are cooled

at several hundred K/s. To optimize their

properties, it is important to have informa-

tion about the crystallization behavior at

these high rates. This information can be

obtained from Flash DSC cooling experi-

ments as shown in the upper diagram.

The lower diagram displays the crystalliza-

tion peak temperature of isotactic polypro-

pylene (iPP) as a function of the cooling

rate. The peak temperature shifts to lower

temperatures at higher cooling rates.

A conventional DSC 1 (red points) was used

for cooling rates between 0.1 K/min and

60 K/min (0.0017 K/s and 1 K/s) and the

Flash DSC 1 for rates between 0.5 K/s and

1 000 K/s. The peak temperatures agree

with one another in the region where the

cooling rates of the instruments overlap.

Above 50 K/s, the formation of the meso-

phase is observed at about 30 °C in a sec-

ond crystallization process (blue points).

At cooling rates above 1 000 K/s, no crys-

tallization occurs. The material remains

amorphous with a glass transition at

about -10 °C.

The complete crystallization behavior is

measured by the Flash DSC 1 in less

than 30 min.

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Reorganization of amorphous iPP Amorphous isotactic polypropylene (iPP) is

produced by cooling from the melt at

4 000 K/s. The material obtained was mea-

sured at heating rates between 5 K/s and

30 000 K/s. The glass transition occurs just

below 0 °C followed by an exothermic peak

due to cold crystallization. The crystallites

melt above 100 °C.

At higher heating rates, the cold crystalliza-

tion peak is shifted to higher temperatures

and melting peak to lower temperatures.

From 1 000 K/s onward, the peak areas be-

come significantly smaller until at 30 000

K/s reorganization no longer occurs in the

sample.

Isothermal crystallization of iPPTo measure the isothermal crystallization

behavior of isotactic polypropylene (iPP),

the melt was first cooled to different crystal-

lization temperatures between 110 °C and

-20 °C at 2 000 K/s. No formation of struc-

ture occurs under these conditions.

Afterward, the crystallization process was

measured isothermally. The exothermic

crystallization peaks have their peak maxi-

mum at times between 0.05 s and 10 s.

The reciprocal peak time is a measure of

the crystallization rate and is displayed as a

function of the crystallization temperature.

The resulting curve exhibits a maximum at

about 20 °C. At these low temperatures,

crystallization takes place very rapidly. The

crystallization process involves homoge-

neous nucleation.

The measurement curves also show the

change of crystallization kinetics with tem-

perature.

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Nanofillers in PAThe properties of polyamide 11 (PA 11) can

be optimized through the addition of

nanoparticles and the use of suitable pro-

cessing conditions (e.g. for the injection

molding of gearwheels). The effect of the

fillers at the actual cooling rates influences

the size of the crystallites and hence the

mechanical properties.

Three PA 11 samples with nanofiller con-

tents of 0%, 2.5% and 5% were measured

at different cooling rates in the Flash DSC 1

and in a conventional DSC 1. The enthalpy

of crystallization at low cooling rates is

constant up to 50 K/s, but becomes smaller

at higher cooling rates. At 200 K/min, the

sample no longer crystallizes.

The influence of the cooling rate on the ef-

fect of the filler become clear when the peak

temperatures are displayed as a function of

the cooling rate. At cooling rates below

0.3 K/s (20 K/min), the unfilled PA 11 crys-

tallizes first. At the technologically important

high cooling rates, this changes and the

nanoparticles accelerate crystallization.

Melting and decomposition of organic substancesThe determination of the melting behavior

of organic substances is difficult if decom-

position occurs in the melting range.

At high heating rates, the decomposition re-

action shifts to higher temperatures and

separation of the two effects becomes pos-

sible. This is shown using saccharin as an

example.

At heating rates between 50 K/s and

100 K/s, melting and decomposition over-

lap. At higher heating rates, the two effects

are separated.

www.mt.com

Flash DSC 1 Specifications

Temperature dataTemperature range Air cooling (Room temperature + 5 K) … 500 °C

IntraCooler (1-stage) -35 °C … 450 °C

IntraCooler (2-stage) -95 °C … 420 °C

Cooling rates (typical) -6 K/min. (-0.1 K/s) … -240 000 K/min (-4 000 K/s)

Heating rates (typical) 30 K/min. (0.5 K/s) … 2 400 000 K/min (40 000 K/s)

Sensor dataSensor material Ceramic

Thermocouples 16

Signal time constant, nitrogen 0.001 s

Sample size 10 ng … 1 µg

DSC SensorSensor type Ultra-fast-sensor 1st generation

Pmax heat flow signal 20 mW

Noise heat flow signal rms < 0.5 µW (typical)

Isothermal drift heat flow signal < 5 µW/h (typical)

Baseline drift heat flow signal (empty sensor) < 100 µW/h (typical)

TerminalTouch control Color TFT, VGA 640 x 480 pixel

Signal generationResolution 0.005 K (0 °C … 250 °C)

0.01 K (-100 °C … 400 °C)

Signal detectionSampling rate Max. 10 kHz (10 000 points per second)

Resolution of temperature signal 2.5 mK

Noise temperature signal rms < 0.01 K (typical)

CommunicationWith personal computer (PC) Ethernet

DimensionsInstrument dimensions (width x depth x height) 45 cm x 60 cm x 50 cm

ApprovalsIEC/EN61010-1:2001, IEC/EN61010-2-010:2003CAN/CSA C22.2 No. 61010-1-04UL Std No. 61010A-1EN61326-1:2006 (class B)EN61326-1:2006 (industrial environments)FCC, Part 15, class AAS/NZS CISPR 22, AS/NZS 61000.4.3Conformity mark: CE

For more information

Mettler-Toledo AG, AnalyticalCH-8603 Schwerzenbach, SwitzerlandTel. +41 44 806 77 11Fax +41 44 806 73 60

Subject to technical changes© 09/2010 Mettler-Toledo AG51725315, Printed in SwitzerlandMarketing MatChar / MarCom Analytical

Quality certificate. Development, production and testing according to ISO 9001.

Environmental management system according to ISO 14001.

“European conformity”. The CE conformity mark provides you with the assurance that our products comply with the EU directives.