TA Instruments

Q SERIES™ THERMAL ANALYZERS

W W W . T A I N S T R U M E N T S . C O M

TA INSTRUMENTS, WORLDWIDE

New Castle, DE USA - 1-302-427-4000 • Crawley, England - 44-1293-658900 • Brussels, Belgium - 32-2-706-0080

Paris, France - 33-1-30-48-94-60 • Etten-Leur, Netherlands - 31-76-508-7270 • Eschborn, Germany - 49-6196-400-600

Milano, Italy - 39-02-27421-283 • Barcelona, Spain - 34-93-600-9300 • Melbourne, Australia - 61-3-9553-0813

Stockholm, Sweden - 46-8-59-46-92-00 • Tokyo, Japan - 81-3-5479-8418 • Shanghai, China - 86-21-63621429

Bangalore, India - 91-80-28398963

More worldwide customers choose TA Instruments than any competitoras their preferred thermal analysis or rheology supplier. We earn this distinction by best meeting customer needs and expectations for hightechnology products, quality manufacturing, timely deliveries, excellenttraining, and superior after-sales support.

SALES AND SERVICE

We pride ourselves in the technical competence and professionalism of our sales force, whose only business is rheology and thermal analysis. TA Instruments is recognized worldwide for its prompt, courteous, and knowledgeable service staff. Their specialized knowledge and experience are major reasons why current customers increasingly endorse our company andproducts to their worldwide colleagues.

INNOVATIVE ENGINEERING

TA Instruments is the recognized leader for supplying innovative technology, investing twice the industry average in research and development. Our new Q Series™ Thermal Analysis modules are theindustry standard. Patented innovations like Modulated DSC®, Tzero™technology, and Hi-Res™ TGA are available only from TA.

QUALITY PRODUCTS

All thermal analyzers and rheometers are manufactured according to ISO 9001:2000 procedures in our New Castle, DE (USA) or our Crawley, UK facilities.Innovative flow manufacturing procedures and a motivated, highly-skilled work forceensure high quality products with industry-leading delivery times.

TECHNICAL SUPPORT

Customers prefer TA Instruments because of our reputation for after-sales support.Our worldwide technical support staff is the largest and most experienced in theindustry. They are accessible daily by telephone, email, or via our website. Multipletraining opportunities are available including on-site training, seminars in our application labs around the world, and convenient web-based courses.

TH E R M O M E C H A N IC A L AN A LY Z E R

THE Q400 IS A SIXTH-GENERATION PRODUCT FROM THE WORLD LEADER

IN THERMAL ANALYSIS. ITS PERFORMANCE, EASE-OF-USE, AND RELIABILITY

APTLY DEMONSTRATE OUR LONG EXPERIENCE IN DESIGNING NOVEL

INSTRUMENTS FOR HIGH SENSITIVITY MECHANICAL MEASUREMENTS OVER A WIDE

TEMPERATURE RANGE.

TMATE C H N OLO G Y

71

TA InnovationsFIRST COMMERCIAL TMA

AUTOMATED PROBE CALIBRATION

MODULATED TMA™

ELECTRONIC APPLICATION OF PROGRAMMABLE FORCE IN TMA

STRESS / STRAIN, CREEP, STRESS RELAXATION, AND DYNAMIC MODES OF OPERATION

T H E R M O M E C H A N IC A L A N A LY Z E R

The Q400EM is a high-performance, research-grade thermomechanical analyzer (TMA), withunmatched flexibility in operating modes, test probes, fixtures, and available signals. For standard TMA applications, the Q400 delivers the same performance and reliability. It is ideal for research, teaching, and quality control applications, with performance equivalent to competitive research models.

Q400

TE C H N I C A L SP E C I F I C AT I O N S 73

Temperature Range (max) -150 to 1,000 ˚C -150 to 1,000 ˚C

Temperature Precision ± 1 ˚C ± 1 ˚C

Furnace Cool Down Time <10 min from 600 ˚C to 50 ˚C <10 min from 600 ˚C to 50 ˚C

(air cooling)

Maximum Sample Size - solid 26 mm (L) x 10 mm (D) 26 mm (L) x 10 mm (D)

Maximum Sample Size - film/fiber

Static Operation 26 mm (L) x 1.0 mm (T) 26 mm (L) x 1.0 mm (T)

x 4.7 mm (W) x 4.7 mm (W)

Dynamic Operation 26 mm (L) x .35 mm (T) —x 4.7 mm (W)

Measurement Precision ± 0.1 % ± 0.1 %

Sensitivity 15 nm 15 nm

Dynamic Baseline Drift <1 µm (-100 to 500 ˚C) <1 µm (-100 to 500 ˚C)

Force Range 0.001 to 1 N 0.001 to 1 N

Force Resolution 0.001 N 0.001 N

Frequency 0.01 to 2 Hz Not Available

Mass Flow Control Included Included

Atmosphere Inert, Oxidizing, Inert, Oxidizing,

(static or controlled flow) or Reactive Gases or Reactive Gases

Q400EM Q400

Standard Included Included

Stress/Strain Included Not Available

Creep Included Not Available

Stress Relaxation Included Not Available

Dynamic TMA (DTMA) Included Not Available

Modulated TMA™ (MTMA™) Included Not Available

Note: The Q400 can be field upgraded to the Q400EM.

TE C H N IC A L SPE C I F IC AT IO N S

OPERATIONAL MODES

A thermomechanical analyzer measures sampledimensional changes under conditions of controlledtemperature, time, force, and atmosphere. Our engineering experience in design and integration ofcritical furnace, temperature, dimension measurement,and atmosphere control components meld with powerful, flexible software to optimize the many teststhat the Q Series™ TMA can perform.

1 FURNACE

The Q400 features a rugged and reliable furnace. Itscustomized electronics provide excellent heating ratecontrol and rapid response over a wide temperaturerange. Furnace raising and lowering is software-controlled. Benefits: The design ensures long life andperformance consistency. Excellent heating rate control provides for superior baseline stability andimproved sensitivity, while the rapid response permitsModulated TMA™ operation. Furnace movement provides operational convenience, and easy access tothe sample chamber.

2 SAMPLE CHAMBER

Located in the furnace core, the easily accessed chamber provides complete temperature and atmosphere control for sample analysis. Purge gas furnace routing is optimized and regulated by a digitalmass flow controller.

Benefits: Enhanced flexibility, data quality, ease-of-use, and productivity. Heating rate control and purge gasrouting provide optimized performance in both standard and temperature modulated modes of operation. The open design simplifies installation of available probes (See Modes of Deformation), sample mounting,and thermocouple placement. Data precision is enhanced by mass flow control of the purge gas.

TMA TE C H N OLO G Y

1 2

3 FORCE MOTOR

A non-contact motor provides a preciselycontrolled, friction-free, calibrated force to thesample via the measurement probe or fixture.The force is programmable from 0.001 to 1 N,and can be increased to 2 N by addition ofweights to a special tray. A precision sinewave generator provides a set of ten individual frequencies for use in dynamicexperiments. Benefits: The motor smoothlygenerates the accurate and precise static,ramped, or oscillatory dynamic force necessary for quality measurements in allmodes of operation. The choice of frequencies allows optimization of dynamicTMA (DTMA) experiments in compression, 3-point bending, or tension modes of deformation.

4 LINEAR VARIABLE

DIFFERENTIAL TRANSDUCER

The heart of the Q400 TMA sample measure-ment system is the precision, moveable-core,linear variable differential transducer (LVDT).Benefits: It generates an accurate outputsignal that is directly proportional to a sampledimension change. Its precise and reliableresponse over a wide temperature range (-150 to 1,000 ˚C) makes for reproducibleTMA results. Its location below the furnaceprotects it from unwanted temperature effectsand ensures stable baseline performance.

TMA TE C H N O L O G Y 75

3

4

MOD E S OF DE F OR M AT IO N

1

3

4

The Q400 offers all the major TMA deformation modes necessaryto characterize solids, foams, films, and fibers. These includecompression, tension, and 3-point bending.

COMPRESSION

In this mode, the sample is subjected to either a static, linear ramp, or dynamic oscillatory force, while under a defined temperature program, and atmosphere. Sample displacement(strain) is recorded by either expansion/penetration experimentsused to measure intrinsic material properties, or by dynamic testsand used to determine viscoelastic parameters (DTMA), detectthermal events, and separate overlapping transitions (MTMA™).

EXPANSION

Expansion measurements determine a material’s coefficient ofthermal expansion (CTE), glass transition temperature (Tg), andcompression modulus. A flat-tipped standard expansion probe(Figure 1) is placed on the sample (a small static force may beapplied), and the sample is subjected to a temperature program.Probe movement records sample expansion or contraction. Thismode is used with most solid samples. The larger surface area ofthe macro-expansion probe (Figure 2) facilitates analysis of softor irregular samples, powders, and films

PENETRATION

Penetration measurements use an extended tip probe (Figure 3)to focus the drive force on a small area of the sample surface.This provides precise measurement of Tg, softening, and meltingbehavior. It is valuable for characterizing coatings without theirremoval from a substrate. The probe operates like the expansionprobe, but under a larger applied force. The hemispherical probe(Figure 4) is an alternate penetration probe for softening pointmeasurements in solids.

2

MO D E S O F DE F O R M AT I O N 77

3-POINT BENDING

In this bending deformation (also known as flexure), the sample is supported at both ends on a two-point, quartz anvil atop the stage(Figure 5). A fixed static force is applied vertically to the sample at its center, via a wedge-shaped, quartz probe. Material properties are determined from the force and the measured probedeflection. This mode is considered to represent “pure” deformation,since clamping effects are eliminated. It is primarily used to determinebending properties of stiff materials (e.g., composites), and for distortiontemperature measurements. Dynamic (DTMA) measurements are alsoavailable with the Q400EM, where a special, low-friction, metallic anvilreplaces the quartz version.

TENSION

Tension studies of the stress/strain properties of films and fibers are performed using a film/fiber probe assembly (Figure 6). An alignment fixture (Figure 7) permits secure, and reproducible, sample positioningin the clamps. The clamped sample is placed in tension between thefixed and moveable sections of the probe assembly. Application of afixed force is used to generate stress/strain and modulus information.Additional measurements include Tg, softening temperatures, cure, andcross-link density. Dynamic tests (e.g. DTMA, MTMA™) in tension canbe performed to determine viscoelastic parameters (e.g., E|, E||, tan δ),and to separate overlapping transitions.

SPECIALTY PROBE/FIXTURE KITS

Additional sample measurement probes and fixtures areavailable for use with both the Q400 and Q400EM inspecialty TMA applications. These include the following:

Dilatometer Probe Kit – for use in volume expansioncoefficient measurements

Parallel Plate Rheometer – for the measurement of lowshear viscosity of materials (10 to 107 Pa.s range) undera fixed static force

The expansion, macro-expansion, and penetrationprobes are supplied with the Q400. These probes, plusthe flexure probe, and the low-friction bending fixture,are included with the Q400EM module. Data analysisprograms relevant to each of the measurementsdescribed are provided in our Advantage™ software.

6

5

7

TMA TH E ORY / MOD E S OF OPE R AT IO N

TMA measures material deformation changes under controlled conditions of force, atmosphere, time and temperature. Force can beapplied in compression, flexure, or tension modes of deformationusing specially designed probes described in pages 76-77. TMA measures intrinsic material properties (e.g., expansion coefficient, glass transition, Young’s modulus), plus processing / product performance parameters (e.g., softening points). These measurements have wide applicability, and can be performedby either the Q400 or the Q400EM.

The Q400 and Q400EM operating modes permit multiple materialproperty measurements. The Q400 features the Standard mode,while the Q400EM additionally offers Stress / Strain, Creep, StressRelaxation, Dynamic TMA and Modulated™ TMA modes asdescribed below.

1 & 2 STANDARD MODE

(Q400/Q400EM)Temperature Ramp: Force is held constant, and displacement ismonitored under a linear temperature ramp to provide intrinsic property measurements.

Isostrain: Strain is held constant, and the force required to maintainthe strain is monitored under a temperature ramp. This permitsassessment of shrinkage forces in materials such as films / fibers.

Force Ramp: Force is ramped, and the resulting strain is measuredat constant temperature to generate force / displacement plots andmodulus assessment.

3 STRESS/STRAIN MODE (Q400EM)Stress or strain is ramped, and the resulting strain or stress is measured at constant temperature. Using customer entered samplegeometry factors, the data provides both stress / strain plots andrelated modulus information. In addition, calculated modulus can bedisplayed as a function of stress, strain, temperature, or time.

Temperature (Time)

ForceStrain

T

Stra

in (

Forc

e)

1

Force (Time)

T

F

Stra

in

2

Strain (Stress)

T

StrainStress

Stre

ss (

Stra

in)

3

TMA TH E O RY / MO D E S O F OP E R AT I O N 79

4 CREEP AND STRESS RELAXATION

TMA can also measure viscoelastic properties using transient (e.g., creep or stress relaxation) tests. These require the Q400EM module. In Creep, input stress is held constant, and resulting strain ismonitored usually as a function of time. In Stress Relaxation, input strainis held constant, and stress decay is measured as a function of time.Both are transient tests used to assess material deformation and recovery properties of materials. The data can also be displayed in units of compliance (creep mode) and stress relaxation modulus (stress relaxation mode).

5 & 6 DYNAMIC TMA MODE (Q400em)In Dynamic TMA (DTMA), a known sinusoidal stress and linear temperature ramp are applied to the sample (Figure 5), and the resulting sinusoidal strain, and sine wave phase difference (δ) are measured (Figure 6a). From this data, storage modulus (El), loss modulus (Ell), and tan δ (Ell / El) are calculated as functions of temperature, time, or stress (Figure 6b). This technique can be usefulin the analysis of thin polymer films.

7 MODULATED TMA™ (MTMA™; Q400em) In Modulated TMA™ (MTMA™), the sample experiences the combinedeffects of a linear temperature ramp and a sinusoidal temperature ofselected amplitude and period (Figure 7). The output signals, afterFourier transformation of the raw data, are total displacement and thechange in thermal expansion coefficient. Both can be resolved into theirreversing and non-reversing component signals. The reversing signalcontains events attributable to dimension changes, and is useful indetecting related events (e.g.,Tg). The non-reversing signal containsevents that relate to time dependent kinetic processes (e.g., stressrelaxation). This technique is unique to the Q400EM.

Temperature

T

Mod

ulat

ed L

engt

h

Mod

ulat

ed T

empe

ratu

re7

Time T2T1

Stra

in /

Stre

ss

4

Temperature (time)

S

T

% S

train

5

6A

6B

AP P L IC AT IO N S

MATERIAL PERFORMANCE

AND SELECTION

Figure 3 is an example of a 3-point bending mode(flexure probe) experiment on a polyvinyl chloride(PVC) sample, using the ASTM International Test Method E2092 to determine the distortion temperature. This test specifies the temperature atwhich a sample of defined dimensions produces acertain deflection under a given force. It has longbeen used for predicting material performance.

INTRINSIC AND PRODUCT

PROPERTY MEASUREMENTS

Figure 1 shows expansion and penetration probemeasurements of Tg, and softening point, of a synthetic rubber using a temperature ramp at constant force. The large CTE changes in theexpansion plot indicate the transition temperatures. In penetration, they may be detected by the sharpmovement of the loaded probe into the changingmaterial structure.

ACCURATE COEFFICIENT

OF THERMAL EXPANSION

MEASUREMENTS

Figure 2 demonstrates the use of the expansionprobe to accurately measure small CTE changes inan aluminum sample over a 200 ˚C temperaturerange. Advantage™ software permits analysis of thecurve slope using an “at point,” “straight line,” or“best fit” method to compute the CTE at a selectedtemperature, or over a range.

-20

-40

71.24 ˚C-17.48 µm

Size: 0.492 x 5.41 x 5.08 mmForce: 78.48 mNDeflection: -17.48 µm

706050403020 80Temperature (˚C)

FIGURE 3

Dim

ensi

on C

hang

e (µ

m)

0

80400

200 µm/m ˚C

Ts 39 ˚C

Ts 40 ˚CTg -44 ˚C

90 µm/m ˚C

PenetrationLoading: 5g

ExpansionLoading: None

Tg -43 ˚C

-40-80-120Temperature (˚C)

FIGURE 1

Dis

plac

emen

t

50

40

20

30

-10

0

10

80

At a Point 127 ˚Cα=25.8 µm/m ˚C

Point-to-Point Methodα=27.6 µm/m ˚C

Average Methodα=26.8 µm/m ˚C

230 ˚C

45˚CAluminumExpansion ProbeSize: 7.62 µmProg.: 5 ˚C/minAtm.: N2

40 120 240200160Temperature (˚C)

FIGURE 2D

imen

sion

Cha

nge

(µm

)60

AP P L I C AT I O N S 81

FILM TENSILE TESTING

Figure 6 displays a strain ramp experiment, at aconstant temperature, on a proprietary film in tension. The plot shows an extensive region wherestress and strain are linearly related, and over whicha tensile modulus can be directly determined.Quantitative modulus data can also be plotted as afunction of stress, strain, time, or temperature. The results show the ability of the Q400EM to function as a mini tensile tester for films and fibers.

FILM PROPERTY TESTING

Figure 5 illustrates a classic isostrain experiment, inthe tension mode, on a food wrapping film. The filmwas strained to 20% at room temperature for 5 minutes, cooled to -50 ˚C and held for 5 more minutes, then heated at 5 ˚C/min to 40 ˚C. The plotshows the force variation required to maintain a setstrain in the film. The test simulates film use from thefreezer to the microwave.

0.000

0.015

0.010

0.005

5 10

Slope = Modulus

150 20Strain (%)

FIGURE 6

Stre

ss (

MPa

)

0.020

-140

-120

-100

-80

-60

-40

-20

0103 ˚C

-93.2 µm 258 ˚C

-108 µm

0 50 100 150 200 250 300-50 350Temperature (˚C)

FIGURE 4

Dim

ensi

on C

hang

e (m

)

20

2005

2025

2020

2015

2010

75

250.2

0.1

0.3

0.0

-25

10 20 30 400 50Time (min)

FIGURE 5D

imen

sion

Cha

nge

(µm

)

Tem

pera

ture

(˚C

)

Forc

e (N

)

2030

MULTILAYER FILM ANALYSIS

Figure 4 shows a compression mode analysis, usinga penetration probe, of a double layer PE/PET filmsample, supported on a metal substrate. The sampletemperature was linearly ramped from ambient to275 ˚C at 5 ˚C/min. The plot shows probe penetra-tions of the PE layer (93.2 µm) at 103 ˚C, and thePET layer (14.8 µm) at 258 ˚C respectively.

AP P L IC AT IO N S

CREEP ANALYSIS

Creep tests help in materials selection for end useswhere stress changes are anticipated. Figure 9illustrates an ambient temperature creep study on a polyethylene film in tension. It reveals theinstantaneous deformation, retardation, and linearregions of strain response to the set stress, plus itsrecovery, with time, on stress removal. The data canalso be plotted as compliance, and recoverable compliance, versus time.

FIBER STRESS/STRAIN

MEASUREMENTS

Stress/strain measurements are widely used toassess and compare materials. Figure 7 shows thedifferent regions of stress/strain behavior in apolyamide fiber (25 µm) in tension, when subjectedto a force ramp at a constant temperature. The fiberundergoes instantaneous deformation, retardation,linear stress/strain response, and yield elongation.Other parameters (e.g., yield stress, Young’s modulus) can be determined.

THERMAL STRESS ANALYSIS

OF FIBERS

Figure 8 displays a tension mode experiment, usinga temperature ramp at a constant strain (1%), toperform a stress analysis on a polyolefin fiber, as received, and after cold drawing. The plot showsthe forces needed to maintain the set strain as a function of temperature. The data has been correlated with key fiber industry processing parameters, such as shrink force, draw temperature,draw ratio, elongation at break, and knot strength.

0.0

0.2

0.4

0.6

0.8

1.0

-1 0 1 2 3 4 5 6 7 8 9 10 11 12Time (min)

FIGURE 9

Creep

Recovery

Stra

in (

%)

1.2

0

1

2

3

0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40Force (N)

Yield Region

Elastic Region

FIGURE 7

Dim

ensi

on C

hang

e (µ

m)

4

0.4

0.2

0.6

0.020 40 60 80 100 120 140 160 180 200

Temperature (˚C)

As Received

Cold Drawn

FIGURE 8Fo

rce

(N)

AP P L I C AT I O N S 83

SEPARATING OVERLAPPING

TRANSITIONS - MODULATED™ TMAFigure 12 shows an MTMA™ study to determinethe Tg of a printed circuit board (PCB). The signalsplotted are the total dimension change, plus itsreversing and non-reversing components. The totalsignal is identical to that from standard TMA, but does not uniquely define the Tg. The componentsignals, however, clearly separate the actual Tgfrom the stress relaxation event induced by non-optimum processing of the PCB.

STRESS RELAXATION ANALYSIS

Figure 10 shows a stress relaxation test in tensionon the same polyolefin film used for the creep studyin Figure 9. A known strain is applied to the film, andmaintained, while its change in stress is monitored.The plot shows a typical decay in the stress relax-ation modulus. Such tests also help engineersdesign materials for end uses where changes indeformation can be expected.

VISCOELASTIC PROPERTY

DETERMINATION - DYNAMIC TMA Figure 11 illustrates a dynamic test, in which asemi-crystalline polyethylene terephthate (PET) filmin tension is subjected to a fixed sinusoidal stressduring a linear temperature ramp. The resultingstrain and phase data are used to calculate thematerial’s viscoelastic properties (e.g., E|, E||, andtan δ). The plotted data shows dramatic moduluschanges as the film is heated through its glass transition temperature.

-20

0

20 20

0

40

-20

0

20

60 80 100 120

131.68 ˚C

140 160 180 200Temperature (˚C)

FIGURE 12

Dim

ensi

on C

hang

e (µ

m)

Non

-Rev

Dim

ensi

on C

hang

e (m

)

Rev

Dim

ensi

on C

hang

e (µ

m)

40

130

135

140

145

0.01 0.1 10.001 10Time (min)

FIGURE 10

Rela

xatio

n M

odul

us (

MPa

)

150

0

500

1000

1500

2000

2500 0.10

0.08

0.06

0.04

0.02

200

0

50

100

150

40 60 80 100 120 140 160Temperature (˚C)

FIGURE 11St

orag

e M

odul

us (

MPa

)

Tan

Del

ta

Loss

Mod

ulus

(M

Pa)

3000

NOT E S

W W W.TA I N S T R UM E N TS .C O M

T–2006